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Review ArticleSynthesis and Reactions of Five-Membered Heterocycles UsingPhase Transfer Catalyst (PTC) Techniques
Ahmed M El-Sayed1 Omyma A Abd Allah1
Ahmed M M El-Saghier1 and Shaaban K Mohamed23
1 Department of Chemistry Faculty of Science Sohag University Sohag 82524 Egypt2 Chemistry and Environmental Division Manchester Metropolitan University Manchester M1 5GD UK3Chemistry Department Faculty of Science Minia University El-Minia 61519 Egypt
Correspondence should be addressed to Omyma A Abd Allah omymatif66yahoocom
Received 1 May 2013 Revised 15 September 2013 Accepted 28 October 2013 Published 25 February 2014
Academic Editor Jorge F Fernandez-Sanchez
Copyright copy 2014 Ahmed M El-Sayed et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited
Phase transfer catalysts (PTCs) have been widely used for the synthesis of organic compounds particularly in both liquid-liquid andsolid-liquid heterogeneous reaction mixtures They are known to accelerate reaction rates by facilitating formation of interphasetransfer of species and making reactions between reagents in two immiscible phases possible Application of PTC instead oftraditional technologies for industrial processes of organic synthesis provides substantial benefits for the environment On the basisof numerous reports it is evident that phase-transfer catalysis is the most efficient way for generation and reactions of many activeintermediates In this review we report various uses of PTC in syntheses and reactions of five-membered heterocycles compoundsand their multifused rings
1 Introduction
Organic synthesis is an essential way to get chemical prod-ucts having practical applications such as pharmaceuti-cals plant protection agents dyes photographic sensitizersand monomers Transformations of starting materials intodesired final products usually require number of chemi-cal operations in which additional reagents catalysts andsolvents are employed Thus during any synthetic methodbesides the desired products many waste materials areproduced because transformations of reactants into productsare neither quantitative nor selective processes This wastecould be regenerated destroyed or disposed This will leadto consuming much energy and creating heavy burden onthe environment Therefore it is of a great importance todevelop and use synthetic methodologies that minimizeor eliminate such problems One of the most commonand efficient methodologies that fulfill this requirement isemploying phase-transfer catalyses techniques [1ndash4] Themost significant advantages of use of PTCs in industrialapplications are [5]
(1) elimination of organic solvents(2) elimination of dangerous inconvenient and expen-
sive reagents such as NaH and NaNH2
(3) increasing the reactivity and selectivity of the activespecies
(4) improving the yield and purity of products to theoptimum records
(5) simplifying the whole synthetic process and makingit safer and objective
(6) reducing industrial wastes and overall costs and sav-ing energy which gives a positive impact on economicand environmental interests
(7) accelerating and performing mimic reactions in anefficient mode
11 Fundamentals of Phase Transfer Catalysis (PTC) Firstphase transfer catalysis was discovered by Jarrouse and Hebdin 1951 when they observed that the quaternary ammonium
Hindawi Publishing CorporationJournal of ChemistryVolume 2014 Article ID 163074 47 pageshttpdxdoiorg1011552014163074
2 Journal of Chemistry
+
+
OHPhCH2NEt3Cl
NaOH
PhCH2NEt3Cl
NaOH
ClOCH2Ph
C2H5Cl C2H5
CN
CN
(1)
(2)
Figure 1
PhCH2CN + NaOH
PhCHCN Na + QX
PhCHCN Na + H2O
PhCHCN Q + NaX
org
org org org org
org org
PhCHCN Q + R-X CHC N + QX
int
int
aq
aq
+
++
+
minus
minus +
+
minus
minus
minus
minus PhR
Figure 2
ClCH2R
BrCH(COOEt)2
N
Ph
NH2
NC
RN
NH
CO2Et
CO2EtPh
NC
3
PhNH-CH = C(CN)2
2andashc
R a = CO2Et b = CONH2 c = COPh
Figure 3
4 5
PTCN
CN
O
Ar
NH2
6
ArNHCOCH2Cl + CH2(CN)2
Figure 4
salt and benzyltriethylammonium chloride accelerated two-phase reaction of benzyl chloridewith cyclohexanol (Figure 1(1)) and the two-phase alkylation reaction of phenylacetoni-trile with benzyl chloride or ethyl chloride [6] (Figure 1 (2))
In addition numerous publications and patents [7ndash12]have been reported during the period of 1950ndash1965 PTCstechniques have been further developed byMakosza et al forthe purpose of obtaining more efficient and pure yield [13ndash16]
12 Mechanism of Phase-Transfer Catalysis All phase-transfer catalyzed reactions involve at least two steps
(1) transfer of one reagent from its ground phase into thesecond phase as an intermediate
(2) reaction of the transferred reagent with the non-transferred reagent for example the alkylation ofphenylacetonitrile with alkyl halide using aqueousNaOH as a base and tetrabutylammonium halide
Journal of Chemistry 3
NH2
PhN
CNCN
NQ
CN
Y
Ph NH
CN
CN
CN
PhN CNCN
PhN CNCN
Y
Y
Y
Q
Q
Organic layer
K2CO3 solid surface
HX +
HXQXXCH2Y
Ph-N
Ph-N
Scheme 1
(QX) as a catalyst can be formulated as shown inFigure 2
The concept of phase-transfer catalysis is not limited toanion transfer but is muchmore general so that in principleone could also transfer cations free radicals or wholemolecule Phase transfer catalysis is classified as liquid-liquidliquid-solid liquid-gas solid-gas or solid-solid systems
2 Application of Phase Transfer Catalysisin Synthesis of Five-Membered Ring ofHeterocyclic Compounds
21 Synthesis of Five-Membered Ring Heterocycles Con-taining One Heteroatom Treatment of anilinomethylene-malononitrile 1 with ethyl chloroacetate chloroaceta-midephenacyl chloride or diethyl bromomalonate in 1 1 1molar ratio (dioxanK
2CO3tetrabutylammonium bromide
(TBAB)) afforded the corresponding substituted pyrroles 2andashc and 3 respectively [17] (Figure 3)
The catalytic cycle which explains the reaction pathwaycan be simplified as in Scheme 1
A simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitriles 6 was achievedby reaction of N-aryl-2-chloroacetamide 4 andmalononitrile5 under solid-liquid PTC condition (CH
3CNK
2CO318-
crown-6) at room temperature [18] (Figure 4)3-Amino-4-ethoxycarbonyl-1-phenyl-5-thioxo-25-dihy-
dro-2-pyrrolidene malononitrile 9a was prepared via reac-tion of malononitrile 5 phenyl isothiocyanate 7 and ethox-ymethylenemalononitrile 8a in 1 1 1 molar ratio under
the PTC mixture of dioxanK2CO3(TBAB) Replacing
of ethyl ethoxymethylenecyanoacetate 8b with 8a gaveethyl[3-amino-4-ethoxy-carbonyl-1-phenyl-5-thioxo-25-di-hydro-2-pyrrolidene]cyanoacetate 9b and 10 under the sameexperimental conditions [19] (Figure 5)
Moreover the reaction of ethyl cyanoacetate 11 withphenyl isothiocyante 7 and ethoxymethylenemalononitrile8a or ethyl ethoxymethylenecyanoacetate 8b in 1 1 1 molarratio under same PTC experimental conditions affordedthe corresponding pyrrole derivatives 12a b and 13 [19](Figure 6)
Reaction of methyl 25-dibromopentanoate 14 with tri-chloroacetamide 15 under solid-liquid technique (CH
3CN
K2CO3TEBACl) yielded methyl N-trichloroacetyl-2-pyr-
rolidine carboxylate 16 [20] (Figure 7)Substituted pyrrolidines 19 were synthesized via the
13-dipolar cycloaddition reaction between imino esters 17(derived from alanine and glycine with alkanes) and alkylacrylate 18 in a mixture of THF or toluene KOH and TBACl[21] (Figure 8)
14-Di(malononitrilemethyleneamino)benzene 20 wasallowed to react with ethyl chloroacetate chloroacetamidephenacyl chloride or diethyl bromomalonate in 1 2molar ratios under solid-liquid PTC technique to give thecorresponding 14-bi(1-pyrrolyl) benzene derivatives 21andashcand 22 [17] (Figure 9)
Pyrrolidine derivatives 24were obtained with thiophenes25 from the reaction of diethyl cyanomalonate 23with phenylisothiocyanate 7 and chloroacetonitrile or chloroacetamideusing the PTC of (DMFK
2CO3TBAB) [22] (Figure 10)
4 Journal of Chemistry
PTCNC CN NC CN
CH2(CN)2 + PhNCS5 7 S NH PhN SH
Ph
PTC NC NH2NC NH2
EtOCH = C(CN) X+ CN
SNCN
PhNS
8a bPh X
CN
109a b
X a = CN b = COOEt
Figure 5
CNCH2COOEt + PhNCS PTC EtOOC CN
NHPh
S
EtOOC CN
SHPhN
PhN
PTC PTC EtOCH=C(CN)2
N
EtOOC EtOOC
EtOOC
CN
CN
CNS S
Ph
N
EtOOC
CN CN
COOEtCOOEt
COOEt
S
Ph
EtOCH=C(CN)(COOEt)
S
NH2
NH2
NH2 NH2
HydrolysisminusPhNH2
O
H2OK2CO3
+
12a
11
8a8b
12b
13
7
Figure 6
NPTC COOCH3
14
16
15 COCCl3
Br(CH2)3CH(Br)COOCH3 + Cl3CCONH2
Figure 7
One-pot reaction of malononitrile 5 carbon disulphideand chloroacetamide in 1 1 1 molar ratio under solid-liquid PT catalysis (benzeneK
2CO3TBAB) has furnished
3-amino-2-carboxyamido-4-cyano-5-mercaptothiophene 26[23] (Figure 11) Also treatment of malononitrile 5 with
CS2and ethyl chloroacetate under the same experimental
conditions gave the corresponding thiophene derivative 27[23] (Figure 11)
Different thiophene compounds (24 and 28ndash30)preparedfrom reaction of diethyl cyanomalonate 23 with carbon
Journal of Chemistry 5
N
RO N
R
O
NH
17 18 19KOHKOH
COORCOORCOOR
R4N XR4N X R1R1
R1
minus
+
+ minus+
Figure 8
HN NH
NC
NC CN
CNPTC
NN
RRNH2
N
CNNC
NNHHN
NC CN
R = CO2Et CONH2 COPh20
22
2BrCH(CO2Et)2
H2N
CO2EtEtO2CCO2EtEtO2C
2ClCH2R
21andashc
Figure 9
EtO2C
Et EtEt
EtEtEtO
OO
O
OO
O OO
O
OOH
NCPhNCS PTC
PTC
SHSH
PhY
ZX
S
EtO2C
YN
ZX
S
25
24a b X= CO2Et Y = CN Z = NH2
24c X = CN Y = CONH2 Z =OHX = CO2Et Y = CN Z = NH2
+
+
CN CN
PhN
PhN
PhNH
XCH2Y
24andashc
Figure 10
CH2(CN)2 + CS2 + ClCH2CONH2PTC
PTC
S SH
H2N
H2NOC
CN
S
H2N CN
5
5
26
CH2(CN)2 + CS2 + ClCH2COOEtEtO2C SCH2CO2Et
27
Figure 11
6 Journal of Chemistry
NCH O
OOO
CS2
NC
O OO
O
NC
O OO
O
S S
SH
SH
Y
PTC
PTC
S
S Y
PTC
PTC
S S YS
NH2
YS
OH
CN
CN
N
NH
S
NC
PhNCS
PTC
EtO2CEtO2C
CO2Et
CO2Et
COPh
Ph
Ph
PhN
PhN
PhNS
NCEtO2C EtO2C EtO2C
S
EtO2CCO2EtEtO2C
OH
Y
Z ZX X
24a b 25a-b X = CO2C2H5 Y = CN Z = NH2
24c 25c X = CO2C2H5 Y = CONH2 Z = NH2
XCH2Y
XCH2Y
a Y = COPh b Y = CN c Y = CONH2
23
7
28andashc 29andashc
30 25andashc 24
+
++
Figure 12
disulphide or phenyl isothiocyanate 7 along with differentactive halocompounds under solid-liquid phase condition(dioxanK
2CO3TBAB) have been reported byAbdAllah and
El-Sayed [22] (Figure 12)2-Thiophenylidenes 31ndash33 were obtained through the
reaction of either malononitrile 5 or ethyl cyanoacetate 11with carbon disulphide along with ethoxymethylenemal-ononitrile 8a or ethyl ethoxymethylenecyanoacetate 8busing liquid-solid technique (dioxanK
2CO3TBAB) [19]
(Figure 13)In this reaction the yield of products was found to be a
temperature dependent Thus at low temperature (40∘C) itaffords the aminothiophene derivative 32a in high yield whileat high temperature hydroxythiophene 32b or 33b was thesolely product but in low yield
The reaction of pyridosultam 34 with 3-chloropropylthiocyanate under the experimental condition (tolueneaqNaOHTBAB) yielded the corresponding dihydrothiophenederivative 35 [24] (Figure 14)
4-Amino-5-cyano-2-hydroxy-3-furancarboxylic acid 37and compound 38were synthesized by treating 1-phenyl-35-pyrazolinedione 36 with bromomalononitrile under solid-liquid condition (dioxanK
2CO3TBAB) (Figure 15) [25]
The reaction pathway for the formation of unexpectedcompound 37was assumed to proceed via catalytic hydrolysisof compound 38 into the furan derivative 37 and phenylhydrazine [25] (Figure 16)
Condensation of salicylaldehyde 39 and its derivativeswith various esters of chloroacetic acids 40 in the pres-ence of TBAB led to the synthesis of benzo[b]furans 41under solventless and microwave irradiation technique [26](Figure 17)
Liquid-liquid PTC reaction of 4-chlorobutyronitrile 42with nonenolizable aldehydes 43 via sequence of an addi-tion cyclization reaction gave tetrahydrofuran-3-carbonitrilederivative 44 [27] (Figure 18)
Fused bis-aroylbenzodifurans 46 have been synthesizedby condensing 24-diacetyl resorcinol 45 with various p-substituted phenacyl bromides [28] (Figure 19)
Methyl or ethyl 3-amino-4-arylthiophenes-2-carbox-ylates 48andashf were synthesized by Thorpe reaction throughthe treatment of 3-hydroxy-2-arylacrylonitriles 47andashf andmethyl or ethyl thioglycolates with hydrochloric acid byusing different PTC conditions (solid-liquid or liquid-liquid)The solid-liquid PTC conditions using 18-crown-6 alongwith potassium hydroxide as a catalyst are the method withexcellent yieldsThe reactions were carried out in acetonitrileat RT [29] (Figure 20)
In Japp-Klingemann reaction the indole derivatives 52have been prepared as indicated in Figure 21 The additionof a suitable PTC catalyst to the reaction could signifi-cantly improve the reaction process Firstly aryl amines49 were diazotized and reacted under alkaline conditionsethyl 2-[2-(13-dioxo-13-dihydro-2H-isoindol-2-yl)ethyl]-3-oxobutanoate 50 using PTC-promoted Japp-Klingemann
Journal of Chemistry 7
PTCK2CO3
DioxaneTBAB
NC
SHS
CNPTC
EtOCH=C(CN)(X)
HCN
PTC
S
S
NC
X
X
CN
SX
CN
HS
NC NH
HS
NC
CNS
31a b
X a = CN b = COOEt
EtOCH=C(CN)(X)
+
PTCEtOOC
S SH
CN
PTC
CN
EtOOC
EtOOC
SX
HCN
S
S S
NH2
NH2
X
OH
S S
NC
CNCNCOOEt
PTC
32a b X a = CN b = COOEt 33b
11
8a b
8a b
5
NCCH2COOEt + CS2
CH2(CN)2 + CS2
Figure 13
NSO2 SO2
N
Me
ClPTC
S
N
N
Me
SN
NH
Me
+
33 34 35
NCSminusSO2
Figure 14
CNHOOC CN
BrCH(CN)2 + HN NH2
NH2
O
ONPTC
HOO
HN
O
ON
Ph Ph36 37 38
Figure 15
CNO
NH2
NH2NH2N
HOOC
HNNO
O
CN
Ph
3738
Ph
H2NH2OOHminus
H2OOHminus
CN
OHO
HOOC
+ PhNHNH2
Figure 16
8 Journal of Chemistry
OH
CHOR + ClCH2COOR1
PTCMicrowave
O
R
39 40 41
COOR1
Figure 17
Ar-CH-OH
NC-CH-CH2-CH2Cl
O Ar
CN
42 43 44
ClCH2CH2CH2CN + Ar-CHO
Figure 18
CH3O
OHHO
H3C
O
K2CO3TBAHSO4 O
OO
CH3
O
X
X
H3CEDC
X = H Cl NO2 CH3 OCH3 OCH3 Br
COCH2Br+ 2X
45
46
Figure 19
CNR
H OH
1 HSCH2COOR1 HCl2 KOH ArCN 18-C-6
H S COOR1COOR1
CNR
S
R NH2
47andashf 48andashf
a phb 4-O-CH3
c benzo[b]furyl-2d thinyl-2e dimethyl 25-thinylf C6H5
R1RCOOMeCOOMeCOOMeCOOMeCOOMeCOOEt
60ndash70∘C
Figure 20
reaction to form the ring-opened aryl hydrazones 51 Thesearyl hydrazones were cyclized and converted into the corre-sponding indole derivatives 52 by adding hydrochloric acidin ethanol [30] (Figure 21)
Synthesis of dimethyl phosphinyl substituted tetra-hydropyrroles 55 via 13-cycloaddition reaction of the azome-thine 53 to electron deficient alkenes such as 120572120573-unsaturatedketones (eg benzylideneacetophenone 54) esters and
nitriles took place in high yield and low diastereoselectivityin phase-transfer catalysis conditions (solid potassium car-bonate triethylbenzylammonium chloride (TEBA)) in aceto-nitrile as a solvent [31] (Figure 22)
When Schiff base 53 and ethyl cinnamate 56 reactedunder different phase-transfer catalysis conditions (10 equiv-alents of aqueous NaOH (50)TEBADMSO) the esterof pyrrolidinecarboxylic acid 57 has not been formed
Journal of Chemistry 9
NH2
R
HClHNO2
N+
NCl
R
NCH3O
COOC2H5
CH3
COOC2H5
COOC2H5
O O
NN
HNO
O
R
NH
N
O
O
HCl
49
50
5152 R
0ndash5∘C
Figure 21
+
N
HCOPh
COPhH5C6
PH3CH3C
H3CH3C
OCl
53
54
NPh
PO
Cl
55
Figure 22
N C6H4-Cl-4PH3CH3C
H3C
H3C
H3C
H3C
O
PhCOOEt
+
NH
NH
H5C6
H5C6
C6H4-Cl-4
C6H4-Cl-4
COOEt
P
COOH
PO
O
NaOHH2OCH3CN
NaOHTEBA H2ODMSO
53
56
57
58
Figure 23
instead the acid itself 58 was obtained as a mixture of twodiastereoisomers [31] (Figure 23)
22 Synthesis of Five-Membered Ring Heterocycles Contain-ing Two Heteroatoms (4Z)-4-(4-amino-13-dithiol-2-ylid-ene)-5-methyl-2-phenyl-24-dihydro-3H-pyrazol-3-one
derivative 60 was the product of a reaction of 3-methyl-1-phenyl-2-pyrazoline-5-one 59 with CS
2and chloroac-
etonitrile in equimolar ratio under solid-liquid technique(benzeneK
2CO3TBAB) [23] (Figure 24)
Similarly 1-phenyl-35-pyrazolidinedione 36 was treatedwith CS
2and ethyl chloroacetate under the same condition
10 Journal of Chemistry
N
OPh
PTCNN
CH3
O
Ph
S
SN
H2N
59 60
+ CS2 + ClCH2CN
H3C
Figure 24
N O
O
Ph
+ + ClCH2COOEtHNHN
HN
HN
O
O
Ph
S
COOEt
S
N N
O
O
Ph
SH
EtOOCH2CS
N
O
OPh
S
S
O
36
61
minusEtOH
CS2
Figure 25
SS COOEt
NC
NH2
NH2
NH2
NH2
SS
COOEt
NCN
S
N
S
SS
CS2ClCH2CNPTC
PTC
CS2ClCH2COOEt
S
S
COOEt
NCN S
N
SO
SS O
62
63
64
Figure 26
Journal of Chemistry 11
S
SS
S
S
S COOEt
COOEt
NC
NH2
NH2
PTC
N
N
NC
SS
CS2Br(CH2)2Br
6562
Figure 27
PhPh
NN
O PTC
N
NHN
H3Cn = 0 1 a n = 067a b b n = 1
66
S
CH3
+ Br(CH2)nCH2Br(CH2)nCH2Br
Figure 28
X-CH2-N-NHAr [CH2=N-N]-Ar
RndashCH=CH2
N
NR
Ar70
69
68
minus+
Figure 29
H3C
H3C
SO2CH2NC + RCHO PTCO
N
N
N
SO2
SO2H3C
H3C
R
PTC
R1
71 72
7371
74
75 R2
SO2CH2NC + R1CH=NR2
Figure 30
Me
ClMe
CH + N=NN
N
H3C
S
CH3
PTCN
N
NN
CH3
CH3
S
CH3
H3C
RR
76 77 78
Figure 31
12 Journal of Chemistry
Br
BrPTC+
79 80 81
N
S
NO
H
PhNH
HNS
H
PhO
Figure 32
X
Y
+ PhNCSKOHDioxan
XYPhHN
KS
N
S
O Ph
X
Y
a X Y = CN b X = CN Y = CO2Etc X Y = CO2Et d X = COPh Y = COCH3
e COCH3 Y = CO2Et f X = COPh Y = CO2Etg X Y = COCH3
Cl
Z
OZ = Cl OEt or NH2
82andashg 83andashg
Figure 33
(benzeneK2CO3TBAB) to give the corresponding (4Z)-4-
(4-oxo-13-dithiolan-2-ylidene)-1-phenylpyrazolidine-35-dione 61 [25] (Figure 25)
The addition reaction of ethyl 34-diamino-5-cyanot-hieno[23-b]thiophene-2-carboxylate 62 to carbon disul-fide followed by cyclization reaction through the treat-ment with chloroacetonitrile or ethyl chloroacetate underPTC conditions (K
2CO3 TBAB dioxane) furnished 34-
bis(4-amino-2-thioxo-13-thiazol-3(2H)-yl)-5-propanoylthi-eno[23-b]thiophene-2-carbonitrile 63 and 34-bis(4-oxo-2-thioxo-13-thiazolidin-3-yl)-5-propanoylthieno[23-b]thio-phene-2-carbonitrile 64 in satisfactory yields [32] (Figure26)
Moreover the addition reaction of compound 62 tocarbon disulfide followed by cycloalkylation reaction with12-dibromoethane at 1 1 1 molar ratio under same PTCconditions afforded the corresponding bis-13-dithiolan-2-ylidene 65 [32] (Figure 27)
Treatment of triazepene compound 66 with dibromidesusing liquid-liquid condition (benzeneNaOHTBAB) fur-nished pyrazole derivatives 67a b [33] (Figure 28)
13-Dipolar cycloaddition of various substituted nitril-imines 68 to the appropriate alkenyl dipolarophiles 69 inaqueous media and in presence of a surfactant afforded anumber of 1-aryl-5-substituted-45-dihydropyrazoles 70 [34](Figure 29)
Preparation of 5-substituted oxazoles 74 or imidazoles75 was achieved by reaction of p-tolylsulphonylmethyl iso-cyanide 71 with aldehydes 72 R
1CH=NR
2or 73 (R
1 R2=
substituted phenyl heteroaryl and alkyl) under liquid-liquidcondition [35 36] (Figure 30)
The interaction of 3-chloro-3-methyl-1-butyne 76 with46-dimethyl-5-arylazo-2-thiopyrimidine 77 under liq-uid-liquid phase (benzeneaq KOHBTEACl) afforded 46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidinyl-(5H)-thiones 78 [37] (Figure 31)
Reaction of 5-phenylmethylene thiohydantoin 79 with12-dibromoethane 80 under liquid-liquid conditions (ben-zeneaq NaOHTBAB) afforded 23-dihydro-6-phenylmeth-ylene-5-oxo-imidazo[23-b]thiazole 81 [38] (Figure 32)
A variety of 4-thiazolidinone derivatives 83andashgwere suc-cessfully synthesized via in situ formation of ketene-NS-acetals 82andashg which in turn was reacted with ethylchloroethyl acetate chloroacetamide or chloroacetyl chlo-ride followed by ring closure to afford the desired 4-thiazolidinones 83andashg [39] (Figure 33)
One of the medicinal applications for PTC techniques issynthesis of sibenadet hydrochloride 87 which is a potentdrug used for treatment of chronic obstructive pulmonarydisease This bioactive molecule was synthesized by O-alkylation of phenylethanol 84 with the alkyl bromide 85under PTC condition to form the alkylated product 86 in97 yield Reaction of 86 with benzothiazole derivative ledto formation of the desired product 86 [40] (Figure 34)
Treatment of an equimolar amount of 2-mercapto-quinazolin-4(3H)-one 88 and dihalocompounds such as 12-dibromoethane and chloroacetyl chloride underwent S- and
Journal of Chemistry 13
OH
+ H2CBr
NaOHH2OTBAHSO4
OCH2
97
Sibenadet hydrochloride
84 8586
87 O
S NH
S
OHO
OO
NH middotHCl
Figure 34
NH
NH
O
SH
ClCH2COCl
Br(CH2)2Br
PTC89
88
O
N
NH
NH
S
OO
N
S
90
Figure 35
Ph
NO
O
SN
CS2 Br(CH2)2Br H
NH
NH
PTC
Ph
S
S
N
Ph
S
N
O
91
CS2Br(CH2)3Br
S
S
SPTC
92b
92a
Figure 36
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
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[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
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[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
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CatalystsJournal of
2 Journal of Chemistry
+
+
OHPhCH2NEt3Cl
NaOH
PhCH2NEt3Cl
NaOH
ClOCH2Ph
C2H5Cl C2H5
CN
CN
(1)
(2)
Figure 1
PhCH2CN + NaOH
PhCHCN Na + QX
PhCHCN Na + H2O
PhCHCN Q + NaX
org
org org org org
org org
PhCHCN Q + R-X CHC N + QX
int
int
aq
aq
+
++
+
minus
minus +
+
minus
minus
minus
minus PhR
Figure 2
ClCH2R
BrCH(COOEt)2
N
Ph
NH2
NC
RN
NH
CO2Et
CO2EtPh
NC
3
PhNH-CH = C(CN)2
2andashc
R a = CO2Et b = CONH2 c = COPh
Figure 3
4 5
PTCN
CN
O
Ar
NH2
6
ArNHCOCH2Cl + CH2(CN)2
Figure 4
salt and benzyltriethylammonium chloride accelerated two-phase reaction of benzyl chloridewith cyclohexanol (Figure 1(1)) and the two-phase alkylation reaction of phenylacetoni-trile with benzyl chloride or ethyl chloride [6] (Figure 1 (2))
In addition numerous publications and patents [7ndash12]have been reported during the period of 1950ndash1965 PTCstechniques have been further developed byMakosza et al forthe purpose of obtaining more efficient and pure yield [13ndash16]
12 Mechanism of Phase-Transfer Catalysis All phase-transfer catalyzed reactions involve at least two steps
(1) transfer of one reagent from its ground phase into thesecond phase as an intermediate
(2) reaction of the transferred reagent with the non-transferred reagent for example the alkylation ofphenylacetonitrile with alkyl halide using aqueousNaOH as a base and tetrabutylammonium halide
Journal of Chemistry 3
NH2
PhN
CNCN
NQ
CN
Y
Ph NH
CN
CN
CN
PhN CNCN
PhN CNCN
Y
Y
Y
Q
Q
Organic layer
K2CO3 solid surface
HX +
HXQXXCH2Y
Ph-N
Ph-N
Scheme 1
(QX) as a catalyst can be formulated as shown inFigure 2
The concept of phase-transfer catalysis is not limited toanion transfer but is muchmore general so that in principleone could also transfer cations free radicals or wholemolecule Phase transfer catalysis is classified as liquid-liquidliquid-solid liquid-gas solid-gas or solid-solid systems
2 Application of Phase Transfer Catalysisin Synthesis of Five-Membered Ring ofHeterocyclic Compounds
21 Synthesis of Five-Membered Ring Heterocycles Con-taining One Heteroatom Treatment of anilinomethylene-malononitrile 1 with ethyl chloroacetate chloroaceta-midephenacyl chloride or diethyl bromomalonate in 1 1 1molar ratio (dioxanK
2CO3tetrabutylammonium bromide
(TBAB)) afforded the corresponding substituted pyrroles 2andashc and 3 respectively [17] (Figure 3)
The catalytic cycle which explains the reaction pathwaycan be simplified as in Scheme 1
A simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitriles 6 was achievedby reaction of N-aryl-2-chloroacetamide 4 andmalononitrile5 under solid-liquid PTC condition (CH
3CNK
2CO318-
crown-6) at room temperature [18] (Figure 4)3-Amino-4-ethoxycarbonyl-1-phenyl-5-thioxo-25-dihy-
dro-2-pyrrolidene malononitrile 9a was prepared via reac-tion of malononitrile 5 phenyl isothiocyanate 7 and ethox-ymethylenemalononitrile 8a in 1 1 1 molar ratio under
the PTC mixture of dioxanK2CO3(TBAB) Replacing
of ethyl ethoxymethylenecyanoacetate 8b with 8a gaveethyl[3-amino-4-ethoxy-carbonyl-1-phenyl-5-thioxo-25-di-hydro-2-pyrrolidene]cyanoacetate 9b and 10 under the sameexperimental conditions [19] (Figure 5)
Moreover the reaction of ethyl cyanoacetate 11 withphenyl isothiocyante 7 and ethoxymethylenemalononitrile8a or ethyl ethoxymethylenecyanoacetate 8b in 1 1 1 molarratio under same PTC experimental conditions affordedthe corresponding pyrrole derivatives 12a b and 13 [19](Figure 6)
Reaction of methyl 25-dibromopentanoate 14 with tri-chloroacetamide 15 under solid-liquid technique (CH
3CN
K2CO3TEBACl) yielded methyl N-trichloroacetyl-2-pyr-
rolidine carboxylate 16 [20] (Figure 7)Substituted pyrrolidines 19 were synthesized via the
13-dipolar cycloaddition reaction between imino esters 17(derived from alanine and glycine with alkanes) and alkylacrylate 18 in a mixture of THF or toluene KOH and TBACl[21] (Figure 8)
14-Di(malononitrilemethyleneamino)benzene 20 wasallowed to react with ethyl chloroacetate chloroacetamidephenacyl chloride or diethyl bromomalonate in 1 2molar ratios under solid-liquid PTC technique to give thecorresponding 14-bi(1-pyrrolyl) benzene derivatives 21andashcand 22 [17] (Figure 9)
Pyrrolidine derivatives 24were obtained with thiophenes25 from the reaction of diethyl cyanomalonate 23with phenylisothiocyanate 7 and chloroacetonitrile or chloroacetamideusing the PTC of (DMFK
2CO3TBAB) [22] (Figure 10)
4 Journal of Chemistry
PTCNC CN NC CN
CH2(CN)2 + PhNCS5 7 S NH PhN SH
Ph
PTC NC NH2NC NH2
EtOCH = C(CN) X+ CN
SNCN
PhNS
8a bPh X
CN
109a b
X a = CN b = COOEt
Figure 5
CNCH2COOEt + PhNCS PTC EtOOC CN
NHPh
S
EtOOC CN
SHPhN
PhN
PTC PTC EtOCH=C(CN)2
N
EtOOC EtOOC
EtOOC
CN
CN
CNS S
Ph
N
EtOOC
CN CN
COOEtCOOEt
COOEt
S
Ph
EtOCH=C(CN)(COOEt)
S
NH2
NH2
NH2 NH2
HydrolysisminusPhNH2
O
H2OK2CO3
+
12a
11
8a8b
12b
13
7
Figure 6
NPTC COOCH3
14
16
15 COCCl3
Br(CH2)3CH(Br)COOCH3 + Cl3CCONH2
Figure 7
One-pot reaction of malononitrile 5 carbon disulphideand chloroacetamide in 1 1 1 molar ratio under solid-liquid PT catalysis (benzeneK
2CO3TBAB) has furnished
3-amino-2-carboxyamido-4-cyano-5-mercaptothiophene 26[23] (Figure 11) Also treatment of malononitrile 5 with
CS2and ethyl chloroacetate under the same experimental
conditions gave the corresponding thiophene derivative 27[23] (Figure 11)
Different thiophene compounds (24 and 28ndash30)preparedfrom reaction of diethyl cyanomalonate 23 with carbon
Journal of Chemistry 5
N
RO N
R
O
NH
17 18 19KOHKOH
COORCOORCOOR
R4N XR4N X R1R1
R1
minus
+
+ minus+
Figure 8
HN NH
NC
NC CN
CNPTC
NN
RRNH2
N
CNNC
NNHHN
NC CN
R = CO2Et CONH2 COPh20
22
2BrCH(CO2Et)2
H2N
CO2EtEtO2CCO2EtEtO2C
2ClCH2R
21andashc
Figure 9
EtO2C
Et EtEt
EtEtEtO
OO
O
OO
O OO
O
OOH
NCPhNCS PTC
PTC
SHSH
PhY
ZX
S
EtO2C
YN
ZX
S
25
24a b X= CO2Et Y = CN Z = NH2
24c X = CN Y = CONH2 Z =OHX = CO2Et Y = CN Z = NH2
+
+
CN CN
PhN
PhN
PhNH
XCH2Y
24andashc
Figure 10
CH2(CN)2 + CS2 + ClCH2CONH2PTC
PTC
S SH
H2N
H2NOC
CN
S
H2N CN
5
5
26
CH2(CN)2 + CS2 + ClCH2COOEtEtO2C SCH2CO2Et
27
Figure 11
6 Journal of Chemistry
NCH O
OOO
CS2
NC
O OO
O
NC
O OO
O
S S
SH
SH
Y
PTC
PTC
S
S Y
PTC
PTC
S S YS
NH2
YS
OH
CN
CN
N
NH
S
NC
PhNCS
PTC
EtO2CEtO2C
CO2Et
CO2Et
COPh
Ph
Ph
PhN
PhN
PhNS
NCEtO2C EtO2C EtO2C
S
EtO2CCO2EtEtO2C
OH
Y
Z ZX X
24a b 25a-b X = CO2C2H5 Y = CN Z = NH2
24c 25c X = CO2C2H5 Y = CONH2 Z = NH2
XCH2Y
XCH2Y
a Y = COPh b Y = CN c Y = CONH2
23
7
28andashc 29andashc
30 25andashc 24
+
++
Figure 12
disulphide or phenyl isothiocyanate 7 along with differentactive halocompounds under solid-liquid phase condition(dioxanK
2CO3TBAB) have been reported byAbdAllah and
El-Sayed [22] (Figure 12)2-Thiophenylidenes 31ndash33 were obtained through the
reaction of either malononitrile 5 or ethyl cyanoacetate 11with carbon disulphide along with ethoxymethylenemal-ononitrile 8a or ethyl ethoxymethylenecyanoacetate 8busing liquid-solid technique (dioxanK
2CO3TBAB) [19]
(Figure 13)In this reaction the yield of products was found to be a
temperature dependent Thus at low temperature (40∘C) itaffords the aminothiophene derivative 32a in high yield whileat high temperature hydroxythiophene 32b or 33b was thesolely product but in low yield
The reaction of pyridosultam 34 with 3-chloropropylthiocyanate under the experimental condition (tolueneaqNaOHTBAB) yielded the corresponding dihydrothiophenederivative 35 [24] (Figure 14)
4-Amino-5-cyano-2-hydroxy-3-furancarboxylic acid 37and compound 38were synthesized by treating 1-phenyl-35-pyrazolinedione 36 with bromomalononitrile under solid-liquid condition (dioxanK
2CO3TBAB) (Figure 15) [25]
The reaction pathway for the formation of unexpectedcompound 37was assumed to proceed via catalytic hydrolysisof compound 38 into the furan derivative 37 and phenylhydrazine [25] (Figure 16)
Condensation of salicylaldehyde 39 and its derivativeswith various esters of chloroacetic acids 40 in the pres-ence of TBAB led to the synthesis of benzo[b]furans 41under solventless and microwave irradiation technique [26](Figure 17)
Liquid-liquid PTC reaction of 4-chlorobutyronitrile 42with nonenolizable aldehydes 43 via sequence of an addi-tion cyclization reaction gave tetrahydrofuran-3-carbonitrilederivative 44 [27] (Figure 18)
Fused bis-aroylbenzodifurans 46 have been synthesizedby condensing 24-diacetyl resorcinol 45 with various p-substituted phenacyl bromides [28] (Figure 19)
Methyl or ethyl 3-amino-4-arylthiophenes-2-carbox-ylates 48andashf were synthesized by Thorpe reaction throughthe treatment of 3-hydroxy-2-arylacrylonitriles 47andashf andmethyl or ethyl thioglycolates with hydrochloric acid byusing different PTC conditions (solid-liquid or liquid-liquid)The solid-liquid PTC conditions using 18-crown-6 alongwith potassium hydroxide as a catalyst are the method withexcellent yieldsThe reactions were carried out in acetonitrileat RT [29] (Figure 20)
In Japp-Klingemann reaction the indole derivatives 52have been prepared as indicated in Figure 21 The additionof a suitable PTC catalyst to the reaction could signifi-cantly improve the reaction process Firstly aryl amines49 were diazotized and reacted under alkaline conditionsethyl 2-[2-(13-dioxo-13-dihydro-2H-isoindol-2-yl)ethyl]-3-oxobutanoate 50 using PTC-promoted Japp-Klingemann
Journal of Chemistry 7
PTCK2CO3
DioxaneTBAB
NC
SHS
CNPTC
EtOCH=C(CN)(X)
HCN
PTC
S
S
NC
X
X
CN
SX
CN
HS
NC NH
HS
NC
CNS
31a b
X a = CN b = COOEt
EtOCH=C(CN)(X)
+
PTCEtOOC
S SH
CN
PTC
CN
EtOOC
EtOOC
SX
HCN
S
S S
NH2
NH2
X
OH
S S
NC
CNCNCOOEt
PTC
32a b X a = CN b = COOEt 33b
11
8a b
8a b
5
NCCH2COOEt + CS2
CH2(CN)2 + CS2
Figure 13
NSO2 SO2
N
Me
ClPTC
S
N
N
Me
SN
NH
Me
+
33 34 35
NCSminusSO2
Figure 14
CNHOOC CN
BrCH(CN)2 + HN NH2
NH2
O
ONPTC
HOO
HN
O
ON
Ph Ph36 37 38
Figure 15
CNO
NH2
NH2NH2N
HOOC
HNNO
O
CN
Ph
3738
Ph
H2NH2OOHminus
H2OOHminus
CN
OHO
HOOC
+ PhNHNH2
Figure 16
8 Journal of Chemistry
OH
CHOR + ClCH2COOR1
PTCMicrowave
O
R
39 40 41
COOR1
Figure 17
Ar-CH-OH
NC-CH-CH2-CH2Cl
O Ar
CN
42 43 44
ClCH2CH2CH2CN + Ar-CHO
Figure 18
CH3O
OHHO
H3C
O
K2CO3TBAHSO4 O
OO
CH3
O
X
X
H3CEDC
X = H Cl NO2 CH3 OCH3 OCH3 Br
COCH2Br+ 2X
45
46
Figure 19
CNR
H OH
1 HSCH2COOR1 HCl2 KOH ArCN 18-C-6
H S COOR1COOR1
CNR
S
R NH2
47andashf 48andashf
a phb 4-O-CH3
c benzo[b]furyl-2d thinyl-2e dimethyl 25-thinylf C6H5
R1RCOOMeCOOMeCOOMeCOOMeCOOMeCOOEt
60ndash70∘C
Figure 20
reaction to form the ring-opened aryl hydrazones 51 Thesearyl hydrazones were cyclized and converted into the corre-sponding indole derivatives 52 by adding hydrochloric acidin ethanol [30] (Figure 21)
Synthesis of dimethyl phosphinyl substituted tetra-hydropyrroles 55 via 13-cycloaddition reaction of the azome-thine 53 to electron deficient alkenes such as 120572120573-unsaturatedketones (eg benzylideneacetophenone 54) esters and
nitriles took place in high yield and low diastereoselectivityin phase-transfer catalysis conditions (solid potassium car-bonate triethylbenzylammonium chloride (TEBA)) in aceto-nitrile as a solvent [31] (Figure 22)
When Schiff base 53 and ethyl cinnamate 56 reactedunder different phase-transfer catalysis conditions (10 equiv-alents of aqueous NaOH (50)TEBADMSO) the esterof pyrrolidinecarboxylic acid 57 has not been formed
Journal of Chemistry 9
NH2
R
HClHNO2
N+
NCl
R
NCH3O
COOC2H5
CH3
COOC2H5
COOC2H5
O O
NN
HNO
O
R
NH
N
O
O
HCl
49
50
5152 R
0ndash5∘C
Figure 21
+
N
HCOPh
COPhH5C6
PH3CH3C
H3CH3C
OCl
53
54
NPh
PO
Cl
55
Figure 22
N C6H4-Cl-4PH3CH3C
H3C
H3C
H3C
H3C
O
PhCOOEt
+
NH
NH
H5C6
H5C6
C6H4-Cl-4
C6H4-Cl-4
COOEt
P
COOH
PO
O
NaOHH2OCH3CN
NaOHTEBA H2ODMSO
53
56
57
58
Figure 23
instead the acid itself 58 was obtained as a mixture of twodiastereoisomers [31] (Figure 23)
22 Synthesis of Five-Membered Ring Heterocycles Contain-ing Two Heteroatoms (4Z)-4-(4-amino-13-dithiol-2-ylid-ene)-5-methyl-2-phenyl-24-dihydro-3H-pyrazol-3-one
derivative 60 was the product of a reaction of 3-methyl-1-phenyl-2-pyrazoline-5-one 59 with CS
2and chloroac-
etonitrile in equimolar ratio under solid-liquid technique(benzeneK
2CO3TBAB) [23] (Figure 24)
Similarly 1-phenyl-35-pyrazolidinedione 36 was treatedwith CS
2and ethyl chloroacetate under the same condition
10 Journal of Chemistry
N
OPh
PTCNN
CH3
O
Ph
S
SN
H2N
59 60
+ CS2 + ClCH2CN
H3C
Figure 24
N O
O
Ph
+ + ClCH2COOEtHNHN
HN
HN
O
O
Ph
S
COOEt
S
N N
O
O
Ph
SH
EtOOCH2CS
N
O
OPh
S
S
O
36
61
minusEtOH
CS2
Figure 25
SS COOEt
NC
NH2
NH2
NH2
NH2
SS
COOEt
NCN
S
N
S
SS
CS2ClCH2CNPTC
PTC
CS2ClCH2COOEt
S
S
COOEt
NCN S
N
SO
SS O
62
63
64
Figure 26
Journal of Chemistry 11
S
SS
S
S
S COOEt
COOEt
NC
NH2
NH2
PTC
N
N
NC
SS
CS2Br(CH2)2Br
6562
Figure 27
PhPh
NN
O PTC
N
NHN
H3Cn = 0 1 a n = 067a b b n = 1
66
S
CH3
+ Br(CH2)nCH2Br(CH2)nCH2Br
Figure 28
X-CH2-N-NHAr [CH2=N-N]-Ar
RndashCH=CH2
N
NR
Ar70
69
68
minus+
Figure 29
H3C
H3C
SO2CH2NC + RCHO PTCO
N
N
N
SO2
SO2H3C
H3C
R
PTC
R1
71 72
7371
74
75 R2
SO2CH2NC + R1CH=NR2
Figure 30
Me
ClMe
CH + N=NN
N
H3C
S
CH3
PTCN
N
NN
CH3
CH3
S
CH3
H3C
RR
76 77 78
Figure 31
12 Journal of Chemistry
Br
BrPTC+
79 80 81
N
S
NO
H
PhNH
HNS
H
PhO
Figure 32
X
Y
+ PhNCSKOHDioxan
XYPhHN
KS
N
S
O Ph
X
Y
a X Y = CN b X = CN Y = CO2Etc X Y = CO2Et d X = COPh Y = COCH3
e COCH3 Y = CO2Et f X = COPh Y = CO2Etg X Y = COCH3
Cl
Z
OZ = Cl OEt or NH2
82andashg 83andashg
Figure 33
(benzeneK2CO3TBAB) to give the corresponding (4Z)-4-
(4-oxo-13-dithiolan-2-ylidene)-1-phenylpyrazolidine-35-dione 61 [25] (Figure 25)
The addition reaction of ethyl 34-diamino-5-cyanot-hieno[23-b]thiophene-2-carboxylate 62 to carbon disul-fide followed by cyclization reaction through the treat-ment with chloroacetonitrile or ethyl chloroacetate underPTC conditions (K
2CO3 TBAB dioxane) furnished 34-
bis(4-amino-2-thioxo-13-thiazol-3(2H)-yl)-5-propanoylthi-eno[23-b]thiophene-2-carbonitrile 63 and 34-bis(4-oxo-2-thioxo-13-thiazolidin-3-yl)-5-propanoylthieno[23-b]thio-phene-2-carbonitrile 64 in satisfactory yields [32] (Figure26)
Moreover the addition reaction of compound 62 tocarbon disulfide followed by cycloalkylation reaction with12-dibromoethane at 1 1 1 molar ratio under same PTCconditions afforded the corresponding bis-13-dithiolan-2-ylidene 65 [32] (Figure 27)
Treatment of triazepene compound 66 with dibromidesusing liquid-liquid condition (benzeneNaOHTBAB) fur-nished pyrazole derivatives 67a b [33] (Figure 28)
13-Dipolar cycloaddition of various substituted nitril-imines 68 to the appropriate alkenyl dipolarophiles 69 inaqueous media and in presence of a surfactant afforded anumber of 1-aryl-5-substituted-45-dihydropyrazoles 70 [34](Figure 29)
Preparation of 5-substituted oxazoles 74 or imidazoles75 was achieved by reaction of p-tolylsulphonylmethyl iso-cyanide 71 with aldehydes 72 R
1CH=NR
2or 73 (R
1 R2=
substituted phenyl heteroaryl and alkyl) under liquid-liquidcondition [35 36] (Figure 30)
The interaction of 3-chloro-3-methyl-1-butyne 76 with46-dimethyl-5-arylazo-2-thiopyrimidine 77 under liq-uid-liquid phase (benzeneaq KOHBTEACl) afforded 46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidinyl-(5H)-thiones 78 [37] (Figure 31)
Reaction of 5-phenylmethylene thiohydantoin 79 with12-dibromoethane 80 under liquid-liquid conditions (ben-zeneaq NaOHTBAB) afforded 23-dihydro-6-phenylmeth-ylene-5-oxo-imidazo[23-b]thiazole 81 [38] (Figure 32)
A variety of 4-thiazolidinone derivatives 83andashgwere suc-cessfully synthesized via in situ formation of ketene-NS-acetals 82andashg which in turn was reacted with ethylchloroethyl acetate chloroacetamide or chloroacetyl chlo-ride followed by ring closure to afford the desired 4-thiazolidinones 83andashg [39] (Figure 33)
One of the medicinal applications for PTC techniques issynthesis of sibenadet hydrochloride 87 which is a potentdrug used for treatment of chronic obstructive pulmonarydisease This bioactive molecule was synthesized by O-alkylation of phenylethanol 84 with the alkyl bromide 85under PTC condition to form the alkylated product 86 in97 yield Reaction of 86 with benzothiazole derivative ledto formation of the desired product 86 [40] (Figure 34)
Treatment of an equimolar amount of 2-mercapto-quinazolin-4(3H)-one 88 and dihalocompounds such as 12-dibromoethane and chloroacetyl chloride underwent S- and
Journal of Chemistry 13
OH
+ H2CBr
NaOHH2OTBAHSO4
OCH2
97
Sibenadet hydrochloride
84 8586
87 O
S NH
S
OHO
OO
NH middotHCl
Figure 34
NH
NH
O
SH
ClCH2COCl
Br(CH2)2Br
PTC89
88
O
N
NH
NH
S
OO
N
S
90
Figure 35
Ph
NO
O
SN
CS2 Br(CH2)2Br H
NH
NH
PTC
Ph
S
S
N
Ph
S
N
O
91
CS2Br(CH2)3Br
S
S
SPTC
92b
92a
Figure 36
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
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[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
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[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
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[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
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[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
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International Journal of
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CatalystsJournal of
Journal of Chemistry 3
NH2
PhN
CNCN
NQ
CN
Y
Ph NH
CN
CN
CN
PhN CNCN
PhN CNCN
Y
Y
Y
Q
Q
Organic layer
K2CO3 solid surface
HX +
HXQXXCH2Y
Ph-N
Ph-N
Scheme 1
(QX) as a catalyst can be formulated as shown inFigure 2
The concept of phase-transfer catalysis is not limited toanion transfer but is muchmore general so that in principleone could also transfer cations free radicals or wholemolecule Phase transfer catalysis is classified as liquid-liquidliquid-solid liquid-gas solid-gas or solid-solid systems
2 Application of Phase Transfer Catalysisin Synthesis of Five-Membered Ring ofHeterocyclic Compounds
21 Synthesis of Five-Membered Ring Heterocycles Con-taining One Heteroatom Treatment of anilinomethylene-malononitrile 1 with ethyl chloroacetate chloroaceta-midephenacyl chloride or diethyl bromomalonate in 1 1 1molar ratio (dioxanK
2CO3tetrabutylammonium bromide
(TBAB)) afforded the corresponding substituted pyrroles 2andashc and 3 respectively [17] (Figure 3)
The catalytic cycle which explains the reaction pathwaycan be simplified as in Scheme 1
A simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitriles 6 was achievedby reaction of N-aryl-2-chloroacetamide 4 andmalononitrile5 under solid-liquid PTC condition (CH
3CNK
2CO318-
crown-6) at room temperature [18] (Figure 4)3-Amino-4-ethoxycarbonyl-1-phenyl-5-thioxo-25-dihy-
dro-2-pyrrolidene malononitrile 9a was prepared via reac-tion of malononitrile 5 phenyl isothiocyanate 7 and ethox-ymethylenemalononitrile 8a in 1 1 1 molar ratio under
the PTC mixture of dioxanK2CO3(TBAB) Replacing
of ethyl ethoxymethylenecyanoacetate 8b with 8a gaveethyl[3-amino-4-ethoxy-carbonyl-1-phenyl-5-thioxo-25-di-hydro-2-pyrrolidene]cyanoacetate 9b and 10 under the sameexperimental conditions [19] (Figure 5)
Moreover the reaction of ethyl cyanoacetate 11 withphenyl isothiocyante 7 and ethoxymethylenemalononitrile8a or ethyl ethoxymethylenecyanoacetate 8b in 1 1 1 molarratio under same PTC experimental conditions affordedthe corresponding pyrrole derivatives 12a b and 13 [19](Figure 6)
Reaction of methyl 25-dibromopentanoate 14 with tri-chloroacetamide 15 under solid-liquid technique (CH
3CN
K2CO3TEBACl) yielded methyl N-trichloroacetyl-2-pyr-
rolidine carboxylate 16 [20] (Figure 7)Substituted pyrrolidines 19 were synthesized via the
13-dipolar cycloaddition reaction between imino esters 17(derived from alanine and glycine with alkanes) and alkylacrylate 18 in a mixture of THF or toluene KOH and TBACl[21] (Figure 8)
14-Di(malononitrilemethyleneamino)benzene 20 wasallowed to react with ethyl chloroacetate chloroacetamidephenacyl chloride or diethyl bromomalonate in 1 2molar ratios under solid-liquid PTC technique to give thecorresponding 14-bi(1-pyrrolyl) benzene derivatives 21andashcand 22 [17] (Figure 9)
Pyrrolidine derivatives 24were obtained with thiophenes25 from the reaction of diethyl cyanomalonate 23with phenylisothiocyanate 7 and chloroacetonitrile or chloroacetamideusing the PTC of (DMFK
2CO3TBAB) [22] (Figure 10)
4 Journal of Chemistry
PTCNC CN NC CN
CH2(CN)2 + PhNCS5 7 S NH PhN SH
Ph
PTC NC NH2NC NH2
EtOCH = C(CN) X+ CN
SNCN
PhNS
8a bPh X
CN
109a b
X a = CN b = COOEt
Figure 5
CNCH2COOEt + PhNCS PTC EtOOC CN
NHPh
S
EtOOC CN
SHPhN
PhN
PTC PTC EtOCH=C(CN)2
N
EtOOC EtOOC
EtOOC
CN
CN
CNS S
Ph
N
EtOOC
CN CN
COOEtCOOEt
COOEt
S
Ph
EtOCH=C(CN)(COOEt)
S
NH2
NH2
NH2 NH2
HydrolysisminusPhNH2
O
H2OK2CO3
+
12a
11
8a8b
12b
13
7
Figure 6
NPTC COOCH3
14
16
15 COCCl3
Br(CH2)3CH(Br)COOCH3 + Cl3CCONH2
Figure 7
One-pot reaction of malononitrile 5 carbon disulphideand chloroacetamide in 1 1 1 molar ratio under solid-liquid PT catalysis (benzeneK
2CO3TBAB) has furnished
3-amino-2-carboxyamido-4-cyano-5-mercaptothiophene 26[23] (Figure 11) Also treatment of malononitrile 5 with
CS2and ethyl chloroacetate under the same experimental
conditions gave the corresponding thiophene derivative 27[23] (Figure 11)
Different thiophene compounds (24 and 28ndash30)preparedfrom reaction of diethyl cyanomalonate 23 with carbon
Journal of Chemistry 5
N
RO N
R
O
NH
17 18 19KOHKOH
COORCOORCOOR
R4N XR4N X R1R1
R1
minus
+
+ minus+
Figure 8
HN NH
NC
NC CN
CNPTC
NN
RRNH2
N
CNNC
NNHHN
NC CN
R = CO2Et CONH2 COPh20
22
2BrCH(CO2Et)2
H2N
CO2EtEtO2CCO2EtEtO2C
2ClCH2R
21andashc
Figure 9
EtO2C
Et EtEt
EtEtEtO
OO
O
OO
O OO
O
OOH
NCPhNCS PTC
PTC
SHSH
PhY
ZX
S
EtO2C
YN
ZX
S
25
24a b X= CO2Et Y = CN Z = NH2
24c X = CN Y = CONH2 Z =OHX = CO2Et Y = CN Z = NH2
+
+
CN CN
PhN
PhN
PhNH
XCH2Y
24andashc
Figure 10
CH2(CN)2 + CS2 + ClCH2CONH2PTC
PTC
S SH
H2N
H2NOC
CN
S
H2N CN
5
5
26
CH2(CN)2 + CS2 + ClCH2COOEtEtO2C SCH2CO2Et
27
Figure 11
6 Journal of Chemistry
NCH O
OOO
CS2
NC
O OO
O
NC
O OO
O
S S
SH
SH
Y
PTC
PTC
S
S Y
PTC
PTC
S S YS
NH2
YS
OH
CN
CN
N
NH
S
NC
PhNCS
PTC
EtO2CEtO2C
CO2Et
CO2Et
COPh
Ph
Ph
PhN
PhN
PhNS
NCEtO2C EtO2C EtO2C
S
EtO2CCO2EtEtO2C
OH
Y
Z ZX X
24a b 25a-b X = CO2C2H5 Y = CN Z = NH2
24c 25c X = CO2C2H5 Y = CONH2 Z = NH2
XCH2Y
XCH2Y
a Y = COPh b Y = CN c Y = CONH2
23
7
28andashc 29andashc
30 25andashc 24
+
++
Figure 12
disulphide or phenyl isothiocyanate 7 along with differentactive halocompounds under solid-liquid phase condition(dioxanK
2CO3TBAB) have been reported byAbdAllah and
El-Sayed [22] (Figure 12)2-Thiophenylidenes 31ndash33 were obtained through the
reaction of either malononitrile 5 or ethyl cyanoacetate 11with carbon disulphide along with ethoxymethylenemal-ononitrile 8a or ethyl ethoxymethylenecyanoacetate 8busing liquid-solid technique (dioxanK
2CO3TBAB) [19]
(Figure 13)In this reaction the yield of products was found to be a
temperature dependent Thus at low temperature (40∘C) itaffords the aminothiophene derivative 32a in high yield whileat high temperature hydroxythiophene 32b or 33b was thesolely product but in low yield
The reaction of pyridosultam 34 with 3-chloropropylthiocyanate under the experimental condition (tolueneaqNaOHTBAB) yielded the corresponding dihydrothiophenederivative 35 [24] (Figure 14)
4-Amino-5-cyano-2-hydroxy-3-furancarboxylic acid 37and compound 38were synthesized by treating 1-phenyl-35-pyrazolinedione 36 with bromomalononitrile under solid-liquid condition (dioxanK
2CO3TBAB) (Figure 15) [25]
The reaction pathway for the formation of unexpectedcompound 37was assumed to proceed via catalytic hydrolysisof compound 38 into the furan derivative 37 and phenylhydrazine [25] (Figure 16)
Condensation of salicylaldehyde 39 and its derivativeswith various esters of chloroacetic acids 40 in the pres-ence of TBAB led to the synthesis of benzo[b]furans 41under solventless and microwave irradiation technique [26](Figure 17)
Liquid-liquid PTC reaction of 4-chlorobutyronitrile 42with nonenolizable aldehydes 43 via sequence of an addi-tion cyclization reaction gave tetrahydrofuran-3-carbonitrilederivative 44 [27] (Figure 18)
Fused bis-aroylbenzodifurans 46 have been synthesizedby condensing 24-diacetyl resorcinol 45 with various p-substituted phenacyl bromides [28] (Figure 19)
Methyl or ethyl 3-amino-4-arylthiophenes-2-carbox-ylates 48andashf were synthesized by Thorpe reaction throughthe treatment of 3-hydroxy-2-arylacrylonitriles 47andashf andmethyl or ethyl thioglycolates with hydrochloric acid byusing different PTC conditions (solid-liquid or liquid-liquid)The solid-liquid PTC conditions using 18-crown-6 alongwith potassium hydroxide as a catalyst are the method withexcellent yieldsThe reactions were carried out in acetonitrileat RT [29] (Figure 20)
In Japp-Klingemann reaction the indole derivatives 52have been prepared as indicated in Figure 21 The additionof a suitable PTC catalyst to the reaction could signifi-cantly improve the reaction process Firstly aryl amines49 were diazotized and reacted under alkaline conditionsethyl 2-[2-(13-dioxo-13-dihydro-2H-isoindol-2-yl)ethyl]-3-oxobutanoate 50 using PTC-promoted Japp-Klingemann
Journal of Chemistry 7
PTCK2CO3
DioxaneTBAB
NC
SHS
CNPTC
EtOCH=C(CN)(X)
HCN
PTC
S
S
NC
X
X
CN
SX
CN
HS
NC NH
HS
NC
CNS
31a b
X a = CN b = COOEt
EtOCH=C(CN)(X)
+
PTCEtOOC
S SH
CN
PTC
CN
EtOOC
EtOOC
SX
HCN
S
S S
NH2
NH2
X
OH
S S
NC
CNCNCOOEt
PTC
32a b X a = CN b = COOEt 33b
11
8a b
8a b
5
NCCH2COOEt + CS2
CH2(CN)2 + CS2
Figure 13
NSO2 SO2
N
Me
ClPTC
S
N
N
Me
SN
NH
Me
+
33 34 35
NCSminusSO2
Figure 14
CNHOOC CN
BrCH(CN)2 + HN NH2
NH2
O
ONPTC
HOO
HN
O
ON
Ph Ph36 37 38
Figure 15
CNO
NH2
NH2NH2N
HOOC
HNNO
O
CN
Ph
3738
Ph
H2NH2OOHminus
H2OOHminus
CN
OHO
HOOC
+ PhNHNH2
Figure 16
8 Journal of Chemistry
OH
CHOR + ClCH2COOR1
PTCMicrowave
O
R
39 40 41
COOR1
Figure 17
Ar-CH-OH
NC-CH-CH2-CH2Cl
O Ar
CN
42 43 44
ClCH2CH2CH2CN + Ar-CHO
Figure 18
CH3O
OHHO
H3C
O
K2CO3TBAHSO4 O
OO
CH3
O
X
X
H3CEDC
X = H Cl NO2 CH3 OCH3 OCH3 Br
COCH2Br+ 2X
45
46
Figure 19
CNR
H OH
1 HSCH2COOR1 HCl2 KOH ArCN 18-C-6
H S COOR1COOR1
CNR
S
R NH2
47andashf 48andashf
a phb 4-O-CH3
c benzo[b]furyl-2d thinyl-2e dimethyl 25-thinylf C6H5
R1RCOOMeCOOMeCOOMeCOOMeCOOMeCOOEt
60ndash70∘C
Figure 20
reaction to form the ring-opened aryl hydrazones 51 Thesearyl hydrazones were cyclized and converted into the corre-sponding indole derivatives 52 by adding hydrochloric acidin ethanol [30] (Figure 21)
Synthesis of dimethyl phosphinyl substituted tetra-hydropyrroles 55 via 13-cycloaddition reaction of the azome-thine 53 to electron deficient alkenes such as 120572120573-unsaturatedketones (eg benzylideneacetophenone 54) esters and
nitriles took place in high yield and low diastereoselectivityin phase-transfer catalysis conditions (solid potassium car-bonate triethylbenzylammonium chloride (TEBA)) in aceto-nitrile as a solvent [31] (Figure 22)
When Schiff base 53 and ethyl cinnamate 56 reactedunder different phase-transfer catalysis conditions (10 equiv-alents of aqueous NaOH (50)TEBADMSO) the esterof pyrrolidinecarboxylic acid 57 has not been formed
Journal of Chemistry 9
NH2
R
HClHNO2
N+
NCl
R
NCH3O
COOC2H5
CH3
COOC2H5
COOC2H5
O O
NN
HNO
O
R
NH
N
O
O
HCl
49
50
5152 R
0ndash5∘C
Figure 21
+
N
HCOPh
COPhH5C6
PH3CH3C
H3CH3C
OCl
53
54
NPh
PO
Cl
55
Figure 22
N C6H4-Cl-4PH3CH3C
H3C
H3C
H3C
H3C
O
PhCOOEt
+
NH
NH
H5C6
H5C6
C6H4-Cl-4
C6H4-Cl-4
COOEt
P
COOH
PO
O
NaOHH2OCH3CN
NaOHTEBA H2ODMSO
53
56
57
58
Figure 23
instead the acid itself 58 was obtained as a mixture of twodiastereoisomers [31] (Figure 23)
22 Synthesis of Five-Membered Ring Heterocycles Contain-ing Two Heteroatoms (4Z)-4-(4-amino-13-dithiol-2-ylid-ene)-5-methyl-2-phenyl-24-dihydro-3H-pyrazol-3-one
derivative 60 was the product of a reaction of 3-methyl-1-phenyl-2-pyrazoline-5-one 59 with CS
2and chloroac-
etonitrile in equimolar ratio under solid-liquid technique(benzeneK
2CO3TBAB) [23] (Figure 24)
Similarly 1-phenyl-35-pyrazolidinedione 36 was treatedwith CS
2and ethyl chloroacetate under the same condition
10 Journal of Chemistry
N
OPh
PTCNN
CH3
O
Ph
S
SN
H2N
59 60
+ CS2 + ClCH2CN
H3C
Figure 24
N O
O
Ph
+ + ClCH2COOEtHNHN
HN
HN
O
O
Ph
S
COOEt
S
N N
O
O
Ph
SH
EtOOCH2CS
N
O
OPh
S
S
O
36
61
minusEtOH
CS2
Figure 25
SS COOEt
NC
NH2
NH2
NH2
NH2
SS
COOEt
NCN
S
N
S
SS
CS2ClCH2CNPTC
PTC
CS2ClCH2COOEt
S
S
COOEt
NCN S
N
SO
SS O
62
63
64
Figure 26
Journal of Chemistry 11
S
SS
S
S
S COOEt
COOEt
NC
NH2
NH2
PTC
N
N
NC
SS
CS2Br(CH2)2Br
6562
Figure 27
PhPh
NN
O PTC
N
NHN
H3Cn = 0 1 a n = 067a b b n = 1
66
S
CH3
+ Br(CH2)nCH2Br(CH2)nCH2Br
Figure 28
X-CH2-N-NHAr [CH2=N-N]-Ar
RndashCH=CH2
N
NR
Ar70
69
68
minus+
Figure 29
H3C
H3C
SO2CH2NC + RCHO PTCO
N
N
N
SO2
SO2H3C
H3C
R
PTC
R1
71 72
7371
74
75 R2
SO2CH2NC + R1CH=NR2
Figure 30
Me
ClMe
CH + N=NN
N
H3C
S
CH3
PTCN
N
NN
CH3
CH3
S
CH3
H3C
RR
76 77 78
Figure 31
12 Journal of Chemistry
Br
BrPTC+
79 80 81
N
S
NO
H
PhNH
HNS
H
PhO
Figure 32
X
Y
+ PhNCSKOHDioxan
XYPhHN
KS
N
S
O Ph
X
Y
a X Y = CN b X = CN Y = CO2Etc X Y = CO2Et d X = COPh Y = COCH3
e COCH3 Y = CO2Et f X = COPh Y = CO2Etg X Y = COCH3
Cl
Z
OZ = Cl OEt or NH2
82andashg 83andashg
Figure 33
(benzeneK2CO3TBAB) to give the corresponding (4Z)-4-
(4-oxo-13-dithiolan-2-ylidene)-1-phenylpyrazolidine-35-dione 61 [25] (Figure 25)
The addition reaction of ethyl 34-diamino-5-cyanot-hieno[23-b]thiophene-2-carboxylate 62 to carbon disul-fide followed by cyclization reaction through the treat-ment with chloroacetonitrile or ethyl chloroacetate underPTC conditions (K
2CO3 TBAB dioxane) furnished 34-
bis(4-amino-2-thioxo-13-thiazol-3(2H)-yl)-5-propanoylthi-eno[23-b]thiophene-2-carbonitrile 63 and 34-bis(4-oxo-2-thioxo-13-thiazolidin-3-yl)-5-propanoylthieno[23-b]thio-phene-2-carbonitrile 64 in satisfactory yields [32] (Figure26)
Moreover the addition reaction of compound 62 tocarbon disulfide followed by cycloalkylation reaction with12-dibromoethane at 1 1 1 molar ratio under same PTCconditions afforded the corresponding bis-13-dithiolan-2-ylidene 65 [32] (Figure 27)
Treatment of triazepene compound 66 with dibromidesusing liquid-liquid condition (benzeneNaOHTBAB) fur-nished pyrazole derivatives 67a b [33] (Figure 28)
13-Dipolar cycloaddition of various substituted nitril-imines 68 to the appropriate alkenyl dipolarophiles 69 inaqueous media and in presence of a surfactant afforded anumber of 1-aryl-5-substituted-45-dihydropyrazoles 70 [34](Figure 29)
Preparation of 5-substituted oxazoles 74 or imidazoles75 was achieved by reaction of p-tolylsulphonylmethyl iso-cyanide 71 with aldehydes 72 R
1CH=NR
2or 73 (R
1 R2=
substituted phenyl heteroaryl and alkyl) under liquid-liquidcondition [35 36] (Figure 30)
The interaction of 3-chloro-3-methyl-1-butyne 76 with46-dimethyl-5-arylazo-2-thiopyrimidine 77 under liq-uid-liquid phase (benzeneaq KOHBTEACl) afforded 46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidinyl-(5H)-thiones 78 [37] (Figure 31)
Reaction of 5-phenylmethylene thiohydantoin 79 with12-dibromoethane 80 under liquid-liquid conditions (ben-zeneaq NaOHTBAB) afforded 23-dihydro-6-phenylmeth-ylene-5-oxo-imidazo[23-b]thiazole 81 [38] (Figure 32)
A variety of 4-thiazolidinone derivatives 83andashgwere suc-cessfully synthesized via in situ formation of ketene-NS-acetals 82andashg which in turn was reacted with ethylchloroethyl acetate chloroacetamide or chloroacetyl chlo-ride followed by ring closure to afford the desired 4-thiazolidinones 83andashg [39] (Figure 33)
One of the medicinal applications for PTC techniques issynthesis of sibenadet hydrochloride 87 which is a potentdrug used for treatment of chronic obstructive pulmonarydisease This bioactive molecule was synthesized by O-alkylation of phenylethanol 84 with the alkyl bromide 85under PTC condition to form the alkylated product 86 in97 yield Reaction of 86 with benzothiazole derivative ledto formation of the desired product 86 [40] (Figure 34)
Treatment of an equimolar amount of 2-mercapto-quinazolin-4(3H)-one 88 and dihalocompounds such as 12-dibromoethane and chloroacetyl chloride underwent S- and
Journal of Chemistry 13
OH
+ H2CBr
NaOHH2OTBAHSO4
OCH2
97
Sibenadet hydrochloride
84 8586
87 O
S NH
S
OHO
OO
NH middotHCl
Figure 34
NH
NH
O
SH
ClCH2COCl
Br(CH2)2Br
PTC89
88
O
N
NH
NH
S
OO
N
S
90
Figure 35
Ph
NO
O
SN
CS2 Br(CH2)2Br H
NH
NH
PTC
Ph
S
S
N
Ph
S
N
O
91
CS2Br(CH2)3Br
S
S
SPTC
92b
92a
Figure 36
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
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Carbohydrate Chemistry
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CatalystsJournal of
4 Journal of Chemistry
PTCNC CN NC CN
CH2(CN)2 + PhNCS5 7 S NH PhN SH
Ph
PTC NC NH2NC NH2
EtOCH = C(CN) X+ CN
SNCN
PhNS
8a bPh X
CN
109a b
X a = CN b = COOEt
Figure 5
CNCH2COOEt + PhNCS PTC EtOOC CN
NHPh
S
EtOOC CN
SHPhN
PhN
PTC PTC EtOCH=C(CN)2
N
EtOOC EtOOC
EtOOC
CN
CN
CNS S
Ph
N
EtOOC
CN CN
COOEtCOOEt
COOEt
S
Ph
EtOCH=C(CN)(COOEt)
S
NH2
NH2
NH2 NH2
HydrolysisminusPhNH2
O
H2OK2CO3
+
12a
11
8a8b
12b
13
7
Figure 6
NPTC COOCH3
14
16
15 COCCl3
Br(CH2)3CH(Br)COOCH3 + Cl3CCONH2
Figure 7
One-pot reaction of malononitrile 5 carbon disulphideand chloroacetamide in 1 1 1 molar ratio under solid-liquid PT catalysis (benzeneK
2CO3TBAB) has furnished
3-amino-2-carboxyamido-4-cyano-5-mercaptothiophene 26[23] (Figure 11) Also treatment of malononitrile 5 with
CS2and ethyl chloroacetate under the same experimental
conditions gave the corresponding thiophene derivative 27[23] (Figure 11)
Different thiophene compounds (24 and 28ndash30)preparedfrom reaction of diethyl cyanomalonate 23 with carbon
Journal of Chemistry 5
N
RO N
R
O
NH
17 18 19KOHKOH
COORCOORCOOR
R4N XR4N X R1R1
R1
minus
+
+ minus+
Figure 8
HN NH
NC
NC CN
CNPTC
NN
RRNH2
N
CNNC
NNHHN
NC CN
R = CO2Et CONH2 COPh20
22
2BrCH(CO2Et)2
H2N
CO2EtEtO2CCO2EtEtO2C
2ClCH2R
21andashc
Figure 9
EtO2C
Et EtEt
EtEtEtO
OO
O
OO
O OO
O
OOH
NCPhNCS PTC
PTC
SHSH
PhY
ZX
S
EtO2C
YN
ZX
S
25
24a b X= CO2Et Y = CN Z = NH2
24c X = CN Y = CONH2 Z =OHX = CO2Et Y = CN Z = NH2
+
+
CN CN
PhN
PhN
PhNH
XCH2Y
24andashc
Figure 10
CH2(CN)2 + CS2 + ClCH2CONH2PTC
PTC
S SH
H2N
H2NOC
CN
S
H2N CN
5
5
26
CH2(CN)2 + CS2 + ClCH2COOEtEtO2C SCH2CO2Et
27
Figure 11
6 Journal of Chemistry
NCH O
OOO
CS2
NC
O OO
O
NC
O OO
O
S S
SH
SH
Y
PTC
PTC
S
S Y
PTC
PTC
S S YS
NH2
YS
OH
CN
CN
N
NH
S
NC
PhNCS
PTC
EtO2CEtO2C
CO2Et
CO2Et
COPh
Ph
Ph
PhN
PhN
PhNS
NCEtO2C EtO2C EtO2C
S
EtO2CCO2EtEtO2C
OH
Y
Z ZX X
24a b 25a-b X = CO2C2H5 Y = CN Z = NH2
24c 25c X = CO2C2H5 Y = CONH2 Z = NH2
XCH2Y
XCH2Y
a Y = COPh b Y = CN c Y = CONH2
23
7
28andashc 29andashc
30 25andashc 24
+
++
Figure 12
disulphide or phenyl isothiocyanate 7 along with differentactive halocompounds under solid-liquid phase condition(dioxanK
2CO3TBAB) have been reported byAbdAllah and
El-Sayed [22] (Figure 12)2-Thiophenylidenes 31ndash33 were obtained through the
reaction of either malononitrile 5 or ethyl cyanoacetate 11with carbon disulphide along with ethoxymethylenemal-ononitrile 8a or ethyl ethoxymethylenecyanoacetate 8busing liquid-solid technique (dioxanK
2CO3TBAB) [19]
(Figure 13)In this reaction the yield of products was found to be a
temperature dependent Thus at low temperature (40∘C) itaffords the aminothiophene derivative 32a in high yield whileat high temperature hydroxythiophene 32b or 33b was thesolely product but in low yield
The reaction of pyridosultam 34 with 3-chloropropylthiocyanate under the experimental condition (tolueneaqNaOHTBAB) yielded the corresponding dihydrothiophenederivative 35 [24] (Figure 14)
4-Amino-5-cyano-2-hydroxy-3-furancarboxylic acid 37and compound 38were synthesized by treating 1-phenyl-35-pyrazolinedione 36 with bromomalononitrile under solid-liquid condition (dioxanK
2CO3TBAB) (Figure 15) [25]
The reaction pathway for the formation of unexpectedcompound 37was assumed to proceed via catalytic hydrolysisof compound 38 into the furan derivative 37 and phenylhydrazine [25] (Figure 16)
Condensation of salicylaldehyde 39 and its derivativeswith various esters of chloroacetic acids 40 in the pres-ence of TBAB led to the synthesis of benzo[b]furans 41under solventless and microwave irradiation technique [26](Figure 17)
Liquid-liquid PTC reaction of 4-chlorobutyronitrile 42with nonenolizable aldehydes 43 via sequence of an addi-tion cyclization reaction gave tetrahydrofuran-3-carbonitrilederivative 44 [27] (Figure 18)
Fused bis-aroylbenzodifurans 46 have been synthesizedby condensing 24-diacetyl resorcinol 45 with various p-substituted phenacyl bromides [28] (Figure 19)
Methyl or ethyl 3-amino-4-arylthiophenes-2-carbox-ylates 48andashf were synthesized by Thorpe reaction throughthe treatment of 3-hydroxy-2-arylacrylonitriles 47andashf andmethyl or ethyl thioglycolates with hydrochloric acid byusing different PTC conditions (solid-liquid or liquid-liquid)The solid-liquid PTC conditions using 18-crown-6 alongwith potassium hydroxide as a catalyst are the method withexcellent yieldsThe reactions were carried out in acetonitrileat RT [29] (Figure 20)
In Japp-Klingemann reaction the indole derivatives 52have been prepared as indicated in Figure 21 The additionof a suitable PTC catalyst to the reaction could signifi-cantly improve the reaction process Firstly aryl amines49 were diazotized and reacted under alkaline conditionsethyl 2-[2-(13-dioxo-13-dihydro-2H-isoindol-2-yl)ethyl]-3-oxobutanoate 50 using PTC-promoted Japp-Klingemann
Journal of Chemistry 7
PTCK2CO3
DioxaneTBAB
NC
SHS
CNPTC
EtOCH=C(CN)(X)
HCN
PTC
S
S
NC
X
X
CN
SX
CN
HS
NC NH
HS
NC
CNS
31a b
X a = CN b = COOEt
EtOCH=C(CN)(X)
+
PTCEtOOC
S SH
CN
PTC
CN
EtOOC
EtOOC
SX
HCN
S
S S
NH2
NH2
X
OH
S S
NC
CNCNCOOEt
PTC
32a b X a = CN b = COOEt 33b
11
8a b
8a b
5
NCCH2COOEt + CS2
CH2(CN)2 + CS2
Figure 13
NSO2 SO2
N
Me
ClPTC
S
N
N
Me
SN
NH
Me
+
33 34 35
NCSminusSO2
Figure 14
CNHOOC CN
BrCH(CN)2 + HN NH2
NH2
O
ONPTC
HOO
HN
O
ON
Ph Ph36 37 38
Figure 15
CNO
NH2
NH2NH2N
HOOC
HNNO
O
CN
Ph
3738
Ph
H2NH2OOHminus
H2OOHminus
CN
OHO
HOOC
+ PhNHNH2
Figure 16
8 Journal of Chemistry
OH
CHOR + ClCH2COOR1
PTCMicrowave
O
R
39 40 41
COOR1
Figure 17
Ar-CH-OH
NC-CH-CH2-CH2Cl
O Ar
CN
42 43 44
ClCH2CH2CH2CN + Ar-CHO
Figure 18
CH3O
OHHO
H3C
O
K2CO3TBAHSO4 O
OO
CH3
O
X
X
H3CEDC
X = H Cl NO2 CH3 OCH3 OCH3 Br
COCH2Br+ 2X
45
46
Figure 19
CNR
H OH
1 HSCH2COOR1 HCl2 KOH ArCN 18-C-6
H S COOR1COOR1
CNR
S
R NH2
47andashf 48andashf
a phb 4-O-CH3
c benzo[b]furyl-2d thinyl-2e dimethyl 25-thinylf C6H5
R1RCOOMeCOOMeCOOMeCOOMeCOOMeCOOEt
60ndash70∘C
Figure 20
reaction to form the ring-opened aryl hydrazones 51 Thesearyl hydrazones were cyclized and converted into the corre-sponding indole derivatives 52 by adding hydrochloric acidin ethanol [30] (Figure 21)
Synthesis of dimethyl phosphinyl substituted tetra-hydropyrroles 55 via 13-cycloaddition reaction of the azome-thine 53 to electron deficient alkenes such as 120572120573-unsaturatedketones (eg benzylideneacetophenone 54) esters and
nitriles took place in high yield and low diastereoselectivityin phase-transfer catalysis conditions (solid potassium car-bonate triethylbenzylammonium chloride (TEBA)) in aceto-nitrile as a solvent [31] (Figure 22)
When Schiff base 53 and ethyl cinnamate 56 reactedunder different phase-transfer catalysis conditions (10 equiv-alents of aqueous NaOH (50)TEBADMSO) the esterof pyrrolidinecarboxylic acid 57 has not been formed
Journal of Chemistry 9
NH2
R
HClHNO2
N+
NCl
R
NCH3O
COOC2H5
CH3
COOC2H5
COOC2H5
O O
NN
HNO
O
R
NH
N
O
O
HCl
49
50
5152 R
0ndash5∘C
Figure 21
+
N
HCOPh
COPhH5C6
PH3CH3C
H3CH3C
OCl
53
54
NPh
PO
Cl
55
Figure 22
N C6H4-Cl-4PH3CH3C
H3C
H3C
H3C
H3C
O
PhCOOEt
+
NH
NH
H5C6
H5C6
C6H4-Cl-4
C6H4-Cl-4
COOEt
P
COOH
PO
O
NaOHH2OCH3CN
NaOHTEBA H2ODMSO
53
56
57
58
Figure 23
instead the acid itself 58 was obtained as a mixture of twodiastereoisomers [31] (Figure 23)
22 Synthesis of Five-Membered Ring Heterocycles Contain-ing Two Heteroatoms (4Z)-4-(4-amino-13-dithiol-2-ylid-ene)-5-methyl-2-phenyl-24-dihydro-3H-pyrazol-3-one
derivative 60 was the product of a reaction of 3-methyl-1-phenyl-2-pyrazoline-5-one 59 with CS
2and chloroac-
etonitrile in equimolar ratio under solid-liquid technique(benzeneK
2CO3TBAB) [23] (Figure 24)
Similarly 1-phenyl-35-pyrazolidinedione 36 was treatedwith CS
2and ethyl chloroacetate under the same condition
10 Journal of Chemistry
N
OPh
PTCNN
CH3
O
Ph
S
SN
H2N
59 60
+ CS2 + ClCH2CN
H3C
Figure 24
N O
O
Ph
+ + ClCH2COOEtHNHN
HN
HN
O
O
Ph
S
COOEt
S
N N
O
O
Ph
SH
EtOOCH2CS
N
O
OPh
S
S
O
36
61
minusEtOH
CS2
Figure 25
SS COOEt
NC
NH2
NH2
NH2
NH2
SS
COOEt
NCN
S
N
S
SS
CS2ClCH2CNPTC
PTC
CS2ClCH2COOEt
S
S
COOEt
NCN S
N
SO
SS O
62
63
64
Figure 26
Journal of Chemistry 11
S
SS
S
S
S COOEt
COOEt
NC
NH2
NH2
PTC
N
N
NC
SS
CS2Br(CH2)2Br
6562
Figure 27
PhPh
NN
O PTC
N
NHN
H3Cn = 0 1 a n = 067a b b n = 1
66
S
CH3
+ Br(CH2)nCH2Br(CH2)nCH2Br
Figure 28
X-CH2-N-NHAr [CH2=N-N]-Ar
RndashCH=CH2
N
NR
Ar70
69
68
minus+
Figure 29
H3C
H3C
SO2CH2NC + RCHO PTCO
N
N
N
SO2
SO2H3C
H3C
R
PTC
R1
71 72
7371
74
75 R2
SO2CH2NC + R1CH=NR2
Figure 30
Me
ClMe
CH + N=NN
N
H3C
S
CH3
PTCN
N
NN
CH3
CH3
S
CH3
H3C
RR
76 77 78
Figure 31
12 Journal of Chemistry
Br
BrPTC+
79 80 81
N
S
NO
H
PhNH
HNS
H
PhO
Figure 32
X
Y
+ PhNCSKOHDioxan
XYPhHN
KS
N
S
O Ph
X
Y
a X Y = CN b X = CN Y = CO2Etc X Y = CO2Et d X = COPh Y = COCH3
e COCH3 Y = CO2Et f X = COPh Y = CO2Etg X Y = COCH3
Cl
Z
OZ = Cl OEt or NH2
82andashg 83andashg
Figure 33
(benzeneK2CO3TBAB) to give the corresponding (4Z)-4-
(4-oxo-13-dithiolan-2-ylidene)-1-phenylpyrazolidine-35-dione 61 [25] (Figure 25)
The addition reaction of ethyl 34-diamino-5-cyanot-hieno[23-b]thiophene-2-carboxylate 62 to carbon disul-fide followed by cyclization reaction through the treat-ment with chloroacetonitrile or ethyl chloroacetate underPTC conditions (K
2CO3 TBAB dioxane) furnished 34-
bis(4-amino-2-thioxo-13-thiazol-3(2H)-yl)-5-propanoylthi-eno[23-b]thiophene-2-carbonitrile 63 and 34-bis(4-oxo-2-thioxo-13-thiazolidin-3-yl)-5-propanoylthieno[23-b]thio-phene-2-carbonitrile 64 in satisfactory yields [32] (Figure26)
Moreover the addition reaction of compound 62 tocarbon disulfide followed by cycloalkylation reaction with12-dibromoethane at 1 1 1 molar ratio under same PTCconditions afforded the corresponding bis-13-dithiolan-2-ylidene 65 [32] (Figure 27)
Treatment of triazepene compound 66 with dibromidesusing liquid-liquid condition (benzeneNaOHTBAB) fur-nished pyrazole derivatives 67a b [33] (Figure 28)
13-Dipolar cycloaddition of various substituted nitril-imines 68 to the appropriate alkenyl dipolarophiles 69 inaqueous media and in presence of a surfactant afforded anumber of 1-aryl-5-substituted-45-dihydropyrazoles 70 [34](Figure 29)
Preparation of 5-substituted oxazoles 74 or imidazoles75 was achieved by reaction of p-tolylsulphonylmethyl iso-cyanide 71 with aldehydes 72 R
1CH=NR
2or 73 (R
1 R2=
substituted phenyl heteroaryl and alkyl) under liquid-liquidcondition [35 36] (Figure 30)
The interaction of 3-chloro-3-methyl-1-butyne 76 with46-dimethyl-5-arylazo-2-thiopyrimidine 77 under liq-uid-liquid phase (benzeneaq KOHBTEACl) afforded 46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidinyl-(5H)-thiones 78 [37] (Figure 31)
Reaction of 5-phenylmethylene thiohydantoin 79 with12-dibromoethane 80 under liquid-liquid conditions (ben-zeneaq NaOHTBAB) afforded 23-dihydro-6-phenylmeth-ylene-5-oxo-imidazo[23-b]thiazole 81 [38] (Figure 32)
A variety of 4-thiazolidinone derivatives 83andashgwere suc-cessfully synthesized via in situ formation of ketene-NS-acetals 82andashg which in turn was reacted with ethylchloroethyl acetate chloroacetamide or chloroacetyl chlo-ride followed by ring closure to afford the desired 4-thiazolidinones 83andashg [39] (Figure 33)
One of the medicinal applications for PTC techniques issynthesis of sibenadet hydrochloride 87 which is a potentdrug used for treatment of chronic obstructive pulmonarydisease This bioactive molecule was synthesized by O-alkylation of phenylethanol 84 with the alkyl bromide 85under PTC condition to form the alkylated product 86 in97 yield Reaction of 86 with benzothiazole derivative ledto formation of the desired product 86 [40] (Figure 34)
Treatment of an equimolar amount of 2-mercapto-quinazolin-4(3H)-one 88 and dihalocompounds such as 12-dibromoethane and chloroacetyl chloride underwent S- and
Journal of Chemistry 13
OH
+ H2CBr
NaOHH2OTBAHSO4
OCH2
97
Sibenadet hydrochloride
84 8586
87 O
S NH
S
OHO
OO
NH middotHCl
Figure 34
NH
NH
O
SH
ClCH2COCl
Br(CH2)2Br
PTC89
88
O
N
NH
NH
S
OO
N
S
90
Figure 35
Ph
NO
O
SN
CS2 Br(CH2)2Br H
NH
NH
PTC
Ph
S
S
N
Ph
S
N
O
91
CS2Br(CH2)3Br
S
S
SPTC
92b
92a
Figure 36
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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ElectrochemistryInternational Journal of
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CatalystsJournal of
Journal of Chemistry 5
N
RO N
R
O
NH
17 18 19KOHKOH
COORCOORCOOR
R4N XR4N X R1R1
R1
minus
+
+ minus+
Figure 8
HN NH
NC
NC CN
CNPTC
NN
RRNH2
N
CNNC
NNHHN
NC CN
R = CO2Et CONH2 COPh20
22
2BrCH(CO2Et)2
H2N
CO2EtEtO2CCO2EtEtO2C
2ClCH2R
21andashc
Figure 9
EtO2C
Et EtEt
EtEtEtO
OO
O
OO
O OO
O
OOH
NCPhNCS PTC
PTC
SHSH
PhY
ZX
S
EtO2C
YN
ZX
S
25
24a b X= CO2Et Y = CN Z = NH2
24c X = CN Y = CONH2 Z =OHX = CO2Et Y = CN Z = NH2
+
+
CN CN
PhN
PhN
PhNH
XCH2Y
24andashc
Figure 10
CH2(CN)2 + CS2 + ClCH2CONH2PTC
PTC
S SH
H2N
H2NOC
CN
S
H2N CN
5
5
26
CH2(CN)2 + CS2 + ClCH2COOEtEtO2C SCH2CO2Et
27
Figure 11
6 Journal of Chemistry
NCH O
OOO
CS2
NC
O OO
O
NC
O OO
O
S S
SH
SH
Y
PTC
PTC
S
S Y
PTC
PTC
S S YS
NH2
YS
OH
CN
CN
N
NH
S
NC
PhNCS
PTC
EtO2CEtO2C
CO2Et
CO2Et
COPh
Ph
Ph
PhN
PhN
PhNS
NCEtO2C EtO2C EtO2C
S
EtO2CCO2EtEtO2C
OH
Y
Z ZX X
24a b 25a-b X = CO2C2H5 Y = CN Z = NH2
24c 25c X = CO2C2H5 Y = CONH2 Z = NH2
XCH2Y
XCH2Y
a Y = COPh b Y = CN c Y = CONH2
23
7
28andashc 29andashc
30 25andashc 24
+
++
Figure 12
disulphide or phenyl isothiocyanate 7 along with differentactive halocompounds under solid-liquid phase condition(dioxanK
2CO3TBAB) have been reported byAbdAllah and
El-Sayed [22] (Figure 12)2-Thiophenylidenes 31ndash33 were obtained through the
reaction of either malononitrile 5 or ethyl cyanoacetate 11with carbon disulphide along with ethoxymethylenemal-ononitrile 8a or ethyl ethoxymethylenecyanoacetate 8busing liquid-solid technique (dioxanK
2CO3TBAB) [19]
(Figure 13)In this reaction the yield of products was found to be a
temperature dependent Thus at low temperature (40∘C) itaffords the aminothiophene derivative 32a in high yield whileat high temperature hydroxythiophene 32b or 33b was thesolely product but in low yield
The reaction of pyridosultam 34 with 3-chloropropylthiocyanate under the experimental condition (tolueneaqNaOHTBAB) yielded the corresponding dihydrothiophenederivative 35 [24] (Figure 14)
4-Amino-5-cyano-2-hydroxy-3-furancarboxylic acid 37and compound 38were synthesized by treating 1-phenyl-35-pyrazolinedione 36 with bromomalononitrile under solid-liquid condition (dioxanK
2CO3TBAB) (Figure 15) [25]
The reaction pathway for the formation of unexpectedcompound 37was assumed to proceed via catalytic hydrolysisof compound 38 into the furan derivative 37 and phenylhydrazine [25] (Figure 16)
Condensation of salicylaldehyde 39 and its derivativeswith various esters of chloroacetic acids 40 in the pres-ence of TBAB led to the synthesis of benzo[b]furans 41under solventless and microwave irradiation technique [26](Figure 17)
Liquid-liquid PTC reaction of 4-chlorobutyronitrile 42with nonenolizable aldehydes 43 via sequence of an addi-tion cyclization reaction gave tetrahydrofuran-3-carbonitrilederivative 44 [27] (Figure 18)
Fused bis-aroylbenzodifurans 46 have been synthesizedby condensing 24-diacetyl resorcinol 45 with various p-substituted phenacyl bromides [28] (Figure 19)
Methyl or ethyl 3-amino-4-arylthiophenes-2-carbox-ylates 48andashf were synthesized by Thorpe reaction throughthe treatment of 3-hydroxy-2-arylacrylonitriles 47andashf andmethyl or ethyl thioglycolates with hydrochloric acid byusing different PTC conditions (solid-liquid or liquid-liquid)The solid-liquid PTC conditions using 18-crown-6 alongwith potassium hydroxide as a catalyst are the method withexcellent yieldsThe reactions were carried out in acetonitrileat RT [29] (Figure 20)
In Japp-Klingemann reaction the indole derivatives 52have been prepared as indicated in Figure 21 The additionof a suitable PTC catalyst to the reaction could signifi-cantly improve the reaction process Firstly aryl amines49 were diazotized and reacted under alkaline conditionsethyl 2-[2-(13-dioxo-13-dihydro-2H-isoindol-2-yl)ethyl]-3-oxobutanoate 50 using PTC-promoted Japp-Klingemann
Journal of Chemistry 7
PTCK2CO3
DioxaneTBAB
NC
SHS
CNPTC
EtOCH=C(CN)(X)
HCN
PTC
S
S
NC
X
X
CN
SX
CN
HS
NC NH
HS
NC
CNS
31a b
X a = CN b = COOEt
EtOCH=C(CN)(X)
+
PTCEtOOC
S SH
CN
PTC
CN
EtOOC
EtOOC
SX
HCN
S
S S
NH2
NH2
X
OH
S S
NC
CNCNCOOEt
PTC
32a b X a = CN b = COOEt 33b
11
8a b
8a b
5
NCCH2COOEt + CS2
CH2(CN)2 + CS2
Figure 13
NSO2 SO2
N
Me
ClPTC
S
N
N
Me
SN
NH
Me
+
33 34 35
NCSminusSO2
Figure 14
CNHOOC CN
BrCH(CN)2 + HN NH2
NH2
O
ONPTC
HOO
HN
O
ON
Ph Ph36 37 38
Figure 15
CNO
NH2
NH2NH2N
HOOC
HNNO
O
CN
Ph
3738
Ph
H2NH2OOHminus
H2OOHminus
CN
OHO
HOOC
+ PhNHNH2
Figure 16
8 Journal of Chemistry
OH
CHOR + ClCH2COOR1
PTCMicrowave
O
R
39 40 41
COOR1
Figure 17
Ar-CH-OH
NC-CH-CH2-CH2Cl
O Ar
CN
42 43 44
ClCH2CH2CH2CN + Ar-CHO
Figure 18
CH3O
OHHO
H3C
O
K2CO3TBAHSO4 O
OO
CH3
O
X
X
H3CEDC
X = H Cl NO2 CH3 OCH3 OCH3 Br
COCH2Br+ 2X
45
46
Figure 19
CNR
H OH
1 HSCH2COOR1 HCl2 KOH ArCN 18-C-6
H S COOR1COOR1
CNR
S
R NH2
47andashf 48andashf
a phb 4-O-CH3
c benzo[b]furyl-2d thinyl-2e dimethyl 25-thinylf C6H5
R1RCOOMeCOOMeCOOMeCOOMeCOOMeCOOEt
60ndash70∘C
Figure 20
reaction to form the ring-opened aryl hydrazones 51 Thesearyl hydrazones were cyclized and converted into the corre-sponding indole derivatives 52 by adding hydrochloric acidin ethanol [30] (Figure 21)
Synthesis of dimethyl phosphinyl substituted tetra-hydropyrroles 55 via 13-cycloaddition reaction of the azome-thine 53 to electron deficient alkenes such as 120572120573-unsaturatedketones (eg benzylideneacetophenone 54) esters and
nitriles took place in high yield and low diastereoselectivityin phase-transfer catalysis conditions (solid potassium car-bonate triethylbenzylammonium chloride (TEBA)) in aceto-nitrile as a solvent [31] (Figure 22)
When Schiff base 53 and ethyl cinnamate 56 reactedunder different phase-transfer catalysis conditions (10 equiv-alents of aqueous NaOH (50)TEBADMSO) the esterof pyrrolidinecarboxylic acid 57 has not been formed
Journal of Chemistry 9
NH2
R
HClHNO2
N+
NCl
R
NCH3O
COOC2H5
CH3
COOC2H5
COOC2H5
O O
NN
HNO
O
R
NH
N
O
O
HCl
49
50
5152 R
0ndash5∘C
Figure 21
+
N
HCOPh
COPhH5C6
PH3CH3C
H3CH3C
OCl
53
54
NPh
PO
Cl
55
Figure 22
N C6H4-Cl-4PH3CH3C
H3C
H3C
H3C
H3C
O
PhCOOEt
+
NH
NH
H5C6
H5C6
C6H4-Cl-4
C6H4-Cl-4
COOEt
P
COOH
PO
O
NaOHH2OCH3CN
NaOHTEBA H2ODMSO
53
56
57
58
Figure 23
instead the acid itself 58 was obtained as a mixture of twodiastereoisomers [31] (Figure 23)
22 Synthesis of Five-Membered Ring Heterocycles Contain-ing Two Heteroatoms (4Z)-4-(4-amino-13-dithiol-2-ylid-ene)-5-methyl-2-phenyl-24-dihydro-3H-pyrazol-3-one
derivative 60 was the product of a reaction of 3-methyl-1-phenyl-2-pyrazoline-5-one 59 with CS
2and chloroac-
etonitrile in equimolar ratio under solid-liquid technique(benzeneK
2CO3TBAB) [23] (Figure 24)
Similarly 1-phenyl-35-pyrazolidinedione 36 was treatedwith CS
2and ethyl chloroacetate under the same condition
10 Journal of Chemistry
N
OPh
PTCNN
CH3
O
Ph
S
SN
H2N
59 60
+ CS2 + ClCH2CN
H3C
Figure 24
N O
O
Ph
+ + ClCH2COOEtHNHN
HN
HN
O
O
Ph
S
COOEt
S
N N
O
O
Ph
SH
EtOOCH2CS
N
O
OPh
S
S
O
36
61
minusEtOH
CS2
Figure 25
SS COOEt
NC
NH2
NH2
NH2
NH2
SS
COOEt
NCN
S
N
S
SS
CS2ClCH2CNPTC
PTC
CS2ClCH2COOEt
S
S
COOEt
NCN S
N
SO
SS O
62
63
64
Figure 26
Journal of Chemistry 11
S
SS
S
S
S COOEt
COOEt
NC
NH2
NH2
PTC
N
N
NC
SS
CS2Br(CH2)2Br
6562
Figure 27
PhPh
NN
O PTC
N
NHN
H3Cn = 0 1 a n = 067a b b n = 1
66
S
CH3
+ Br(CH2)nCH2Br(CH2)nCH2Br
Figure 28
X-CH2-N-NHAr [CH2=N-N]-Ar
RndashCH=CH2
N
NR
Ar70
69
68
minus+
Figure 29
H3C
H3C
SO2CH2NC + RCHO PTCO
N
N
N
SO2
SO2H3C
H3C
R
PTC
R1
71 72
7371
74
75 R2
SO2CH2NC + R1CH=NR2
Figure 30
Me
ClMe
CH + N=NN
N
H3C
S
CH3
PTCN
N
NN
CH3
CH3
S
CH3
H3C
RR
76 77 78
Figure 31
12 Journal of Chemistry
Br
BrPTC+
79 80 81
N
S
NO
H
PhNH
HNS
H
PhO
Figure 32
X
Y
+ PhNCSKOHDioxan
XYPhHN
KS
N
S
O Ph
X
Y
a X Y = CN b X = CN Y = CO2Etc X Y = CO2Et d X = COPh Y = COCH3
e COCH3 Y = CO2Et f X = COPh Y = CO2Etg X Y = COCH3
Cl
Z
OZ = Cl OEt or NH2
82andashg 83andashg
Figure 33
(benzeneK2CO3TBAB) to give the corresponding (4Z)-4-
(4-oxo-13-dithiolan-2-ylidene)-1-phenylpyrazolidine-35-dione 61 [25] (Figure 25)
The addition reaction of ethyl 34-diamino-5-cyanot-hieno[23-b]thiophene-2-carboxylate 62 to carbon disul-fide followed by cyclization reaction through the treat-ment with chloroacetonitrile or ethyl chloroacetate underPTC conditions (K
2CO3 TBAB dioxane) furnished 34-
bis(4-amino-2-thioxo-13-thiazol-3(2H)-yl)-5-propanoylthi-eno[23-b]thiophene-2-carbonitrile 63 and 34-bis(4-oxo-2-thioxo-13-thiazolidin-3-yl)-5-propanoylthieno[23-b]thio-phene-2-carbonitrile 64 in satisfactory yields [32] (Figure26)
Moreover the addition reaction of compound 62 tocarbon disulfide followed by cycloalkylation reaction with12-dibromoethane at 1 1 1 molar ratio under same PTCconditions afforded the corresponding bis-13-dithiolan-2-ylidene 65 [32] (Figure 27)
Treatment of triazepene compound 66 with dibromidesusing liquid-liquid condition (benzeneNaOHTBAB) fur-nished pyrazole derivatives 67a b [33] (Figure 28)
13-Dipolar cycloaddition of various substituted nitril-imines 68 to the appropriate alkenyl dipolarophiles 69 inaqueous media and in presence of a surfactant afforded anumber of 1-aryl-5-substituted-45-dihydropyrazoles 70 [34](Figure 29)
Preparation of 5-substituted oxazoles 74 or imidazoles75 was achieved by reaction of p-tolylsulphonylmethyl iso-cyanide 71 with aldehydes 72 R
1CH=NR
2or 73 (R
1 R2=
substituted phenyl heteroaryl and alkyl) under liquid-liquidcondition [35 36] (Figure 30)
The interaction of 3-chloro-3-methyl-1-butyne 76 with46-dimethyl-5-arylazo-2-thiopyrimidine 77 under liq-uid-liquid phase (benzeneaq KOHBTEACl) afforded 46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidinyl-(5H)-thiones 78 [37] (Figure 31)
Reaction of 5-phenylmethylene thiohydantoin 79 with12-dibromoethane 80 under liquid-liquid conditions (ben-zeneaq NaOHTBAB) afforded 23-dihydro-6-phenylmeth-ylene-5-oxo-imidazo[23-b]thiazole 81 [38] (Figure 32)
A variety of 4-thiazolidinone derivatives 83andashgwere suc-cessfully synthesized via in situ formation of ketene-NS-acetals 82andashg which in turn was reacted with ethylchloroethyl acetate chloroacetamide or chloroacetyl chlo-ride followed by ring closure to afford the desired 4-thiazolidinones 83andashg [39] (Figure 33)
One of the medicinal applications for PTC techniques issynthesis of sibenadet hydrochloride 87 which is a potentdrug used for treatment of chronic obstructive pulmonarydisease This bioactive molecule was synthesized by O-alkylation of phenylethanol 84 with the alkyl bromide 85under PTC condition to form the alkylated product 86 in97 yield Reaction of 86 with benzothiazole derivative ledto formation of the desired product 86 [40] (Figure 34)
Treatment of an equimolar amount of 2-mercapto-quinazolin-4(3H)-one 88 and dihalocompounds such as 12-dibromoethane and chloroacetyl chloride underwent S- and
Journal of Chemistry 13
OH
+ H2CBr
NaOHH2OTBAHSO4
OCH2
97
Sibenadet hydrochloride
84 8586
87 O
S NH
S
OHO
OO
NH middotHCl
Figure 34
NH
NH
O
SH
ClCH2COCl
Br(CH2)2Br
PTC89
88
O
N
NH
NH
S
OO
N
S
90
Figure 35
Ph
NO
O
SN
CS2 Br(CH2)2Br H
NH
NH
PTC
Ph
S
S
N
Ph
S
N
O
91
CS2Br(CH2)3Br
S
S
SPTC
92b
92a
Figure 36
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
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Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
6 Journal of Chemistry
NCH O
OOO
CS2
NC
O OO
O
NC
O OO
O
S S
SH
SH
Y
PTC
PTC
S
S Y
PTC
PTC
S S YS
NH2
YS
OH
CN
CN
N
NH
S
NC
PhNCS
PTC
EtO2CEtO2C
CO2Et
CO2Et
COPh
Ph
Ph
PhN
PhN
PhNS
NCEtO2C EtO2C EtO2C
S
EtO2CCO2EtEtO2C
OH
Y
Z ZX X
24a b 25a-b X = CO2C2H5 Y = CN Z = NH2
24c 25c X = CO2C2H5 Y = CONH2 Z = NH2
XCH2Y
XCH2Y
a Y = COPh b Y = CN c Y = CONH2
23
7
28andashc 29andashc
30 25andashc 24
+
++
Figure 12
disulphide or phenyl isothiocyanate 7 along with differentactive halocompounds under solid-liquid phase condition(dioxanK
2CO3TBAB) have been reported byAbdAllah and
El-Sayed [22] (Figure 12)2-Thiophenylidenes 31ndash33 were obtained through the
reaction of either malononitrile 5 or ethyl cyanoacetate 11with carbon disulphide along with ethoxymethylenemal-ononitrile 8a or ethyl ethoxymethylenecyanoacetate 8busing liquid-solid technique (dioxanK
2CO3TBAB) [19]
(Figure 13)In this reaction the yield of products was found to be a
temperature dependent Thus at low temperature (40∘C) itaffords the aminothiophene derivative 32a in high yield whileat high temperature hydroxythiophene 32b or 33b was thesolely product but in low yield
The reaction of pyridosultam 34 with 3-chloropropylthiocyanate under the experimental condition (tolueneaqNaOHTBAB) yielded the corresponding dihydrothiophenederivative 35 [24] (Figure 14)
4-Amino-5-cyano-2-hydroxy-3-furancarboxylic acid 37and compound 38were synthesized by treating 1-phenyl-35-pyrazolinedione 36 with bromomalononitrile under solid-liquid condition (dioxanK
2CO3TBAB) (Figure 15) [25]
The reaction pathway for the formation of unexpectedcompound 37was assumed to proceed via catalytic hydrolysisof compound 38 into the furan derivative 37 and phenylhydrazine [25] (Figure 16)
Condensation of salicylaldehyde 39 and its derivativeswith various esters of chloroacetic acids 40 in the pres-ence of TBAB led to the synthesis of benzo[b]furans 41under solventless and microwave irradiation technique [26](Figure 17)
Liquid-liquid PTC reaction of 4-chlorobutyronitrile 42with nonenolizable aldehydes 43 via sequence of an addi-tion cyclization reaction gave tetrahydrofuran-3-carbonitrilederivative 44 [27] (Figure 18)
Fused bis-aroylbenzodifurans 46 have been synthesizedby condensing 24-diacetyl resorcinol 45 with various p-substituted phenacyl bromides [28] (Figure 19)
Methyl or ethyl 3-amino-4-arylthiophenes-2-carbox-ylates 48andashf were synthesized by Thorpe reaction throughthe treatment of 3-hydroxy-2-arylacrylonitriles 47andashf andmethyl or ethyl thioglycolates with hydrochloric acid byusing different PTC conditions (solid-liquid or liquid-liquid)The solid-liquid PTC conditions using 18-crown-6 alongwith potassium hydroxide as a catalyst are the method withexcellent yieldsThe reactions were carried out in acetonitrileat RT [29] (Figure 20)
In Japp-Klingemann reaction the indole derivatives 52have been prepared as indicated in Figure 21 The additionof a suitable PTC catalyst to the reaction could signifi-cantly improve the reaction process Firstly aryl amines49 were diazotized and reacted under alkaline conditionsethyl 2-[2-(13-dioxo-13-dihydro-2H-isoindol-2-yl)ethyl]-3-oxobutanoate 50 using PTC-promoted Japp-Klingemann
Journal of Chemistry 7
PTCK2CO3
DioxaneTBAB
NC
SHS
CNPTC
EtOCH=C(CN)(X)
HCN
PTC
S
S
NC
X
X
CN
SX
CN
HS
NC NH
HS
NC
CNS
31a b
X a = CN b = COOEt
EtOCH=C(CN)(X)
+
PTCEtOOC
S SH
CN
PTC
CN
EtOOC
EtOOC
SX
HCN
S
S S
NH2
NH2
X
OH
S S
NC
CNCNCOOEt
PTC
32a b X a = CN b = COOEt 33b
11
8a b
8a b
5
NCCH2COOEt + CS2
CH2(CN)2 + CS2
Figure 13
NSO2 SO2
N
Me
ClPTC
S
N
N
Me
SN
NH
Me
+
33 34 35
NCSminusSO2
Figure 14
CNHOOC CN
BrCH(CN)2 + HN NH2
NH2
O
ONPTC
HOO
HN
O
ON
Ph Ph36 37 38
Figure 15
CNO
NH2
NH2NH2N
HOOC
HNNO
O
CN
Ph
3738
Ph
H2NH2OOHminus
H2OOHminus
CN
OHO
HOOC
+ PhNHNH2
Figure 16
8 Journal of Chemistry
OH
CHOR + ClCH2COOR1
PTCMicrowave
O
R
39 40 41
COOR1
Figure 17
Ar-CH-OH
NC-CH-CH2-CH2Cl
O Ar
CN
42 43 44
ClCH2CH2CH2CN + Ar-CHO
Figure 18
CH3O
OHHO
H3C
O
K2CO3TBAHSO4 O
OO
CH3
O
X
X
H3CEDC
X = H Cl NO2 CH3 OCH3 OCH3 Br
COCH2Br+ 2X
45
46
Figure 19
CNR
H OH
1 HSCH2COOR1 HCl2 KOH ArCN 18-C-6
H S COOR1COOR1
CNR
S
R NH2
47andashf 48andashf
a phb 4-O-CH3
c benzo[b]furyl-2d thinyl-2e dimethyl 25-thinylf C6H5
R1RCOOMeCOOMeCOOMeCOOMeCOOMeCOOEt
60ndash70∘C
Figure 20
reaction to form the ring-opened aryl hydrazones 51 Thesearyl hydrazones were cyclized and converted into the corre-sponding indole derivatives 52 by adding hydrochloric acidin ethanol [30] (Figure 21)
Synthesis of dimethyl phosphinyl substituted tetra-hydropyrroles 55 via 13-cycloaddition reaction of the azome-thine 53 to electron deficient alkenes such as 120572120573-unsaturatedketones (eg benzylideneacetophenone 54) esters and
nitriles took place in high yield and low diastereoselectivityin phase-transfer catalysis conditions (solid potassium car-bonate triethylbenzylammonium chloride (TEBA)) in aceto-nitrile as a solvent [31] (Figure 22)
When Schiff base 53 and ethyl cinnamate 56 reactedunder different phase-transfer catalysis conditions (10 equiv-alents of aqueous NaOH (50)TEBADMSO) the esterof pyrrolidinecarboxylic acid 57 has not been formed
Journal of Chemistry 9
NH2
R
HClHNO2
N+
NCl
R
NCH3O
COOC2H5
CH3
COOC2H5
COOC2H5
O O
NN
HNO
O
R
NH
N
O
O
HCl
49
50
5152 R
0ndash5∘C
Figure 21
+
N
HCOPh
COPhH5C6
PH3CH3C
H3CH3C
OCl
53
54
NPh
PO
Cl
55
Figure 22
N C6H4-Cl-4PH3CH3C
H3C
H3C
H3C
H3C
O
PhCOOEt
+
NH
NH
H5C6
H5C6
C6H4-Cl-4
C6H4-Cl-4
COOEt
P
COOH
PO
O
NaOHH2OCH3CN
NaOHTEBA H2ODMSO
53
56
57
58
Figure 23
instead the acid itself 58 was obtained as a mixture of twodiastereoisomers [31] (Figure 23)
22 Synthesis of Five-Membered Ring Heterocycles Contain-ing Two Heteroatoms (4Z)-4-(4-amino-13-dithiol-2-ylid-ene)-5-methyl-2-phenyl-24-dihydro-3H-pyrazol-3-one
derivative 60 was the product of a reaction of 3-methyl-1-phenyl-2-pyrazoline-5-one 59 with CS
2and chloroac-
etonitrile in equimolar ratio under solid-liquid technique(benzeneK
2CO3TBAB) [23] (Figure 24)
Similarly 1-phenyl-35-pyrazolidinedione 36 was treatedwith CS
2and ethyl chloroacetate under the same condition
10 Journal of Chemistry
N
OPh
PTCNN
CH3
O
Ph
S
SN
H2N
59 60
+ CS2 + ClCH2CN
H3C
Figure 24
N O
O
Ph
+ + ClCH2COOEtHNHN
HN
HN
O
O
Ph
S
COOEt
S
N N
O
O
Ph
SH
EtOOCH2CS
N
O
OPh
S
S
O
36
61
minusEtOH
CS2
Figure 25
SS COOEt
NC
NH2
NH2
NH2
NH2
SS
COOEt
NCN
S
N
S
SS
CS2ClCH2CNPTC
PTC
CS2ClCH2COOEt
S
S
COOEt
NCN S
N
SO
SS O
62
63
64
Figure 26
Journal of Chemistry 11
S
SS
S
S
S COOEt
COOEt
NC
NH2
NH2
PTC
N
N
NC
SS
CS2Br(CH2)2Br
6562
Figure 27
PhPh
NN
O PTC
N
NHN
H3Cn = 0 1 a n = 067a b b n = 1
66
S
CH3
+ Br(CH2)nCH2Br(CH2)nCH2Br
Figure 28
X-CH2-N-NHAr [CH2=N-N]-Ar
RndashCH=CH2
N
NR
Ar70
69
68
minus+
Figure 29
H3C
H3C
SO2CH2NC + RCHO PTCO
N
N
N
SO2
SO2H3C
H3C
R
PTC
R1
71 72
7371
74
75 R2
SO2CH2NC + R1CH=NR2
Figure 30
Me
ClMe
CH + N=NN
N
H3C
S
CH3
PTCN
N
NN
CH3
CH3
S
CH3
H3C
RR
76 77 78
Figure 31
12 Journal of Chemistry
Br
BrPTC+
79 80 81
N
S
NO
H
PhNH
HNS
H
PhO
Figure 32
X
Y
+ PhNCSKOHDioxan
XYPhHN
KS
N
S
O Ph
X
Y
a X Y = CN b X = CN Y = CO2Etc X Y = CO2Et d X = COPh Y = COCH3
e COCH3 Y = CO2Et f X = COPh Y = CO2Etg X Y = COCH3
Cl
Z
OZ = Cl OEt or NH2
82andashg 83andashg
Figure 33
(benzeneK2CO3TBAB) to give the corresponding (4Z)-4-
(4-oxo-13-dithiolan-2-ylidene)-1-phenylpyrazolidine-35-dione 61 [25] (Figure 25)
The addition reaction of ethyl 34-diamino-5-cyanot-hieno[23-b]thiophene-2-carboxylate 62 to carbon disul-fide followed by cyclization reaction through the treat-ment with chloroacetonitrile or ethyl chloroacetate underPTC conditions (K
2CO3 TBAB dioxane) furnished 34-
bis(4-amino-2-thioxo-13-thiazol-3(2H)-yl)-5-propanoylthi-eno[23-b]thiophene-2-carbonitrile 63 and 34-bis(4-oxo-2-thioxo-13-thiazolidin-3-yl)-5-propanoylthieno[23-b]thio-phene-2-carbonitrile 64 in satisfactory yields [32] (Figure26)
Moreover the addition reaction of compound 62 tocarbon disulfide followed by cycloalkylation reaction with12-dibromoethane at 1 1 1 molar ratio under same PTCconditions afforded the corresponding bis-13-dithiolan-2-ylidene 65 [32] (Figure 27)
Treatment of triazepene compound 66 with dibromidesusing liquid-liquid condition (benzeneNaOHTBAB) fur-nished pyrazole derivatives 67a b [33] (Figure 28)
13-Dipolar cycloaddition of various substituted nitril-imines 68 to the appropriate alkenyl dipolarophiles 69 inaqueous media and in presence of a surfactant afforded anumber of 1-aryl-5-substituted-45-dihydropyrazoles 70 [34](Figure 29)
Preparation of 5-substituted oxazoles 74 or imidazoles75 was achieved by reaction of p-tolylsulphonylmethyl iso-cyanide 71 with aldehydes 72 R
1CH=NR
2or 73 (R
1 R2=
substituted phenyl heteroaryl and alkyl) under liquid-liquidcondition [35 36] (Figure 30)
The interaction of 3-chloro-3-methyl-1-butyne 76 with46-dimethyl-5-arylazo-2-thiopyrimidine 77 under liq-uid-liquid phase (benzeneaq KOHBTEACl) afforded 46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidinyl-(5H)-thiones 78 [37] (Figure 31)
Reaction of 5-phenylmethylene thiohydantoin 79 with12-dibromoethane 80 under liquid-liquid conditions (ben-zeneaq NaOHTBAB) afforded 23-dihydro-6-phenylmeth-ylene-5-oxo-imidazo[23-b]thiazole 81 [38] (Figure 32)
A variety of 4-thiazolidinone derivatives 83andashgwere suc-cessfully synthesized via in situ formation of ketene-NS-acetals 82andashg which in turn was reacted with ethylchloroethyl acetate chloroacetamide or chloroacetyl chlo-ride followed by ring closure to afford the desired 4-thiazolidinones 83andashg [39] (Figure 33)
One of the medicinal applications for PTC techniques issynthesis of sibenadet hydrochloride 87 which is a potentdrug used for treatment of chronic obstructive pulmonarydisease This bioactive molecule was synthesized by O-alkylation of phenylethanol 84 with the alkyl bromide 85under PTC condition to form the alkylated product 86 in97 yield Reaction of 86 with benzothiazole derivative ledto formation of the desired product 86 [40] (Figure 34)
Treatment of an equimolar amount of 2-mercapto-quinazolin-4(3H)-one 88 and dihalocompounds such as 12-dibromoethane and chloroacetyl chloride underwent S- and
Journal of Chemistry 13
OH
+ H2CBr
NaOHH2OTBAHSO4
OCH2
97
Sibenadet hydrochloride
84 8586
87 O
S NH
S
OHO
OO
NH middotHCl
Figure 34
NH
NH
O
SH
ClCH2COCl
Br(CH2)2Br
PTC89
88
O
N
NH
NH
S
OO
N
S
90
Figure 35
Ph
NO
O
SN
CS2 Br(CH2)2Br H
NH
NH
PTC
Ph
S
S
N
Ph
S
N
O
91
CS2Br(CH2)3Br
S
S
SPTC
92b
92a
Figure 36
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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CatalystsJournal of
Journal of Chemistry 7
PTCK2CO3
DioxaneTBAB
NC
SHS
CNPTC
EtOCH=C(CN)(X)
HCN
PTC
S
S
NC
X
X
CN
SX
CN
HS
NC NH
HS
NC
CNS
31a b
X a = CN b = COOEt
EtOCH=C(CN)(X)
+
PTCEtOOC
S SH
CN
PTC
CN
EtOOC
EtOOC
SX
HCN
S
S S
NH2
NH2
X
OH
S S
NC
CNCNCOOEt
PTC
32a b X a = CN b = COOEt 33b
11
8a b
8a b
5
NCCH2COOEt + CS2
CH2(CN)2 + CS2
Figure 13
NSO2 SO2
N
Me
ClPTC
S
N
N
Me
SN
NH
Me
+
33 34 35
NCSminusSO2
Figure 14
CNHOOC CN
BrCH(CN)2 + HN NH2
NH2
O
ONPTC
HOO
HN
O
ON
Ph Ph36 37 38
Figure 15
CNO
NH2
NH2NH2N
HOOC
HNNO
O
CN
Ph
3738
Ph
H2NH2OOHminus
H2OOHminus
CN
OHO
HOOC
+ PhNHNH2
Figure 16
8 Journal of Chemistry
OH
CHOR + ClCH2COOR1
PTCMicrowave
O
R
39 40 41
COOR1
Figure 17
Ar-CH-OH
NC-CH-CH2-CH2Cl
O Ar
CN
42 43 44
ClCH2CH2CH2CN + Ar-CHO
Figure 18
CH3O
OHHO
H3C
O
K2CO3TBAHSO4 O
OO
CH3
O
X
X
H3CEDC
X = H Cl NO2 CH3 OCH3 OCH3 Br
COCH2Br+ 2X
45
46
Figure 19
CNR
H OH
1 HSCH2COOR1 HCl2 KOH ArCN 18-C-6
H S COOR1COOR1
CNR
S
R NH2
47andashf 48andashf
a phb 4-O-CH3
c benzo[b]furyl-2d thinyl-2e dimethyl 25-thinylf C6H5
R1RCOOMeCOOMeCOOMeCOOMeCOOMeCOOEt
60ndash70∘C
Figure 20
reaction to form the ring-opened aryl hydrazones 51 Thesearyl hydrazones were cyclized and converted into the corre-sponding indole derivatives 52 by adding hydrochloric acidin ethanol [30] (Figure 21)
Synthesis of dimethyl phosphinyl substituted tetra-hydropyrroles 55 via 13-cycloaddition reaction of the azome-thine 53 to electron deficient alkenes such as 120572120573-unsaturatedketones (eg benzylideneacetophenone 54) esters and
nitriles took place in high yield and low diastereoselectivityin phase-transfer catalysis conditions (solid potassium car-bonate triethylbenzylammonium chloride (TEBA)) in aceto-nitrile as a solvent [31] (Figure 22)
When Schiff base 53 and ethyl cinnamate 56 reactedunder different phase-transfer catalysis conditions (10 equiv-alents of aqueous NaOH (50)TEBADMSO) the esterof pyrrolidinecarboxylic acid 57 has not been formed
Journal of Chemistry 9
NH2
R
HClHNO2
N+
NCl
R
NCH3O
COOC2H5
CH3
COOC2H5
COOC2H5
O O
NN
HNO
O
R
NH
N
O
O
HCl
49
50
5152 R
0ndash5∘C
Figure 21
+
N
HCOPh
COPhH5C6
PH3CH3C
H3CH3C
OCl
53
54
NPh
PO
Cl
55
Figure 22
N C6H4-Cl-4PH3CH3C
H3C
H3C
H3C
H3C
O
PhCOOEt
+
NH
NH
H5C6
H5C6
C6H4-Cl-4
C6H4-Cl-4
COOEt
P
COOH
PO
O
NaOHH2OCH3CN
NaOHTEBA H2ODMSO
53
56
57
58
Figure 23
instead the acid itself 58 was obtained as a mixture of twodiastereoisomers [31] (Figure 23)
22 Synthesis of Five-Membered Ring Heterocycles Contain-ing Two Heteroatoms (4Z)-4-(4-amino-13-dithiol-2-ylid-ene)-5-methyl-2-phenyl-24-dihydro-3H-pyrazol-3-one
derivative 60 was the product of a reaction of 3-methyl-1-phenyl-2-pyrazoline-5-one 59 with CS
2and chloroac-
etonitrile in equimolar ratio under solid-liquid technique(benzeneK
2CO3TBAB) [23] (Figure 24)
Similarly 1-phenyl-35-pyrazolidinedione 36 was treatedwith CS
2and ethyl chloroacetate under the same condition
10 Journal of Chemistry
N
OPh
PTCNN
CH3
O
Ph
S
SN
H2N
59 60
+ CS2 + ClCH2CN
H3C
Figure 24
N O
O
Ph
+ + ClCH2COOEtHNHN
HN
HN
O
O
Ph
S
COOEt
S
N N
O
O
Ph
SH
EtOOCH2CS
N
O
OPh
S
S
O
36
61
minusEtOH
CS2
Figure 25
SS COOEt
NC
NH2
NH2
NH2
NH2
SS
COOEt
NCN
S
N
S
SS
CS2ClCH2CNPTC
PTC
CS2ClCH2COOEt
S
S
COOEt
NCN S
N
SO
SS O
62
63
64
Figure 26
Journal of Chemistry 11
S
SS
S
S
S COOEt
COOEt
NC
NH2
NH2
PTC
N
N
NC
SS
CS2Br(CH2)2Br
6562
Figure 27
PhPh
NN
O PTC
N
NHN
H3Cn = 0 1 a n = 067a b b n = 1
66
S
CH3
+ Br(CH2)nCH2Br(CH2)nCH2Br
Figure 28
X-CH2-N-NHAr [CH2=N-N]-Ar
RndashCH=CH2
N
NR
Ar70
69
68
minus+
Figure 29
H3C
H3C
SO2CH2NC + RCHO PTCO
N
N
N
SO2
SO2H3C
H3C
R
PTC
R1
71 72
7371
74
75 R2
SO2CH2NC + R1CH=NR2
Figure 30
Me
ClMe
CH + N=NN
N
H3C
S
CH3
PTCN
N
NN
CH3
CH3
S
CH3
H3C
RR
76 77 78
Figure 31
12 Journal of Chemistry
Br
BrPTC+
79 80 81
N
S
NO
H
PhNH
HNS
H
PhO
Figure 32
X
Y
+ PhNCSKOHDioxan
XYPhHN
KS
N
S
O Ph
X
Y
a X Y = CN b X = CN Y = CO2Etc X Y = CO2Et d X = COPh Y = COCH3
e COCH3 Y = CO2Et f X = COPh Y = CO2Etg X Y = COCH3
Cl
Z
OZ = Cl OEt or NH2
82andashg 83andashg
Figure 33
(benzeneK2CO3TBAB) to give the corresponding (4Z)-4-
(4-oxo-13-dithiolan-2-ylidene)-1-phenylpyrazolidine-35-dione 61 [25] (Figure 25)
The addition reaction of ethyl 34-diamino-5-cyanot-hieno[23-b]thiophene-2-carboxylate 62 to carbon disul-fide followed by cyclization reaction through the treat-ment with chloroacetonitrile or ethyl chloroacetate underPTC conditions (K
2CO3 TBAB dioxane) furnished 34-
bis(4-amino-2-thioxo-13-thiazol-3(2H)-yl)-5-propanoylthi-eno[23-b]thiophene-2-carbonitrile 63 and 34-bis(4-oxo-2-thioxo-13-thiazolidin-3-yl)-5-propanoylthieno[23-b]thio-phene-2-carbonitrile 64 in satisfactory yields [32] (Figure26)
Moreover the addition reaction of compound 62 tocarbon disulfide followed by cycloalkylation reaction with12-dibromoethane at 1 1 1 molar ratio under same PTCconditions afforded the corresponding bis-13-dithiolan-2-ylidene 65 [32] (Figure 27)
Treatment of triazepene compound 66 with dibromidesusing liquid-liquid condition (benzeneNaOHTBAB) fur-nished pyrazole derivatives 67a b [33] (Figure 28)
13-Dipolar cycloaddition of various substituted nitril-imines 68 to the appropriate alkenyl dipolarophiles 69 inaqueous media and in presence of a surfactant afforded anumber of 1-aryl-5-substituted-45-dihydropyrazoles 70 [34](Figure 29)
Preparation of 5-substituted oxazoles 74 or imidazoles75 was achieved by reaction of p-tolylsulphonylmethyl iso-cyanide 71 with aldehydes 72 R
1CH=NR
2or 73 (R
1 R2=
substituted phenyl heteroaryl and alkyl) under liquid-liquidcondition [35 36] (Figure 30)
The interaction of 3-chloro-3-methyl-1-butyne 76 with46-dimethyl-5-arylazo-2-thiopyrimidine 77 under liq-uid-liquid phase (benzeneaq KOHBTEACl) afforded 46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidinyl-(5H)-thiones 78 [37] (Figure 31)
Reaction of 5-phenylmethylene thiohydantoin 79 with12-dibromoethane 80 under liquid-liquid conditions (ben-zeneaq NaOHTBAB) afforded 23-dihydro-6-phenylmeth-ylene-5-oxo-imidazo[23-b]thiazole 81 [38] (Figure 32)
A variety of 4-thiazolidinone derivatives 83andashgwere suc-cessfully synthesized via in situ formation of ketene-NS-acetals 82andashg which in turn was reacted with ethylchloroethyl acetate chloroacetamide or chloroacetyl chlo-ride followed by ring closure to afford the desired 4-thiazolidinones 83andashg [39] (Figure 33)
One of the medicinal applications for PTC techniques issynthesis of sibenadet hydrochloride 87 which is a potentdrug used for treatment of chronic obstructive pulmonarydisease This bioactive molecule was synthesized by O-alkylation of phenylethanol 84 with the alkyl bromide 85under PTC condition to form the alkylated product 86 in97 yield Reaction of 86 with benzothiazole derivative ledto formation of the desired product 86 [40] (Figure 34)
Treatment of an equimolar amount of 2-mercapto-quinazolin-4(3H)-one 88 and dihalocompounds such as 12-dibromoethane and chloroacetyl chloride underwent S- and
Journal of Chemistry 13
OH
+ H2CBr
NaOHH2OTBAHSO4
OCH2
97
Sibenadet hydrochloride
84 8586
87 O
S NH
S
OHO
OO
NH middotHCl
Figure 34
NH
NH
O
SH
ClCH2COCl
Br(CH2)2Br
PTC89
88
O
N
NH
NH
S
OO
N
S
90
Figure 35
Ph
NO
O
SN
CS2 Br(CH2)2Br H
NH
NH
PTC
Ph
S
S
N
Ph
S
N
O
91
CS2Br(CH2)3Br
S
S
SPTC
92b
92a
Figure 36
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
8 Journal of Chemistry
OH
CHOR + ClCH2COOR1
PTCMicrowave
O
R
39 40 41
COOR1
Figure 17
Ar-CH-OH
NC-CH-CH2-CH2Cl
O Ar
CN
42 43 44
ClCH2CH2CH2CN + Ar-CHO
Figure 18
CH3O
OHHO
H3C
O
K2CO3TBAHSO4 O
OO
CH3
O
X
X
H3CEDC
X = H Cl NO2 CH3 OCH3 OCH3 Br
COCH2Br+ 2X
45
46
Figure 19
CNR
H OH
1 HSCH2COOR1 HCl2 KOH ArCN 18-C-6
H S COOR1COOR1
CNR
S
R NH2
47andashf 48andashf
a phb 4-O-CH3
c benzo[b]furyl-2d thinyl-2e dimethyl 25-thinylf C6H5
R1RCOOMeCOOMeCOOMeCOOMeCOOMeCOOEt
60ndash70∘C
Figure 20
reaction to form the ring-opened aryl hydrazones 51 Thesearyl hydrazones were cyclized and converted into the corre-sponding indole derivatives 52 by adding hydrochloric acidin ethanol [30] (Figure 21)
Synthesis of dimethyl phosphinyl substituted tetra-hydropyrroles 55 via 13-cycloaddition reaction of the azome-thine 53 to electron deficient alkenes such as 120572120573-unsaturatedketones (eg benzylideneacetophenone 54) esters and
nitriles took place in high yield and low diastereoselectivityin phase-transfer catalysis conditions (solid potassium car-bonate triethylbenzylammonium chloride (TEBA)) in aceto-nitrile as a solvent [31] (Figure 22)
When Schiff base 53 and ethyl cinnamate 56 reactedunder different phase-transfer catalysis conditions (10 equiv-alents of aqueous NaOH (50)TEBADMSO) the esterof pyrrolidinecarboxylic acid 57 has not been formed
Journal of Chemistry 9
NH2
R
HClHNO2
N+
NCl
R
NCH3O
COOC2H5
CH3
COOC2H5
COOC2H5
O O
NN
HNO
O
R
NH
N
O
O
HCl
49
50
5152 R
0ndash5∘C
Figure 21
+
N
HCOPh
COPhH5C6
PH3CH3C
H3CH3C
OCl
53
54
NPh
PO
Cl
55
Figure 22
N C6H4-Cl-4PH3CH3C
H3C
H3C
H3C
H3C
O
PhCOOEt
+
NH
NH
H5C6
H5C6
C6H4-Cl-4
C6H4-Cl-4
COOEt
P
COOH
PO
O
NaOHH2OCH3CN
NaOHTEBA H2ODMSO
53
56
57
58
Figure 23
instead the acid itself 58 was obtained as a mixture of twodiastereoisomers [31] (Figure 23)
22 Synthesis of Five-Membered Ring Heterocycles Contain-ing Two Heteroatoms (4Z)-4-(4-amino-13-dithiol-2-ylid-ene)-5-methyl-2-phenyl-24-dihydro-3H-pyrazol-3-one
derivative 60 was the product of a reaction of 3-methyl-1-phenyl-2-pyrazoline-5-one 59 with CS
2and chloroac-
etonitrile in equimolar ratio under solid-liquid technique(benzeneK
2CO3TBAB) [23] (Figure 24)
Similarly 1-phenyl-35-pyrazolidinedione 36 was treatedwith CS
2and ethyl chloroacetate under the same condition
10 Journal of Chemistry
N
OPh
PTCNN
CH3
O
Ph
S
SN
H2N
59 60
+ CS2 + ClCH2CN
H3C
Figure 24
N O
O
Ph
+ + ClCH2COOEtHNHN
HN
HN
O
O
Ph
S
COOEt
S
N N
O
O
Ph
SH
EtOOCH2CS
N
O
OPh
S
S
O
36
61
minusEtOH
CS2
Figure 25
SS COOEt
NC
NH2
NH2
NH2
NH2
SS
COOEt
NCN
S
N
S
SS
CS2ClCH2CNPTC
PTC
CS2ClCH2COOEt
S
S
COOEt
NCN S
N
SO
SS O
62
63
64
Figure 26
Journal of Chemistry 11
S
SS
S
S
S COOEt
COOEt
NC
NH2
NH2
PTC
N
N
NC
SS
CS2Br(CH2)2Br
6562
Figure 27
PhPh
NN
O PTC
N
NHN
H3Cn = 0 1 a n = 067a b b n = 1
66
S
CH3
+ Br(CH2)nCH2Br(CH2)nCH2Br
Figure 28
X-CH2-N-NHAr [CH2=N-N]-Ar
RndashCH=CH2
N
NR
Ar70
69
68
minus+
Figure 29
H3C
H3C
SO2CH2NC + RCHO PTCO
N
N
N
SO2
SO2H3C
H3C
R
PTC
R1
71 72
7371
74
75 R2
SO2CH2NC + R1CH=NR2
Figure 30
Me
ClMe
CH + N=NN
N
H3C
S
CH3
PTCN
N
NN
CH3
CH3
S
CH3
H3C
RR
76 77 78
Figure 31
12 Journal of Chemistry
Br
BrPTC+
79 80 81
N
S
NO
H
PhNH
HNS
H
PhO
Figure 32
X
Y
+ PhNCSKOHDioxan
XYPhHN
KS
N
S
O Ph
X
Y
a X Y = CN b X = CN Y = CO2Etc X Y = CO2Et d X = COPh Y = COCH3
e COCH3 Y = CO2Et f X = COPh Y = CO2Etg X Y = COCH3
Cl
Z
OZ = Cl OEt or NH2
82andashg 83andashg
Figure 33
(benzeneK2CO3TBAB) to give the corresponding (4Z)-4-
(4-oxo-13-dithiolan-2-ylidene)-1-phenylpyrazolidine-35-dione 61 [25] (Figure 25)
The addition reaction of ethyl 34-diamino-5-cyanot-hieno[23-b]thiophene-2-carboxylate 62 to carbon disul-fide followed by cyclization reaction through the treat-ment with chloroacetonitrile or ethyl chloroacetate underPTC conditions (K
2CO3 TBAB dioxane) furnished 34-
bis(4-amino-2-thioxo-13-thiazol-3(2H)-yl)-5-propanoylthi-eno[23-b]thiophene-2-carbonitrile 63 and 34-bis(4-oxo-2-thioxo-13-thiazolidin-3-yl)-5-propanoylthieno[23-b]thio-phene-2-carbonitrile 64 in satisfactory yields [32] (Figure26)
Moreover the addition reaction of compound 62 tocarbon disulfide followed by cycloalkylation reaction with12-dibromoethane at 1 1 1 molar ratio under same PTCconditions afforded the corresponding bis-13-dithiolan-2-ylidene 65 [32] (Figure 27)
Treatment of triazepene compound 66 with dibromidesusing liquid-liquid condition (benzeneNaOHTBAB) fur-nished pyrazole derivatives 67a b [33] (Figure 28)
13-Dipolar cycloaddition of various substituted nitril-imines 68 to the appropriate alkenyl dipolarophiles 69 inaqueous media and in presence of a surfactant afforded anumber of 1-aryl-5-substituted-45-dihydropyrazoles 70 [34](Figure 29)
Preparation of 5-substituted oxazoles 74 or imidazoles75 was achieved by reaction of p-tolylsulphonylmethyl iso-cyanide 71 with aldehydes 72 R
1CH=NR
2or 73 (R
1 R2=
substituted phenyl heteroaryl and alkyl) under liquid-liquidcondition [35 36] (Figure 30)
The interaction of 3-chloro-3-methyl-1-butyne 76 with46-dimethyl-5-arylazo-2-thiopyrimidine 77 under liq-uid-liquid phase (benzeneaq KOHBTEACl) afforded 46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidinyl-(5H)-thiones 78 [37] (Figure 31)
Reaction of 5-phenylmethylene thiohydantoin 79 with12-dibromoethane 80 under liquid-liquid conditions (ben-zeneaq NaOHTBAB) afforded 23-dihydro-6-phenylmeth-ylene-5-oxo-imidazo[23-b]thiazole 81 [38] (Figure 32)
A variety of 4-thiazolidinone derivatives 83andashgwere suc-cessfully synthesized via in situ formation of ketene-NS-acetals 82andashg which in turn was reacted with ethylchloroethyl acetate chloroacetamide or chloroacetyl chlo-ride followed by ring closure to afford the desired 4-thiazolidinones 83andashg [39] (Figure 33)
One of the medicinal applications for PTC techniques issynthesis of sibenadet hydrochloride 87 which is a potentdrug used for treatment of chronic obstructive pulmonarydisease This bioactive molecule was synthesized by O-alkylation of phenylethanol 84 with the alkyl bromide 85under PTC condition to form the alkylated product 86 in97 yield Reaction of 86 with benzothiazole derivative ledto formation of the desired product 86 [40] (Figure 34)
Treatment of an equimolar amount of 2-mercapto-quinazolin-4(3H)-one 88 and dihalocompounds such as 12-dibromoethane and chloroacetyl chloride underwent S- and
Journal of Chemistry 13
OH
+ H2CBr
NaOHH2OTBAHSO4
OCH2
97
Sibenadet hydrochloride
84 8586
87 O
S NH
S
OHO
OO
NH middotHCl
Figure 34
NH
NH
O
SH
ClCH2COCl
Br(CH2)2Br
PTC89
88
O
N
NH
NH
S
OO
N
S
90
Figure 35
Ph
NO
O
SN
CS2 Br(CH2)2Br H
NH
NH
PTC
Ph
S
S
N
Ph
S
N
O
91
CS2Br(CH2)3Br
S
S
SPTC
92b
92a
Figure 36
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 9
NH2
R
HClHNO2
N+
NCl
R
NCH3O
COOC2H5
CH3
COOC2H5
COOC2H5
O O
NN
HNO
O
R
NH
N
O
O
HCl
49
50
5152 R
0ndash5∘C
Figure 21
+
N
HCOPh
COPhH5C6
PH3CH3C
H3CH3C
OCl
53
54
NPh
PO
Cl
55
Figure 22
N C6H4-Cl-4PH3CH3C
H3C
H3C
H3C
H3C
O
PhCOOEt
+
NH
NH
H5C6
H5C6
C6H4-Cl-4
C6H4-Cl-4
COOEt
P
COOH
PO
O
NaOHH2OCH3CN
NaOHTEBA H2ODMSO
53
56
57
58
Figure 23
instead the acid itself 58 was obtained as a mixture of twodiastereoisomers [31] (Figure 23)
22 Synthesis of Five-Membered Ring Heterocycles Contain-ing Two Heteroatoms (4Z)-4-(4-amino-13-dithiol-2-ylid-ene)-5-methyl-2-phenyl-24-dihydro-3H-pyrazol-3-one
derivative 60 was the product of a reaction of 3-methyl-1-phenyl-2-pyrazoline-5-one 59 with CS
2and chloroac-
etonitrile in equimolar ratio under solid-liquid technique(benzeneK
2CO3TBAB) [23] (Figure 24)
Similarly 1-phenyl-35-pyrazolidinedione 36 was treatedwith CS
2and ethyl chloroacetate under the same condition
10 Journal of Chemistry
N
OPh
PTCNN
CH3
O
Ph
S
SN
H2N
59 60
+ CS2 + ClCH2CN
H3C
Figure 24
N O
O
Ph
+ + ClCH2COOEtHNHN
HN
HN
O
O
Ph
S
COOEt
S
N N
O
O
Ph
SH
EtOOCH2CS
N
O
OPh
S
S
O
36
61
minusEtOH
CS2
Figure 25
SS COOEt
NC
NH2
NH2
NH2
NH2
SS
COOEt
NCN
S
N
S
SS
CS2ClCH2CNPTC
PTC
CS2ClCH2COOEt
S
S
COOEt
NCN S
N
SO
SS O
62
63
64
Figure 26
Journal of Chemistry 11
S
SS
S
S
S COOEt
COOEt
NC
NH2
NH2
PTC
N
N
NC
SS
CS2Br(CH2)2Br
6562
Figure 27
PhPh
NN
O PTC
N
NHN
H3Cn = 0 1 a n = 067a b b n = 1
66
S
CH3
+ Br(CH2)nCH2Br(CH2)nCH2Br
Figure 28
X-CH2-N-NHAr [CH2=N-N]-Ar
RndashCH=CH2
N
NR
Ar70
69
68
minus+
Figure 29
H3C
H3C
SO2CH2NC + RCHO PTCO
N
N
N
SO2
SO2H3C
H3C
R
PTC
R1
71 72
7371
74
75 R2
SO2CH2NC + R1CH=NR2
Figure 30
Me
ClMe
CH + N=NN
N
H3C
S
CH3
PTCN
N
NN
CH3
CH3
S
CH3
H3C
RR
76 77 78
Figure 31
12 Journal of Chemistry
Br
BrPTC+
79 80 81
N
S
NO
H
PhNH
HNS
H
PhO
Figure 32
X
Y
+ PhNCSKOHDioxan
XYPhHN
KS
N
S
O Ph
X
Y
a X Y = CN b X = CN Y = CO2Etc X Y = CO2Et d X = COPh Y = COCH3
e COCH3 Y = CO2Et f X = COPh Y = CO2Etg X Y = COCH3
Cl
Z
OZ = Cl OEt or NH2
82andashg 83andashg
Figure 33
(benzeneK2CO3TBAB) to give the corresponding (4Z)-4-
(4-oxo-13-dithiolan-2-ylidene)-1-phenylpyrazolidine-35-dione 61 [25] (Figure 25)
The addition reaction of ethyl 34-diamino-5-cyanot-hieno[23-b]thiophene-2-carboxylate 62 to carbon disul-fide followed by cyclization reaction through the treat-ment with chloroacetonitrile or ethyl chloroacetate underPTC conditions (K
2CO3 TBAB dioxane) furnished 34-
bis(4-amino-2-thioxo-13-thiazol-3(2H)-yl)-5-propanoylthi-eno[23-b]thiophene-2-carbonitrile 63 and 34-bis(4-oxo-2-thioxo-13-thiazolidin-3-yl)-5-propanoylthieno[23-b]thio-phene-2-carbonitrile 64 in satisfactory yields [32] (Figure26)
Moreover the addition reaction of compound 62 tocarbon disulfide followed by cycloalkylation reaction with12-dibromoethane at 1 1 1 molar ratio under same PTCconditions afforded the corresponding bis-13-dithiolan-2-ylidene 65 [32] (Figure 27)
Treatment of triazepene compound 66 with dibromidesusing liquid-liquid condition (benzeneNaOHTBAB) fur-nished pyrazole derivatives 67a b [33] (Figure 28)
13-Dipolar cycloaddition of various substituted nitril-imines 68 to the appropriate alkenyl dipolarophiles 69 inaqueous media and in presence of a surfactant afforded anumber of 1-aryl-5-substituted-45-dihydropyrazoles 70 [34](Figure 29)
Preparation of 5-substituted oxazoles 74 or imidazoles75 was achieved by reaction of p-tolylsulphonylmethyl iso-cyanide 71 with aldehydes 72 R
1CH=NR
2or 73 (R
1 R2=
substituted phenyl heteroaryl and alkyl) under liquid-liquidcondition [35 36] (Figure 30)
The interaction of 3-chloro-3-methyl-1-butyne 76 with46-dimethyl-5-arylazo-2-thiopyrimidine 77 under liq-uid-liquid phase (benzeneaq KOHBTEACl) afforded 46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidinyl-(5H)-thiones 78 [37] (Figure 31)
Reaction of 5-phenylmethylene thiohydantoin 79 with12-dibromoethane 80 under liquid-liquid conditions (ben-zeneaq NaOHTBAB) afforded 23-dihydro-6-phenylmeth-ylene-5-oxo-imidazo[23-b]thiazole 81 [38] (Figure 32)
A variety of 4-thiazolidinone derivatives 83andashgwere suc-cessfully synthesized via in situ formation of ketene-NS-acetals 82andashg which in turn was reacted with ethylchloroethyl acetate chloroacetamide or chloroacetyl chlo-ride followed by ring closure to afford the desired 4-thiazolidinones 83andashg [39] (Figure 33)
One of the medicinal applications for PTC techniques issynthesis of sibenadet hydrochloride 87 which is a potentdrug used for treatment of chronic obstructive pulmonarydisease This bioactive molecule was synthesized by O-alkylation of phenylethanol 84 with the alkyl bromide 85under PTC condition to form the alkylated product 86 in97 yield Reaction of 86 with benzothiazole derivative ledto formation of the desired product 86 [40] (Figure 34)
Treatment of an equimolar amount of 2-mercapto-quinazolin-4(3H)-one 88 and dihalocompounds such as 12-dibromoethane and chloroacetyl chloride underwent S- and
Journal of Chemistry 13
OH
+ H2CBr
NaOHH2OTBAHSO4
OCH2
97
Sibenadet hydrochloride
84 8586
87 O
S NH
S
OHO
OO
NH middotHCl
Figure 34
NH
NH
O
SH
ClCH2COCl
Br(CH2)2Br
PTC89
88
O
N
NH
NH
S
OO
N
S
90
Figure 35
Ph
NO
O
SN
CS2 Br(CH2)2Br H
NH
NH
PTC
Ph
S
S
N
Ph
S
N
O
91
CS2Br(CH2)3Br
S
S
SPTC
92b
92a
Figure 36
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
10 Journal of Chemistry
N
OPh
PTCNN
CH3
O
Ph
S
SN
H2N
59 60
+ CS2 + ClCH2CN
H3C
Figure 24
N O
O
Ph
+ + ClCH2COOEtHNHN
HN
HN
O
O
Ph
S
COOEt
S
N N
O
O
Ph
SH
EtOOCH2CS
N
O
OPh
S
S
O
36
61
minusEtOH
CS2
Figure 25
SS COOEt
NC
NH2
NH2
NH2
NH2
SS
COOEt
NCN
S
N
S
SS
CS2ClCH2CNPTC
PTC
CS2ClCH2COOEt
S
S
COOEt
NCN S
N
SO
SS O
62
63
64
Figure 26
Journal of Chemistry 11
S
SS
S
S
S COOEt
COOEt
NC
NH2
NH2
PTC
N
N
NC
SS
CS2Br(CH2)2Br
6562
Figure 27
PhPh
NN
O PTC
N
NHN
H3Cn = 0 1 a n = 067a b b n = 1
66
S
CH3
+ Br(CH2)nCH2Br(CH2)nCH2Br
Figure 28
X-CH2-N-NHAr [CH2=N-N]-Ar
RndashCH=CH2
N
NR
Ar70
69
68
minus+
Figure 29
H3C
H3C
SO2CH2NC + RCHO PTCO
N
N
N
SO2
SO2H3C
H3C
R
PTC
R1
71 72
7371
74
75 R2
SO2CH2NC + R1CH=NR2
Figure 30
Me
ClMe
CH + N=NN
N
H3C
S
CH3
PTCN
N
NN
CH3
CH3
S
CH3
H3C
RR
76 77 78
Figure 31
12 Journal of Chemistry
Br
BrPTC+
79 80 81
N
S
NO
H
PhNH
HNS
H
PhO
Figure 32
X
Y
+ PhNCSKOHDioxan
XYPhHN
KS
N
S
O Ph
X
Y
a X Y = CN b X = CN Y = CO2Etc X Y = CO2Et d X = COPh Y = COCH3
e COCH3 Y = CO2Et f X = COPh Y = CO2Etg X Y = COCH3
Cl
Z
OZ = Cl OEt or NH2
82andashg 83andashg
Figure 33
(benzeneK2CO3TBAB) to give the corresponding (4Z)-4-
(4-oxo-13-dithiolan-2-ylidene)-1-phenylpyrazolidine-35-dione 61 [25] (Figure 25)
The addition reaction of ethyl 34-diamino-5-cyanot-hieno[23-b]thiophene-2-carboxylate 62 to carbon disul-fide followed by cyclization reaction through the treat-ment with chloroacetonitrile or ethyl chloroacetate underPTC conditions (K
2CO3 TBAB dioxane) furnished 34-
bis(4-amino-2-thioxo-13-thiazol-3(2H)-yl)-5-propanoylthi-eno[23-b]thiophene-2-carbonitrile 63 and 34-bis(4-oxo-2-thioxo-13-thiazolidin-3-yl)-5-propanoylthieno[23-b]thio-phene-2-carbonitrile 64 in satisfactory yields [32] (Figure26)
Moreover the addition reaction of compound 62 tocarbon disulfide followed by cycloalkylation reaction with12-dibromoethane at 1 1 1 molar ratio under same PTCconditions afforded the corresponding bis-13-dithiolan-2-ylidene 65 [32] (Figure 27)
Treatment of triazepene compound 66 with dibromidesusing liquid-liquid condition (benzeneNaOHTBAB) fur-nished pyrazole derivatives 67a b [33] (Figure 28)
13-Dipolar cycloaddition of various substituted nitril-imines 68 to the appropriate alkenyl dipolarophiles 69 inaqueous media and in presence of a surfactant afforded anumber of 1-aryl-5-substituted-45-dihydropyrazoles 70 [34](Figure 29)
Preparation of 5-substituted oxazoles 74 or imidazoles75 was achieved by reaction of p-tolylsulphonylmethyl iso-cyanide 71 with aldehydes 72 R
1CH=NR
2or 73 (R
1 R2=
substituted phenyl heteroaryl and alkyl) under liquid-liquidcondition [35 36] (Figure 30)
The interaction of 3-chloro-3-methyl-1-butyne 76 with46-dimethyl-5-arylazo-2-thiopyrimidine 77 under liq-uid-liquid phase (benzeneaq KOHBTEACl) afforded 46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidinyl-(5H)-thiones 78 [37] (Figure 31)
Reaction of 5-phenylmethylene thiohydantoin 79 with12-dibromoethane 80 under liquid-liquid conditions (ben-zeneaq NaOHTBAB) afforded 23-dihydro-6-phenylmeth-ylene-5-oxo-imidazo[23-b]thiazole 81 [38] (Figure 32)
A variety of 4-thiazolidinone derivatives 83andashgwere suc-cessfully synthesized via in situ formation of ketene-NS-acetals 82andashg which in turn was reacted with ethylchloroethyl acetate chloroacetamide or chloroacetyl chlo-ride followed by ring closure to afford the desired 4-thiazolidinones 83andashg [39] (Figure 33)
One of the medicinal applications for PTC techniques issynthesis of sibenadet hydrochloride 87 which is a potentdrug used for treatment of chronic obstructive pulmonarydisease This bioactive molecule was synthesized by O-alkylation of phenylethanol 84 with the alkyl bromide 85under PTC condition to form the alkylated product 86 in97 yield Reaction of 86 with benzothiazole derivative ledto formation of the desired product 86 [40] (Figure 34)
Treatment of an equimolar amount of 2-mercapto-quinazolin-4(3H)-one 88 and dihalocompounds such as 12-dibromoethane and chloroacetyl chloride underwent S- and
Journal of Chemistry 13
OH
+ H2CBr
NaOHH2OTBAHSO4
OCH2
97
Sibenadet hydrochloride
84 8586
87 O
S NH
S
OHO
OO
NH middotHCl
Figure 34
NH
NH
O
SH
ClCH2COCl
Br(CH2)2Br
PTC89
88
O
N
NH
NH
S
OO
N
S
90
Figure 35
Ph
NO
O
SN
CS2 Br(CH2)2Br H
NH
NH
PTC
Ph
S
S
N
Ph
S
N
O
91
CS2Br(CH2)3Br
S
S
SPTC
92b
92a
Figure 36
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
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[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
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[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
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[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
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CatalystsJournal of
Journal of Chemistry 11
S
SS
S
S
S COOEt
COOEt
NC
NH2
NH2
PTC
N
N
NC
SS
CS2Br(CH2)2Br
6562
Figure 27
PhPh
NN
O PTC
N
NHN
H3Cn = 0 1 a n = 067a b b n = 1
66
S
CH3
+ Br(CH2)nCH2Br(CH2)nCH2Br
Figure 28
X-CH2-N-NHAr [CH2=N-N]-Ar
RndashCH=CH2
N
NR
Ar70
69
68
minus+
Figure 29
H3C
H3C
SO2CH2NC + RCHO PTCO
N
N
N
SO2
SO2H3C
H3C
R
PTC
R1
71 72
7371
74
75 R2
SO2CH2NC + R1CH=NR2
Figure 30
Me
ClMe
CH + N=NN
N
H3C
S
CH3
PTCN
N
NN
CH3
CH3
S
CH3
H3C
RR
76 77 78
Figure 31
12 Journal of Chemistry
Br
BrPTC+
79 80 81
N
S
NO
H
PhNH
HNS
H
PhO
Figure 32
X
Y
+ PhNCSKOHDioxan
XYPhHN
KS
N
S
O Ph
X
Y
a X Y = CN b X = CN Y = CO2Etc X Y = CO2Et d X = COPh Y = COCH3
e COCH3 Y = CO2Et f X = COPh Y = CO2Etg X Y = COCH3
Cl
Z
OZ = Cl OEt or NH2
82andashg 83andashg
Figure 33
(benzeneK2CO3TBAB) to give the corresponding (4Z)-4-
(4-oxo-13-dithiolan-2-ylidene)-1-phenylpyrazolidine-35-dione 61 [25] (Figure 25)
The addition reaction of ethyl 34-diamino-5-cyanot-hieno[23-b]thiophene-2-carboxylate 62 to carbon disul-fide followed by cyclization reaction through the treat-ment with chloroacetonitrile or ethyl chloroacetate underPTC conditions (K
2CO3 TBAB dioxane) furnished 34-
bis(4-amino-2-thioxo-13-thiazol-3(2H)-yl)-5-propanoylthi-eno[23-b]thiophene-2-carbonitrile 63 and 34-bis(4-oxo-2-thioxo-13-thiazolidin-3-yl)-5-propanoylthieno[23-b]thio-phene-2-carbonitrile 64 in satisfactory yields [32] (Figure26)
Moreover the addition reaction of compound 62 tocarbon disulfide followed by cycloalkylation reaction with12-dibromoethane at 1 1 1 molar ratio under same PTCconditions afforded the corresponding bis-13-dithiolan-2-ylidene 65 [32] (Figure 27)
Treatment of triazepene compound 66 with dibromidesusing liquid-liquid condition (benzeneNaOHTBAB) fur-nished pyrazole derivatives 67a b [33] (Figure 28)
13-Dipolar cycloaddition of various substituted nitril-imines 68 to the appropriate alkenyl dipolarophiles 69 inaqueous media and in presence of a surfactant afforded anumber of 1-aryl-5-substituted-45-dihydropyrazoles 70 [34](Figure 29)
Preparation of 5-substituted oxazoles 74 or imidazoles75 was achieved by reaction of p-tolylsulphonylmethyl iso-cyanide 71 with aldehydes 72 R
1CH=NR
2or 73 (R
1 R2=
substituted phenyl heteroaryl and alkyl) under liquid-liquidcondition [35 36] (Figure 30)
The interaction of 3-chloro-3-methyl-1-butyne 76 with46-dimethyl-5-arylazo-2-thiopyrimidine 77 under liq-uid-liquid phase (benzeneaq KOHBTEACl) afforded 46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidinyl-(5H)-thiones 78 [37] (Figure 31)
Reaction of 5-phenylmethylene thiohydantoin 79 with12-dibromoethane 80 under liquid-liquid conditions (ben-zeneaq NaOHTBAB) afforded 23-dihydro-6-phenylmeth-ylene-5-oxo-imidazo[23-b]thiazole 81 [38] (Figure 32)
A variety of 4-thiazolidinone derivatives 83andashgwere suc-cessfully synthesized via in situ formation of ketene-NS-acetals 82andashg which in turn was reacted with ethylchloroethyl acetate chloroacetamide or chloroacetyl chlo-ride followed by ring closure to afford the desired 4-thiazolidinones 83andashg [39] (Figure 33)
One of the medicinal applications for PTC techniques issynthesis of sibenadet hydrochloride 87 which is a potentdrug used for treatment of chronic obstructive pulmonarydisease This bioactive molecule was synthesized by O-alkylation of phenylethanol 84 with the alkyl bromide 85under PTC condition to form the alkylated product 86 in97 yield Reaction of 86 with benzothiazole derivative ledto formation of the desired product 86 [40] (Figure 34)
Treatment of an equimolar amount of 2-mercapto-quinazolin-4(3H)-one 88 and dihalocompounds such as 12-dibromoethane and chloroacetyl chloride underwent S- and
Journal of Chemistry 13
OH
+ H2CBr
NaOHH2OTBAHSO4
OCH2
97
Sibenadet hydrochloride
84 8586
87 O
S NH
S
OHO
OO
NH middotHCl
Figure 34
NH
NH
O
SH
ClCH2COCl
Br(CH2)2Br
PTC89
88
O
N
NH
NH
S
OO
N
S
90
Figure 35
Ph
NO
O
SN
CS2 Br(CH2)2Br H
NH
NH
PTC
Ph
S
S
N
Ph
S
N
O
91
CS2Br(CH2)3Br
S
S
SPTC
92b
92a
Figure 36
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
12 Journal of Chemistry
Br
BrPTC+
79 80 81
N
S
NO
H
PhNH
HNS
H
PhO
Figure 32
X
Y
+ PhNCSKOHDioxan
XYPhHN
KS
N
S
O Ph
X
Y
a X Y = CN b X = CN Y = CO2Etc X Y = CO2Et d X = COPh Y = COCH3
e COCH3 Y = CO2Et f X = COPh Y = CO2Etg X Y = COCH3
Cl
Z
OZ = Cl OEt or NH2
82andashg 83andashg
Figure 33
(benzeneK2CO3TBAB) to give the corresponding (4Z)-4-
(4-oxo-13-dithiolan-2-ylidene)-1-phenylpyrazolidine-35-dione 61 [25] (Figure 25)
The addition reaction of ethyl 34-diamino-5-cyanot-hieno[23-b]thiophene-2-carboxylate 62 to carbon disul-fide followed by cyclization reaction through the treat-ment with chloroacetonitrile or ethyl chloroacetate underPTC conditions (K
2CO3 TBAB dioxane) furnished 34-
bis(4-amino-2-thioxo-13-thiazol-3(2H)-yl)-5-propanoylthi-eno[23-b]thiophene-2-carbonitrile 63 and 34-bis(4-oxo-2-thioxo-13-thiazolidin-3-yl)-5-propanoylthieno[23-b]thio-phene-2-carbonitrile 64 in satisfactory yields [32] (Figure26)
Moreover the addition reaction of compound 62 tocarbon disulfide followed by cycloalkylation reaction with12-dibromoethane at 1 1 1 molar ratio under same PTCconditions afforded the corresponding bis-13-dithiolan-2-ylidene 65 [32] (Figure 27)
Treatment of triazepene compound 66 with dibromidesusing liquid-liquid condition (benzeneNaOHTBAB) fur-nished pyrazole derivatives 67a b [33] (Figure 28)
13-Dipolar cycloaddition of various substituted nitril-imines 68 to the appropriate alkenyl dipolarophiles 69 inaqueous media and in presence of a surfactant afforded anumber of 1-aryl-5-substituted-45-dihydropyrazoles 70 [34](Figure 29)
Preparation of 5-substituted oxazoles 74 or imidazoles75 was achieved by reaction of p-tolylsulphonylmethyl iso-cyanide 71 with aldehydes 72 R
1CH=NR
2or 73 (R
1 R2=
substituted phenyl heteroaryl and alkyl) under liquid-liquidcondition [35 36] (Figure 30)
The interaction of 3-chloro-3-methyl-1-butyne 76 with46-dimethyl-5-arylazo-2-thiopyrimidine 77 under liq-uid-liquid phase (benzeneaq KOHBTEACl) afforded 46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidinyl-(5H)-thiones 78 [37] (Figure 31)
Reaction of 5-phenylmethylene thiohydantoin 79 with12-dibromoethane 80 under liquid-liquid conditions (ben-zeneaq NaOHTBAB) afforded 23-dihydro-6-phenylmeth-ylene-5-oxo-imidazo[23-b]thiazole 81 [38] (Figure 32)
A variety of 4-thiazolidinone derivatives 83andashgwere suc-cessfully synthesized via in situ formation of ketene-NS-acetals 82andashg which in turn was reacted with ethylchloroethyl acetate chloroacetamide or chloroacetyl chlo-ride followed by ring closure to afford the desired 4-thiazolidinones 83andashg [39] (Figure 33)
One of the medicinal applications for PTC techniques issynthesis of sibenadet hydrochloride 87 which is a potentdrug used for treatment of chronic obstructive pulmonarydisease This bioactive molecule was synthesized by O-alkylation of phenylethanol 84 with the alkyl bromide 85under PTC condition to form the alkylated product 86 in97 yield Reaction of 86 with benzothiazole derivative ledto formation of the desired product 86 [40] (Figure 34)
Treatment of an equimolar amount of 2-mercapto-quinazolin-4(3H)-one 88 and dihalocompounds such as 12-dibromoethane and chloroacetyl chloride underwent S- and
Journal of Chemistry 13
OH
+ H2CBr
NaOHH2OTBAHSO4
OCH2
97
Sibenadet hydrochloride
84 8586
87 O
S NH
S
OHO
OO
NH middotHCl
Figure 34
NH
NH
O
SH
ClCH2COCl
Br(CH2)2Br
PTC89
88
O
N
NH
NH
S
OO
N
S
90
Figure 35
Ph
NO
O
SN
CS2 Br(CH2)2Br H
NH
NH
PTC
Ph
S
S
N
Ph
S
N
O
91
CS2Br(CH2)3Br
S
S
SPTC
92b
92a
Figure 36
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 13
OH
+ H2CBr
NaOHH2OTBAHSO4
OCH2
97
Sibenadet hydrochloride
84 8586
87 O
S NH
S
OHO
OO
NH middotHCl
Figure 34
NH
NH
O
SH
ClCH2COCl
Br(CH2)2Br
PTC89
88
O
N
NH
NH
S
OO
N
S
90
Figure 35
Ph
NO
O
SN
CS2 Br(CH2)2Br H
NH
NH
PTC
Ph
S
S
N
Ph
S
N
O
91
CS2Br(CH2)3Br
S
S
SPTC
92b
92a
Figure 36
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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ElectrochemistryInternational Journal of
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CatalystsJournal of
14 Journal of Chemistry
H3C
H3CH3C
H3CNH
NH Ph
X
NN
Ph
O
NN
Ph
O
NN
R
XO
BrCH2COOEtPTCTBAB
93 X = S 95a bX a = S b = O94 X = O
Figure 37
NHPh
N
HN
H
Ph H O
+
Br
Br
Br
Br
PTC
PTC
PhH
H
N
O
N NN Ph
OH
96
N
O
OO
O
O
N
NNN
N
Ph
NHN H
H
HN HN
PhPh
97
98 99a 99b
+ +
Figure 38
CNNC
CH3
CNNC
N NN
H3C
H3CH3C
H3C
CH3
CH3CH3 CH3
CH3
CH3Cl 50 NaOH aq
TEBA
Anastrozole
100
101
CNNC
Figure 39
SN
R(Ar)
N
NN N
N N
NR(Ar)S
PTC
+
++
102 103 104
Figure 40
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
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Carbohydrate Chemistry
International Journal of
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CatalystsJournal of
Journal of Chemistry 15
+
NN
NN
NN
N N
N
NN
N
R
R
R
105
NCl
N
ClN
Cl
R
R
R
Bu4NBrCHCl3-H2ONaN3
R = OMe (a) OEt (b) Me (c) H (d) Br (e)
106andashe
Figure 41
NC CN+ CS2 + XCH2Y
SS
H2N
Y Y
NH2
aY = COOEtb Y = CN
5107a b
PTC
X = Cl Br
Figure 42
+ CS2 + ClCH2CO2C2H5
S S
H3C
C2H5O2C CO2C2H5
CH3
H3COC COCH3
109108
Figure 43
H2N NH2
CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et
S NPh
110
5 7
Figure 44
NN
O
NN
O
S
S
NN
PhPh
Ph
S
S
NC
NC
63 111
CH3CH3
CH3
+ CS2 + ClCH2CN
Figure 45
16 Journal of Chemistry
HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
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[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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HNN
O
O
Ph
HNN
O
O
Ph
S
S
R HN
N
S
O
R
S
Ph36 112
+ CS2 + ClCH2RminusH2O
R = CN COOEt
Figure 46
S S S
O
S
OH
Br PTCCH3+
113 115114
Figure 47
N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)
The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS
2 yielded 13-dithioxane derivative 92a
or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)
Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K
2CO3as liquid-solid
phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)
23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)
Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)
24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of
alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)
Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)
3 Synthesis of Fused Five-MemberedRing Heterocycles
Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in
1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC
condition [23] (Figure 42)Another different thienothiophene 109 was synthesized
via the reaction of acetylacetone 108 with CS2and ethyl
chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)
Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)
Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS
2and
chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)
1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS
2along with chloroacetonitrile or ethyl chloroacetate
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
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[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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CatalystsJournal of
Journal of Chemistry 17
NN
OAr
N
O
O
Ph
NN
N
O
O
OAr
Ph
NN
OAr
H
HNN
OAr
HH
NN
OAr
H
H
HZ
NN
OAr
PTC
X
X
X
X
or
Or
Z
X Y
116
117
118a 118b
119
120
Brminus
CO2CH3
CO2CH3
CO2CH3
X = CO2CH3
Z = CN CO2C2H5
X = H CO2C2H5
Y = CO2C2H5 CO2CH3 CO2CH2H5
H3CO2C
+
H(CO2C2H5)
Figure 48
NN
NH2 NH2
SHHS
NH2 NH2NH2
NH2NH2
CNNC+ 2XCH2Y PTC
N NS S
H2N
Y Y
X = Cl Br
Y = COOEt CN PhCO CONH2
NN ClCl
CNNC
+ 2HSCH2COOEt PTC
121 122
123
Figure 49
under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)
Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH
2Cl2aq
NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)
Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the
cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)
Under solid-liquid technique (dioxanK2CO3TBAB)
bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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CatalystsJournal of
18 Journal of Chemistry
N
NH2
NH2
NH2
SY
Y = COOEt CN PhCO CONH2
NC
NH
SH
NH2
CNNC+ XCH2Y
PTC
N
N S
H2N
Y
Y
X = Cl Br
PTC1 2
1 1
124
125
126
H3CS
H3CS
H3CS
Figure 50
NH2
NH2
PTC
PTC
X = Cl Br
Y
HN
Z Y
NZ
R
R
NH
Z
HN
R
N
N
Y
Z = CN CO2C2H5
Z = CN CO2C2H5
R = CN CO2C2H5 COPh
R = CN CO2C2H5 COPh
Y = S OX = Cl Br
CH2NH2
Y = NH2 OH
127 128 129 130
131a b
132
+ XCH2R
+ XCH2R
CH2NH2
Figure 51
phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)
Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)
Using solid-liquid technique (dioxanK2CO3TBAB)
2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio
which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)
Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK
2CO3TBAB) afforded the
corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 19
N N N N
NH2
Cl Cl
NH2 NH2 NH2 NH2CNNC
PTC
NH
NH
COOEtEtOOC+ HClH2NCH2COOEt
133 134
H2N
Figure 52
SZ
HS
PTC
PTC
S
S
NH
Ph(p-Cl)
Ph(p-Cl)
Ph(p-Cl)
+ ClCH2CO2C2H5
C2H5O2C
C2H5O2C
CO2C2H5
1 1
1 2Z = CN CHO PhCO
Y = NH2 H Ph
135
136
137
CN
NH
SN S
Y
YH2N
Figure 53
N
O
NPh
Ph
N N
SS
Ph
PhN
S
NH
S
HO
Ph
Ph
SNC
NN
S
N
N N
S
Ph Ph
N N
SPhOC
Ph N N
SPhOC
S
NPh
Ph
N N
SS
NC
PTCNH
OS
NN
S
S
N N
S
PhOC
138
139
140
+
+
+
141 142
147
146
143
145
144
ClCH2CN
C2H5O2CClCH2CO2Et
PhCOCH2Br
(1 1 1)PTC
ClCH2CN(1 1 2)PTC
(1 1 1)PTC
ClCH2CO2Et(1 1 2)PTC
(1 1 1)PTC
PhCOCH2Br
(1 1 2)PTC
CS2
NH2
NH2
NH2
NH2
NH2EtO2C EtO2C
COPh
SCH2COPh
NH2
NH2
SCH2COPh
Figure 54
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
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Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
20 Journal of Chemistry
SSS
NH
S
PTC
EtOOCCOOEt
CN
CN
NC NH2NH2
COPh+ PhCOCH2Br
14831b
Figure 55
PTC CNCN
CNCN
NH2NH2
PhOC+ PhCOCH2Br
150a b
a X = CN b X = COOEt a Y = NH2 b Y = OH
PhPh149a b
HSNS
X
N
Y
Figure 56
OO OH R
O
O OO O
R
+ PhCOCH2Br
CH3 CH3
R = 4-ClC6H4 4-MeOC6H4minus
151 152
Figure 57
R R
OO
OHHO OO
R
OO
R
+ PhCOCH2Br
154153
R = p-Cl-C6H4 p-MeOC6H4
p
Figure 58
HO
R
O
OH
R
O
OO OO
R R
+ PhCOCH2Br
155 156R = p-Cl-C6H4minus pndashMeOC6H4minus
Figure 59
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
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[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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CatalystsJournal of
Journal of Chemistry 21
OO
X OO
OO
+
HO OH
R(Ar)
(Ar)R
COCH2Br
(Ar)R
R(Ar)
ArAr
157 158
Figure 60
NN
OPTC
N
N O
CN
PhPh
63 159
H3C
NH2
H3C
+ BrCH(CN)2
Figure 61
Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK
2CO3TBAB)
while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)
Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS
2along with chloroacetonitrile ethyl chloroacetate
or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK
2CO3TBAB] as a PTC gave the corresponding
thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)
Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK
2CO3TBAB) as a PTC [19] (Figure 55)
In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)
26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K
2CO3TBAHSO
4) [53]
(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)
difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)
Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)
Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)
Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)
Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK
2CO3TBAB) [57] (Figure 62)
By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-
diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo
[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS
2to give 165
which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)
Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK
2CO3TBAB) yielded the corresponding
pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained
by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)
2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS
2or PhNCS along with 3-methyl-1-phenyl-2-pyr-
azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174
and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-
2-one 176 with chloroacetonitrile using solid-liquid
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
22 Journal of Chemistry
N
NO
N
NO
H3CNH2
H3C
+ ClCH2CN
161160CH3CH3
Figure 62
N
NHO
N
NO
+ ClCH2CN
NH2
162 163CH3
CH3
PTCDioxan
Figure 63
O
O O
O
S
SS
S+
Br
Br
Br
Br
KS
KS
PTC
COCH3
COCH3
COCH3
COCH3
H3COC
H3COC
164165 166
Figure 64
N
O
O N
O
O
S
S
X
S
S
NX
O
HN
Ar
Ph
+ CS2 + XCH2CN PTCHN
Ar
Ph
CN minusH2OHN
CNPh
Ar
X = CN COOEtX = CN CO2Et167168
Ar = p-ClC6H4 p-NO2C6H4
Figure 65
N
NN
O
O
NN
N
NH
N
NN
HN
S
S
O
O
+
NH2
SHPh
Ph
Ph
Br
Br
Br
Br
PTC
171169 170
Figure 66
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
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[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Analytical ChemistryInternational Journal of
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CatalystsJournal of
Journal of Chemistry 23
N
N
O
S
O
S N
NN
X
S
S NX
H2N CN
CNNC + X=C=S
CH3
Ph
NH
NH
CN
NH2
NH2
CNNH2
NH2
NH
H3C
HN
X = S NPh172
174
175
63
173
Ph
Figure 67
N
HN
O
N
NO
CH3
+ ClCH2CNPTC
CH3
NH2
167 177
Figure 68
OO
O
NO
OO
Me
MeON
PTC
Me
H3C178
179180
+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus
Figure 69
N
N
S
SN
NN
S
S+ BrCH2CH2Br
181 182
NH
Ph
H3C
Ph
H3C
Figure 70
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
24 Journal of Chemistry
N
SS
O
HN
X
N
SS
O
YN
SS
O
Z
X
SN
SS
O
N
SN
SS
O
BrBr
Ph
PTC
NH2
XH
YH
ZH
HSCH2CH2XH
H2NNHCSNH2
Ph
Ph
X = O S NH
Y = Z = NH O
Ph
X = NH O
HN
Ph
NH2
183
184
185
186
187
Figure 71
technique (dioxanK2CO3TBAB) gave the corresponding
oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-
(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH
2Cl2Li(OH)CTPPCl) the
corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)
The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)
4 Synthesis of Spiro Five-MemberedRing Heterocycles
Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-
liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)
Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS
2andmalononitrile 5 or ethyl cyanoac-
etate 11 using solid-liquid technique (dioxanK2CO3TBAB)
yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)
1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK
2CO3TBAB) to furnish the corre-
sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)
5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles
51 Alkylation and Acylation
511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)
N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK
2CO3TBAHSO
4) according to (Figure 75)
N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202
Journal of Chemistry 25
N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
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[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
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N
O
O
S
S
N
O
O
XHN
OEt
Ph
+ CS2 + NCCH2X PTCHN
Ph
CN
X = CN COOEt188189
5 or 11
Figure 72
N
NO
X
YN
NO
X
YN
NO
N
S
NHN
NO
COPh
Br
BrPh
XH
YH
XH
YH
H2NNHCSNH2
COPh
PhX = NH SY = O S NH
COPh
Ph
X = NH SY = O S NH
COPh
Ph
NH2
190
191
192
193
Figure 73
NH
N
RNH
R
NH
R+ +
RXPTC
161 162 163 164
Figure 74
O
O
N
O
O
NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR
198 199 200
Figure 75
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
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Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
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CatalystsJournal of
26 Journal of Chemistry
NH
+R
X
N
R
R998400998400
CH2
R998400
R998400
R998400998400
CH2R998400998400998400 R998400998400998400
201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3
R998400998400998400 = H 5-CH3 7-CH3 X =
Figure 76
NH
O N
O
R1
R2
R3R1 R2
R3
Cl
a R1 = H R2 = CH3
b c R1 = CH3 R2 = CH3 R3 = H
204 205a b 206andashc
+
Figure 77
NH
O
R
NO
R
N
R(CH2)Cl2 THF NaNH2
Bu4NHSO4 CH3PPh3BraqNaOH
207 208204Cl
R = H
(a) R = H(b) R = CH3
Figure 78
The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)
2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO
4) [69] (Figure 77)
Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208
via its reaction with sodamide using solid-liquid technique(THFNaNH
2CH3Ph3Br) [70] (Figure 78)
Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K
2CO3and TBAB
to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)
13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Journal of
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Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 27
NH
Ph
PTCMW N-R∙
Ph
209 210
R-Br
Figure 79
N
N
NNH
N
N
NN
+2
Ar Ar
Ar
Ar
NH + Br(CH2)3Br + HN
211 213
Ar
Ar
Br
Br
Ar998400Ar998400
Ar998400
Ar
214212
(CH2)3
Figure 80
NH
NH N
H
CNCNCNDimethyl carbonate
K2CO3 TBAB
215 216a 216b
DMF 126∘C 26 h
Figure 81
from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)
Indole-2-acetonitrile 215 was treated with (CH3)2CO3in
a mixture of [DMFTBABK2CO3] to afford 1-methylindole-
2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)
Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding
1-alkylated derivatives 219 and 220 respectively [74](Figure 82)
Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)
Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)
Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
28 Journal of Chemistry
NH
NH N
N+
+
ClCHF2
CH3
CH3
ClCHF2
CHF2
CH3
CH3
CHF2
217 219
218 220
Figure 82
N
Br
R1
R
+ NuH
N
Nu
R1
R
R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et
Nu = SAr O-Ar NR(Ar cylic)
221 222
Figure 83
NH
N
+ Br(CH2)6Br
(CH2)6Br223224
Figure 84
TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)
The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH
2(3-
t-BuPz)2] 231 However the reaction of 3-isopropylpyra-
zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH
2(5-isoPrPz)
2] 233 (3-isopropylpyra-
zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-
isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane
[CH2(3-iPrPz)
2] 235 [78] (Figure 86)
N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl
3or benzeneaq
KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)
N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO
4) pro-
duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)
A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 29
NH
N NN
NH
N
NN
NN
NH
NN
N
R
+( )
( )Br
+ BrCH2CH2Br
NN
+ RX
n = 2 3
1 1
2 1
225
225
226
227
228
229
226a b
CH2CH2
CH2CH2Br
R = linear or branched alkyl C1ndashC6
n
n
Figure 85
NH
N NN
NN
NN
NN
NN
NN
NH
N NN
NN
+
+
i-Pr
CH2
CH2
CH2
i-Pr i-Pr
CH2
i-Pr
i-Pri-Pr
i-Pr
230231
232 233 234
235
ButButBut
+ CH2Br2
+ CH2Br2
Figure 86
Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)
1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the
alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)
1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)
Using the PTC condition such as (CH2Cl2KOHTEBA)
a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
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Analytical Methods in Chemistry
Journal of
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
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CatalystsJournal of
30 Journal of Chemistry
NH
N
NH
N
N
N
R
N
N
ArAr
+ RX
+ CH2 =CH-CH2-X
Ar
Ar
Ar Ar
Ar
Ar
236 237
236 238
Figure 87
NS
NN
O
NS
N
N
R
O
RNS
N
N
R
OR
OO OO
+
H
O
OCH3
RX or R2SO4
(1H-isomer) (2H-isomer)
239 240a 240b
Figure 88
N
N N
R
N
N N
N
R
NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3
241 242
Figure 89
NH
N
N
N
R
NH
N
R
+
+
+ RX
RX = EtI nndashBuCl BnCl
243 244a 244b
Figure 90
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
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Organic Chemistry International
ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 31
NH
N
N
N
R
+ RBr
R = CH3(CH2)n n = 3ndash13243
245
Figure 91
+ RX PTC
246 247
N
N
RN
H
HNH
CH3CH3
Figure 92
N
NH
N
N
N
N
N
NH
N
N
N
N
+
+
250b
249 251a
250a
251b
O2N
O2N
248
O2NO2N
O2NO2N
CH3
CH3
CH2Ph
CH2Ph
+ PhCH2Cl
+ CH3I
Figure 93
N NH N N
R
R252a b 254
R1
+ CH3(CH2)nCH2Br(CH2)nCH3
R2
Or TBAB Na2CO3 CH3CN
253
a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2
TEAI NaOH C6H5CH3
Figure 94
NH
N
O N
N
OR
256 257
CH3
+ RXK2CO3TEBACl
CH3
CH3CN
Figure 95
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
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Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
32 Journal of Chemistry
N
NH
Ph PTCN
Ph
258 259
+ ClCHF2
CHF2
Figure 96
N NH
R
N N
R
260 261 262
TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3
Figure 97
O NH
O
O N
O
PhO N
O
Ph
+
263 264a 264b
H3C
H3C
H3C
H3C
H3C
H3C+ PhCH2Cl
Figure 98
NN
NH
NN
NR
267 268
NN
NH
NN
N
NN
N+
267 269a 269b
N
N NH
N
N NR
265 266
+ RX
+ RX
+ ArX Arminus
Arminus
Figure 99
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
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Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Journal of
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Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 33
NN
NH
NN
N
267 270
+ ClCHF2
CHF2
Figure 100
NNH
N N N
RN
NN
RN
NN R
271272
273a 273b 273c
+ +
CH3
CH3
CH3CH3
K2CO3 KOH CH3CNBu4NBr
R = alkyl benzyl
+ RBr
Figure 101
NN
NNHPh
NN
N
NPh
NN
N
NPh
+
274 275a 275b
+ ClCHF2
CHF2
CHF2
Figure 102
methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)
Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)
N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH
3CNK
2CO3TEBACl) at room
temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-
ifluromethane under liquid-liquid condition (CH2Cl2aq
NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)
The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide
261 under PTC condition (TBABK2CO3CH3CN) [89]
(Figure 97)Competitive N versus O benzylation of 55-dimethyl-
3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-
ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)
Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
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[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
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[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
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CatalystsJournal of
34 Journal of Chemistry
N
NH
N
N
S N
NN
N
SR
xN
x
x
x
H
xN
x
x
x
+
F
N
NH
N
N
OPTC
N
N
NN
O
N
N NN
O
+N
N
N
O
Br
290 291289
278
276 277
Arminus
Arminus
ArminusArminus
Arminus
Arminus
+ RX
279ndash288
Pyrazole imidazole 1 2 4-triazole indazole benzotriazole
NO2
NO2
+ Br-(CH2)n- Br
n
n
Figure 103
O
OSMDBTTBMSO
TBMSO NN
N N
NHCOMeRXPTC
O
OSMDBTTBMSO
TBMSO NN
N N
NRCOMe
+
O
OSMDBTTBMSO
TBMSO NN
N N
NCOMe
R
292 293a293b
R = Me PhCH2 CH2 CH = CH2 X = Br I-
Figure 104
Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH
2Cl2aq NaOH
BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)
Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu
4NBr
produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)
The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH
2Cl2aq NaOHBzTEACl) gave
a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a
in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)
A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 35
N
N N
NH
PTCMW
N
N N
N
R
294 295
+ RX
NH2NH2
Figure 105
S
N NArO
+ O
O
Cl S
N N
NHArO
OO
Cl
296 297 298
NH2
CH3
Figure 106
NPh
MeO
S
O
OMe
H
PTC
299300
NHPh
MeO
S
O
OMe
HCH2=CH-CH2Br
CH2
Figure 107
NNH
R
NN
R
PTC+ ClCH2CH2NH2R998400 R998400
CH2CH2NH2
70∘C
301ndash303 304ndash306
301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3
Figure 108
NH
NR
PTC
NNR
PTC
NNR
R1
R1R1
ClCH2CH2Cl
CH2CH2Cl
minusHCl
CH = CH
301ndash303 307ndash309
301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me
Figure 109
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
36 Journal of Chemistry
OOH
OH
HOO
310 311
O OO
O
312 313
OO
O
315
314
+ 2C12H25Br OC12H25
+ Br (CH2)12Br
X(CH2)nX
n = 1 4 5 X = Brn
12
H25C12O
Figure 110
OOMe
H
OH
Crotyl OO
OMe
H
O BenzylHOHO
Crotyl O
316 317
CH2Cl2TBABBenzyl bromideNaOH
Figure 111
N NH
S
O
H
Ph
OMe
OMe
HN N
O
H
OMe
OMe
PhN NH
O
Ph
H
OMe
MeO
PTC
318 319a b
S-(CH2)n-S
Br(CH2)nBr
Figure 112
S
N
O
SS
N
O
S
S
N
O
S
RRX
322 320
Arminus Arminus ArminusBrCH2CH2Br
321andashh
R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N
Figure 113
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
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[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
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[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
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CatalystsJournal of
Journal of Chemistry 37
N
O Br
N
O+
323 324
CO2 t-Bu CO2 t-Bu
Figure 114
N
N
NH
S
O O
Br
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
+
O
N
HHO
H H
O
Ph
O
O
Ph
O
O
Ph
N
N
S
O
325 326 327
R1
R1
R2
R2
R3
R3
Figure 115
systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)
N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl
adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with
different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)
5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)
N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)
Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due
to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)
In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)
512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
38 Journal of Chemistry
N
NH
SO
Ph
N
N
O
Ph
SR
SR
PTC
91
RXCS2SR1
328a b(a) R1 = H R = Et(b) R1 = R = PhCH2
Figure 116
N NH
S
O
H
Ph
OMe
OMe
318
N N
S
O
H
Ph
OMe
OMe
329
ClCH2COCl
COCH2Cl
Figure 117
S
N
S N
NS
NOS
SSBr
O
PiperazineS SHet
O
N
N
OHHS
N
S b
332330 331ab
CH2
Arminus
Arminus ArminusArminus
HetminusH+
HetH = a NH2
Figure 118
NN O
Ph
NN
O
Ph
R
NN R
Ph
+
333
+ RX
H3CH3CH3C
334andashe 335andashe
Figure 119
NN
N N
+NH
O
NN
N NO
O
336 337 338
(CH2)4BrHO
NH4
( )
Figure 120
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
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[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 39
NH
N + F
N
SOO
F340 339 341
NH
+ SO 2ClFNS
OO
F339 343342
SO2Cl
ArminusArminus
Arminus
ArminusArminus
Arminus
Arminus
Figure 121
O
O
F
F NO
NH
N
O
O
S
ON
OO
ClF
F+PTC
344 345
346
SO2Cl
H3C
H3C
CH3
CH3
Figure 122
NNH +
Cl
Cl
O
NN
O
NN
347 348 349
Figure 123
S
NH
O+ Cl P
O
OEt
S O
P
OEtO
350 351 352
S-sec-Bu
P-S-sec-Bu
Figure 124
R
353
O
O Br
R
354
O
O
CH2
Figure 125
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
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CatalystsJournal of
40 Journal of Chemistry
NN
N Cl
Cl
-
356PTC N
N
N
Cl
CH3CH3
NN
N
Cl
355 357
CH3
NO2NO2
NO2
NO2
CH3M+
O2N H3CH3C
minusHNO2
Figure 126
NH
PTC
N
NH
PTC
N
S
PTC N
NS
N
NH
361
360
358 359
362
363
+ ClCH2CH2BrSH
H2C
CH2
+ ClCH2CH2Br
+ ClCH2CH2Br
SH
H2C
H2C
CH2
Figure 127
ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)
Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)
4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH
2Cl2and TBAB
as a catalyst [103] (Figure 111)
513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide
or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)
514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK
2CO3TBAB) as a PTC
yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)
4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
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Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
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Analytical Methods in Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Journal of
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Analytical ChemistryInternational Journal of
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Quantum Chemistry
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Organic Chemistry International
ElectrochemistryInternational Journal of
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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 41
S
NO
S
ArCHOPTC S
NO
S
385384
ArminusArminus Arminus
Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--
Figure 128
S
NO
S
HCHOPTC
PTC
S
NO
SHO
S
NO
S
CN
NC
387
388
S
NO
S PTC
N N
S
OS
390
386
389
Arminus
Arminus
Arminus
ArminusArminus
Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4
Ar998400
Ar998400
Ar998400
Ar998400CH=C(CN)2
Ar998400 = Ph 4-N(Me)2-C6H4
CNCH2CONH2
-
- -
Figure 129
OR
PhN O
O
R
Ph
OR
Ph
Cl
Cl
N O
Cl
R
Ph
391 392
CHCl3NaOH
Figure 130
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
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Carbohydrate Chemistry
International Journal of
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Chromatography Research International
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CatalystsJournal of
42 Journal of Chemistry
NH
R
R
NaOHN
R
Cl
R
NH
R
CHO
NaOHN
Cl
R
OCl
Cl393
394
395 396
+ CHCl3
+ CHCl3
TBAHSO4
TBAHSO4
Figure 131
NS
O
OMe
PTC NS
O
OMe
SMe
NMe
SMe
Way A
NMe
SMe
SO
minus
NSO
SMe
O
NS
OMe
SMeMeS
N
Me
SMe
SMe
401
400
Way B
+ RS-SRR = Me minusSO2
minusSO2
CH3
minusSMe
minusSMe
Ominus
Ominus
Figure 132
bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)
2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH
2Cl250 aq NaOH using TBAB
as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-
ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS
2and halocompounds such as ethyl bromide or
benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)
Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)
515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
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[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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Carbohydrate Chemistry
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Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
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CatalystsJournal of
Journal of Chemistry 43
solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)
In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)
Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH
2O K2CO3and TBACl
as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)
52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)
N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K
2CO3TBAB) [109]
(Figure 122)
53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)
54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)
55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)
Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-
azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)
Vinylation of indole 358with ClCH2CH2Br was achieved
under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly
under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)
56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)
57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK
2CO3
TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)
58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl
3NaOH
BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)
Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO
4H)
to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)
59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH
3CNK
2CO3
TBAHSO4) gave the corresponding 2-methylamino-benzal-
dehyde dithioacetals 401 [24] (Figure 132)
Abbreviations
PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO
4 Tetrabutylammonium hydrogen sulphate
CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
44 Journal of Chemistry
TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide
Conflict of Interests
The authors declare that they have no conflict of interests
References
[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987
[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993
[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994
[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-
ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000
[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951
[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959
[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova
Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of
polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000
[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997
[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975
[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999
[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995
[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001
[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino
acids via selective mono-N-alkylation of trichloroacetamide
by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992
[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001
[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002
[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992
[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005
[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000
[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000
[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000
[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003
[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011
[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005
[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005
[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011
[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997
[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002
[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 45
[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002
[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005
[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002
[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007
[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008
[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005
[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007
[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010
[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002
[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008
[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993
[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994
[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009
[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000
[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995
[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001
[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003
[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998
[55] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998
[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002
[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999
[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003
[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995
[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995
[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002
[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993
[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997
[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001
[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994
[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003
[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
46 Journal of Chemistry
[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007
[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003
[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998
[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998
[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001
[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005
[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008
[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998
[77] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998
[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000
[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998
[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996
[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996
[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996
[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993
[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999
[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999
[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993
[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000
[89] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003
[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001
[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994
[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999
[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010
[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996
[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993
[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000
[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995
[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001
[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001
[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Journal of Chemistry 47
[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005
[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996
[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990
[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990
[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004
[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003
[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995
[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of
N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002
[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000
[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993
[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991
[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of
Submit your manuscripts athttpwwwhindawicom
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Inorganic ChemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
International Journal ofPhotoenergy
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Carbohydrate Chemistry
International Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Advances in
Physical Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom
Analytical Methods in Chemistry
Journal of
Volume 2014
Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014
SpectroscopyInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014
Medicinal ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Chromatography Research International
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Applied ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Theoretical ChemistryJournal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Spectroscopy
Analytical ChemistryInternational Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Journal of
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Quantum Chemistry
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
Organic Chemistry International
ElectrochemistryInternational Journal of
Hindawi Publishing Corporation httpwwwhindawicom Volume 2014
Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014
CatalystsJournal of