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F2 , explosive
aq. NaO
HR
OH
Alcohol
Cl2 , hu
NU
CLEO
PHILIC
aq Ag
2 OR
OH
Alcohol
ALK
AN
ES B
r2 , SU
BSTITU
TION
H2 O
(ether)R
OH
Alcohol
(Substitution reaction)
I2 , reversible reactionN
aOR
'R
OR
'E
ther (use H
IO3 , conc H
NO
3 , as oxidising agent
NH
3R
NH
2P
ri. Am
ine
HX, M
arkovnikov ruleR
NH
2 R
2 NH
Sec. am
ine
ALK
ENES
(addition of HX)
HX, + P
eroxide A
nti Markovnikov rule
R2 N
HR
3 NTer. A
mine
KC
NR
CN
Cyanide
CH
LOR
OD
ER
IVA
TIVE
SA
gCN
RN
CIsocyanide
(i) HC
l/ Anhydrous ZnC
l2K
NO
2 or NaN
O2
RO
NO
Alkyl nitrite
(ii) PC
l5A
gNO
2R
NO
2N
itroalkane(iii) P
Cl3
R'C
OO
Ag
R'C
OO
RE
ster(iv) S
OC
l2N
aI (dry acetone)R
IA
lkyl iodide
ALC
OH
OLS
BR
OM
OD
ER
IVA
TIVE
S (Substitution reactn)
(i) 48% H
Br/ conc. H
2 SO
4(R
Cl or R
Br only)
(ii) NaB
r/ conc. H2 S
O4
(iii) P + B
r2 (or PB
r3 ) ELIM
INA
TION
REA
CTIO
NS
ALK
EN
E
IOD
OD
ER
IVA
TIVE
S(D
ehydrohalogenation) , alc. KO
H(i) R
ed P4 / I2
(ii) KI / 95%
H3 P
O4
+ Mg, dry ether
RM
gXG
rignard's R
eagent
RC
l or RB
r to R
I N
aI in dry acetone(FIN
KE
LSTE
IN reaction)
REA
CTIO
N W
ITH M
ETALS
+ Na , dry ether
R-R
(alkane)
RC
l or RB
r to R
F A
gF or SbF
3 , Hg
2 F2, C
oF2
, SW
AR
TS reaction
(2n-C)
RED
UC
TION
REA
CTIO
N R
H (A
lkane)R
eagents: 1. Zn- C
u couple , alcohol2. R
ed P4 , H
I3. LiA
lH4
William
son's ether synthesis
Ethanolic solution
Hunsdiecker reaction
Finkelstein reaction
+ Cl2 or Br2, dark Nucleophilic subs. + NaOH H2O / FeCl3, Anhyd AlCl3, (very low reactivity 623 K, 300 atm dil HCl + NaCl I2 or Fe fillings. due to resonance)
C6H6
Benzene + I2, conc HNO3 or Halogenation Cl Cl HIO4 Cl2 or Br2 +
FeCl3, Anhyd AlCl3 C6H5NH2 (aniline) (minor) Cl
(major) Diazotisation NaNO2 + conc. HCl Cl Cl 273 - 298 K Nitration
conc. HNO3 / + Cu2Cl2 Electrophilic subst. conc. H2SO4
Sandmeyer's reaction (major product - (minor) NO2
para substituted) (major) C6H5N2
+Cl- Cu2Br2
Sandmeyer's reaction Cl Cl Sulphonation
KI conc. H2SO4, +
(minor) SO3H(major)
Cl Cl Friedel Crafts alkylation CH3Cl + Anhyd AlCl3 +
(minor) CH3
(major)
Cl Cl Friedel Crafts acylation CH3COCl or (CH3CO)2O +
Anhydrous AlCl3 (minor) COCH3
(major) + Mg, dry ether ArMgX
(Grignard's reagent)
+ Na, dry ether Ar.Ar With Metals FITTIG REACTION (eg: C6H5.C6H5 -Biphenyl)
+ Na + RX ,dry ether Ar _ R WURTZ FITTIG REACTION (eg: C6H5.CH3)
Cl
NO2
SO3H
CH3
OHOH
(Phenol)
COCH3
RC
HO
(aldehydes) Active M
etals R
ON
a + H2
(to pri. Alcohol)
Na, K
, Mg , A
l R
ED
UC
TION
(i) H2 + N
i /Pt / P
d R
CO
R' (ketones)
or (ii) NaB
H4
Acetylation R
'CO
OR
(to sec. Alcohol)
or (iii)LiAlH
4 (i) R
'CO
OH
+ conc. H2 S
O4
(ii) R'C
OC
l / pyridine R
CO
OH
RE
DU
CTIO
N (iii) (R
'CO
)2 O / H
+
(carboxylic acids) (i)LiA
lH4 (expensive reagent)
(ii) H2 O
1o alc.
No turbidity
Lucas Test
2o alc.
Turbidity in 5 mins.
RO
H + conc. H
2 SO
4 H
Cl + A
nhyd. ZnCl2
3o alc.
Imm
ediate turbidity
RC
OO
R' (Esters)
RE
DU
CTIO
N (i) P
Cl3 or
Alkyl H
alide H
2 + Ni / P
t / Pd
(ii) PB
r3 or (iii) P
4 + I2 or (iv) S
OC
l2 or (i) A
CID
CA
TALY
SE
D H
YD
RO
LYS
IS (v) P
Cl5
(dil H2 S
O4 + steam
) M
AR
KO
WN
IKO
FF AD
DITIO
N D
ehydration A
lkene + H2 O
Alkenes of H
2 O a) conc. H
2 SO
4 , 443 K or
b) conc. H3 P
O4 or
C=C
(ii) HY
DR
OB
OR
ATIO
N O
XIDA
TION
c) Al2 O
3 , 623 K or
AN
TI-MA
RK
OW
NIK
OFF A
DD
ITION
d) A
nhyd ZnCl2
OF H
2 O 1
o alc. A
ldehyde D
ehydrogenation 2
o alc.K
etone C
u, 573 K 3
o alc.A
lkeneR
CO
Cl (Acyl C
hloride) R
ED
UC
TION
( to pri. Alcohol)
LiAlH
4 or NaB
H4
1o alc.
Aldehyde
Acid
+ HC
HO
+ H2 O
1o alcohol
Oxidation
2o alc.
Ketone (containing sam
e no. of C- atom
s)
Grignard's
+ Other aldehyde + H
2 O 2
o alc. (i) K
2 Cr2 O
7 / H2 S
O4
3o alc.
Ketone (containing less no. of C
- atoms)
Reagent
(ii) KM
nO4 / H
2 SO
4
+ Ketone + H
2 O 3
o alcohol (iii) C
rO3 /anhydrous condtn.
623 K C
H2 = C
H2
RX (Alkyl halide)
aq NaO
H or aq A
g2 O
C2 H
5 OH
+ Al2 O
3
473 K C
2 H5 O
C2 H
5
RN
H2
HN
O2 (N
itrous acid) 443 K
CH
2 = CH
2
(Primary Am
ine) (for 1
o alcohol) C
2 H5 O
H + conc. H
2 SO
4
410 K C
2 H5 O
C2 H
5
Cleavage of O_H bond
( Esterification )
Pri > Sec > TertCleavage of C_ O bond
Tert > Sec > PriD
ehydration
(containing same
no. of C -atom
s)(containing sam
e
Na, Mg, Al C6H5ONa + 1/2 H2
Acidic Nature NaOH C6H5ONa + H2O Blue litmus Turns Red
R'COOH ,conc. H2SO4 C6H5OCOR' Esterification
Acetylation (R'CO)2O ,conc. H2SO4 C6H5OCOR' R'COCl , pyridine
Benzoylation C6H5OCOC6H5
C6H5COCl , Schotten-Bauman reaction
dil HNO3
298 K + Nitration
conc. HNO3
+ conc. H2SO4 Picric acid
Cl2 water Br water
Cle
avag
e o
f O
_ H b
ond
Elec
trop
hilic
Arom
atic
Subs
titut
ion
OHNO2
OH
NO2
OH
NO2
NO2O2N
OHBrBrBr2 water
(polar solvent) Halogenation
NaOH H + / HCl (white ppt)570 - 620 K
Br2 in CS2
273 K +(non-polar solvent)
Friedel Crafts Alkylation NaOH H + / HCl RX / Anhyd. AlCl3 + 623 K, 320 atm
conc. H2SO4
288 K Sulphonation
NaNO2 + HCl H2O 273 - 278 K (warm) conc. H2SO4
(Diazotisation) 373 K
CH3 CH3 CH _ CH3 HOO_C_CH3
O2 H2O / H + CHCl3 + aq NaOH (air) Riemer Tiemann reaction (salicylaldehyde)
Cumene
C6H5N2+Cl- , alkali N N
Coupling reaction
4- Hydroxyazobenzene [orange dye]
NaOH (i) CO2, 398 K, 4-7atmos. (ii) H+ / H2O Salicylic acid Kolbe's reaction
Zn dust
OxidationNa2Cr2O7 / conc. H2SO4 Benzoquinone
SO3H SO3Na
Benzene sulphonicacid
Cl ONa
NH2 N2+Cl-
Br
Br
OH Br OH
Br
OH
R
OHR
OHSO3H
OH
SO3H
OHCHO
OH
ONa OHCOOH
Cle
avag
e o
f C
-O
bon
d
O
O
RCH2OH Oxidation Na (Primary alcohol) (i)KMnO4 in acidic/ alkaline/
neutral medium OR NaOH(ii)K2Cr2O7/H
+ OR Acidic (iii)CrO3 / H
+ Nature NaHCO3 or Na2CO3
RCH=CHR' (i)K2Cr2O7 / H2SO4 OR Blue litmusSubstituted alkene (ii)KMnO4 / H
+ OR(iii) KMnO4 / OH-
PCl5
RC N H2O / H+ or OH- PCl3 Nitriles Hydrolysis Cleavage of
C- OH bond SOCl2
RCONH2 H+ / H2O R'OH , conc. H2SO4
Amides (esterification)
RMgX (i) CO2 (dry ice) Grignard's reagent (ii) Hydrolysis (H2O / H+) NaOH NaOH + CaO , ,
(soda lime) [Decarboxylation]
RCOCl (i)H2O/H+ OR Acyl chloride (ii)Base followed by acidification
NaOH Kolbe'sElectrolytic method
RCOOR' (i)H+ / H2O Esters (ii)OH- / H2O followed by
acidification Dehydration P2O5 ,
(RCO)2O + H2O Anhydride Reduction
(i)LAH/ether OR(ii)B2H6
+NH3
RCONH2 RCN(amide) (nitrile)
(i)Cl2 or Br2 / Red P4 (ii)H2O - Halo carboxylic acid
[Hell-Volhard Zelinsky (HVZ) reaction]
RCOONa + H2 (g)
RCOONa + H2O
RCOONa + H2O + CO2 (g)
Red
RCOCl + POCl3 + HCl
RCOCl + H3PO3
RCOCl + SO2 + HCl
RCOOR' + H2O
RCOONa(n+1) C
R H + Na2CO3
(n- C)
RCOONa(n+1) C
R R(2n- C)
(RCO)2O + H2O
RCH2OH(alcohol)
RCOONH4
RCH_COOH
X
,P2O5
a
Reduction
Basic N
ature O
H-
(i) H
2 + Pd,P
t (H
Cl)
[Seperation &
Purification
(ii) Pd _ C
/ethanol of am
ine](iii) S
n + conc. HC
l(iv) Fe + conc. H
Cl
Acylation
(i)CH
3 CO
Cl
(ii)(CH
3 CO
)2 O Substitution
(Pyridine)
+NH
3 , alcohol B
enzoylation(i)K
CN
C6 H
5 CO
Cl
(ii) LAH
or Na(H
g) + C2 H
5 OH
[increase in no. of C-atom
s] C
arbylamine reaction O
R
Isocyanide reaction(i) LA
H(1
0 amines, C
HC
l3 + alc. NaO
H)
(ii) H2 O
TES
T FOR
PR
IMA
RY
AM
INE
S
RC
ON
H2
Br2 + N
aOH
Alkyl
H2 O
[Hoffm
ann's Brom
amide
NaN
O2 /H
Cl
amine
degradation reaction] 273-278 K
[ QU
AN
TITATIV
E E
STIM
ATIO
N]
Diazotisation
Aryl
Gabriel's Pthalim
ide synthesisam
ine D
iazonium salt
(i) KO
H(ii) R
X(iii) O
H-
C6 H
5 SO2 C
l2 S
ec. H
insberg's reagent
Fe + HC
l --> FeCl2 + H
2FeC
l2 + H2 O
--> HC
l + Fe(OH
)2(regenerated)
RXCO
NH
CO
RN
O2
RN
H3 +C
l -R
NH
2
RN
HC
OC
6 H5
Nucleophilic
RN
C + K
Cl + H
2 Opoisonous
[RN
2 +Cl -]
RO
H + N
2
[C6 H
5 N2 ] +C
l -
Pri.
Tert.
RN
HS
O2 C
6 H5
(soluble in KOH
)
R2 N
SO
2 C6 H
5(insoluble in KO
H)
No reaction R
NH
CO
CH
3 + HC
l
RN
HC
OC
H3
+C
H3 C
OO
H
C6H5NO2 REDUCTION (nitrobenzene) (i)H2+Ni or Pd or Pt
(ii)Sn + conc. HCl(preferred)(iii)Fe + conc. HCl
(iv)H2 + Pd (ethanol)(v)SnCl2 + conc. HCl
C6H5CONH2 Br2 + alc. NaOH (Benzamide) Hoffmann Bromamide Reaction (n+1)C
Red litmus
AS BASE(Less acidic than NH3
due to resonance) HCl
H2SO4
Alkylation (RX)
CH3COCl NUCLEOPHILIC Pyridine SUBSTITUTION Acylation
(CH3CO)2O conc. H2SO4
Benzoylation
[Schotten Baumann Reaction]
Carbylamine reactionCHCl3+alc. KOH + heat
REACTION OF -NH2 GROUP
DiazotizationNaNO2 + HCl [273-278K]
Bromination Br2 + H2O + 3HBr (bromine water)
ELECTROPHILIC SUBSTITUTION
Nitrationconc.HNO3 + conc H2SO4
(288 K)47% 2%
51%
453-473 K conc. H2SO4
Aniliniumhydrogen Sulphanic ZWITTERsulphate acid ION
(CH3CO)2O Br2 H+ or OH-
Pyridine, Acylation CH3COOH (Protection of NH2 group) Bromination
ELECTROPHILIC SUBSTn (CH3CO)2O conc HNO3
(after protecting the amino group) Pyridine con H2SO4, 298K
Sulphonation
No effect
[C6H5NH3]+Cl-
Less basic than NH3due to resonance.
[C6H5NH3]2+S042-
C6H5NHR C6H5NR2 [C6H5NR3]+X-
C6H5NHCOCH3 + HCl
C6H5NHCOCH3 + CH3COOH
C6H5COCl,NaOH
C6H5NHCOC6H5 + HCl
C6H5NC + KCl + H2O
C6H5N2+Cl- + NaCl + H2O
NH2Br
Br
Br
2,4,6-Tribromoaniline[white ppt]
NO2
NH2
NO2
NH2NO2
NH2
+ +
NH3+HSO4
- NH2
SO3H
NH3+-
SO3-
NHCOCH3
Br
NHCOCH3
Br
NH2
NHCOCH3 NHCOCH3
H+ or OH-
NH2
(after protecting the amino group) Pyridine con H2SO4, 298K
Freidal Crafts Reaction No product, due to salt formation with AlCl3
C6 H
5 NH
2 + NaN
O2 + 2H
Cl
C6 H
5 N2 C
l + NaC
l + H2 O
Benzene D
iazonium C
hloride
Reaction is also know
n as Diazotization
Very useful as synthetic reagent
H3 P
O2 + H
2 O
C2 H
5 OH
273-278 K
C6 H
6+ N
2+ H
3 PO
3+ H
Cl
C6 H
6+ N
2 + CH
3 CH
O + H
Cl
H2 O
, 283 K
C6 H
5 OH
CuC
l/HC
l O
H S
andmayer's react n
p-Hydroxyazo benzene
Orange D
ye C
u/HC
l [TEST FO
R PH
ENO
L] G
atterman react n
Reactions involving retention of
Reactions involving displacem
entdiazo grp(N
2 +) [Coupling react n]
of N2 +X group
CuB
r/HB
r S
andmayer's react n
Cu/H
Br
Gatterm
an react n
C6 H
5 NH
2
OH
p- Am
inoazobenzene K
I , Y
ellow dye
[TEST FOR
ANILIN
E] , to dryness
HB
F4
Fluoroboric acid aq. N
aNO
2
CuC
N ,
or Cu/K
CN
Na + C
2 H5 O
H or LA
H
C6 H
5 N2 +X
-
OH
N N
+ Cl + H
2 O
NH
2N
N
+ Cl + H
2 O
C6 H
5 OH
+ N2
+ HC
l
C6 H
5 Cl + N
2
C6 H
5 Cl + N
2 + CuC
l
C6 H
5 Br + N
2
C6 H
5 Br + N
2 + CuB
r
C6 H
5 I + N2 + K
Cl
C6 H
5 N2 +B
F4
C6 H
5 F + N2 + B
F3
C6 H
5 NO
2+ N
2 + NaB
F4
C6 H
5 CN
+ N2
+ CuC
l
C6 H
5 CH
2 NH
2
OXIDATION CrO3 in anhydrous medium or PCC (Pyridinium chloro chromate)
1o Alcohol 2o Alcohol ROH R
DEHYDROGENATION Cu or Ag at 573K
HC = CH HCHO
Alkenes OZONOLYSIS OZONOLYSIS Alkene (i) O3 (i) O3 (ii) Zn dust and (ii) Zn dust + H2O H2O Symmetric Disubstituted
alkene other aldehydes
HC CH CH3CHO
Alkynes HYDRATION H2O + dil. H2SO4 Alkynes dil. H2SO4 + H2O + + HgSO4
HgSO4 HCHO can't be prepared
HCHO can't be prepared
Acid Chloride Acid Chloride RCOCl + H2 , Pd-BaSO4 poisoned with S
or quinoline (ROSENMUND REACTION)
(i) SnCl2 + HCl (ii) H2O / H+ (STEPHEN REACTION )
Nitriles RCN RCN (i) DIBAL-H (Diisobutylaluminium hydride)
(ii) H2O
Esters (i) DIBAL-H(ii) H2O
C = C
C C
CrO3Chromic anhydride
CH_OHR
(SymmetricTetrasubstituted)
+ R2Cd(Dialkylcadmium)
(i) + Grignard's reagent(ii) H2O / H+
HCN + OH- H2O / H+
(base as catalyst) Aldehydes White ppt.
NaHSO3
Ketones No.for ketones for aldehydes
HCHO 1o Alcohol
(i) Grignard's reagent RCHO 2o Alcohol(ii) H2O / H+
Ketone 3o Alcohol
Nucleophilic Addition
Aldehyde RCH RCH H+ / H2O
Alcohol + dry HCl
+ H2O
Ketal
NH3 ( H+NH2
- ) C = NH. (Imine) (Ammonia)
RNH2 C = NR' (Substituted imine) [schiff's base] (Primary amine)
NH2OH C = NOH. (Oxime) (Hydroxyl amine)
NH2NH2 C = N.NH2
(Hydrazine)
C6H5NHNH2 C = NNHC6H5
(Phenyl hydrazine) NO2
2,4-DNP C = N _ NH_ _ Red, Orange or Yellow ppt
COH
CNC
OH
COOH
CSO3H
ONaC
SO3Na
OH
Other aldehydes
OR'
OHR'OH OR'
OR'hemiacetal acetal
CH2OH
CH2OH+ Ketone
H+ / H2OC
R
R
O-CH2
O-CH2
(Hydrazone)
(Phenyl hydrazone)
NO 2,4-DNP C = N _ NH_ _ Red, Orange or Yellow ppt(2,4-dinitrophenyl hydrazine) (2,4-DNP hydrazone) (Test for >C=O group)
C = N _ NHCONH2 (semicarbazone) (Semicarbazide) (NH2NHCONH2)
Aldehydes 1o Alcohol NaBH4 or LiAlH4
or H2 + Ni/Pd/Pt Ketones 2o alcohol
HCHO Doesn't reduce
Reduction Zn amalgam + conc. HCl other ald. RCH3 (Alkanes) [Clemmensen reduction]
Ketones RCH2R (Alkanes)
(i) NH2NH2 hydrazine Alkane [ RCH3 or RCH2R](ii) KOH or NaOH + Ethylene glycol. [Wolf-Kishner reduction]
Aldehydes contg. No reaction no a - hydrogen
Aldol Condensation dil. Alkali(catalyst) other aldehydes b - hydroxyaldehyde [aldol] only by aldehydes & ketones containing a- hydrogen Ketones b - hydroxyketone [ketol]
HCHO CH3OH + HCOONa Reduction Oxidation
Cannizaro reaction product Product only by aldehydes contg no a- H atoms. CH3CHO No reaction
(contains a - H)
Ketones No reaction
Aldehydes Silver mirror Tollen's reagent, heat [Test for aldehydes]Ammonical silver nitrate soltn. Ketones No ppt.
Aldehydes Reddish brown ppt. Oxidation Fehling's solution, heat [Test for aldehydes]
[Fehling's A =aq. CuSO4Fehling's B = alkaline sodium Ketones No ppt. potassium tartarate]
Aldehydes Carboxylic acid(i) HNO3, (ii) KMnO4 + H2SO4
(iii) K2Cr2O7 + H2SO4 Ketones Carboxylic acids contg. lesser no. of C-atoms
HCHO No effect
CH3CHO Yellow ppt CHI3 Haloform reaction + I2 + NaOH (NaOI) CH3COCH3 Yellow ppt CHI5 only by compounds contg. CH3CO- group CH3CH2COCH2CH3 No effect. [IODOFORM TEST]