Hindawi Publishing CorporationISRN Organic ChemistryVolume 2013 Article ID 951749 12 pageshttpdxdoiorg1011552013951749

Research ArticleZSM-5-SO

3H An Efficient Catalyst for

Acylation of Sulfonamides Amines Alcohols andPhenols under Solvent-Free Conditions

Ahmad Reza Massah12 Roozbeh Javad Kalbasi12

Mahdiehsadat Khalifesoltani2 and Fariba Moshtagh Kordesofla2

1 Department of Chemistry Islamic Azad University Shahreza Branch Shahreza Isfahan 86145-311 Iran2 Razi Chemistry Research Center Islamic Azad University Shahreza Branch Shahreza Isfahan 86145-311 Iran

Correspondence should be addressed to Ahmad Reza Massah massahiaushacir

Received 9 June 2013 Accepted 23 July 2013

Academic Editors F Felluga and C Thomas

Copyright copy 2013 Ahmad Reza Massah 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

Sulfonamides amines alcohols and phenols were efficiently acylated with carboxylic acid anhydrides and chlorides using ZSM-5-SO3H as catalyst under mild and solvent-free conditions Also direct esterification of alcohols with carboxylic acids occurred

readily in the presence of this catalyst Different types of amides and esters were obtained in moderate to high yields and purityafter a simple workup No chromatographic separation is needed for isolation of the acylated product The catalyst was recoveredand reused for up to four times without a noticeable decrease in catalytic activity

1 Introduction

The acylation of alcohols phenols and amines is one ofthe most frequently used processes in organic chemistry Itprovides an economical and efficient method for protectinghydroxyl groups during oxidation peptide coupling and gly-cosidation reactions [1] Acylation is usually carried outby treatment of an alcohol or amine with carboxylic acidchlorides or anhydrides in the presence of an acid or a basecatalyst in a suitable organic solvent Basic catalysts suchas 4-(dimethylamino) pyridine (DMAP) [2] tributylphos-phines [3] 4-pyrrolidinopyridine [4] and acidic catalystslike Sc(OTf)

3[5] Gd(OTf)

3[6] lanthanide(III) tosylates [7]

RuCl3[8] Al(HSO

4)3[9]Bi(OTf)

3[10] and LiClO

4[11]

catalyze acylation reactions with acid chloride or anhydrideas the acylating agent under homogenous conditions Useof homogenous catalysts poses serious problems such asdifficulty in the separation and recovery of the catalystdisposal of the spent catalyst and corrosion problems Solidacid catalysts such as commercial zeolites [12] and mont-morillonite K-10 or KSF clay [13] and ZnO [14] have beenreported for the acylation of alcohols with acetic anhydride

Though acylation of alcohols can also be brought aboutby the action of Lewis acid reagents in conjunction withcarboxylic acids the Lewis acid is destroyed in the workupprocedure resulting in substantial waste production [15]Some heterogenized homogenous catalysts have also beenreported for the acylation of alcohols and amines [16] Mostof the methods have some disadvantages such as exothermicreaction formation of by-products complicated conditionsand excess acylating agents and require longer reactiontimes use of halogenated solvents and expensive moisture-sensitive toxic reagents Apart from these difficulties someof the above methods do not satisfy the requirements ofgreen synthesis due to the inability to recover and reusethe catalyst Thus due to high importance of the acylationreactions development of easily separable and reusable solidcatalyst having high activity for the acylation reaction is ofgreat practical importance

The use of reusable heterogeneous solid acid catalystsreceived much attention because of their special advantagessuch as stability (toward air and moisture) lack of cor-rosion ease of handling recovery low waste generationand environmental friendliness such as zeolites clays and

2 ISRN Organic Chemistry

+O

O O

Cl

O

or X

OR X

RR998400R998400 R998400998400

ZSM-5-SO3H

Solvent-free rt or 80∘C R998400(R998400998400)

X = NH2 NHR OH SO

2NH

2

R = CH3 C

6H

5

R998400= CH

3 C

2H

5 n-C

3H

7 iso-C

3H

7 C

4H

9 C

5H

11 C

6H

5

R998400998400= CH

3 C

2H

5 C

6H

5

p-CH3C

6H

5

Scheme 1

+ OH

O

O

O

R OH R

N

R998400 R998400

ZSM-5-SO3H

Solvent-free 80ndash120∘C

R = C5H

11 C

6H

13 C

7H

15 C

8H

17 C

9H

19 C

10H

21 (CH

2)2 C

6H

4CH

2

R998400= CH

3 C

2H

5 (CH

2)2 C

6H

4CH

2

Scheme 2

heteropolyacids [17] Among zeolites ZSM-5 is an alumi-nosilicate zeolite and is composed of several pentasil unitslinked together by oxygen bridges to form pentasil chainZSM-5 has high silicon to aluminum ratio whenever an Al3+cation replaces a Si4+ cation an addition of positive chargeis required to keep the material charge neutral with protonas the cation and the material becomes very acidic The veryregular 3D structure and the acidity of ZSM-5 can be utilizedfor acid-catalyzed reactions [18]

Recently as a part of our ongoing research project todevelop newer environmentally benign synthetic method-ologies using solid acid catalyst [19ndash22] ZSM-5-SO

3H was

synthesized for the first time in our group andwas used in theacylation of aldehydes [23] andMannich reaction [24] Basedon our previous works on solvent-free reactions particularlyin acylation reactions [25ndash28] herein we wish to report ourresults on the acylation of alcohols phenols aliphatic andaromatic amines and sulfonamides with some carboxylicacid anhydrides and chlorides (Scheme 1) and also acylationof alcohols with carboxylic acids (Scheme 2) under solvent-free conditions

2 Experimental

All chemicals were purchased from Merck and Fluka chem-ical companies Infrared spectra were recorded on a Perkin-Elmer V IR spectrophotometer 1HNMR and 13CNMR spec-tra were recorded on a Bruker (400MHz) spectrometer inCDCl

3 All reactionswere conducted open to the atmosphere

and the yields refer to isolated products The products werecharacterized by comparison of their spectral and physicaldata with those of authentic samples ZSM-5 and ZSM-5-SO3H were synthesized following the procedure previously

reported [19]

21 General Procedure for Acylation of Amines Amine(2mmol) and ZSM-5-SO

3H (001 g) were ground altogether

into fine powder and carboxylic acid anhydride (2mmolbenzoic anhydride 4mmol acetic anhydride or 22mmol ofother anhydride) or carboxylic acid chloride (2mmol) wasadded under vigorous stirring at low temperature in an icebath and then was stirred at room temperature The progressof the reaction was monitored by TLC Upon completionof the reaction CH

2Cl2(20mL) was added and the catalyst

was filtered and washed with additional solvent (10mL) Thefiltrate was washed with NaHCO

3(5 10mL) water (10mL)

and dried over anhydrous Na2SO4 and the solvent was

evaporated to yield the product The products were obtainedin high purity (gt95)

22 General Procedure for Acylation of Sulfonamides Sulfon-amide (1mmol) and ZSM-5-SO

3H (001 g) were ground

altogether into fine powder and carboxylic acid anhydride(15mmol) was added under vigorous stirring at room tem-peratureThe progress of the reaction wasmonitored by TLCUpon completion of the reaction the products were obtainedas described in previous procedure in high yield and purity

23 General Procedure for Acylation of Alcohols and Phe-nols Alcohol (1mmol) and ZSM-5-SO

3H (001ndash005 g) were

ground altogether into fine powder and carboxylic acidanhydride (1mmol benzoic anhydride 2mmol acetic anhy-dride or 12mmol of other anhydride) or carboxylic acidchloride (12mmol) was added under vigorous stirring atroom temperature (for acetic anhydride) 80∘C (for benzoicanhydride and benzoyl chloride) or 50∘C (for other anhy-drides) The progress of the reaction was monitored by TLCUpon completion of the reaction the products were obtainedas described in previous procedure in high yield and purity

24 General Procedure for Acylation of Alcohols with Car-boxylic Acids Alcohol (1mmol) and ZSM-5-SO

3H (0025ndash

01 g)were ground altogether into fine powder and carboxylicacid or dicarboxylic acid (12ndash24mmol) was added undervigorous stirring at 80ndash120∘C The progress of the reactionwas monitored by TLC Upon completion of the reactionCH2Cl2(30mL) was added and the catalyst was filtered

and washed with additional solvent (10mL) The filtrate waswashed with NaHCO

3(5 30mL) water (20mL) dried over

anhydrous Na2SO4and the solvent was evaporated to yield

the product The products were obtained in high purity(gt95)

ISRN Organic Chemistry 3

Table 1 The best conditions for ZSM-5-SO3H catalyzed acylation of alcohols and amines

Entry Amine or alcohol (mmol) Acylating agent (mmol) ZSM-5-SO3H (g) Temperature (∘C)1 Amine (2) Benzoic anhydride (2) 001 rt2 Amine (2) Acetic anhydride (4) 001 rt3 Amine (2) Aliphatic anhydride (22) 001 rt4 Amine (2) Benzoyl chloride (2) 0005 rt5 Sulfonamide (1) Aliphatic anhydride (15) 001 rt6 Alcohol (1)a Acetic anhydride or chloride (2) 001 rt7 Alcohol (1)a Benzoic anhydride (1) 005 808 Alcohol (1) Carboxylic acidb (12) 0025 1009 Alcohol (2) Dicarboxylic acid (45) 005 10010 Diol (1) Carboxylic acid (5) 01 120aPhenol was acylated the same as alcoholsbAlcohols were acylated with acetic acid at 80∘C in the presence of 005 g of catalyst

241 Spectral Data of Some Isolated Products 119873-(2-Meth-ylphenyl) benzamide (Table 2 entry 5) mp = 265∘C FT-IR(KBr cmminus1) 3242 3055 1649 1604 1525 1488 1307 748 7121H NMR (400MHz CDCl

3) 120575 (ppm) 234 (s 3H) 715 (t

1H 119869 = 72Hz) 725 (dd 2H 1198691= 76 119869

2= 76Hz) 750

(dd 2H 1198691= 76 119869

2= 76Hz) 758 (t 1H 119869 = 72Hz) 794

minus786 (m 4H) 13C NMR (100MHz CDCl3) 120575 (ppm) 179

1233 1254 1269 1271 1288 1294 1306 1319 1350 13581657119873-(24-Dimethylphenyl) benzamide (Table 2 entry 6)

mp = 192∘C FT-IR (KBr cmminus1) 3266 3023 1648 1602 15171308 1279 817 709 1H NMR (400MHz CDCl

3) 120575 (ppm)

232 (s 3H) 235 (s 3H) 706ndash711 (m 2H) 752ndash759 (m 3H)768 (br 1H) 777 (d 1H 119869 = 76Hz) 791 (d 2H 119869 = 76Hz)13C NMR (100MHz CDCl

3) 120575 (ppm) 178 209 1236 1271

1274 1288 1298 1313 1317 1331 1351 1352 1658119873-(3-Chlorophenyl) benzamide (Table 2 entry 8) mp =

120∘C FT-IR (KBr cmminus1) 3296 3072 1651 1591 1522 14191294 1250 777 700 1H NMR (400MHz CDCl

3) 120575 (ppm)

712ndash726 (m 2H) 743ndash753 (m 4H) 779ndash784 (m 3H) 831(s 1H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 1185 1206

1246 1271 1288 1300 1321 1345 1346 1391 1662119873-(3-Nitrophenyl) benzamide (Table 2 entry 9) mp =

157∘C FT-IR (KBr cmminus1) 3361 3065 1662 1593 1529 14171351 1299 799 706 1H NMR (400MHz CDCl

3) 120575 (ppm)

763ndash751 (m 4H) 792 (d 2H 119869 = 72Hz) 803 (d 1H119869 = 80Hz) 813 (d 2H 119869 = 88Hz) 853 (s 1H) 13C NMR(100MHz CDCl

3) 120575 (ppm) 1150 1191 1259 1271 1290

1300 1325 1340 1391 1487 1660119873-Hexyl benzamide (Table 2 entry 11) mp = 40∘C FT-

IR (KBr cmminus1) 3342 3080 2924 2856 1631 1576 1528 14831310 1273 717 694 1H NMR (400MHz CDCl

3) 120575 (ppm)

088 (t 3H 119869 = 68Hz) 140ndash124 (m 6H) 159 (quint 2H119869 = 72Hz) 340 (q 2H 119869 = 68Hz) 676 (br 1H) 738ndash746 (m 3H) 779 (d 2H 119869 = 72Hz) 13C NMR (400MHzCDCl

3) 120575 (ppm) 140 226 267 296 315 402 1270 1284

1312 1349 1677119873119873-(Diisopropyl) benzamide (Table 2 entry 12) FT-IR

(KBr cmminus1) 3076 2969 1627 1444 1373 1340 1211 1158 779705 1HNMR (400MHz CDCl

3) 120575 (ppm) 120 (br 6H) 140

(br 6H) 368 (br 1H) 387 (br 1H) 734minus729 (m 2H) 741ndash734 (m 3H)119873-(4-Methylphenyl) acetamide (Table 2 entry 16) mp =

154∘C FT-IR (KBr cmminus1) 3293 3065 1663 1605 1551 15081448 1401 1365 1320 1263 821 753 508 1HNMR (400MHzCDCl

3) 120575 (ppm) 216 (s 3H) 233 (s 3H) 712 (d 2H 119869 =

84Hz) 740 (d 2H 119869 = 84Hz) 780 (br 1H) 13C NMR(100MHz CDCl

3) 120575 (ppm) 209 244 1202 1294 1339

1355 1687119873119873-(Dibenzyl) acetamide (Table 2 entry 18) FT-IR

(KBr cmminus1) 3061 2926 1648 1421 1239 734 699 1H NMR(400MHz CDCl

3) 120575 (ppm) 225 (s 3H) 447 (s 2H) 463 (s

2H) 720 (d 2H 119869 = 72Hz) 726 (d 2H 119869 = 68Hz) 729ndash737 (m 4H) 741 (t 2H 119869 = 72Hz) 13C NMR (100MHzCDCl

3) 120575 (ppm) 217 480 508 1265 1275 1277 1283

1286 1290 1365 1374 1711119873-(4-Methylphenylsulfonyl) acetamide (Table 2 entry

29) FT-IR (KBr cmminus1) 3293 1720 1441 1331 1213 1000 866667 537 1H NMR (400MHz CDCl

3) 120575 (ppm) 190 (s 3H)

237 (s 3H) 740 (d 2H 119869 = 79Hz) 779 (d 2H 119869 = 81Hz)1201 (s 1H) 13CNMR (100MHz CDCl

3) 120575 (ppm) 215 326

1280 1300 1369 1446 1691119873-(4-Methylphenylsulfonyl) pentanamide (Table 2

entry 30) FT-IR (KBr cmminus1) 3251 2953 2871 1711 14461342 1167 1082 855 748 663 551 1H NMR (400MHzCDCl

3) 120575 (ppm) 077 (t 3H 119869 = 72Hz) 115 (sext 2H

119869 = 74Hz) 137 (quint 2H 119869 = 71Hz) 218 (t 2H119869 = 72Hz) 237 (s 3H) 339 (d 2H 119869 = 81Hz) 779 (d2H 119869 = 82Hz) 1196 (s 1H) 13C NMR (100MHz CDCl

3)

120575 (ppm) 139 215 218 265 355 1279 1299 1371 14501719

n-Butyl benzoate (Table 3 entry 1) FT-IR (KBr cmminus1)3066 2960 2873 1720 1602 1453 1275 1110 711 1H NMR(400MHz CDCl

3) 120575 (ppm) 101 (t 3H 119869 = 72Hz) 151

(sext 2H 119869 = 76Hz) 178 (quint 2H 119869 = 72Hz) 436 (t2H 119869 = 68Hz) 746ndash757 (m 3H) 808 (d 2H 119869 = 72Hz)13C NMR (100MHz CDCl

3) 120575 (ppm) 138 193 308 648

1283 1296 1306 1328 1667n-Pentyl benzoate (Table 3 entry 2) FT-IR (KBr cmminus1)

3067 2958 2862 1720 1602 1453 1274 1110 711 1H NMR

4 ISRN Organic Chemistry

Table 2 ZSM-5-SO3H catalyzed acylation of amines under solvent-free conditions

Entry Amine Acylating agent Products Time min(yield )

1 NH2 C

OO C

ONH C

O5 (91)

2 NH2H

3CO C

OO C

ONH C

OH

3CO 5 (95)

3NH

2

OCH3

CO

O CO

NH CO

OCH35 (92)

4 NH2

H3C C

OO C

ONH C

OH

3C 5 (92)

120 (90)a

5

CH3

NH2

CO

O CO

NH CO

CH3

5 (90)

6

CH3

NH2

H3C C

OO C

O

NH CO

CH3

H3C

5 (82)

7 Cl NH2 C

OO C

ONHCl C

O15 (90)

8Cl

NH2

CO

O CO

NH

Cl

CO

15 (85)

9 NH2

O2N

CO

O CO

NH COO

2N

25 (83)

10 NH2 C

OO C

ONH C

O2 (90)

11 NH2 C

OO C

ONH C

O3 (93)

12 NH

CO

O CO

N CO

30 (90)

13 NH2 C

O

O CO

CH3

H3C NH C

OCH

3 2 (88)

14 NH2

H3CO C

O

O CO

CH3

H3C NH C

OCH

3H3CO 2 (92)

15 NH2

OCH3

CO

O CO

CH3

H3C NH C

OCH

3

OCH32 (91)

ISRN Organic Chemistry 5

Table 2 Continued

Entry Amine Acylating agent Products Time min(yield )

16 NH2H

3C C

O

O CO

CH3H

3C NH C

OCH

3H3C 2 (91)

17

CH3

NH2

CO

O CO

CH3

H3C NH C

OCH

3

CH3

2 (88)

18 NH CO

O CO

CH3

H3C N C

O

2CH

3 10 (78)

20 NH2 CO

O CO

CH3

H3C NH C

OCH

3 2 (86)

21 NH2

CO

Cl CO

NH 2 (90)

22 NH2H

3C Cl

CO

NH CO

H3C 2 (92)

23 NH2

CH3

ClCO

NH CO

CH3

2 (88)

24 NH2 ClC

O

NH CO

2 (90)

25 NH2 ClC

O

NH CO

2 (94)

26 NH2

H3C C

O

O CO

H3C(CH

2)3

(CH2)3CH

3

NH CO

H3C (CH

2)3CH

35 (80)

27 NH2

H3C C

O

O CO

(CH3)2HC CH(CH

3)2

NH CO

H3C CH(CH

3)2

5 (70)

28 NH2 C

O

O CO

H3C CH

3

NH CO

CH3

2 (88)

29 H3C SO

2NH

2 CO

O CO

H3C CH

3C

O

H3C CH

3SO

2NH 5 (92)

30 H3C SO

2NH

2 CO

O CO

H3C(CH

2)3 (CH

2)3CH

3

C

O

H3C (CH

2)3CH

3SO

2NH 15 (80)

a20mmol scale

(400MHz CDCl3) 120575 (ppm) 093 (t 3H 119869 = 72Hz) 149ndash

132 (m 4H) 176 (quint 2H 119869 = 68Hz) 431 (t 2H 119869 =68Hz) 741-751 (m 3H) 806 (d 2H 119869 = 76Hz) 13C NMR(100MHz CDCl

3) 120575 (ppm) 140 224 282 284 535 651

1283 1295 1305 1328 1667

n-Hexyl benzoate (Table 3 entry 3) FT-IR (KBr cmminus1)3066 2956 2931 2860 1721 1602 1453 1274 1111 711 1HNMR (400MHz CDCl

3) 120575 (ppm) 094 (t 3H 119869 = 72Hz)

151ndash130 (m 6H) 180 (quint 2H 119869 = 68Hz) 435 (t 2H 119869 =68Hz) 746ndash758 (m 3H) 808 (d 2H 119869 = 72Hz) 13CNMR

6 ISRN Organic Chemistry

Table 3 ZSM-5-SO3H catalyzed acylation of alcohols and phenols under solvent-free conditions

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

1 OH CO

O CO

CO

H3C(CH

2)3O 10 (80)

2 OH2 C

OO C

OCO

H3C(CH

2)4O 15 (81)

3 OH3 C

OO C

OCO

H3C(CH

2)5O 15 (83)

4OH C

OO C

OO C

O25 (70)

5 7OH C

OO C

OCO

H3C(CH

2)9O

10 (90)15 (89)a

6 CH2OH C

OO C

OCO

CH2O 10 (89)

7 OH3 C

O

O CO

H3C CH

3

CO

CH3

H3C(CH

2)5O 10 (88)

8 OH5 C

O

O CO

H3C CH

3CO

CH3

H3C(CH

2)7O 5 (95)

9 OH7 C

O

O CO

H3C CH

3CO

CH3

H3C(CH

2)9O 3 (95)

10 OH5 C

O

ClH3C C

OCH

3H

3C(CH

2)7O 5 (93)

11 OH7 ClC

O

H3C C

OCH

3H

3C(CH

2)9O 5 (95)

12 CH2OH

ClCO

H3C C

OCH

3CH

2O 5 (95)

13 OH CO

O CO

H3C CH

3

O CO

CH3

5 (96)

14 OH CO

O CO

O CO

5 (75)

15 OH CO

O CO

H3C(CH

2)3

(CH2)3CH

3

O CO

(CH2)3CH

35 (81)

16 OH7 OHC

OCO

H3C(CH

2)9O 3 (88)

17 OH5 OHC

OCO

H3C(CH

2)7O 4 (85)

18 OH4 OHC

OCO

H3C(CH

2)6O

4 (80)6 (75)a

ISRN Organic Chemistry 7

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

19 OH3 OHC

OCO

H3C(CH

2)6O 5 (75)

20 OH2 OHC

OCO

H3C(CH

2)4O 5 (68)

21 OH OHCO

CO

H3C(CH

2)3O 5 (61)

22 OH7 OHC

OMe C

OMeH

3C(CH

2)9O 2 (75)

23 OH5 OHMe C

OMeC

OH

3C(CH

2)7O 3 (69)

24 OH3 OHMe C

OMeC

OH

3C(CH

2)5O 3 (61)

25 OH7 OHCO

H3C C

OCH

3H

3C(CH

2)9O 1 (80)

26 OH5 OHC

O

H3C C

OCH

3H

3C(CH

2)7O 2 (75)

27 OH3 OHC

O

H3C C

OCH

3H

3C(CH

2)5O 2 (60)

28 CH2OH C

O

OHH3C C

OCH

3CH

2O 2 (82)

29 OH7 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)9O 2 (85)

30 OH5 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)7O 2 (80)

31 OHHOOHC

OCH

2C C

OO O C

OCH

2H

2

(CH2)2

5 (84)

32 OH4 OHC

OCH

2O C

OCH

2

(CH2)6H

3C 1 (68)

33 OH5 OHC

OCH

2O C

OCH

2

H3C (CH

2)7

1 (70)

34 OH7 OHC

OCH

2O C

OCH

2

H3C (CH

2)8

1 (74)

35 OH2

OHN

O

HO

O

NO

O

O

OH

3C-(H

2C)

4(CH

2)4-CH

3

5 (33)

8 ISRN Organic Chemistry

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

36 OH3

OHHON

OON

O

O

O

OH

3C-(H

2C)

5(CH

2)5-CH

3

5 (43)

37 OH4 OHHO

O O O O

H3C-(H

2C)

6-O O-(CH

2)6-CH

3

5 (70)

38 OH5 OHHO

O O O O

H3C-(H

2C)

7-O O-(CH

2)7-CH

3

5 (75)

a20mmol scale

(100MHz CDCl3) 1667 1328 1306 1295 1283 651 315

287 257 226 140n-Decyl benzoate (Table 3 entry 5) FT-IR (KBr cmminus1)

3068 2926 2856 1721 1602 1457 1274 1111 711 1H NMR(400MHz CDCl

3) 120575 (ppm) 091 (t 3H 119869 = 72Hz) 152ndash

125 (m 14H) 180 (quint 2H 119869 = 72Hz) 435 (t 2H119869 = 68Hz) 747ndash758 (m 3H) 807 (d 2H 119869 = 72Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 141 227 261 288 293

294 296 319 651 1283 1295 1306 1328 1666n-Hexyl acetate (Table 3 entry 7) FT-IR (KBr cmminus1)

2957 2933 1742 1462 1367 1240 1039 1H NMR (400MHzCDCl

3) 120575 (ppm) 084 (t 3H 119869 = 68Hz) 135ndash120 (m

6H) 156 (quint 2H 119869 = 68Hz) 199 (s 3H) 401 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 139 209

225 256 286 314 646 1712n-Octyl acetate (Table 3 entry 8) FT-IR (KBr cmminus1)

2929 2859 1743 1463 1367 1239 1040 1H NMR (400MHzCDCl

3) 120575 (ppm) 086 (t 3H 119869 = 68Hz) 138ndash121 (m 10H)

160 (m 2H) 203 (s 3H) 404 (t 2H 119869 = 68Hz) 13C NMR(400MHz CDCl

3) 120575 (ppm) 140 209 226 259 286 291

292 318 646 1711n-Decyl acetate (Table 3 entry 9) FT-IR (KBr cmminus1)

2927 2858 1743 1464 1366 1239 1041 1H NMR (400MHzCDCl

3) 120575 (ppm) 087 (t 3H 119869 = 68Hz) 139ndash121 (m

14H) 160 (quint 2H 119869 = 68Hz) 203 (s 3H) 404 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 209

226 259 286 292 293 295 319 646 1711Benzyl acetate (Table 3 entry 12) FT-IR (KBr cmminus1)

3034 2954 1742 1455 1380 1230 1027 747 698 1H NMR(400MHz CDCl

3) 120575 (ppm) 214 (s 3H) 516 (s 2H) 743ndash

735 (m 5H) 13C NMR (100MHz CDCl3) 120575 (ppm) 210

663 769 772 775 1283 1283 1286 1360 1709n-Octyl-4-methylbenzoate (Table 3 entry 23) FT-IR

(KBr cmminus1) 1719 1612 1464 1274 1107 752 1H NMR(400MHz CDCl

3) 120575 (ppm) 092 (t 3H 119869 = 68Hz) 127ndash

142 (m 10H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 68Hz) 726 (d 1H 119869 = 80Hz) 796 (d 1H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 216

227 261 288 292 293 318 649 767 770 774 1279 12901296 1434 1668

n-Hexyl-4-methylbenzoate (Table 3 entry 24) FT-IR(KBr cmminus1) 17193 16126 12742 11069 7539 1H NMR(400MHz CDCl

3) 120575 (ppm) 093 (t 3H 119869 = 72Hz) 133ndash

142 (m 6H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 64Hz) 726 (d 2H 119869 = 80Hz) 796 (d 2H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 140 217

226 257 287 315 650 770 772 1278 12904 1296 14341668

Decyl propanoate (Table 3 entry 29) IR (KBr cmminus1)1740 1464 1186 1083 749 1H NMR (400MHz CDCl

3)

120575 (ppm) 089 (t 3H 119869 = 64Hz) 115 (t 3H 119869 = 76Hz) 122ndash138 (m 14H) 158ndash167 (m 2H) 233 (q 2H 119869 = 76Hz) 407(t 2H 119869 = 68Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm)

92 141 227 259 276 287 293 293 295 319 645 1746Octyl propanoate (Table 3 entry 30) IR (KBr cmminus1)

1740 1464 1186 1083 723 1H NMR (400MHz CDCl3)

120575 (ppm) 086 (t 3H 119869 = 64Hz) 112 (t 3H 119869 = 76Hz)122ndash138 (m 10H) 159 (quint 2H 119869 = 72Hz) 230 (q 2H119869 = 76Hz) 404 (t 2H 119869 = 68Hz) 13C NMR (100MHzCDCl

3) 120575 (ppm) 91 140 226 259 276 286 292 292 318

644 1745Ethane-12-diylbis(2-phenylacetate) (Table 3 entry 31) IR

(KBr cmminus1) 1738 1454 1245 1139 726 1H NMR (400MHzCDCl

3) 120575 (ppm) 364 (s 4H) 431ndash436 (m 4H) 728ndash740

(m 10H) 13C NMR (100MHz CDCl3) 120575 (ppm) 411 624

1272 1286 1293 1338 1713n-Heptyl phenylacetate (Table 3 entry 32) IR (KBr

cmminus1) 1737 1456 1251 1155 721 1HNMR (400MHz CDCl3)

120575 (ppm) 095 (t 3H 119869 = 64Hz) 126ndash141 (m 8H) 161ndash172(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash728 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 226 258

286 289 318 415 650 768 772 775 1270 1286 12931343 1717

n-Octyl phenylacetate (Table 3 entry 33) IR (KBr cmminus1)1737 1456 1252 1154 7212 1H NMR (400MHz CDCl

3)

120575 (ppm) 095 (t 3H 119869 = 68Hz) 124ndash141 (m 10H) 162ndash171(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 227 259

286 292 318 415 650 768 771 774 1270 1286 12931343

ISRN Organic Chemistry 9

n-Decyl phenylacetate (Table 3 entry 34) IR (KBr cmminus1)1738 1456 1251 1155 721 1H NMR (400MHz CDCl

3)

120575 (ppm) 093 (t 3H 119869 = 64Hz) 127ndash138 (m 14H) 161ndash168(m 2H) 366 (s 2H) 412 (t 2H 119869 = 68Hz) 739ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 142 227 259

286 292 293 295 319 415 651 768 771 774 1270 12861293 1343

Dipentylpyridine-26-dicarboxylate (Table 3 entry 35)IR (KBr cmminus1) 1741 1465 12440 1149 759 1H NMR(400MHz CDCl

3) 120575 (ppm) 094 (t 6H 119869 = 80Hz) 136ndash

150 (m 8H) 185 (quint 4H 119869 = 68Hz) 443 (t 4H 119869 =68Hz) 802 (t 1H 119869 = 76Hz) 828 (d 2H 119869 = 80Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 224 281 283 664

767 771 773 774 1277 1381 1487 1647Dihexylpyridine-26-dicarboxylate (Table 3 entry 36) IR

(KBr cmminus1) 1722 1241 1144 753 1H NMR (400MHzCDCl

3) 120575 (ppm) 082ndash093 (m 6H) 181 (quint 4H 119869 =

72Hz) 122ndash138 (m 8H) 138-148 (m 4H) 439 (t 4H119869 = 72Hz) 799 (t 1H 119869 = 80Hz) 824 (d 2H 119869 = 76Hz)

Diheptyl glutarate (Table 3 entry 37) IR (KBr cmminus1)1738 1465 1148 1065 725 1H NMR (400MHz CDCl

3)

120575 (ppm) 088 (t 6H 119869 = 68Hz) 122ndash138 (m 16H) 160(quint 4H 119869 = 68Hz) 195 (quint 4H 119869 = 72Hz) 237 (t4H 119869 = 72Hz) 406 (t 4H 119869 = 68Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 140 202 226 259 286 289 317 334

646 1731Dioctyl glutarate (Table 3 entry 38) IR (KBr cmminus1) 1737

1465 1064 722 1H NMR (400MHz CDCl3) 120575 (ppm) 090

(t 6H 119869 = 64Hz) 124ndash140 (m 20H) 159ndash168 (m 4H)192ndash202 (m 4H) 236ndash248 (m 4H) 408 (t 4H 119869 =56Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 141 199 202

226 259 286 292 292 318 330 332 334 647 647 17301731

3 Results and Discussion

As a starting point for this work the reaction was optimizedin order to find the best conditions especially in agree-ment with green chemistry (Table 1) To find the optimumconditions for acylation of amines and sulfonamides withcarboxylic acid anhydrides and chlorides several sets of reac-tion conditions were examined (Table 1 entries 1ndash5) Thusunder the best conditions amines (2mmol) were acylated atroom temperature almost quantitatively with carboxylic acidanhydrides or chlorides (2ndash4mmol) in the presence of 0005ndash001 g of ZSM-5-SO

3H without use of any solvents (Table 1

entries 1ndash4) Acylation of sulfonamides (1mmol) occurredonly with aliphatic anhydrides (15mmol) in the presenceof 001 g of catalyst at room temperature under solvent-freeconditions (Table 1 entry 5)

Then the reactionwas exploredwith a variety of aromaticand aliphatic amines to evaluate the scope and limitations ofthis method (Table 2) The results showed that the differentaromatic amines containing various electron-donating and -withdrawing groups as well as aliphatic amines reacted withcarboxylic acid chlorides or anhydrides within 5ndash30minutesto produce the corresponding amides in 70ndash95 yield

Benzoic anhydride and benzoyl chloridewas used as aromaticacylating agents Also acylation of amines were examinedusing different aliphatic acylating agents including aceticpentanoic and isobutanoic anhydridesThe excellent activityof ZSM-5-SO

3Hwas demonstrated by the good to high yields

obtained for anilines having electron-withdrawing groupssuch as Cl and NO

2(Table 2 entries 7ndash9) However the

best yields were obtained with substrates bearing electron-donating groups such as methoxy especially in the para-position (Table 2 entries 2 and 14) Also very good resultswere obtained when secondary amines were acylated in thepresence of ZSM-5-SO

3H and the corresponding amides

were obtained in 78ndash90 yields in 10ndash30 minutes at roomtemperature under solvent-free conditions (Table 2 entries 12and 18) Finally this method was used for the acylation of 4-methylbenzenesulfonamide as a weak nucleophile with aceticand pentanoic anhydrides Interestingly the corresponding119873-acyl sulfonamides were obtained in 80 and 92 yieldsafter 5 and 15 minutes in high purity (Table 2 entries 29 and30)

To demonstrate the versatility of this protocol the acyla-tion of alcohols andphenolswas investigated using carboxylicacids carboxylic acid anhydrides and chlorides as acylatingagents At first several sets of reaction conditions wereexamined to find the best conditions for acylation of alcoholsIn the optimum conditions alcohols and phenols (1mmol)were acylated at room temperature with acetic anhydridesor chlorides (2mmol) in the presence of 001 g of ZSM-5-SO3H under the solvent-free conditions (Table 1 entry 6)

Acylation with benzoic anhydride was done at 80∘C using005 g of catalyst (Table 1 entry 7) When carboxylic acidswere used as acylating agents the reactions were done at 80ndash120∘C (Table 1 entries 8ndash10)

Using a simple experimental procedure the ZSM-5-SO3H catalyzed acylation of benzylic primary and second-

ary alcohols proceeded efficiently using carboxylic acidanhydrides and chlorides (Table 3 entries 1ndash15) Differentcarboxylic acid anhydrides and chlorides such as benzoicanhydride acetic anhydride pentanoic anhydride and acetylchloride were used as acylating agent and the correspondingesters were obtained in high isolated yields and purityafter short reaction times under the solvent-free conditionsPrimary alcohols were acylated faster than secondary ones(Table 3 entries 4) and sterically hindered alcohols such astert-butyl alcohol remained unchanged It was interesting tonote that phenols were also satisfactorily acylated generatingthe corresponding esters in 75ndash95 yields (Table 3 entries13ndash15)

In order to generalize the catalytic efficiency of ZSM-5-SO3H for direct acylating with carboxylic acids the acy-

lation of alcohols was tried with different carboxylic acid(Table 3 entries 16ndash38) while most literature methods fordirect acylation of alcohols employ only acetic acid [29ndash31] Acylation with acetic propanoic phenyl acetic benzoicacid and 4-methylbenzoic acid resulted in good yield ofthe esters under the solvent-free conditions Also pleasingresults were obtained when acylation of alcohols was donewith dicarboxylic acids such as glutaric acid and pyridine-16-dicarboxylic acid and the corresponding diester was

10 ISRN Organic Chemistry

CH3

CH3

CH3

CH3

NH2

ZSM-5-SO3H

Ac2O (2 eq)

OH

+

O

+

NHO O

1000

CH3

NH2

ZSM-5-SO3H

H3C

Ac2O (2 eq)

NH

+ +

O

0 100

HO O

O

CH3

CH3

ZSM-5-SO3H

Ac2O (2 eq)

OH

OH+

O

+7

7

7 7

7

7O

O

20 80

O

CH3

ZSM-5-SO3H

H3C

NO2

NO2

Ac2O (1 eq)

OH OH

+

O

+

O O

O

80 20

CH3

CH3

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH

OH+

O

+ O

O

0 100

O

CH3

CH3

NH2

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH+

HN

+ O

O

0 100

O

rt 5 min

rt 3 min

rt 2 min

rt 2 min

Scheme 3

obtained in high purity in absence of solvent (Table 3 entries35ndash38) It is noteworthy that in contrast to most reportedmethods that need excess of acetic acid in this methodacylation of alcohols was carried out using only 12ndash20 eqof carboxylic acid Also acylation of ethylene glycol as adiol was carried out with phenylacetic acid under solvent-free conditions and the corresponding ester was obtainedin 84 after 5 minutes It should be mentioned that several

efforts to use this method for direct acylation of amines forthe synthesis of amides were not successful

The importance of selectivity in organic chemistryencouraged us to consider the selectivity of acylation ofdifferent alcohols and amines Several reactions were car-ried out using carboxylic acid anhydrides and chlorides asacylating agents and surprisingly the excellent selectivitywas found For example aromatic amines such as 4-methyl

ISRN Organic Chemistry 11

aniline can be converted into the amide in the presence ofphenol On the other hand aromatic amines were acylatedselectively in the presence of aliphatic alcohol Furthermorethe reactions of alcohols with acylating agent were so fastin comparison to those of the phenol that the selectiveacylation of aliphatic alcohols in the presence of phenolsappeared to be a distinct possibility The result showedthat selective acylation of phenols with or without electron-donating group in the presence of phenols with electron-withdrawing group is possible with this method As wellas carboxylic acid anhydrides and chlorides the excellentselectivity was observed when carboxylic acids were usedas acylating agent Acylation of alcohols was carried outselectively in the presence of phenols Also acylation ofalcohols was done in the presence of amines selectivelywhile as mentioned above this selectivity is reversed whencarboxylic acid anhydrides were used as acylating agent(Scheme 3)

To show another advantage of the present acylationmethod and the importance of scale-up ability for laboratoryand industrial purposes a few amines and phenols wereacylated in large scale successfully without considerable lim-itation For example acylation of 4-methyl aniline (Table 2entry 4) 1-decanol with benzoic anhydride (Table 3 entry5) and 1-heptanol with benzoic acid (Table 3 entry 18) wascarried out in 20mmol scales as well as the 1mmol ones Theonly difference is the reaction time Reaction in large scaleneeds more time that is because of the difficulty in stirringthe reaction mixture under solvent-free conditions

Finally we were interested to study the reusability ofthe catalysts due to economical and environmental aspectsFor this purpose the reaction of 1-heptanol with benzoicanhydride and benzoic acid was chosen as model reactionsAt the end of each run the catalyst was recovered fromthe reaction mixture by addition of dichloromethane simplefiltration and drying at 100∘C and then reused The recycledZSM-5-SO

3H was used for further runs and its activity did

not show any significant decrease even after four runs

4 Conclusion

In conclusion we have described a highly efficient and che-moselective synthetic route for the acylation of sulfonamidesamines alcohols and phenols with carboxylic acids car-boxylic acid chlorides and anhydrides in the presence ofZSM-5-SO

3H under solvent-free conditions This method

has advantages in terms of low cost and nontoxic nature of thecatalyst high yield and purity of the products short reactiontimes operational simplicity and easy workup In additionrecyclability of this protocol is attractive and useful Directacylation of alcohols with different carboxylic acids is anotheradvantage of this protocol

Acknowledgment

The support from Islamic Azad University Shahreza Branch(IAUSH) Research Council is gratefully acknowledged

References

[1] T W Greene and P G M Wuts Protective Groups in OrganicSynthesis Wiley New York NY USA 3rd edition 1999

[2] W Steglich andGHofle ldquoNN-dimethyl-4-pyridinamine a veryeffective acylation catalystrdquo Angewandte Chemie vol 8 no 12pp 980ndash981 1969

[3] E Vedejs and S T Diver ldquoTributylphosphine a remarkableacylation catalystrdquo Journal of the American Chemical Societyvol 115 no 8 pp 3358ndash3359 1993

[4] E F V Scriven ldquo4-Dialkylaminopyridines super acylation andalkylation catalystsrdquo Chemical Society Reviews vol 12 no 2 pp129ndash161 1983

[5] K Ishihara M Kubota H Kurihara and H Yamamoto ldquoScan-dium trifluoromethanesulfonate as an extremely active Lewisacid catalyst in acylation of alcohols with acid anhydrides andmixed anhydridesrdquo The Journal of Organic Chemistry vol 61no 14 pp 4560ndash4567 1996

[6] R Alleti W S Oh M Perambuduru Z Afrasiabi E Sinn andV P Reddy ldquoGadolinium triflate immobilized in imidazoliumbased ionic liquids a recyclable catalyst and green solvent foracetylation of alcohols and aminesrdquo Green Chemistry vol 7 no4 pp 203ndash206 2005

[7] T N Parac-Vogt K Deleersnyder and K Binnemans ldquoLan-thanide(III) tosylates as new acylation catalystsrdquo EuropeanJournal of Organic Chemistry vol 2005 no 9 pp 1810ndash18152005

[8] K D Surya ldquoRuthenium(III) chloride catalyzed acylation ofalcohols phenols thiols and aminesrdquo Tetrahedron Letters vol45 no 14 pp 2919ndash2922 2004

[9] F M Shirini M A Zolfigol M Abedini and P SalehildquoAl(HSO

4)3catalyzed acetylation and formylation of alcoholsrdquo

Bulletin of the Korean Chemical Society vol 24 no 11 pp 1683ndash1685 2003

[10] A Orita C Tanahashi A Kakuda and J Otera ldquoHighly pow-erful and practical acylation of alcohols with acid anhydridecatalyzed by Bi(OTf)

3rdquo Journal of Organic Chemistry vol 66

no 26 pp 8926ndash8934 2001[11] Y Nakae I Kusaki and T Sato ldquoLithium perchlorate catalyzed

acetylation of alcohols under mild reaction conditionsrdquo Synlettvol 2001 no 10 pp 1584ndash1586 2001

[12] R Ballini G Bosica S Carloni L Ciaralli R Maggi and GSartori ldquoZeolite HSZ-360 as a new reusable catalyst for thedirect acetylation of alcohols and phenols under solventlessconditionsrdquo Tetrahedron Letters vol 39 no 33 pp 6049ndash60521998

[13] B M Choudary V Bhaskar M L Kantam K Koteswara Raoand K V Raghavan ldquoAcylation of alcohols with carboxylicacids via the evolution of compatible acidic sites in montmo-rillonitesrdquo Green Chemistry vol 2 pp 67ndash70 2000

[14] M H Sarvari and H Sharghi ldquoZinc oxide (ZnO) as a newhighly efficient and reusable catalyst for acylation of alcoholsphenols and amines under solvent free conditionsrdquo Tetrahe-dron vol 61 no 46 pp 10903ndash10907 2005

[15] J Izumi I Shiina and T Mukaiyama ldquoAn efficient esterifica-tion reaction between equimolar amounts of free carboxylicacids and alcohols by the combined use of octamethylcyclote-trasiloxane and a catalytic amount of titanium(iv) chloridetris(trifluoromethanesulfonate)rdquo Chemistry Letters vol 2 pp141ndash142 1995

[16] R Alleti M Perambuduru S Samantha and V P ReddyldquoGadolinium triflate an efficient and convenient catalyst for

12 ISRN Organic Chemistry

acetylation of alcohols and aminesrdquo Journal of Molecular Catal-ysis A vol 226 no 1 pp 57ndash59 2005

[17] F Shirini K RaMoghadam and T Naghdi ldquo13-Dichloro-55-dimethylhydantoin an efficient catalyst for the solvent freesynthesis of 18-dioxo-octahydro-xanthenesrdquo Iranian Journal ofCatalysis vol 2 pp 55ndash59 2012

[18] A DyerAn Introduction to Zeolite Molecular Sieves JohnWileyamp Sons Inc New York NY USA 1988

[19] A R Massah R J Kalbasi and M Azadi ldquoHighly selectiveoxidation of alcohols using MnO

2TiO2-ZrO2as a novel het-

erogeneous catalystrdquo Comptes Rendus Chimie vol 15 no 5 pp428ndash436 2012

[20] A R Massah R J Kalbasi and M Toghyani ldquoSulfonatedpolystyrenemontmorillonite nanocomposite as a new andefficient catalyst for the solvent-free Mannich reactionrdquo IranianJournal of Catalysis vol 2 no 1 pp 41ndash49 2012

[21] R J Kalbasi M Ghiaci and A R Massah ldquoHighly selectivevapor phase nitration of toluene to 4-nitro toluene usingmodified and unmodified H

3PO4ZSM-5rdquo Applied Catalysis A

vol 353 no 1 pp 1ndash8 2009[22] R J Kalbasi A Abbaspourrad A R Massah and F Zamani

ldquoHighly selective vapor-phase acylation of veratrole overH3PO4TiO2-ZrO2 using ethyl acetate as a green and efficient

acylating agentrdquo Chinese Journal of Chemistry vol 28 no 2 pp273ndash284 2010

[23] A R Massah R J Kalbasi and A Shafiei ldquoZSM-5-SO3H as

a novel efficient and reusable catalyst for the chemoselectivesynthesis and deprotection of 11-diacetates under eco-friendlyconditionsrdquoMonatshefte fur Chemie vol 143 no 4 pp 643ndash6522012

[24] A R Massah R J Kalbasi and N Samah ldquoHighly selectivesynthesis of 120573-amino carbonyl compounds over ZSM-5-SO

3H

under solvent-free conditionsrdquo Bulletin of the Korean ChemicalSociety vol 32 no 5 pp 1703ndash1708 2011

[25] A R Massah F Kazemi D Azadi et al ldquoA mild and chemos-elective solvent-free method for the synthesis of N-aryl and N-alkysulfonamidesrdquo Letters inOrganic Chemistry vol 3 no 3 pp235ndash241 2006

[26] A R Massah B Asadi M Hoseinpour A Molseghi R JKalbasi and H Javaherian Naghash ldquoA novel and efficientsolvent-free and heterogeneous method for the synthesis ofprimary secondary and bis-N-acylsulfonamides using metalhydrogen sulfate catalystsrdquo Tetrahedron vol 65 no 36 pp7696ndash7705 2009

[27] A R Massah H Adibi R Khodarahmi et al ldquoSynthesisin vitro antibacterial and carbonic anhydrase II inhibitoryactivities of N-acylsulfonamides using silica sulfuric acid asan efficient catalyst under both solvent-free and heterogeneousconditionsrdquo Bioorganic andMedicinal Chemistry vol 16 no 10pp 5465ndash5472 2008

[28] A R Massah M Dabagh S Shahidi H J Naghash AR Momeni and H Aliyan ldquoP

2O5SiO2as an efficient and

recyclable catalyst for N-acylation of sulfonamides under het-erogeneous and solvent-free conditionsrdquo Journal of the IranianChemical Society vol 6 no 2 pp 405ndash411 2009

[29] P Pushpaletha and M Lalithambika ldquoModified attapulgite anefficient solid acid catalyst for acetylation of alcohols usingacetic acidrdquo Applied Clay Science vol 51 no 4 pp 424ndash4302011

[30] L Osiglio G Romanelli and M Blanco ldquoAlcohol acetylationwith acetic acid using borated zirconia as catalystrdquo Journal ofMolecular Catalysis A vol 316 no 1ndash2 pp 52ndash58 2010

[31] P R Likhar R Arundhathi S Ghosh and M L KantamldquoPolyaniline nanofiber supported FeCl

3 an efficient and

reusable heterogeneous catalyst for the acylation of alcohols andamines with acetic acidrdquo Journal of Molecular Catalysis A vol302 no 1ndash2 pp 142ndash149 2009

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

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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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Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Medicinal ChemistryInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Chromatography Research International

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

2 ISRN Organic Chemistry

+O

O O

Cl

O

or X

OR X

RR998400R998400 R998400998400

ZSM-5-SO3H

Solvent-free rt or 80∘C R998400(R998400998400)

X = NH2 NHR OH SO

2NH

2

R = CH3 C

6H

5

R998400= CH

3 C

2H

5 n-C

3H

7 iso-C

3H

7 C

4H

9 C

5H

11 C

6H

5

R998400998400= CH

3 C

2H

5 C

6H

5

p-CH3C

6H

5

Scheme 1

+ OH

O

O

O

R OH R

N

R998400 R998400

ZSM-5-SO3H

Solvent-free 80ndash120∘C

R = C5H

11 C

6H

13 C

7H

15 C

8H

17 C

9H

19 C

10H

21 (CH

2)2 C

6H

4CH

2

R998400= CH

3 C

2H

5 (CH

2)2 C

6H

4CH

2

Scheme 2

heteropolyacids [17] Among zeolites ZSM-5 is an alumi-nosilicate zeolite and is composed of several pentasil unitslinked together by oxygen bridges to form pentasil chainZSM-5 has high silicon to aluminum ratio whenever an Al3+cation replaces a Si4+ cation an addition of positive chargeis required to keep the material charge neutral with protonas the cation and the material becomes very acidic The veryregular 3D structure and the acidity of ZSM-5 can be utilizedfor acid-catalyzed reactions [18]

Recently as a part of our ongoing research project todevelop newer environmentally benign synthetic method-ologies using solid acid catalyst [19ndash22] ZSM-5-SO

3H was

synthesized for the first time in our group andwas used in theacylation of aldehydes [23] andMannich reaction [24] Basedon our previous works on solvent-free reactions particularlyin acylation reactions [25ndash28] herein we wish to report ourresults on the acylation of alcohols phenols aliphatic andaromatic amines and sulfonamides with some carboxylicacid anhydrides and chlorides (Scheme 1) and also acylationof alcohols with carboxylic acids (Scheme 2) under solvent-free conditions

2 Experimental

All chemicals were purchased from Merck and Fluka chem-ical companies Infrared spectra were recorded on a Perkin-Elmer V IR spectrophotometer 1HNMR and 13CNMR spec-tra were recorded on a Bruker (400MHz) spectrometer inCDCl

3 All reactionswere conducted open to the atmosphere

and the yields refer to isolated products The products werecharacterized by comparison of their spectral and physicaldata with those of authentic samples ZSM-5 and ZSM-5-SO3H were synthesized following the procedure previously

reported [19]

21 General Procedure for Acylation of Amines Amine(2mmol) and ZSM-5-SO

3H (001 g) were ground altogether

into fine powder and carboxylic acid anhydride (2mmolbenzoic anhydride 4mmol acetic anhydride or 22mmol ofother anhydride) or carboxylic acid chloride (2mmol) wasadded under vigorous stirring at low temperature in an icebath and then was stirred at room temperature The progressof the reaction was monitored by TLC Upon completionof the reaction CH

2Cl2(20mL) was added and the catalyst

was filtered and washed with additional solvent (10mL) Thefiltrate was washed with NaHCO

3(5 10mL) water (10mL)

and dried over anhydrous Na2SO4 and the solvent was

evaporated to yield the product The products were obtainedin high purity (gt95)

22 General Procedure for Acylation of Sulfonamides Sulfon-amide (1mmol) and ZSM-5-SO

3H (001 g) were ground

altogether into fine powder and carboxylic acid anhydride(15mmol) was added under vigorous stirring at room tem-peratureThe progress of the reaction wasmonitored by TLCUpon completion of the reaction the products were obtainedas described in previous procedure in high yield and purity

23 General Procedure for Acylation of Alcohols and Phe-nols Alcohol (1mmol) and ZSM-5-SO

3H (001ndash005 g) were

ground altogether into fine powder and carboxylic acidanhydride (1mmol benzoic anhydride 2mmol acetic anhy-dride or 12mmol of other anhydride) or carboxylic acidchloride (12mmol) was added under vigorous stirring atroom temperature (for acetic anhydride) 80∘C (for benzoicanhydride and benzoyl chloride) or 50∘C (for other anhy-drides) The progress of the reaction was monitored by TLCUpon completion of the reaction the products were obtainedas described in previous procedure in high yield and purity

24 General Procedure for Acylation of Alcohols with Car-boxylic Acids Alcohol (1mmol) and ZSM-5-SO

3H (0025ndash

01 g)were ground altogether into fine powder and carboxylicacid or dicarboxylic acid (12ndash24mmol) was added undervigorous stirring at 80ndash120∘C The progress of the reactionwas monitored by TLC Upon completion of the reactionCH2Cl2(30mL) was added and the catalyst was filtered

and washed with additional solvent (10mL) The filtrate waswashed with NaHCO

3(5 30mL) water (20mL) dried over

anhydrous Na2SO4and the solvent was evaporated to yield

the product The products were obtained in high purity(gt95)

ISRN Organic Chemistry 3

Table 1 The best conditions for ZSM-5-SO3H catalyzed acylation of alcohols and amines

Entry Amine or alcohol (mmol) Acylating agent (mmol) ZSM-5-SO3H (g) Temperature (∘C)1 Amine (2) Benzoic anhydride (2) 001 rt2 Amine (2) Acetic anhydride (4) 001 rt3 Amine (2) Aliphatic anhydride (22) 001 rt4 Amine (2) Benzoyl chloride (2) 0005 rt5 Sulfonamide (1) Aliphatic anhydride (15) 001 rt6 Alcohol (1)a Acetic anhydride or chloride (2) 001 rt7 Alcohol (1)a Benzoic anhydride (1) 005 808 Alcohol (1) Carboxylic acidb (12) 0025 1009 Alcohol (2) Dicarboxylic acid (45) 005 10010 Diol (1) Carboxylic acid (5) 01 120aPhenol was acylated the same as alcoholsbAlcohols were acylated with acetic acid at 80∘C in the presence of 005 g of catalyst

241 Spectral Data of Some Isolated Products 119873-(2-Meth-ylphenyl) benzamide (Table 2 entry 5) mp = 265∘C FT-IR(KBr cmminus1) 3242 3055 1649 1604 1525 1488 1307 748 7121H NMR (400MHz CDCl

3) 120575 (ppm) 234 (s 3H) 715 (t

1H 119869 = 72Hz) 725 (dd 2H 1198691= 76 119869

2= 76Hz) 750

(dd 2H 1198691= 76 119869

2= 76Hz) 758 (t 1H 119869 = 72Hz) 794

minus786 (m 4H) 13C NMR (100MHz CDCl3) 120575 (ppm) 179

1233 1254 1269 1271 1288 1294 1306 1319 1350 13581657119873-(24-Dimethylphenyl) benzamide (Table 2 entry 6)

mp = 192∘C FT-IR (KBr cmminus1) 3266 3023 1648 1602 15171308 1279 817 709 1H NMR (400MHz CDCl

3) 120575 (ppm)

232 (s 3H) 235 (s 3H) 706ndash711 (m 2H) 752ndash759 (m 3H)768 (br 1H) 777 (d 1H 119869 = 76Hz) 791 (d 2H 119869 = 76Hz)13C NMR (100MHz CDCl

3) 120575 (ppm) 178 209 1236 1271

1274 1288 1298 1313 1317 1331 1351 1352 1658119873-(3-Chlorophenyl) benzamide (Table 2 entry 8) mp =

120∘C FT-IR (KBr cmminus1) 3296 3072 1651 1591 1522 14191294 1250 777 700 1H NMR (400MHz CDCl

3) 120575 (ppm)

712ndash726 (m 2H) 743ndash753 (m 4H) 779ndash784 (m 3H) 831(s 1H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 1185 1206

1246 1271 1288 1300 1321 1345 1346 1391 1662119873-(3-Nitrophenyl) benzamide (Table 2 entry 9) mp =

157∘C FT-IR (KBr cmminus1) 3361 3065 1662 1593 1529 14171351 1299 799 706 1H NMR (400MHz CDCl

3) 120575 (ppm)

763ndash751 (m 4H) 792 (d 2H 119869 = 72Hz) 803 (d 1H119869 = 80Hz) 813 (d 2H 119869 = 88Hz) 853 (s 1H) 13C NMR(100MHz CDCl

3) 120575 (ppm) 1150 1191 1259 1271 1290

1300 1325 1340 1391 1487 1660119873-Hexyl benzamide (Table 2 entry 11) mp = 40∘C FT-

IR (KBr cmminus1) 3342 3080 2924 2856 1631 1576 1528 14831310 1273 717 694 1H NMR (400MHz CDCl

3) 120575 (ppm)

088 (t 3H 119869 = 68Hz) 140ndash124 (m 6H) 159 (quint 2H119869 = 72Hz) 340 (q 2H 119869 = 68Hz) 676 (br 1H) 738ndash746 (m 3H) 779 (d 2H 119869 = 72Hz) 13C NMR (400MHzCDCl

3) 120575 (ppm) 140 226 267 296 315 402 1270 1284

1312 1349 1677119873119873-(Diisopropyl) benzamide (Table 2 entry 12) FT-IR

(KBr cmminus1) 3076 2969 1627 1444 1373 1340 1211 1158 779705 1HNMR (400MHz CDCl

3) 120575 (ppm) 120 (br 6H) 140

(br 6H) 368 (br 1H) 387 (br 1H) 734minus729 (m 2H) 741ndash734 (m 3H)119873-(4-Methylphenyl) acetamide (Table 2 entry 16) mp =

154∘C FT-IR (KBr cmminus1) 3293 3065 1663 1605 1551 15081448 1401 1365 1320 1263 821 753 508 1HNMR (400MHzCDCl

3) 120575 (ppm) 216 (s 3H) 233 (s 3H) 712 (d 2H 119869 =

84Hz) 740 (d 2H 119869 = 84Hz) 780 (br 1H) 13C NMR(100MHz CDCl

3) 120575 (ppm) 209 244 1202 1294 1339

1355 1687119873119873-(Dibenzyl) acetamide (Table 2 entry 18) FT-IR

(KBr cmminus1) 3061 2926 1648 1421 1239 734 699 1H NMR(400MHz CDCl

3) 120575 (ppm) 225 (s 3H) 447 (s 2H) 463 (s

2H) 720 (d 2H 119869 = 72Hz) 726 (d 2H 119869 = 68Hz) 729ndash737 (m 4H) 741 (t 2H 119869 = 72Hz) 13C NMR (100MHzCDCl

3) 120575 (ppm) 217 480 508 1265 1275 1277 1283

1286 1290 1365 1374 1711119873-(4-Methylphenylsulfonyl) acetamide (Table 2 entry

29) FT-IR (KBr cmminus1) 3293 1720 1441 1331 1213 1000 866667 537 1H NMR (400MHz CDCl

3) 120575 (ppm) 190 (s 3H)

237 (s 3H) 740 (d 2H 119869 = 79Hz) 779 (d 2H 119869 = 81Hz)1201 (s 1H) 13CNMR (100MHz CDCl

3) 120575 (ppm) 215 326

1280 1300 1369 1446 1691119873-(4-Methylphenylsulfonyl) pentanamide (Table 2

entry 30) FT-IR (KBr cmminus1) 3251 2953 2871 1711 14461342 1167 1082 855 748 663 551 1H NMR (400MHzCDCl

3) 120575 (ppm) 077 (t 3H 119869 = 72Hz) 115 (sext 2H

119869 = 74Hz) 137 (quint 2H 119869 = 71Hz) 218 (t 2H119869 = 72Hz) 237 (s 3H) 339 (d 2H 119869 = 81Hz) 779 (d2H 119869 = 82Hz) 1196 (s 1H) 13C NMR (100MHz CDCl

3)

120575 (ppm) 139 215 218 265 355 1279 1299 1371 14501719

n-Butyl benzoate (Table 3 entry 1) FT-IR (KBr cmminus1)3066 2960 2873 1720 1602 1453 1275 1110 711 1H NMR(400MHz CDCl

3) 120575 (ppm) 101 (t 3H 119869 = 72Hz) 151

(sext 2H 119869 = 76Hz) 178 (quint 2H 119869 = 72Hz) 436 (t2H 119869 = 68Hz) 746ndash757 (m 3H) 808 (d 2H 119869 = 72Hz)13C NMR (100MHz CDCl

3) 120575 (ppm) 138 193 308 648

1283 1296 1306 1328 1667n-Pentyl benzoate (Table 3 entry 2) FT-IR (KBr cmminus1)

3067 2958 2862 1720 1602 1453 1274 1110 711 1H NMR

4 ISRN Organic Chemistry

Table 2 ZSM-5-SO3H catalyzed acylation of amines under solvent-free conditions

Entry Amine Acylating agent Products Time min(yield )

1 NH2 C

OO C

ONH C

O5 (91)

2 NH2H

3CO C

OO C

ONH C

OH

3CO 5 (95)

3NH

2

OCH3

CO

O CO

NH CO

OCH35 (92)

4 NH2

H3C C

OO C

ONH C

OH

3C 5 (92)

120 (90)a

5

CH3

NH2

CO

O CO

NH CO

CH3

5 (90)

6

CH3

NH2

H3C C

OO C

O

NH CO

CH3

H3C

5 (82)

7 Cl NH2 C

OO C

ONHCl C

O15 (90)

8Cl

NH2

CO

O CO

NH

Cl

CO

15 (85)

9 NH2

O2N

CO

O CO

NH COO

2N

25 (83)

10 NH2 C

OO C

ONH C

O2 (90)

11 NH2 C

OO C

ONH C

O3 (93)

12 NH

CO

O CO

N CO

30 (90)

13 NH2 C

O

O CO

CH3

H3C NH C

OCH

3 2 (88)

14 NH2

H3CO C

O

O CO

CH3

H3C NH C

OCH

3H3CO 2 (92)

15 NH2

OCH3

CO

O CO

CH3

H3C NH C

OCH

3

OCH32 (91)

ISRN Organic Chemistry 5

Table 2 Continued

Entry Amine Acylating agent Products Time min(yield )

16 NH2H

3C C

O

O CO

CH3H

3C NH C

OCH

3H3C 2 (91)

17

CH3

NH2

CO

O CO

CH3

H3C NH C

OCH

3

CH3

2 (88)

18 NH CO

O CO

CH3

H3C N C

O

2CH

3 10 (78)

20 NH2 CO

O CO

CH3

H3C NH C

OCH

3 2 (86)

21 NH2

CO

Cl CO

NH 2 (90)

22 NH2H

3C Cl

CO

NH CO

H3C 2 (92)

23 NH2

CH3

ClCO

NH CO

CH3

2 (88)

24 NH2 ClC

O

NH CO

2 (90)

25 NH2 ClC

O

NH CO

2 (94)

26 NH2

H3C C

O

O CO

H3C(CH

2)3

(CH2)3CH

3

NH CO

H3C (CH

2)3CH

35 (80)

27 NH2

H3C C

O

O CO

(CH3)2HC CH(CH

3)2

NH CO

H3C CH(CH

3)2

5 (70)

28 NH2 C

O

O CO

H3C CH

3

NH CO

CH3

2 (88)

29 H3C SO

2NH

2 CO

O CO

H3C CH

3C

O

H3C CH

3SO

2NH 5 (92)

30 H3C SO

2NH

2 CO

O CO

H3C(CH

2)3 (CH

2)3CH

3

C

O

H3C (CH

2)3CH

3SO

2NH 15 (80)

a20mmol scale

(400MHz CDCl3) 120575 (ppm) 093 (t 3H 119869 = 72Hz) 149ndash

132 (m 4H) 176 (quint 2H 119869 = 68Hz) 431 (t 2H 119869 =68Hz) 741-751 (m 3H) 806 (d 2H 119869 = 76Hz) 13C NMR(100MHz CDCl

3) 120575 (ppm) 140 224 282 284 535 651

1283 1295 1305 1328 1667

n-Hexyl benzoate (Table 3 entry 3) FT-IR (KBr cmminus1)3066 2956 2931 2860 1721 1602 1453 1274 1111 711 1HNMR (400MHz CDCl

3) 120575 (ppm) 094 (t 3H 119869 = 72Hz)

151ndash130 (m 6H) 180 (quint 2H 119869 = 68Hz) 435 (t 2H 119869 =68Hz) 746ndash758 (m 3H) 808 (d 2H 119869 = 72Hz) 13CNMR

6 ISRN Organic Chemistry

Table 3 ZSM-5-SO3H catalyzed acylation of alcohols and phenols under solvent-free conditions

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

1 OH CO

O CO

CO

H3C(CH

2)3O 10 (80)

2 OH2 C

OO C

OCO

H3C(CH

2)4O 15 (81)

3 OH3 C

OO C

OCO

H3C(CH

2)5O 15 (83)

4OH C

OO C

OO C

O25 (70)

5 7OH C

OO C

OCO

H3C(CH

2)9O

10 (90)15 (89)a

6 CH2OH C

OO C

OCO

CH2O 10 (89)

7 OH3 C

O

O CO

H3C CH

3

CO

CH3

H3C(CH

2)5O 10 (88)

8 OH5 C

O

O CO

H3C CH

3CO

CH3

H3C(CH

2)7O 5 (95)

9 OH7 C

O

O CO

H3C CH

3CO

CH3

H3C(CH

2)9O 3 (95)

10 OH5 C

O

ClH3C C

OCH

3H

3C(CH

2)7O 5 (93)

11 OH7 ClC

O

H3C C

OCH

3H

3C(CH

2)9O 5 (95)

12 CH2OH

ClCO

H3C C

OCH

3CH

2O 5 (95)

13 OH CO

O CO

H3C CH

3

O CO

CH3

5 (96)

14 OH CO

O CO

O CO

5 (75)

15 OH CO

O CO

H3C(CH

2)3

(CH2)3CH

3

O CO

(CH2)3CH

35 (81)

16 OH7 OHC

OCO

H3C(CH

2)9O 3 (88)

17 OH5 OHC

OCO

H3C(CH

2)7O 4 (85)

18 OH4 OHC

OCO

H3C(CH

2)6O

4 (80)6 (75)a

ISRN Organic Chemistry 7

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

19 OH3 OHC

OCO

H3C(CH

2)6O 5 (75)

20 OH2 OHC

OCO

H3C(CH

2)4O 5 (68)

21 OH OHCO

CO

H3C(CH

2)3O 5 (61)

22 OH7 OHC

OMe C

OMeH

3C(CH

2)9O 2 (75)

23 OH5 OHMe C

OMeC

OH

3C(CH

2)7O 3 (69)

24 OH3 OHMe C

OMeC

OH

3C(CH

2)5O 3 (61)

25 OH7 OHCO

H3C C

OCH

3H

3C(CH

2)9O 1 (80)

26 OH5 OHC

O

H3C C

OCH

3H

3C(CH

2)7O 2 (75)

27 OH3 OHC

O

H3C C

OCH

3H

3C(CH

2)5O 2 (60)

28 CH2OH C

O

OHH3C C

OCH

3CH

2O 2 (82)

29 OH7 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)9O 2 (85)

30 OH5 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)7O 2 (80)

31 OHHOOHC

OCH

2C C

OO O C

OCH

2H

2

(CH2)2

5 (84)

32 OH4 OHC

OCH

2O C

OCH

2

(CH2)6H

3C 1 (68)

33 OH5 OHC

OCH

2O C

OCH

2

H3C (CH

2)7

1 (70)

34 OH7 OHC

OCH

2O C

OCH

2

H3C (CH

2)8

1 (74)

35 OH2

OHN

O

HO

O

NO

O

O

OH

3C-(H

2C)

4(CH

2)4-CH

3

5 (33)

8 ISRN Organic Chemistry

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

36 OH3

OHHON

OON

O

O

O

OH

3C-(H

2C)

5(CH

2)5-CH

3

5 (43)

37 OH4 OHHO

O O O O

H3C-(H

2C)

6-O O-(CH

2)6-CH

3

5 (70)

38 OH5 OHHO

O O O O

H3C-(H

2C)

7-O O-(CH

2)7-CH

3

5 (75)

a20mmol scale

(100MHz CDCl3) 1667 1328 1306 1295 1283 651 315

287 257 226 140n-Decyl benzoate (Table 3 entry 5) FT-IR (KBr cmminus1)

3068 2926 2856 1721 1602 1457 1274 1111 711 1H NMR(400MHz CDCl

3) 120575 (ppm) 091 (t 3H 119869 = 72Hz) 152ndash

125 (m 14H) 180 (quint 2H 119869 = 72Hz) 435 (t 2H119869 = 68Hz) 747ndash758 (m 3H) 807 (d 2H 119869 = 72Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 141 227 261 288 293

294 296 319 651 1283 1295 1306 1328 1666n-Hexyl acetate (Table 3 entry 7) FT-IR (KBr cmminus1)

2957 2933 1742 1462 1367 1240 1039 1H NMR (400MHzCDCl

3) 120575 (ppm) 084 (t 3H 119869 = 68Hz) 135ndash120 (m

6H) 156 (quint 2H 119869 = 68Hz) 199 (s 3H) 401 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 139 209

225 256 286 314 646 1712n-Octyl acetate (Table 3 entry 8) FT-IR (KBr cmminus1)

2929 2859 1743 1463 1367 1239 1040 1H NMR (400MHzCDCl

3) 120575 (ppm) 086 (t 3H 119869 = 68Hz) 138ndash121 (m 10H)

160 (m 2H) 203 (s 3H) 404 (t 2H 119869 = 68Hz) 13C NMR(400MHz CDCl

3) 120575 (ppm) 140 209 226 259 286 291

292 318 646 1711n-Decyl acetate (Table 3 entry 9) FT-IR (KBr cmminus1)

2927 2858 1743 1464 1366 1239 1041 1H NMR (400MHzCDCl

3) 120575 (ppm) 087 (t 3H 119869 = 68Hz) 139ndash121 (m

14H) 160 (quint 2H 119869 = 68Hz) 203 (s 3H) 404 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 209

226 259 286 292 293 295 319 646 1711Benzyl acetate (Table 3 entry 12) FT-IR (KBr cmminus1)

3034 2954 1742 1455 1380 1230 1027 747 698 1H NMR(400MHz CDCl

3) 120575 (ppm) 214 (s 3H) 516 (s 2H) 743ndash

735 (m 5H) 13C NMR (100MHz CDCl3) 120575 (ppm) 210

663 769 772 775 1283 1283 1286 1360 1709n-Octyl-4-methylbenzoate (Table 3 entry 23) FT-IR

(KBr cmminus1) 1719 1612 1464 1274 1107 752 1H NMR(400MHz CDCl

3) 120575 (ppm) 092 (t 3H 119869 = 68Hz) 127ndash

142 (m 10H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 68Hz) 726 (d 1H 119869 = 80Hz) 796 (d 1H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 216

227 261 288 292 293 318 649 767 770 774 1279 12901296 1434 1668

n-Hexyl-4-methylbenzoate (Table 3 entry 24) FT-IR(KBr cmminus1) 17193 16126 12742 11069 7539 1H NMR(400MHz CDCl

3) 120575 (ppm) 093 (t 3H 119869 = 72Hz) 133ndash

142 (m 6H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 64Hz) 726 (d 2H 119869 = 80Hz) 796 (d 2H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 140 217

226 257 287 315 650 770 772 1278 12904 1296 14341668

Decyl propanoate (Table 3 entry 29) IR (KBr cmminus1)1740 1464 1186 1083 749 1H NMR (400MHz CDCl

3)

120575 (ppm) 089 (t 3H 119869 = 64Hz) 115 (t 3H 119869 = 76Hz) 122ndash138 (m 14H) 158ndash167 (m 2H) 233 (q 2H 119869 = 76Hz) 407(t 2H 119869 = 68Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm)

92 141 227 259 276 287 293 293 295 319 645 1746Octyl propanoate (Table 3 entry 30) IR (KBr cmminus1)

1740 1464 1186 1083 723 1H NMR (400MHz CDCl3)

120575 (ppm) 086 (t 3H 119869 = 64Hz) 112 (t 3H 119869 = 76Hz)122ndash138 (m 10H) 159 (quint 2H 119869 = 72Hz) 230 (q 2H119869 = 76Hz) 404 (t 2H 119869 = 68Hz) 13C NMR (100MHzCDCl

3) 120575 (ppm) 91 140 226 259 276 286 292 292 318

644 1745Ethane-12-diylbis(2-phenylacetate) (Table 3 entry 31) IR

(KBr cmminus1) 1738 1454 1245 1139 726 1H NMR (400MHzCDCl

3) 120575 (ppm) 364 (s 4H) 431ndash436 (m 4H) 728ndash740

(m 10H) 13C NMR (100MHz CDCl3) 120575 (ppm) 411 624

1272 1286 1293 1338 1713n-Heptyl phenylacetate (Table 3 entry 32) IR (KBr

cmminus1) 1737 1456 1251 1155 721 1HNMR (400MHz CDCl3)

120575 (ppm) 095 (t 3H 119869 = 64Hz) 126ndash141 (m 8H) 161ndash172(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash728 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 226 258

286 289 318 415 650 768 772 775 1270 1286 12931343 1717

n-Octyl phenylacetate (Table 3 entry 33) IR (KBr cmminus1)1737 1456 1252 1154 7212 1H NMR (400MHz CDCl

3)

120575 (ppm) 095 (t 3H 119869 = 68Hz) 124ndash141 (m 10H) 162ndash171(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 227 259

286 292 318 415 650 768 771 774 1270 1286 12931343

ISRN Organic Chemistry 9

n-Decyl phenylacetate (Table 3 entry 34) IR (KBr cmminus1)1738 1456 1251 1155 721 1H NMR (400MHz CDCl

3)

120575 (ppm) 093 (t 3H 119869 = 64Hz) 127ndash138 (m 14H) 161ndash168(m 2H) 366 (s 2H) 412 (t 2H 119869 = 68Hz) 739ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 142 227 259

286 292 293 295 319 415 651 768 771 774 1270 12861293 1343

Dipentylpyridine-26-dicarboxylate (Table 3 entry 35)IR (KBr cmminus1) 1741 1465 12440 1149 759 1H NMR(400MHz CDCl

3) 120575 (ppm) 094 (t 6H 119869 = 80Hz) 136ndash

150 (m 8H) 185 (quint 4H 119869 = 68Hz) 443 (t 4H 119869 =68Hz) 802 (t 1H 119869 = 76Hz) 828 (d 2H 119869 = 80Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 224 281 283 664

767 771 773 774 1277 1381 1487 1647Dihexylpyridine-26-dicarboxylate (Table 3 entry 36) IR

(KBr cmminus1) 1722 1241 1144 753 1H NMR (400MHzCDCl

3) 120575 (ppm) 082ndash093 (m 6H) 181 (quint 4H 119869 =

72Hz) 122ndash138 (m 8H) 138-148 (m 4H) 439 (t 4H119869 = 72Hz) 799 (t 1H 119869 = 80Hz) 824 (d 2H 119869 = 76Hz)

Diheptyl glutarate (Table 3 entry 37) IR (KBr cmminus1)1738 1465 1148 1065 725 1H NMR (400MHz CDCl

3)

120575 (ppm) 088 (t 6H 119869 = 68Hz) 122ndash138 (m 16H) 160(quint 4H 119869 = 68Hz) 195 (quint 4H 119869 = 72Hz) 237 (t4H 119869 = 72Hz) 406 (t 4H 119869 = 68Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 140 202 226 259 286 289 317 334

646 1731Dioctyl glutarate (Table 3 entry 38) IR (KBr cmminus1) 1737

1465 1064 722 1H NMR (400MHz CDCl3) 120575 (ppm) 090

(t 6H 119869 = 64Hz) 124ndash140 (m 20H) 159ndash168 (m 4H)192ndash202 (m 4H) 236ndash248 (m 4H) 408 (t 4H 119869 =56Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 141 199 202

226 259 286 292 292 318 330 332 334 647 647 17301731

3 Results and Discussion

As a starting point for this work the reaction was optimizedin order to find the best conditions especially in agree-ment with green chemistry (Table 1) To find the optimumconditions for acylation of amines and sulfonamides withcarboxylic acid anhydrides and chlorides several sets of reac-tion conditions were examined (Table 1 entries 1ndash5) Thusunder the best conditions amines (2mmol) were acylated atroom temperature almost quantitatively with carboxylic acidanhydrides or chlorides (2ndash4mmol) in the presence of 0005ndash001 g of ZSM-5-SO

3H without use of any solvents (Table 1

entries 1ndash4) Acylation of sulfonamides (1mmol) occurredonly with aliphatic anhydrides (15mmol) in the presenceof 001 g of catalyst at room temperature under solvent-freeconditions (Table 1 entry 5)

Then the reactionwas exploredwith a variety of aromaticand aliphatic amines to evaluate the scope and limitations ofthis method (Table 2) The results showed that the differentaromatic amines containing various electron-donating and -withdrawing groups as well as aliphatic amines reacted withcarboxylic acid chlorides or anhydrides within 5ndash30minutesto produce the corresponding amides in 70ndash95 yield

Benzoic anhydride and benzoyl chloridewas used as aromaticacylating agents Also acylation of amines were examinedusing different aliphatic acylating agents including aceticpentanoic and isobutanoic anhydridesThe excellent activityof ZSM-5-SO

3Hwas demonstrated by the good to high yields

obtained for anilines having electron-withdrawing groupssuch as Cl and NO

2(Table 2 entries 7ndash9) However the

best yields were obtained with substrates bearing electron-donating groups such as methoxy especially in the para-position (Table 2 entries 2 and 14) Also very good resultswere obtained when secondary amines were acylated in thepresence of ZSM-5-SO

3H and the corresponding amides

were obtained in 78ndash90 yields in 10ndash30 minutes at roomtemperature under solvent-free conditions (Table 2 entries 12and 18) Finally this method was used for the acylation of 4-methylbenzenesulfonamide as a weak nucleophile with aceticand pentanoic anhydrides Interestingly the corresponding119873-acyl sulfonamides were obtained in 80 and 92 yieldsafter 5 and 15 minutes in high purity (Table 2 entries 29 and30)

To demonstrate the versatility of this protocol the acyla-tion of alcohols andphenolswas investigated using carboxylicacids carboxylic acid anhydrides and chlorides as acylatingagents At first several sets of reaction conditions wereexamined to find the best conditions for acylation of alcoholsIn the optimum conditions alcohols and phenols (1mmol)were acylated at room temperature with acetic anhydridesor chlorides (2mmol) in the presence of 001 g of ZSM-5-SO3H under the solvent-free conditions (Table 1 entry 6)

Acylation with benzoic anhydride was done at 80∘C using005 g of catalyst (Table 1 entry 7) When carboxylic acidswere used as acylating agents the reactions were done at 80ndash120∘C (Table 1 entries 8ndash10)

Using a simple experimental procedure the ZSM-5-SO3H catalyzed acylation of benzylic primary and second-

ary alcohols proceeded efficiently using carboxylic acidanhydrides and chlorides (Table 3 entries 1ndash15) Differentcarboxylic acid anhydrides and chlorides such as benzoicanhydride acetic anhydride pentanoic anhydride and acetylchloride were used as acylating agent and the correspondingesters were obtained in high isolated yields and purityafter short reaction times under the solvent-free conditionsPrimary alcohols were acylated faster than secondary ones(Table 3 entries 4) and sterically hindered alcohols such astert-butyl alcohol remained unchanged It was interesting tonote that phenols were also satisfactorily acylated generatingthe corresponding esters in 75ndash95 yields (Table 3 entries13ndash15)

In order to generalize the catalytic efficiency of ZSM-5-SO3H for direct acylating with carboxylic acids the acy-

lation of alcohols was tried with different carboxylic acid(Table 3 entries 16ndash38) while most literature methods fordirect acylation of alcohols employ only acetic acid [29ndash31] Acylation with acetic propanoic phenyl acetic benzoicacid and 4-methylbenzoic acid resulted in good yield ofthe esters under the solvent-free conditions Also pleasingresults were obtained when acylation of alcohols was donewith dicarboxylic acids such as glutaric acid and pyridine-16-dicarboxylic acid and the corresponding diester was

10 ISRN Organic Chemistry

CH3

CH3

CH3

CH3

NH2

ZSM-5-SO3H

Ac2O (2 eq)

OH

+

O

+

NHO O

1000

CH3

NH2

ZSM-5-SO3H

H3C

Ac2O (2 eq)

NH

+ +

O

0 100

HO O

O

CH3

CH3

ZSM-5-SO3H

Ac2O (2 eq)

OH

OH+

O

+7

7

7 7

7

7O

O

20 80

O

CH3

ZSM-5-SO3H

H3C

NO2

NO2

Ac2O (1 eq)

OH OH

+

O

+

O O

O

80 20

CH3

CH3

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH

OH+

O

+ O

O

0 100

O

CH3

CH3

NH2

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH+

HN

+ O

O

0 100

O

rt 5 min

rt 3 min

rt 2 min

rt 2 min

Scheme 3

obtained in high purity in absence of solvent (Table 3 entries35ndash38) It is noteworthy that in contrast to most reportedmethods that need excess of acetic acid in this methodacylation of alcohols was carried out using only 12ndash20 eqof carboxylic acid Also acylation of ethylene glycol as adiol was carried out with phenylacetic acid under solvent-free conditions and the corresponding ester was obtainedin 84 after 5 minutes It should be mentioned that several

efforts to use this method for direct acylation of amines forthe synthesis of amides were not successful

The importance of selectivity in organic chemistryencouraged us to consider the selectivity of acylation ofdifferent alcohols and amines Several reactions were car-ried out using carboxylic acid anhydrides and chlorides asacylating agents and surprisingly the excellent selectivitywas found For example aromatic amines such as 4-methyl

ISRN Organic Chemistry 11

aniline can be converted into the amide in the presence ofphenol On the other hand aromatic amines were acylatedselectively in the presence of aliphatic alcohol Furthermorethe reactions of alcohols with acylating agent were so fastin comparison to those of the phenol that the selectiveacylation of aliphatic alcohols in the presence of phenolsappeared to be a distinct possibility The result showedthat selective acylation of phenols with or without electron-donating group in the presence of phenols with electron-withdrawing group is possible with this method As wellas carboxylic acid anhydrides and chlorides the excellentselectivity was observed when carboxylic acids were usedas acylating agent Acylation of alcohols was carried outselectively in the presence of phenols Also acylation ofalcohols was done in the presence of amines selectivelywhile as mentioned above this selectivity is reversed whencarboxylic acid anhydrides were used as acylating agent(Scheme 3)

To show another advantage of the present acylationmethod and the importance of scale-up ability for laboratoryand industrial purposes a few amines and phenols wereacylated in large scale successfully without considerable lim-itation For example acylation of 4-methyl aniline (Table 2entry 4) 1-decanol with benzoic anhydride (Table 3 entry5) and 1-heptanol with benzoic acid (Table 3 entry 18) wascarried out in 20mmol scales as well as the 1mmol ones Theonly difference is the reaction time Reaction in large scaleneeds more time that is because of the difficulty in stirringthe reaction mixture under solvent-free conditions

Finally we were interested to study the reusability ofthe catalysts due to economical and environmental aspectsFor this purpose the reaction of 1-heptanol with benzoicanhydride and benzoic acid was chosen as model reactionsAt the end of each run the catalyst was recovered fromthe reaction mixture by addition of dichloromethane simplefiltration and drying at 100∘C and then reused The recycledZSM-5-SO

3H was used for further runs and its activity did

not show any significant decrease even after four runs

4 Conclusion

In conclusion we have described a highly efficient and che-moselective synthetic route for the acylation of sulfonamidesamines alcohols and phenols with carboxylic acids car-boxylic acid chlorides and anhydrides in the presence ofZSM-5-SO

3H under solvent-free conditions This method

has advantages in terms of low cost and nontoxic nature of thecatalyst high yield and purity of the products short reactiontimes operational simplicity and easy workup In additionrecyclability of this protocol is attractive and useful Directacylation of alcohols with different carboxylic acids is anotheradvantage of this protocol

Acknowledgment

The support from Islamic Azad University Shahreza Branch(IAUSH) Research Council is gratefully acknowledged

References

[1] T W Greene and P G M Wuts Protective Groups in OrganicSynthesis Wiley New York NY USA 3rd edition 1999

[2] W Steglich andGHofle ldquoNN-dimethyl-4-pyridinamine a veryeffective acylation catalystrdquo Angewandte Chemie vol 8 no 12pp 980ndash981 1969

[3] E Vedejs and S T Diver ldquoTributylphosphine a remarkableacylation catalystrdquo Journal of the American Chemical Societyvol 115 no 8 pp 3358ndash3359 1993

[4] E F V Scriven ldquo4-Dialkylaminopyridines super acylation andalkylation catalystsrdquo Chemical Society Reviews vol 12 no 2 pp129ndash161 1983

[5] K Ishihara M Kubota H Kurihara and H Yamamoto ldquoScan-dium trifluoromethanesulfonate as an extremely active Lewisacid catalyst in acylation of alcohols with acid anhydrides andmixed anhydridesrdquo The Journal of Organic Chemistry vol 61no 14 pp 4560ndash4567 1996

[6] R Alleti W S Oh M Perambuduru Z Afrasiabi E Sinn andV P Reddy ldquoGadolinium triflate immobilized in imidazoliumbased ionic liquids a recyclable catalyst and green solvent foracetylation of alcohols and aminesrdquo Green Chemistry vol 7 no4 pp 203ndash206 2005

[7] T N Parac-Vogt K Deleersnyder and K Binnemans ldquoLan-thanide(III) tosylates as new acylation catalystsrdquo EuropeanJournal of Organic Chemistry vol 2005 no 9 pp 1810ndash18152005

[8] K D Surya ldquoRuthenium(III) chloride catalyzed acylation ofalcohols phenols thiols and aminesrdquo Tetrahedron Letters vol45 no 14 pp 2919ndash2922 2004

[9] F M Shirini M A Zolfigol M Abedini and P SalehildquoAl(HSO

4)3catalyzed acetylation and formylation of alcoholsrdquo

Bulletin of the Korean Chemical Society vol 24 no 11 pp 1683ndash1685 2003

[10] A Orita C Tanahashi A Kakuda and J Otera ldquoHighly pow-erful and practical acylation of alcohols with acid anhydridecatalyzed by Bi(OTf)

3rdquo Journal of Organic Chemistry vol 66

no 26 pp 8926ndash8934 2001[11] Y Nakae I Kusaki and T Sato ldquoLithium perchlorate catalyzed

acetylation of alcohols under mild reaction conditionsrdquo Synlettvol 2001 no 10 pp 1584ndash1586 2001

[12] R Ballini G Bosica S Carloni L Ciaralli R Maggi and GSartori ldquoZeolite HSZ-360 as a new reusable catalyst for thedirect acetylation of alcohols and phenols under solventlessconditionsrdquo Tetrahedron Letters vol 39 no 33 pp 6049ndash60521998

[13] B M Choudary V Bhaskar M L Kantam K Koteswara Raoand K V Raghavan ldquoAcylation of alcohols with carboxylicacids via the evolution of compatible acidic sites in montmo-rillonitesrdquo Green Chemistry vol 2 pp 67ndash70 2000

[14] M H Sarvari and H Sharghi ldquoZinc oxide (ZnO) as a newhighly efficient and reusable catalyst for acylation of alcoholsphenols and amines under solvent free conditionsrdquo Tetrahe-dron vol 61 no 46 pp 10903ndash10907 2005

[15] J Izumi I Shiina and T Mukaiyama ldquoAn efficient esterifica-tion reaction between equimolar amounts of free carboxylicacids and alcohols by the combined use of octamethylcyclote-trasiloxane and a catalytic amount of titanium(iv) chloridetris(trifluoromethanesulfonate)rdquo Chemistry Letters vol 2 pp141ndash142 1995

[16] R Alleti M Perambuduru S Samantha and V P ReddyldquoGadolinium triflate an efficient and convenient catalyst for

12 ISRN Organic Chemistry

acetylation of alcohols and aminesrdquo Journal of Molecular Catal-ysis A vol 226 no 1 pp 57ndash59 2005

[17] F Shirini K RaMoghadam and T Naghdi ldquo13-Dichloro-55-dimethylhydantoin an efficient catalyst for the solvent freesynthesis of 18-dioxo-octahydro-xanthenesrdquo Iranian Journal ofCatalysis vol 2 pp 55ndash59 2012

[18] A DyerAn Introduction to Zeolite Molecular Sieves JohnWileyamp Sons Inc New York NY USA 1988

[19] A R Massah R J Kalbasi and M Azadi ldquoHighly selectiveoxidation of alcohols using MnO

2TiO2-ZrO2as a novel het-

erogeneous catalystrdquo Comptes Rendus Chimie vol 15 no 5 pp428ndash436 2012

[20] A R Massah R J Kalbasi and M Toghyani ldquoSulfonatedpolystyrenemontmorillonite nanocomposite as a new andefficient catalyst for the solvent-free Mannich reactionrdquo IranianJournal of Catalysis vol 2 no 1 pp 41ndash49 2012

[21] R J Kalbasi M Ghiaci and A R Massah ldquoHighly selectivevapor phase nitration of toluene to 4-nitro toluene usingmodified and unmodified H

3PO4ZSM-5rdquo Applied Catalysis A

vol 353 no 1 pp 1ndash8 2009[22] R J Kalbasi A Abbaspourrad A R Massah and F Zamani

ldquoHighly selective vapor-phase acylation of veratrole overH3PO4TiO2-ZrO2 using ethyl acetate as a green and efficient

acylating agentrdquo Chinese Journal of Chemistry vol 28 no 2 pp273ndash284 2010

[23] A R Massah R J Kalbasi and A Shafiei ldquoZSM-5-SO3H as

a novel efficient and reusable catalyst for the chemoselectivesynthesis and deprotection of 11-diacetates under eco-friendlyconditionsrdquoMonatshefte fur Chemie vol 143 no 4 pp 643ndash6522012

[24] A R Massah R J Kalbasi and N Samah ldquoHighly selectivesynthesis of 120573-amino carbonyl compounds over ZSM-5-SO

3H

under solvent-free conditionsrdquo Bulletin of the Korean ChemicalSociety vol 32 no 5 pp 1703ndash1708 2011

[25] A R Massah F Kazemi D Azadi et al ldquoA mild and chemos-elective solvent-free method for the synthesis of N-aryl and N-alkysulfonamidesrdquo Letters inOrganic Chemistry vol 3 no 3 pp235ndash241 2006

[26] A R Massah B Asadi M Hoseinpour A Molseghi R JKalbasi and H Javaherian Naghash ldquoA novel and efficientsolvent-free and heterogeneous method for the synthesis ofprimary secondary and bis-N-acylsulfonamides using metalhydrogen sulfate catalystsrdquo Tetrahedron vol 65 no 36 pp7696ndash7705 2009

[27] A R Massah H Adibi R Khodarahmi et al ldquoSynthesisin vitro antibacterial and carbonic anhydrase II inhibitoryactivities of N-acylsulfonamides using silica sulfuric acid asan efficient catalyst under both solvent-free and heterogeneousconditionsrdquo Bioorganic andMedicinal Chemistry vol 16 no 10pp 5465ndash5472 2008

[28] A R Massah M Dabagh S Shahidi H J Naghash AR Momeni and H Aliyan ldquoP

2O5SiO2as an efficient and

recyclable catalyst for N-acylation of sulfonamides under het-erogeneous and solvent-free conditionsrdquo Journal of the IranianChemical Society vol 6 no 2 pp 405ndash411 2009

[29] P Pushpaletha and M Lalithambika ldquoModified attapulgite anefficient solid acid catalyst for acetylation of alcohols usingacetic acidrdquo Applied Clay Science vol 51 no 4 pp 424ndash4302011

[30] L Osiglio G Romanelli and M Blanco ldquoAlcohol acetylationwith acetic acid using borated zirconia as catalystrdquo Journal ofMolecular Catalysis A vol 316 no 1ndash2 pp 52ndash58 2010

[31] P R Likhar R Arundhathi S Ghosh and M L KantamldquoPolyaniline nanofiber supported FeCl

3 an efficient and

reusable heterogeneous catalyst for the acylation of alcohols andamines with acetic acidrdquo Journal of Molecular Catalysis A vol302 no 1ndash2 pp 142ndash149 2009

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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International Journal ofPhotoenergy

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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

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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

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Organic Chemistry International

ElectrochemistryInternational Journal of

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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CatalystsJournal of

ISRN Organic Chemistry 3

Table 1 The best conditions for ZSM-5-SO3H catalyzed acylation of alcohols and amines

Entry Amine or alcohol (mmol) Acylating agent (mmol) ZSM-5-SO3H (g) Temperature (∘C)1 Amine (2) Benzoic anhydride (2) 001 rt2 Amine (2) Acetic anhydride (4) 001 rt3 Amine (2) Aliphatic anhydride (22) 001 rt4 Amine (2) Benzoyl chloride (2) 0005 rt5 Sulfonamide (1) Aliphatic anhydride (15) 001 rt6 Alcohol (1)a Acetic anhydride or chloride (2) 001 rt7 Alcohol (1)a Benzoic anhydride (1) 005 808 Alcohol (1) Carboxylic acidb (12) 0025 1009 Alcohol (2) Dicarboxylic acid (45) 005 10010 Diol (1) Carboxylic acid (5) 01 120aPhenol was acylated the same as alcoholsbAlcohols were acylated with acetic acid at 80∘C in the presence of 005 g of catalyst

241 Spectral Data of Some Isolated Products 119873-(2-Meth-ylphenyl) benzamide (Table 2 entry 5) mp = 265∘C FT-IR(KBr cmminus1) 3242 3055 1649 1604 1525 1488 1307 748 7121H NMR (400MHz CDCl

3) 120575 (ppm) 234 (s 3H) 715 (t

1H 119869 = 72Hz) 725 (dd 2H 1198691= 76 119869

2= 76Hz) 750

(dd 2H 1198691= 76 119869

2= 76Hz) 758 (t 1H 119869 = 72Hz) 794

minus786 (m 4H) 13C NMR (100MHz CDCl3) 120575 (ppm) 179

1233 1254 1269 1271 1288 1294 1306 1319 1350 13581657119873-(24-Dimethylphenyl) benzamide (Table 2 entry 6)

mp = 192∘C FT-IR (KBr cmminus1) 3266 3023 1648 1602 15171308 1279 817 709 1H NMR (400MHz CDCl

3) 120575 (ppm)

232 (s 3H) 235 (s 3H) 706ndash711 (m 2H) 752ndash759 (m 3H)768 (br 1H) 777 (d 1H 119869 = 76Hz) 791 (d 2H 119869 = 76Hz)13C NMR (100MHz CDCl

3) 120575 (ppm) 178 209 1236 1271

1274 1288 1298 1313 1317 1331 1351 1352 1658119873-(3-Chlorophenyl) benzamide (Table 2 entry 8) mp =

120∘C FT-IR (KBr cmminus1) 3296 3072 1651 1591 1522 14191294 1250 777 700 1H NMR (400MHz CDCl

3) 120575 (ppm)

712ndash726 (m 2H) 743ndash753 (m 4H) 779ndash784 (m 3H) 831(s 1H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 1185 1206

1246 1271 1288 1300 1321 1345 1346 1391 1662119873-(3-Nitrophenyl) benzamide (Table 2 entry 9) mp =

157∘C FT-IR (KBr cmminus1) 3361 3065 1662 1593 1529 14171351 1299 799 706 1H NMR (400MHz CDCl

3) 120575 (ppm)

763ndash751 (m 4H) 792 (d 2H 119869 = 72Hz) 803 (d 1H119869 = 80Hz) 813 (d 2H 119869 = 88Hz) 853 (s 1H) 13C NMR(100MHz CDCl

3) 120575 (ppm) 1150 1191 1259 1271 1290

1300 1325 1340 1391 1487 1660119873-Hexyl benzamide (Table 2 entry 11) mp = 40∘C FT-

IR (KBr cmminus1) 3342 3080 2924 2856 1631 1576 1528 14831310 1273 717 694 1H NMR (400MHz CDCl

3) 120575 (ppm)

088 (t 3H 119869 = 68Hz) 140ndash124 (m 6H) 159 (quint 2H119869 = 72Hz) 340 (q 2H 119869 = 68Hz) 676 (br 1H) 738ndash746 (m 3H) 779 (d 2H 119869 = 72Hz) 13C NMR (400MHzCDCl

3) 120575 (ppm) 140 226 267 296 315 402 1270 1284

1312 1349 1677119873119873-(Diisopropyl) benzamide (Table 2 entry 12) FT-IR

(KBr cmminus1) 3076 2969 1627 1444 1373 1340 1211 1158 779705 1HNMR (400MHz CDCl

3) 120575 (ppm) 120 (br 6H) 140

(br 6H) 368 (br 1H) 387 (br 1H) 734minus729 (m 2H) 741ndash734 (m 3H)119873-(4-Methylphenyl) acetamide (Table 2 entry 16) mp =

154∘C FT-IR (KBr cmminus1) 3293 3065 1663 1605 1551 15081448 1401 1365 1320 1263 821 753 508 1HNMR (400MHzCDCl

3) 120575 (ppm) 216 (s 3H) 233 (s 3H) 712 (d 2H 119869 =

84Hz) 740 (d 2H 119869 = 84Hz) 780 (br 1H) 13C NMR(100MHz CDCl

3) 120575 (ppm) 209 244 1202 1294 1339

1355 1687119873119873-(Dibenzyl) acetamide (Table 2 entry 18) FT-IR

(KBr cmminus1) 3061 2926 1648 1421 1239 734 699 1H NMR(400MHz CDCl

3) 120575 (ppm) 225 (s 3H) 447 (s 2H) 463 (s

2H) 720 (d 2H 119869 = 72Hz) 726 (d 2H 119869 = 68Hz) 729ndash737 (m 4H) 741 (t 2H 119869 = 72Hz) 13C NMR (100MHzCDCl

3) 120575 (ppm) 217 480 508 1265 1275 1277 1283

1286 1290 1365 1374 1711119873-(4-Methylphenylsulfonyl) acetamide (Table 2 entry

29) FT-IR (KBr cmminus1) 3293 1720 1441 1331 1213 1000 866667 537 1H NMR (400MHz CDCl

3) 120575 (ppm) 190 (s 3H)

237 (s 3H) 740 (d 2H 119869 = 79Hz) 779 (d 2H 119869 = 81Hz)1201 (s 1H) 13CNMR (100MHz CDCl

3) 120575 (ppm) 215 326

1280 1300 1369 1446 1691119873-(4-Methylphenylsulfonyl) pentanamide (Table 2

entry 30) FT-IR (KBr cmminus1) 3251 2953 2871 1711 14461342 1167 1082 855 748 663 551 1H NMR (400MHzCDCl

3) 120575 (ppm) 077 (t 3H 119869 = 72Hz) 115 (sext 2H

119869 = 74Hz) 137 (quint 2H 119869 = 71Hz) 218 (t 2H119869 = 72Hz) 237 (s 3H) 339 (d 2H 119869 = 81Hz) 779 (d2H 119869 = 82Hz) 1196 (s 1H) 13C NMR (100MHz CDCl

3)

120575 (ppm) 139 215 218 265 355 1279 1299 1371 14501719

n-Butyl benzoate (Table 3 entry 1) FT-IR (KBr cmminus1)3066 2960 2873 1720 1602 1453 1275 1110 711 1H NMR(400MHz CDCl

3) 120575 (ppm) 101 (t 3H 119869 = 72Hz) 151

(sext 2H 119869 = 76Hz) 178 (quint 2H 119869 = 72Hz) 436 (t2H 119869 = 68Hz) 746ndash757 (m 3H) 808 (d 2H 119869 = 72Hz)13C NMR (100MHz CDCl

3) 120575 (ppm) 138 193 308 648

1283 1296 1306 1328 1667n-Pentyl benzoate (Table 3 entry 2) FT-IR (KBr cmminus1)

3067 2958 2862 1720 1602 1453 1274 1110 711 1H NMR

4 ISRN Organic Chemistry

Table 2 ZSM-5-SO3H catalyzed acylation of amines under solvent-free conditions

Entry Amine Acylating agent Products Time min(yield )

1 NH2 C

OO C

ONH C

O5 (91)

2 NH2H

3CO C

OO C

ONH C

OH

3CO 5 (95)

3NH

2

OCH3

CO

O CO

NH CO

OCH35 (92)

4 NH2

H3C C

OO C

ONH C

OH

3C 5 (92)

120 (90)a

5

CH3

NH2

CO

O CO

NH CO

CH3

5 (90)

6

CH3

NH2

H3C C

OO C

O

NH CO

CH3

H3C

5 (82)

7 Cl NH2 C

OO C

ONHCl C

O15 (90)

8Cl

NH2

CO

O CO

NH

Cl

CO

15 (85)

9 NH2

O2N

CO

O CO

NH COO

2N

25 (83)

10 NH2 C

OO C

ONH C

O2 (90)

11 NH2 C

OO C

ONH C

O3 (93)

12 NH

CO

O CO

N CO

30 (90)

13 NH2 C

O

O CO

CH3

H3C NH C

OCH

3 2 (88)

14 NH2

H3CO C

O

O CO

CH3

H3C NH C

OCH

3H3CO 2 (92)

15 NH2

OCH3

CO

O CO

CH3

H3C NH C

OCH

3

OCH32 (91)

ISRN Organic Chemistry 5

Table 2 Continued

Entry Amine Acylating agent Products Time min(yield )

16 NH2H

3C C

O

O CO

CH3H

3C NH C

OCH

3H3C 2 (91)

17

CH3

NH2

CO

O CO

CH3

H3C NH C

OCH

3

CH3

2 (88)

18 NH CO

O CO

CH3

H3C N C

O

2CH

3 10 (78)

20 NH2 CO

O CO

CH3

H3C NH C

OCH

3 2 (86)

21 NH2

CO

Cl CO

NH 2 (90)

22 NH2H

3C Cl

CO

NH CO

H3C 2 (92)

23 NH2

CH3

ClCO

NH CO

CH3

2 (88)

24 NH2 ClC

O

NH CO

2 (90)

25 NH2 ClC

O

NH CO

2 (94)

26 NH2

H3C C

O

O CO

H3C(CH

2)3

(CH2)3CH

3

NH CO

H3C (CH

2)3CH

35 (80)

27 NH2

H3C C

O

O CO

(CH3)2HC CH(CH

3)2

NH CO

H3C CH(CH

3)2

5 (70)

28 NH2 C

O

O CO

H3C CH

3

NH CO

CH3

2 (88)

29 H3C SO

2NH

2 CO

O CO

H3C CH

3C

O

H3C CH

3SO

2NH 5 (92)

30 H3C SO

2NH

2 CO

O CO

H3C(CH

2)3 (CH

2)3CH

3

C

O

H3C (CH

2)3CH

3SO

2NH 15 (80)

a20mmol scale

(400MHz CDCl3) 120575 (ppm) 093 (t 3H 119869 = 72Hz) 149ndash

132 (m 4H) 176 (quint 2H 119869 = 68Hz) 431 (t 2H 119869 =68Hz) 741-751 (m 3H) 806 (d 2H 119869 = 76Hz) 13C NMR(100MHz CDCl

3) 120575 (ppm) 140 224 282 284 535 651

1283 1295 1305 1328 1667

n-Hexyl benzoate (Table 3 entry 3) FT-IR (KBr cmminus1)3066 2956 2931 2860 1721 1602 1453 1274 1111 711 1HNMR (400MHz CDCl

3) 120575 (ppm) 094 (t 3H 119869 = 72Hz)

151ndash130 (m 6H) 180 (quint 2H 119869 = 68Hz) 435 (t 2H 119869 =68Hz) 746ndash758 (m 3H) 808 (d 2H 119869 = 72Hz) 13CNMR

6 ISRN Organic Chemistry

Table 3 ZSM-5-SO3H catalyzed acylation of alcohols and phenols under solvent-free conditions

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

1 OH CO

O CO

CO

H3C(CH

2)3O 10 (80)

2 OH2 C

OO C

OCO

H3C(CH

2)4O 15 (81)

3 OH3 C

OO C

OCO

H3C(CH

2)5O 15 (83)

4OH C

OO C

OO C

O25 (70)

5 7OH C

OO C

OCO

H3C(CH

2)9O

10 (90)15 (89)a

6 CH2OH C

OO C

OCO

CH2O 10 (89)

7 OH3 C

O

O CO

H3C CH

3

CO

CH3

H3C(CH

2)5O 10 (88)

8 OH5 C

O

O CO

H3C CH

3CO

CH3

H3C(CH

2)7O 5 (95)

9 OH7 C

O

O CO

H3C CH

3CO

CH3

H3C(CH

2)9O 3 (95)

10 OH5 C

O

ClH3C C

OCH

3H

3C(CH

2)7O 5 (93)

11 OH7 ClC

O

H3C C

OCH

3H

3C(CH

2)9O 5 (95)

12 CH2OH

ClCO

H3C C

OCH

3CH

2O 5 (95)

13 OH CO

O CO

H3C CH

3

O CO

CH3

5 (96)

14 OH CO

O CO

O CO

5 (75)

15 OH CO

O CO

H3C(CH

2)3

(CH2)3CH

3

O CO

(CH2)3CH

35 (81)

16 OH7 OHC

OCO

H3C(CH

2)9O 3 (88)

17 OH5 OHC

OCO

H3C(CH

2)7O 4 (85)

18 OH4 OHC

OCO

H3C(CH

2)6O

4 (80)6 (75)a

ISRN Organic Chemistry 7

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

19 OH3 OHC

OCO

H3C(CH

2)6O 5 (75)

20 OH2 OHC

OCO

H3C(CH

2)4O 5 (68)

21 OH OHCO

CO

H3C(CH

2)3O 5 (61)

22 OH7 OHC

OMe C

OMeH

3C(CH

2)9O 2 (75)

23 OH5 OHMe C

OMeC

OH

3C(CH

2)7O 3 (69)

24 OH3 OHMe C

OMeC

OH

3C(CH

2)5O 3 (61)

25 OH7 OHCO

H3C C

OCH

3H

3C(CH

2)9O 1 (80)

26 OH5 OHC

O

H3C C

OCH

3H

3C(CH

2)7O 2 (75)

27 OH3 OHC

O

H3C C

OCH

3H

3C(CH

2)5O 2 (60)

28 CH2OH C

O

OHH3C C

OCH

3CH

2O 2 (82)

29 OH7 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)9O 2 (85)

30 OH5 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)7O 2 (80)

31 OHHOOHC

OCH

2C C

OO O C

OCH

2H

2

(CH2)2

5 (84)

32 OH4 OHC

OCH

2O C

OCH

2

(CH2)6H

3C 1 (68)

33 OH5 OHC

OCH

2O C

OCH

2

H3C (CH

2)7

1 (70)

34 OH7 OHC

OCH

2O C

OCH

2

H3C (CH

2)8

1 (74)

35 OH2

OHN

O

HO

O

NO

O

O

OH

3C-(H

2C)

4(CH

2)4-CH

3

5 (33)

8 ISRN Organic Chemistry

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

36 OH3

OHHON

OON

O

O

O

OH

3C-(H

2C)

5(CH

2)5-CH

3

5 (43)

37 OH4 OHHO

O O O O

H3C-(H

2C)

6-O O-(CH

2)6-CH

3

5 (70)

38 OH5 OHHO

O O O O

H3C-(H

2C)

7-O O-(CH

2)7-CH

3

5 (75)

a20mmol scale

(100MHz CDCl3) 1667 1328 1306 1295 1283 651 315

287 257 226 140n-Decyl benzoate (Table 3 entry 5) FT-IR (KBr cmminus1)

3068 2926 2856 1721 1602 1457 1274 1111 711 1H NMR(400MHz CDCl

3) 120575 (ppm) 091 (t 3H 119869 = 72Hz) 152ndash

125 (m 14H) 180 (quint 2H 119869 = 72Hz) 435 (t 2H119869 = 68Hz) 747ndash758 (m 3H) 807 (d 2H 119869 = 72Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 141 227 261 288 293

294 296 319 651 1283 1295 1306 1328 1666n-Hexyl acetate (Table 3 entry 7) FT-IR (KBr cmminus1)

2957 2933 1742 1462 1367 1240 1039 1H NMR (400MHzCDCl

3) 120575 (ppm) 084 (t 3H 119869 = 68Hz) 135ndash120 (m

6H) 156 (quint 2H 119869 = 68Hz) 199 (s 3H) 401 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 139 209

225 256 286 314 646 1712n-Octyl acetate (Table 3 entry 8) FT-IR (KBr cmminus1)

2929 2859 1743 1463 1367 1239 1040 1H NMR (400MHzCDCl

3) 120575 (ppm) 086 (t 3H 119869 = 68Hz) 138ndash121 (m 10H)

160 (m 2H) 203 (s 3H) 404 (t 2H 119869 = 68Hz) 13C NMR(400MHz CDCl

3) 120575 (ppm) 140 209 226 259 286 291

292 318 646 1711n-Decyl acetate (Table 3 entry 9) FT-IR (KBr cmminus1)

2927 2858 1743 1464 1366 1239 1041 1H NMR (400MHzCDCl

3) 120575 (ppm) 087 (t 3H 119869 = 68Hz) 139ndash121 (m

14H) 160 (quint 2H 119869 = 68Hz) 203 (s 3H) 404 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 209

226 259 286 292 293 295 319 646 1711Benzyl acetate (Table 3 entry 12) FT-IR (KBr cmminus1)

3034 2954 1742 1455 1380 1230 1027 747 698 1H NMR(400MHz CDCl

3) 120575 (ppm) 214 (s 3H) 516 (s 2H) 743ndash

735 (m 5H) 13C NMR (100MHz CDCl3) 120575 (ppm) 210

663 769 772 775 1283 1283 1286 1360 1709n-Octyl-4-methylbenzoate (Table 3 entry 23) FT-IR

(KBr cmminus1) 1719 1612 1464 1274 1107 752 1H NMR(400MHz CDCl

3) 120575 (ppm) 092 (t 3H 119869 = 68Hz) 127ndash

142 (m 10H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 68Hz) 726 (d 1H 119869 = 80Hz) 796 (d 1H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 216

227 261 288 292 293 318 649 767 770 774 1279 12901296 1434 1668

n-Hexyl-4-methylbenzoate (Table 3 entry 24) FT-IR(KBr cmminus1) 17193 16126 12742 11069 7539 1H NMR(400MHz CDCl

3) 120575 (ppm) 093 (t 3H 119869 = 72Hz) 133ndash

142 (m 6H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 64Hz) 726 (d 2H 119869 = 80Hz) 796 (d 2H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 140 217

226 257 287 315 650 770 772 1278 12904 1296 14341668

Decyl propanoate (Table 3 entry 29) IR (KBr cmminus1)1740 1464 1186 1083 749 1H NMR (400MHz CDCl

3)

120575 (ppm) 089 (t 3H 119869 = 64Hz) 115 (t 3H 119869 = 76Hz) 122ndash138 (m 14H) 158ndash167 (m 2H) 233 (q 2H 119869 = 76Hz) 407(t 2H 119869 = 68Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm)

92 141 227 259 276 287 293 293 295 319 645 1746Octyl propanoate (Table 3 entry 30) IR (KBr cmminus1)

1740 1464 1186 1083 723 1H NMR (400MHz CDCl3)

120575 (ppm) 086 (t 3H 119869 = 64Hz) 112 (t 3H 119869 = 76Hz)122ndash138 (m 10H) 159 (quint 2H 119869 = 72Hz) 230 (q 2H119869 = 76Hz) 404 (t 2H 119869 = 68Hz) 13C NMR (100MHzCDCl

3) 120575 (ppm) 91 140 226 259 276 286 292 292 318

644 1745Ethane-12-diylbis(2-phenylacetate) (Table 3 entry 31) IR

(KBr cmminus1) 1738 1454 1245 1139 726 1H NMR (400MHzCDCl

3) 120575 (ppm) 364 (s 4H) 431ndash436 (m 4H) 728ndash740

(m 10H) 13C NMR (100MHz CDCl3) 120575 (ppm) 411 624

1272 1286 1293 1338 1713n-Heptyl phenylacetate (Table 3 entry 32) IR (KBr

cmminus1) 1737 1456 1251 1155 721 1HNMR (400MHz CDCl3)

120575 (ppm) 095 (t 3H 119869 = 64Hz) 126ndash141 (m 8H) 161ndash172(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash728 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 226 258

286 289 318 415 650 768 772 775 1270 1286 12931343 1717

n-Octyl phenylacetate (Table 3 entry 33) IR (KBr cmminus1)1737 1456 1252 1154 7212 1H NMR (400MHz CDCl

3)

120575 (ppm) 095 (t 3H 119869 = 68Hz) 124ndash141 (m 10H) 162ndash171(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 227 259

286 292 318 415 650 768 771 774 1270 1286 12931343

ISRN Organic Chemistry 9

n-Decyl phenylacetate (Table 3 entry 34) IR (KBr cmminus1)1738 1456 1251 1155 721 1H NMR (400MHz CDCl

3)

120575 (ppm) 093 (t 3H 119869 = 64Hz) 127ndash138 (m 14H) 161ndash168(m 2H) 366 (s 2H) 412 (t 2H 119869 = 68Hz) 739ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 142 227 259

286 292 293 295 319 415 651 768 771 774 1270 12861293 1343

Dipentylpyridine-26-dicarboxylate (Table 3 entry 35)IR (KBr cmminus1) 1741 1465 12440 1149 759 1H NMR(400MHz CDCl

3) 120575 (ppm) 094 (t 6H 119869 = 80Hz) 136ndash

150 (m 8H) 185 (quint 4H 119869 = 68Hz) 443 (t 4H 119869 =68Hz) 802 (t 1H 119869 = 76Hz) 828 (d 2H 119869 = 80Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 224 281 283 664

767 771 773 774 1277 1381 1487 1647Dihexylpyridine-26-dicarboxylate (Table 3 entry 36) IR

(KBr cmminus1) 1722 1241 1144 753 1H NMR (400MHzCDCl

3) 120575 (ppm) 082ndash093 (m 6H) 181 (quint 4H 119869 =

72Hz) 122ndash138 (m 8H) 138-148 (m 4H) 439 (t 4H119869 = 72Hz) 799 (t 1H 119869 = 80Hz) 824 (d 2H 119869 = 76Hz)

Diheptyl glutarate (Table 3 entry 37) IR (KBr cmminus1)1738 1465 1148 1065 725 1H NMR (400MHz CDCl

3)

120575 (ppm) 088 (t 6H 119869 = 68Hz) 122ndash138 (m 16H) 160(quint 4H 119869 = 68Hz) 195 (quint 4H 119869 = 72Hz) 237 (t4H 119869 = 72Hz) 406 (t 4H 119869 = 68Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 140 202 226 259 286 289 317 334

646 1731Dioctyl glutarate (Table 3 entry 38) IR (KBr cmminus1) 1737

1465 1064 722 1H NMR (400MHz CDCl3) 120575 (ppm) 090

(t 6H 119869 = 64Hz) 124ndash140 (m 20H) 159ndash168 (m 4H)192ndash202 (m 4H) 236ndash248 (m 4H) 408 (t 4H 119869 =56Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 141 199 202

226 259 286 292 292 318 330 332 334 647 647 17301731

3 Results and Discussion

As a starting point for this work the reaction was optimizedin order to find the best conditions especially in agree-ment with green chemistry (Table 1) To find the optimumconditions for acylation of amines and sulfonamides withcarboxylic acid anhydrides and chlorides several sets of reac-tion conditions were examined (Table 1 entries 1ndash5) Thusunder the best conditions amines (2mmol) were acylated atroom temperature almost quantitatively with carboxylic acidanhydrides or chlorides (2ndash4mmol) in the presence of 0005ndash001 g of ZSM-5-SO

3H without use of any solvents (Table 1

entries 1ndash4) Acylation of sulfonamides (1mmol) occurredonly with aliphatic anhydrides (15mmol) in the presenceof 001 g of catalyst at room temperature under solvent-freeconditions (Table 1 entry 5)

Then the reactionwas exploredwith a variety of aromaticand aliphatic amines to evaluate the scope and limitations ofthis method (Table 2) The results showed that the differentaromatic amines containing various electron-donating and -withdrawing groups as well as aliphatic amines reacted withcarboxylic acid chlorides or anhydrides within 5ndash30minutesto produce the corresponding amides in 70ndash95 yield

Benzoic anhydride and benzoyl chloridewas used as aromaticacylating agents Also acylation of amines were examinedusing different aliphatic acylating agents including aceticpentanoic and isobutanoic anhydridesThe excellent activityof ZSM-5-SO

3Hwas demonstrated by the good to high yields

obtained for anilines having electron-withdrawing groupssuch as Cl and NO

2(Table 2 entries 7ndash9) However the

best yields were obtained with substrates bearing electron-donating groups such as methoxy especially in the para-position (Table 2 entries 2 and 14) Also very good resultswere obtained when secondary amines were acylated in thepresence of ZSM-5-SO

3H and the corresponding amides

were obtained in 78ndash90 yields in 10ndash30 minutes at roomtemperature under solvent-free conditions (Table 2 entries 12and 18) Finally this method was used for the acylation of 4-methylbenzenesulfonamide as a weak nucleophile with aceticand pentanoic anhydrides Interestingly the corresponding119873-acyl sulfonamides were obtained in 80 and 92 yieldsafter 5 and 15 minutes in high purity (Table 2 entries 29 and30)

To demonstrate the versatility of this protocol the acyla-tion of alcohols andphenolswas investigated using carboxylicacids carboxylic acid anhydrides and chlorides as acylatingagents At first several sets of reaction conditions wereexamined to find the best conditions for acylation of alcoholsIn the optimum conditions alcohols and phenols (1mmol)were acylated at room temperature with acetic anhydridesor chlorides (2mmol) in the presence of 001 g of ZSM-5-SO3H under the solvent-free conditions (Table 1 entry 6)

Acylation with benzoic anhydride was done at 80∘C using005 g of catalyst (Table 1 entry 7) When carboxylic acidswere used as acylating agents the reactions were done at 80ndash120∘C (Table 1 entries 8ndash10)

Using a simple experimental procedure the ZSM-5-SO3H catalyzed acylation of benzylic primary and second-

ary alcohols proceeded efficiently using carboxylic acidanhydrides and chlorides (Table 3 entries 1ndash15) Differentcarboxylic acid anhydrides and chlorides such as benzoicanhydride acetic anhydride pentanoic anhydride and acetylchloride were used as acylating agent and the correspondingesters were obtained in high isolated yields and purityafter short reaction times under the solvent-free conditionsPrimary alcohols were acylated faster than secondary ones(Table 3 entries 4) and sterically hindered alcohols such astert-butyl alcohol remained unchanged It was interesting tonote that phenols were also satisfactorily acylated generatingthe corresponding esters in 75ndash95 yields (Table 3 entries13ndash15)

In order to generalize the catalytic efficiency of ZSM-5-SO3H for direct acylating with carboxylic acids the acy-

lation of alcohols was tried with different carboxylic acid(Table 3 entries 16ndash38) while most literature methods fordirect acylation of alcohols employ only acetic acid [29ndash31] Acylation with acetic propanoic phenyl acetic benzoicacid and 4-methylbenzoic acid resulted in good yield ofthe esters under the solvent-free conditions Also pleasingresults were obtained when acylation of alcohols was donewith dicarboxylic acids such as glutaric acid and pyridine-16-dicarboxylic acid and the corresponding diester was

10 ISRN Organic Chemistry

CH3

CH3

CH3

CH3

NH2

ZSM-5-SO3H

Ac2O (2 eq)

OH

+

O

+

NHO O

1000

CH3

NH2

ZSM-5-SO3H

H3C

Ac2O (2 eq)

NH

+ +

O

0 100

HO O

O

CH3

CH3

ZSM-5-SO3H

Ac2O (2 eq)

OH

OH+

O

+7

7

7 7

7

7O

O

20 80

O

CH3

ZSM-5-SO3H

H3C

NO2

NO2

Ac2O (1 eq)

OH OH

+

O

+

O O

O

80 20

CH3

CH3

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH

OH+

O

+ O

O

0 100

O

CH3

CH3

NH2

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH+

HN

+ O

O

0 100

O

rt 5 min

rt 3 min

rt 2 min

rt 2 min

Scheme 3

obtained in high purity in absence of solvent (Table 3 entries35ndash38) It is noteworthy that in contrast to most reportedmethods that need excess of acetic acid in this methodacylation of alcohols was carried out using only 12ndash20 eqof carboxylic acid Also acylation of ethylene glycol as adiol was carried out with phenylacetic acid under solvent-free conditions and the corresponding ester was obtainedin 84 after 5 minutes It should be mentioned that several

efforts to use this method for direct acylation of amines forthe synthesis of amides were not successful

The importance of selectivity in organic chemistryencouraged us to consider the selectivity of acylation ofdifferent alcohols and amines Several reactions were car-ried out using carboxylic acid anhydrides and chlorides asacylating agents and surprisingly the excellent selectivitywas found For example aromatic amines such as 4-methyl

ISRN Organic Chemistry 11

aniline can be converted into the amide in the presence ofphenol On the other hand aromatic amines were acylatedselectively in the presence of aliphatic alcohol Furthermorethe reactions of alcohols with acylating agent were so fastin comparison to those of the phenol that the selectiveacylation of aliphatic alcohols in the presence of phenolsappeared to be a distinct possibility The result showedthat selective acylation of phenols with or without electron-donating group in the presence of phenols with electron-withdrawing group is possible with this method As wellas carboxylic acid anhydrides and chlorides the excellentselectivity was observed when carboxylic acids were usedas acylating agent Acylation of alcohols was carried outselectively in the presence of phenols Also acylation ofalcohols was done in the presence of amines selectivelywhile as mentioned above this selectivity is reversed whencarboxylic acid anhydrides were used as acylating agent(Scheme 3)

To show another advantage of the present acylationmethod and the importance of scale-up ability for laboratoryand industrial purposes a few amines and phenols wereacylated in large scale successfully without considerable lim-itation For example acylation of 4-methyl aniline (Table 2entry 4) 1-decanol with benzoic anhydride (Table 3 entry5) and 1-heptanol with benzoic acid (Table 3 entry 18) wascarried out in 20mmol scales as well as the 1mmol ones Theonly difference is the reaction time Reaction in large scaleneeds more time that is because of the difficulty in stirringthe reaction mixture under solvent-free conditions

Finally we were interested to study the reusability ofthe catalysts due to economical and environmental aspectsFor this purpose the reaction of 1-heptanol with benzoicanhydride and benzoic acid was chosen as model reactionsAt the end of each run the catalyst was recovered fromthe reaction mixture by addition of dichloromethane simplefiltration and drying at 100∘C and then reused The recycledZSM-5-SO

3H was used for further runs and its activity did

not show any significant decrease even after four runs

4 Conclusion

In conclusion we have described a highly efficient and che-moselective synthetic route for the acylation of sulfonamidesamines alcohols and phenols with carboxylic acids car-boxylic acid chlorides and anhydrides in the presence ofZSM-5-SO

3H under solvent-free conditions This method

has advantages in terms of low cost and nontoxic nature of thecatalyst high yield and purity of the products short reactiontimes operational simplicity and easy workup In additionrecyclability of this protocol is attractive and useful Directacylation of alcohols with different carboxylic acids is anotheradvantage of this protocol

Acknowledgment

The support from Islamic Azad University Shahreza Branch(IAUSH) Research Council is gratefully acknowledged

References

[1] T W Greene and P G M Wuts Protective Groups in OrganicSynthesis Wiley New York NY USA 3rd edition 1999

[2] W Steglich andGHofle ldquoNN-dimethyl-4-pyridinamine a veryeffective acylation catalystrdquo Angewandte Chemie vol 8 no 12pp 980ndash981 1969

[3] E Vedejs and S T Diver ldquoTributylphosphine a remarkableacylation catalystrdquo Journal of the American Chemical Societyvol 115 no 8 pp 3358ndash3359 1993

[4] E F V Scriven ldquo4-Dialkylaminopyridines super acylation andalkylation catalystsrdquo Chemical Society Reviews vol 12 no 2 pp129ndash161 1983

[5] K Ishihara M Kubota H Kurihara and H Yamamoto ldquoScan-dium trifluoromethanesulfonate as an extremely active Lewisacid catalyst in acylation of alcohols with acid anhydrides andmixed anhydridesrdquo The Journal of Organic Chemistry vol 61no 14 pp 4560ndash4567 1996

[6] R Alleti W S Oh M Perambuduru Z Afrasiabi E Sinn andV P Reddy ldquoGadolinium triflate immobilized in imidazoliumbased ionic liquids a recyclable catalyst and green solvent foracetylation of alcohols and aminesrdquo Green Chemistry vol 7 no4 pp 203ndash206 2005

[7] T N Parac-Vogt K Deleersnyder and K Binnemans ldquoLan-thanide(III) tosylates as new acylation catalystsrdquo EuropeanJournal of Organic Chemistry vol 2005 no 9 pp 1810ndash18152005

[8] K D Surya ldquoRuthenium(III) chloride catalyzed acylation ofalcohols phenols thiols and aminesrdquo Tetrahedron Letters vol45 no 14 pp 2919ndash2922 2004

[9] F M Shirini M A Zolfigol M Abedini and P SalehildquoAl(HSO

4)3catalyzed acetylation and formylation of alcoholsrdquo

Bulletin of the Korean Chemical Society vol 24 no 11 pp 1683ndash1685 2003

[10] A Orita C Tanahashi A Kakuda and J Otera ldquoHighly pow-erful and practical acylation of alcohols with acid anhydridecatalyzed by Bi(OTf)

3rdquo Journal of Organic Chemistry vol 66

no 26 pp 8926ndash8934 2001[11] Y Nakae I Kusaki and T Sato ldquoLithium perchlorate catalyzed

acetylation of alcohols under mild reaction conditionsrdquo Synlettvol 2001 no 10 pp 1584ndash1586 2001

[12] R Ballini G Bosica S Carloni L Ciaralli R Maggi and GSartori ldquoZeolite HSZ-360 as a new reusable catalyst for thedirect acetylation of alcohols and phenols under solventlessconditionsrdquo Tetrahedron Letters vol 39 no 33 pp 6049ndash60521998

[13] B M Choudary V Bhaskar M L Kantam K Koteswara Raoand K V Raghavan ldquoAcylation of alcohols with carboxylicacids via the evolution of compatible acidic sites in montmo-rillonitesrdquo Green Chemistry vol 2 pp 67ndash70 2000

[14] M H Sarvari and H Sharghi ldquoZinc oxide (ZnO) as a newhighly efficient and reusable catalyst for acylation of alcoholsphenols and amines under solvent free conditionsrdquo Tetrahe-dron vol 61 no 46 pp 10903ndash10907 2005

[15] J Izumi I Shiina and T Mukaiyama ldquoAn efficient esterifica-tion reaction between equimolar amounts of free carboxylicacids and alcohols by the combined use of octamethylcyclote-trasiloxane and a catalytic amount of titanium(iv) chloridetris(trifluoromethanesulfonate)rdquo Chemistry Letters vol 2 pp141ndash142 1995

[16] R Alleti M Perambuduru S Samantha and V P ReddyldquoGadolinium triflate an efficient and convenient catalyst for

12 ISRN Organic Chemistry

acetylation of alcohols and aminesrdquo Journal of Molecular Catal-ysis A vol 226 no 1 pp 57ndash59 2005

[17] F Shirini K RaMoghadam and T Naghdi ldquo13-Dichloro-55-dimethylhydantoin an efficient catalyst for the solvent freesynthesis of 18-dioxo-octahydro-xanthenesrdquo Iranian Journal ofCatalysis vol 2 pp 55ndash59 2012

[18] A DyerAn Introduction to Zeolite Molecular Sieves JohnWileyamp Sons Inc New York NY USA 1988

[19] A R Massah R J Kalbasi and M Azadi ldquoHighly selectiveoxidation of alcohols using MnO

2TiO2-ZrO2as a novel het-

erogeneous catalystrdquo Comptes Rendus Chimie vol 15 no 5 pp428ndash436 2012

[20] A R Massah R J Kalbasi and M Toghyani ldquoSulfonatedpolystyrenemontmorillonite nanocomposite as a new andefficient catalyst for the solvent-free Mannich reactionrdquo IranianJournal of Catalysis vol 2 no 1 pp 41ndash49 2012

[21] R J Kalbasi M Ghiaci and A R Massah ldquoHighly selectivevapor phase nitration of toluene to 4-nitro toluene usingmodified and unmodified H

3PO4ZSM-5rdquo Applied Catalysis A

vol 353 no 1 pp 1ndash8 2009[22] R J Kalbasi A Abbaspourrad A R Massah and F Zamani

ldquoHighly selective vapor-phase acylation of veratrole overH3PO4TiO2-ZrO2 using ethyl acetate as a green and efficient

acylating agentrdquo Chinese Journal of Chemistry vol 28 no 2 pp273ndash284 2010

[23] A R Massah R J Kalbasi and A Shafiei ldquoZSM-5-SO3H as

a novel efficient and reusable catalyst for the chemoselectivesynthesis and deprotection of 11-diacetates under eco-friendlyconditionsrdquoMonatshefte fur Chemie vol 143 no 4 pp 643ndash6522012

[24] A R Massah R J Kalbasi and N Samah ldquoHighly selectivesynthesis of 120573-amino carbonyl compounds over ZSM-5-SO

3H

under solvent-free conditionsrdquo Bulletin of the Korean ChemicalSociety vol 32 no 5 pp 1703ndash1708 2011

[25] A R Massah F Kazemi D Azadi et al ldquoA mild and chemos-elective solvent-free method for the synthesis of N-aryl and N-alkysulfonamidesrdquo Letters inOrganic Chemistry vol 3 no 3 pp235ndash241 2006

[26] A R Massah B Asadi M Hoseinpour A Molseghi R JKalbasi and H Javaherian Naghash ldquoA novel and efficientsolvent-free and heterogeneous method for the synthesis ofprimary secondary and bis-N-acylsulfonamides using metalhydrogen sulfate catalystsrdquo Tetrahedron vol 65 no 36 pp7696ndash7705 2009

[27] A R Massah H Adibi R Khodarahmi et al ldquoSynthesisin vitro antibacterial and carbonic anhydrase II inhibitoryactivities of N-acylsulfonamides using silica sulfuric acid asan efficient catalyst under both solvent-free and heterogeneousconditionsrdquo Bioorganic andMedicinal Chemistry vol 16 no 10pp 5465ndash5472 2008

[28] A R Massah M Dabagh S Shahidi H J Naghash AR Momeni and H Aliyan ldquoP

2O5SiO2as an efficient and

recyclable catalyst for N-acylation of sulfonamides under het-erogeneous and solvent-free conditionsrdquo Journal of the IranianChemical Society vol 6 no 2 pp 405ndash411 2009

[29] P Pushpaletha and M Lalithambika ldquoModified attapulgite anefficient solid acid catalyst for acetylation of alcohols usingacetic acidrdquo Applied Clay Science vol 51 no 4 pp 424ndash4302011

[30] L Osiglio G Romanelli and M Blanco ldquoAlcohol acetylationwith acetic acid using borated zirconia as catalystrdquo Journal ofMolecular Catalysis A vol 316 no 1ndash2 pp 52ndash58 2010

[31] P R Likhar R Arundhathi S Ghosh and M L KantamldquoPolyaniline nanofiber supported FeCl

3 an efficient and

reusable heterogeneous catalyst for the acylation of alcohols andamines with acetic acidrdquo Journal of Molecular Catalysis A vol302 no 1ndash2 pp 142ndash149 2009

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

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CatalystsJournal of

4 ISRN Organic Chemistry

Table 2 ZSM-5-SO3H catalyzed acylation of amines under solvent-free conditions

Entry Amine Acylating agent Products Time min(yield )

1 NH2 C

OO C

ONH C

O5 (91)

2 NH2H

3CO C

OO C

ONH C

OH

3CO 5 (95)

3NH

2

OCH3

CO

O CO

NH CO

OCH35 (92)

4 NH2

H3C C

OO C

ONH C

OH

3C 5 (92)

120 (90)a

5

CH3

NH2

CO

O CO

NH CO

CH3

5 (90)

6

CH3

NH2

H3C C

OO C

O

NH CO

CH3

H3C

5 (82)

7 Cl NH2 C

OO C

ONHCl C

O15 (90)

8Cl

NH2

CO

O CO

NH

Cl

CO

15 (85)

9 NH2

O2N

CO

O CO

NH COO

2N

25 (83)

10 NH2 C

OO C

ONH C

O2 (90)

11 NH2 C

OO C

ONH C

O3 (93)

12 NH

CO

O CO

N CO

30 (90)

13 NH2 C

O

O CO

CH3

H3C NH C

OCH

3 2 (88)

14 NH2

H3CO C

O

O CO

CH3

H3C NH C

OCH

3H3CO 2 (92)

15 NH2

OCH3

CO

O CO

CH3

H3C NH C

OCH

3

OCH32 (91)

ISRN Organic Chemistry 5

Table 2 Continued

Entry Amine Acylating agent Products Time min(yield )

16 NH2H

3C C

O

O CO

CH3H

3C NH C

OCH

3H3C 2 (91)

17

CH3

NH2

CO

O CO

CH3

H3C NH C

OCH

3

CH3

2 (88)

18 NH CO

O CO

CH3

H3C N C

O

2CH

3 10 (78)

20 NH2 CO

O CO

CH3

H3C NH C

OCH

3 2 (86)

21 NH2

CO

Cl CO

NH 2 (90)

22 NH2H

3C Cl

CO

NH CO

H3C 2 (92)

23 NH2

CH3

ClCO

NH CO

CH3

2 (88)

24 NH2 ClC

O

NH CO

2 (90)

25 NH2 ClC

O

NH CO

2 (94)

26 NH2

H3C C

O

O CO

H3C(CH

2)3

(CH2)3CH

3

NH CO

H3C (CH

2)3CH

35 (80)

27 NH2

H3C C

O

O CO

(CH3)2HC CH(CH

3)2

NH CO

H3C CH(CH

3)2

5 (70)

28 NH2 C

O

O CO

H3C CH

3

NH CO

CH3

2 (88)

29 H3C SO

2NH

2 CO

O CO

H3C CH

3C

O

H3C CH

3SO

2NH 5 (92)

30 H3C SO

2NH

2 CO

O CO

H3C(CH

2)3 (CH

2)3CH

3

C

O

H3C (CH

2)3CH

3SO

2NH 15 (80)

a20mmol scale

(400MHz CDCl3) 120575 (ppm) 093 (t 3H 119869 = 72Hz) 149ndash

132 (m 4H) 176 (quint 2H 119869 = 68Hz) 431 (t 2H 119869 =68Hz) 741-751 (m 3H) 806 (d 2H 119869 = 76Hz) 13C NMR(100MHz CDCl

3) 120575 (ppm) 140 224 282 284 535 651

1283 1295 1305 1328 1667

n-Hexyl benzoate (Table 3 entry 3) FT-IR (KBr cmminus1)3066 2956 2931 2860 1721 1602 1453 1274 1111 711 1HNMR (400MHz CDCl

3) 120575 (ppm) 094 (t 3H 119869 = 72Hz)

151ndash130 (m 6H) 180 (quint 2H 119869 = 68Hz) 435 (t 2H 119869 =68Hz) 746ndash758 (m 3H) 808 (d 2H 119869 = 72Hz) 13CNMR

6 ISRN Organic Chemistry

Table 3 ZSM-5-SO3H catalyzed acylation of alcohols and phenols under solvent-free conditions

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

1 OH CO

O CO

CO

H3C(CH

2)3O 10 (80)

2 OH2 C

OO C

OCO

H3C(CH

2)4O 15 (81)

3 OH3 C

OO C

OCO

H3C(CH

2)5O 15 (83)

4OH C

OO C

OO C

O25 (70)

5 7OH C

OO C

OCO

H3C(CH

2)9O

10 (90)15 (89)a

6 CH2OH C

OO C

OCO

CH2O 10 (89)

7 OH3 C

O

O CO

H3C CH

3

CO

CH3

H3C(CH

2)5O 10 (88)

8 OH5 C

O

O CO

H3C CH

3CO

CH3

H3C(CH

2)7O 5 (95)

9 OH7 C

O

O CO

H3C CH

3CO

CH3

H3C(CH

2)9O 3 (95)

10 OH5 C

O

ClH3C C

OCH

3H

3C(CH

2)7O 5 (93)

11 OH7 ClC

O

H3C C

OCH

3H

3C(CH

2)9O 5 (95)

12 CH2OH

ClCO

H3C C

OCH

3CH

2O 5 (95)

13 OH CO

O CO

H3C CH

3

O CO

CH3

5 (96)

14 OH CO

O CO

O CO

5 (75)

15 OH CO

O CO

H3C(CH

2)3

(CH2)3CH

3

O CO

(CH2)3CH

35 (81)

16 OH7 OHC

OCO

H3C(CH

2)9O 3 (88)

17 OH5 OHC

OCO

H3C(CH

2)7O 4 (85)

18 OH4 OHC

OCO

H3C(CH

2)6O

4 (80)6 (75)a

ISRN Organic Chemistry 7

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

19 OH3 OHC

OCO

H3C(CH

2)6O 5 (75)

20 OH2 OHC

OCO

H3C(CH

2)4O 5 (68)

21 OH OHCO

CO

H3C(CH

2)3O 5 (61)

22 OH7 OHC

OMe C

OMeH

3C(CH

2)9O 2 (75)

23 OH5 OHMe C

OMeC

OH

3C(CH

2)7O 3 (69)

24 OH3 OHMe C

OMeC

OH

3C(CH

2)5O 3 (61)

25 OH7 OHCO

H3C C

OCH

3H

3C(CH

2)9O 1 (80)

26 OH5 OHC

O

H3C C

OCH

3H

3C(CH

2)7O 2 (75)

27 OH3 OHC

O

H3C C

OCH

3H

3C(CH

2)5O 2 (60)

28 CH2OH C

O

OHH3C C

OCH

3CH

2O 2 (82)

29 OH7 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)9O 2 (85)

30 OH5 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)7O 2 (80)

31 OHHOOHC

OCH

2C C

OO O C

OCH

2H

2

(CH2)2

5 (84)

32 OH4 OHC

OCH

2O C

OCH

2

(CH2)6H

3C 1 (68)

33 OH5 OHC

OCH

2O C

OCH

2

H3C (CH

2)7

1 (70)

34 OH7 OHC

OCH

2O C

OCH

2

H3C (CH

2)8

1 (74)

35 OH2

OHN

O

HO

O

NO

O

O

OH

3C-(H

2C)

4(CH

2)4-CH

3

5 (33)

8 ISRN Organic Chemistry

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

36 OH3

OHHON

OON

O

O

O

OH

3C-(H

2C)

5(CH

2)5-CH

3

5 (43)

37 OH4 OHHO

O O O O

H3C-(H

2C)

6-O O-(CH

2)6-CH

3

5 (70)

38 OH5 OHHO

O O O O

H3C-(H

2C)

7-O O-(CH

2)7-CH

3

5 (75)

a20mmol scale

(100MHz CDCl3) 1667 1328 1306 1295 1283 651 315

287 257 226 140n-Decyl benzoate (Table 3 entry 5) FT-IR (KBr cmminus1)

3068 2926 2856 1721 1602 1457 1274 1111 711 1H NMR(400MHz CDCl

3) 120575 (ppm) 091 (t 3H 119869 = 72Hz) 152ndash

125 (m 14H) 180 (quint 2H 119869 = 72Hz) 435 (t 2H119869 = 68Hz) 747ndash758 (m 3H) 807 (d 2H 119869 = 72Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 141 227 261 288 293

294 296 319 651 1283 1295 1306 1328 1666n-Hexyl acetate (Table 3 entry 7) FT-IR (KBr cmminus1)

2957 2933 1742 1462 1367 1240 1039 1H NMR (400MHzCDCl

3) 120575 (ppm) 084 (t 3H 119869 = 68Hz) 135ndash120 (m

6H) 156 (quint 2H 119869 = 68Hz) 199 (s 3H) 401 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 139 209

225 256 286 314 646 1712n-Octyl acetate (Table 3 entry 8) FT-IR (KBr cmminus1)

2929 2859 1743 1463 1367 1239 1040 1H NMR (400MHzCDCl

3) 120575 (ppm) 086 (t 3H 119869 = 68Hz) 138ndash121 (m 10H)

160 (m 2H) 203 (s 3H) 404 (t 2H 119869 = 68Hz) 13C NMR(400MHz CDCl

3) 120575 (ppm) 140 209 226 259 286 291

292 318 646 1711n-Decyl acetate (Table 3 entry 9) FT-IR (KBr cmminus1)

2927 2858 1743 1464 1366 1239 1041 1H NMR (400MHzCDCl

3) 120575 (ppm) 087 (t 3H 119869 = 68Hz) 139ndash121 (m

14H) 160 (quint 2H 119869 = 68Hz) 203 (s 3H) 404 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 209

226 259 286 292 293 295 319 646 1711Benzyl acetate (Table 3 entry 12) FT-IR (KBr cmminus1)

3034 2954 1742 1455 1380 1230 1027 747 698 1H NMR(400MHz CDCl

3) 120575 (ppm) 214 (s 3H) 516 (s 2H) 743ndash

735 (m 5H) 13C NMR (100MHz CDCl3) 120575 (ppm) 210

663 769 772 775 1283 1283 1286 1360 1709n-Octyl-4-methylbenzoate (Table 3 entry 23) FT-IR

(KBr cmminus1) 1719 1612 1464 1274 1107 752 1H NMR(400MHz CDCl

3) 120575 (ppm) 092 (t 3H 119869 = 68Hz) 127ndash

142 (m 10H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 68Hz) 726 (d 1H 119869 = 80Hz) 796 (d 1H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 216

227 261 288 292 293 318 649 767 770 774 1279 12901296 1434 1668

n-Hexyl-4-methylbenzoate (Table 3 entry 24) FT-IR(KBr cmminus1) 17193 16126 12742 11069 7539 1H NMR(400MHz CDCl

3) 120575 (ppm) 093 (t 3H 119869 = 72Hz) 133ndash

142 (m 6H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 64Hz) 726 (d 2H 119869 = 80Hz) 796 (d 2H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 140 217

226 257 287 315 650 770 772 1278 12904 1296 14341668

Decyl propanoate (Table 3 entry 29) IR (KBr cmminus1)1740 1464 1186 1083 749 1H NMR (400MHz CDCl

3)

120575 (ppm) 089 (t 3H 119869 = 64Hz) 115 (t 3H 119869 = 76Hz) 122ndash138 (m 14H) 158ndash167 (m 2H) 233 (q 2H 119869 = 76Hz) 407(t 2H 119869 = 68Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm)

92 141 227 259 276 287 293 293 295 319 645 1746Octyl propanoate (Table 3 entry 30) IR (KBr cmminus1)

1740 1464 1186 1083 723 1H NMR (400MHz CDCl3)

120575 (ppm) 086 (t 3H 119869 = 64Hz) 112 (t 3H 119869 = 76Hz)122ndash138 (m 10H) 159 (quint 2H 119869 = 72Hz) 230 (q 2H119869 = 76Hz) 404 (t 2H 119869 = 68Hz) 13C NMR (100MHzCDCl

3) 120575 (ppm) 91 140 226 259 276 286 292 292 318

644 1745Ethane-12-diylbis(2-phenylacetate) (Table 3 entry 31) IR

(KBr cmminus1) 1738 1454 1245 1139 726 1H NMR (400MHzCDCl

3) 120575 (ppm) 364 (s 4H) 431ndash436 (m 4H) 728ndash740

(m 10H) 13C NMR (100MHz CDCl3) 120575 (ppm) 411 624

1272 1286 1293 1338 1713n-Heptyl phenylacetate (Table 3 entry 32) IR (KBr

cmminus1) 1737 1456 1251 1155 721 1HNMR (400MHz CDCl3)

120575 (ppm) 095 (t 3H 119869 = 64Hz) 126ndash141 (m 8H) 161ndash172(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash728 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 226 258

286 289 318 415 650 768 772 775 1270 1286 12931343 1717

n-Octyl phenylacetate (Table 3 entry 33) IR (KBr cmminus1)1737 1456 1252 1154 7212 1H NMR (400MHz CDCl

3)

120575 (ppm) 095 (t 3H 119869 = 68Hz) 124ndash141 (m 10H) 162ndash171(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 227 259

286 292 318 415 650 768 771 774 1270 1286 12931343

ISRN Organic Chemistry 9

n-Decyl phenylacetate (Table 3 entry 34) IR (KBr cmminus1)1738 1456 1251 1155 721 1H NMR (400MHz CDCl

3)

120575 (ppm) 093 (t 3H 119869 = 64Hz) 127ndash138 (m 14H) 161ndash168(m 2H) 366 (s 2H) 412 (t 2H 119869 = 68Hz) 739ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 142 227 259

286 292 293 295 319 415 651 768 771 774 1270 12861293 1343

Dipentylpyridine-26-dicarboxylate (Table 3 entry 35)IR (KBr cmminus1) 1741 1465 12440 1149 759 1H NMR(400MHz CDCl

3) 120575 (ppm) 094 (t 6H 119869 = 80Hz) 136ndash

150 (m 8H) 185 (quint 4H 119869 = 68Hz) 443 (t 4H 119869 =68Hz) 802 (t 1H 119869 = 76Hz) 828 (d 2H 119869 = 80Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 224 281 283 664

767 771 773 774 1277 1381 1487 1647Dihexylpyridine-26-dicarboxylate (Table 3 entry 36) IR

(KBr cmminus1) 1722 1241 1144 753 1H NMR (400MHzCDCl

3) 120575 (ppm) 082ndash093 (m 6H) 181 (quint 4H 119869 =

72Hz) 122ndash138 (m 8H) 138-148 (m 4H) 439 (t 4H119869 = 72Hz) 799 (t 1H 119869 = 80Hz) 824 (d 2H 119869 = 76Hz)

Diheptyl glutarate (Table 3 entry 37) IR (KBr cmminus1)1738 1465 1148 1065 725 1H NMR (400MHz CDCl

3)

120575 (ppm) 088 (t 6H 119869 = 68Hz) 122ndash138 (m 16H) 160(quint 4H 119869 = 68Hz) 195 (quint 4H 119869 = 72Hz) 237 (t4H 119869 = 72Hz) 406 (t 4H 119869 = 68Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 140 202 226 259 286 289 317 334

646 1731Dioctyl glutarate (Table 3 entry 38) IR (KBr cmminus1) 1737

1465 1064 722 1H NMR (400MHz CDCl3) 120575 (ppm) 090

(t 6H 119869 = 64Hz) 124ndash140 (m 20H) 159ndash168 (m 4H)192ndash202 (m 4H) 236ndash248 (m 4H) 408 (t 4H 119869 =56Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 141 199 202

226 259 286 292 292 318 330 332 334 647 647 17301731

3 Results and Discussion

As a starting point for this work the reaction was optimizedin order to find the best conditions especially in agree-ment with green chemistry (Table 1) To find the optimumconditions for acylation of amines and sulfonamides withcarboxylic acid anhydrides and chlorides several sets of reac-tion conditions were examined (Table 1 entries 1ndash5) Thusunder the best conditions amines (2mmol) were acylated atroom temperature almost quantitatively with carboxylic acidanhydrides or chlorides (2ndash4mmol) in the presence of 0005ndash001 g of ZSM-5-SO

3H without use of any solvents (Table 1

entries 1ndash4) Acylation of sulfonamides (1mmol) occurredonly with aliphatic anhydrides (15mmol) in the presenceof 001 g of catalyst at room temperature under solvent-freeconditions (Table 1 entry 5)

Then the reactionwas exploredwith a variety of aromaticand aliphatic amines to evaluate the scope and limitations ofthis method (Table 2) The results showed that the differentaromatic amines containing various electron-donating and -withdrawing groups as well as aliphatic amines reacted withcarboxylic acid chlorides or anhydrides within 5ndash30minutesto produce the corresponding amides in 70ndash95 yield

Benzoic anhydride and benzoyl chloridewas used as aromaticacylating agents Also acylation of amines were examinedusing different aliphatic acylating agents including aceticpentanoic and isobutanoic anhydridesThe excellent activityof ZSM-5-SO

3Hwas demonstrated by the good to high yields

obtained for anilines having electron-withdrawing groupssuch as Cl and NO

2(Table 2 entries 7ndash9) However the

best yields were obtained with substrates bearing electron-donating groups such as methoxy especially in the para-position (Table 2 entries 2 and 14) Also very good resultswere obtained when secondary amines were acylated in thepresence of ZSM-5-SO

3H and the corresponding amides

were obtained in 78ndash90 yields in 10ndash30 minutes at roomtemperature under solvent-free conditions (Table 2 entries 12and 18) Finally this method was used for the acylation of 4-methylbenzenesulfonamide as a weak nucleophile with aceticand pentanoic anhydrides Interestingly the corresponding119873-acyl sulfonamides were obtained in 80 and 92 yieldsafter 5 and 15 minutes in high purity (Table 2 entries 29 and30)

To demonstrate the versatility of this protocol the acyla-tion of alcohols andphenolswas investigated using carboxylicacids carboxylic acid anhydrides and chlorides as acylatingagents At first several sets of reaction conditions wereexamined to find the best conditions for acylation of alcoholsIn the optimum conditions alcohols and phenols (1mmol)were acylated at room temperature with acetic anhydridesor chlorides (2mmol) in the presence of 001 g of ZSM-5-SO3H under the solvent-free conditions (Table 1 entry 6)

Acylation with benzoic anhydride was done at 80∘C using005 g of catalyst (Table 1 entry 7) When carboxylic acidswere used as acylating agents the reactions were done at 80ndash120∘C (Table 1 entries 8ndash10)

Using a simple experimental procedure the ZSM-5-SO3H catalyzed acylation of benzylic primary and second-

ary alcohols proceeded efficiently using carboxylic acidanhydrides and chlorides (Table 3 entries 1ndash15) Differentcarboxylic acid anhydrides and chlorides such as benzoicanhydride acetic anhydride pentanoic anhydride and acetylchloride were used as acylating agent and the correspondingesters were obtained in high isolated yields and purityafter short reaction times under the solvent-free conditionsPrimary alcohols were acylated faster than secondary ones(Table 3 entries 4) and sterically hindered alcohols such astert-butyl alcohol remained unchanged It was interesting tonote that phenols were also satisfactorily acylated generatingthe corresponding esters in 75ndash95 yields (Table 3 entries13ndash15)

In order to generalize the catalytic efficiency of ZSM-5-SO3H for direct acylating with carboxylic acids the acy-

lation of alcohols was tried with different carboxylic acid(Table 3 entries 16ndash38) while most literature methods fordirect acylation of alcohols employ only acetic acid [29ndash31] Acylation with acetic propanoic phenyl acetic benzoicacid and 4-methylbenzoic acid resulted in good yield ofthe esters under the solvent-free conditions Also pleasingresults were obtained when acylation of alcohols was donewith dicarboxylic acids such as glutaric acid and pyridine-16-dicarboxylic acid and the corresponding diester was

10 ISRN Organic Chemistry

CH3

CH3

CH3

CH3

NH2

ZSM-5-SO3H

Ac2O (2 eq)

OH

+

O

+

NHO O

1000

CH3

NH2

ZSM-5-SO3H

H3C

Ac2O (2 eq)

NH

+ +

O

0 100

HO O

O

CH3

CH3

ZSM-5-SO3H

Ac2O (2 eq)

OH

OH+

O

+7

7

7 7

7

7O

O

20 80

O

CH3

ZSM-5-SO3H

H3C

NO2

NO2

Ac2O (1 eq)

OH OH

+

O

+

O O

O

80 20

CH3

CH3

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH

OH+

O

+ O

O

0 100

O

CH3

CH3

NH2

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH+

HN

+ O

O

0 100

O

rt 5 min

rt 3 min

rt 2 min

rt 2 min

Scheme 3

obtained in high purity in absence of solvent (Table 3 entries35ndash38) It is noteworthy that in contrast to most reportedmethods that need excess of acetic acid in this methodacylation of alcohols was carried out using only 12ndash20 eqof carboxylic acid Also acylation of ethylene glycol as adiol was carried out with phenylacetic acid under solvent-free conditions and the corresponding ester was obtainedin 84 after 5 minutes It should be mentioned that several

efforts to use this method for direct acylation of amines forthe synthesis of amides were not successful

The importance of selectivity in organic chemistryencouraged us to consider the selectivity of acylation ofdifferent alcohols and amines Several reactions were car-ried out using carboxylic acid anhydrides and chlorides asacylating agents and surprisingly the excellent selectivitywas found For example aromatic amines such as 4-methyl

ISRN Organic Chemistry 11

aniline can be converted into the amide in the presence ofphenol On the other hand aromatic amines were acylatedselectively in the presence of aliphatic alcohol Furthermorethe reactions of alcohols with acylating agent were so fastin comparison to those of the phenol that the selectiveacylation of aliphatic alcohols in the presence of phenolsappeared to be a distinct possibility The result showedthat selective acylation of phenols with or without electron-donating group in the presence of phenols with electron-withdrawing group is possible with this method As wellas carboxylic acid anhydrides and chlorides the excellentselectivity was observed when carboxylic acids were usedas acylating agent Acylation of alcohols was carried outselectively in the presence of phenols Also acylation ofalcohols was done in the presence of amines selectivelywhile as mentioned above this selectivity is reversed whencarboxylic acid anhydrides were used as acylating agent(Scheme 3)

To show another advantage of the present acylationmethod and the importance of scale-up ability for laboratoryand industrial purposes a few amines and phenols wereacylated in large scale successfully without considerable lim-itation For example acylation of 4-methyl aniline (Table 2entry 4) 1-decanol with benzoic anhydride (Table 3 entry5) and 1-heptanol with benzoic acid (Table 3 entry 18) wascarried out in 20mmol scales as well as the 1mmol ones Theonly difference is the reaction time Reaction in large scaleneeds more time that is because of the difficulty in stirringthe reaction mixture under solvent-free conditions

Finally we were interested to study the reusability ofthe catalysts due to economical and environmental aspectsFor this purpose the reaction of 1-heptanol with benzoicanhydride and benzoic acid was chosen as model reactionsAt the end of each run the catalyst was recovered fromthe reaction mixture by addition of dichloromethane simplefiltration and drying at 100∘C and then reused The recycledZSM-5-SO

3H was used for further runs and its activity did

not show any significant decrease even after four runs

4 Conclusion

In conclusion we have described a highly efficient and che-moselective synthetic route for the acylation of sulfonamidesamines alcohols and phenols with carboxylic acids car-boxylic acid chlorides and anhydrides in the presence ofZSM-5-SO

3H under solvent-free conditions This method

has advantages in terms of low cost and nontoxic nature of thecatalyst high yield and purity of the products short reactiontimes operational simplicity and easy workup In additionrecyclability of this protocol is attractive and useful Directacylation of alcohols with different carboxylic acids is anotheradvantage of this protocol

Acknowledgment

The support from Islamic Azad University Shahreza Branch(IAUSH) Research Council is gratefully acknowledged

References

[1] T W Greene and P G M Wuts Protective Groups in OrganicSynthesis Wiley New York NY USA 3rd edition 1999

[2] W Steglich andGHofle ldquoNN-dimethyl-4-pyridinamine a veryeffective acylation catalystrdquo Angewandte Chemie vol 8 no 12pp 980ndash981 1969

[3] E Vedejs and S T Diver ldquoTributylphosphine a remarkableacylation catalystrdquo Journal of the American Chemical Societyvol 115 no 8 pp 3358ndash3359 1993

[4] E F V Scriven ldquo4-Dialkylaminopyridines super acylation andalkylation catalystsrdquo Chemical Society Reviews vol 12 no 2 pp129ndash161 1983

[5] K Ishihara M Kubota H Kurihara and H Yamamoto ldquoScan-dium trifluoromethanesulfonate as an extremely active Lewisacid catalyst in acylation of alcohols with acid anhydrides andmixed anhydridesrdquo The Journal of Organic Chemistry vol 61no 14 pp 4560ndash4567 1996

[6] R Alleti W S Oh M Perambuduru Z Afrasiabi E Sinn andV P Reddy ldquoGadolinium triflate immobilized in imidazoliumbased ionic liquids a recyclable catalyst and green solvent foracetylation of alcohols and aminesrdquo Green Chemistry vol 7 no4 pp 203ndash206 2005

[7] T N Parac-Vogt K Deleersnyder and K Binnemans ldquoLan-thanide(III) tosylates as new acylation catalystsrdquo EuropeanJournal of Organic Chemistry vol 2005 no 9 pp 1810ndash18152005

[8] K D Surya ldquoRuthenium(III) chloride catalyzed acylation ofalcohols phenols thiols and aminesrdquo Tetrahedron Letters vol45 no 14 pp 2919ndash2922 2004

[9] F M Shirini M A Zolfigol M Abedini and P SalehildquoAl(HSO

4)3catalyzed acetylation and formylation of alcoholsrdquo

Bulletin of the Korean Chemical Society vol 24 no 11 pp 1683ndash1685 2003

[10] A Orita C Tanahashi A Kakuda and J Otera ldquoHighly pow-erful and practical acylation of alcohols with acid anhydridecatalyzed by Bi(OTf)

3rdquo Journal of Organic Chemistry vol 66

no 26 pp 8926ndash8934 2001[11] Y Nakae I Kusaki and T Sato ldquoLithium perchlorate catalyzed

acetylation of alcohols under mild reaction conditionsrdquo Synlettvol 2001 no 10 pp 1584ndash1586 2001

[12] R Ballini G Bosica S Carloni L Ciaralli R Maggi and GSartori ldquoZeolite HSZ-360 as a new reusable catalyst for thedirect acetylation of alcohols and phenols under solventlessconditionsrdquo Tetrahedron Letters vol 39 no 33 pp 6049ndash60521998

[13] B M Choudary V Bhaskar M L Kantam K Koteswara Raoand K V Raghavan ldquoAcylation of alcohols with carboxylicacids via the evolution of compatible acidic sites in montmo-rillonitesrdquo Green Chemistry vol 2 pp 67ndash70 2000

[14] M H Sarvari and H Sharghi ldquoZinc oxide (ZnO) as a newhighly efficient and reusable catalyst for acylation of alcoholsphenols and amines under solvent free conditionsrdquo Tetrahe-dron vol 61 no 46 pp 10903ndash10907 2005

[15] J Izumi I Shiina and T Mukaiyama ldquoAn efficient esterifica-tion reaction between equimolar amounts of free carboxylicacids and alcohols by the combined use of octamethylcyclote-trasiloxane and a catalytic amount of titanium(iv) chloridetris(trifluoromethanesulfonate)rdquo Chemistry Letters vol 2 pp141ndash142 1995

[16] R Alleti M Perambuduru S Samantha and V P ReddyldquoGadolinium triflate an efficient and convenient catalyst for

12 ISRN Organic Chemistry

acetylation of alcohols and aminesrdquo Journal of Molecular Catal-ysis A vol 226 no 1 pp 57ndash59 2005

[17] F Shirini K RaMoghadam and T Naghdi ldquo13-Dichloro-55-dimethylhydantoin an efficient catalyst for the solvent freesynthesis of 18-dioxo-octahydro-xanthenesrdquo Iranian Journal ofCatalysis vol 2 pp 55ndash59 2012

[18] A DyerAn Introduction to Zeolite Molecular Sieves JohnWileyamp Sons Inc New York NY USA 1988

[19] A R Massah R J Kalbasi and M Azadi ldquoHighly selectiveoxidation of alcohols using MnO

2TiO2-ZrO2as a novel het-

erogeneous catalystrdquo Comptes Rendus Chimie vol 15 no 5 pp428ndash436 2012

[20] A R Massah R J Kalbasi and M Toghyani ldquoSulfonatedpolystyrenemontmorillonite nanocomposite as a new andefficient catalyst for the solvent-free Mannich reactionrdquo IranianJournal of Catalysis vol 2 no 1 pp 41ndash49 2012

[21] R J Kalbasi M Ghiaci and A R Massah ldquoHighly selectivevapor phase nitration of toluene to 4-nitro toluene usingmodified and unmodified H

3PO4ZSM-5rdquo Applied Catalysis A

vol 353 no 1 pp 1ndash8 2009[22] R J Kalbasi A Abbaspourrad A R Massah and F Zamani

ldquoHighly selective vapor-phase acylation of veratrole overH3PO4TiO2-ZrO2 using ethyl acetate as a green and efficient

acylating agentrdquo Chinese Journal of Chemistry vol 28 no 2 pp273ndash284 2010

[23] A R Massah R J Kalbasi and A Shafiei ldquoZSM-5-SO3H as

a novel efficient and reusable catalyst for the chemoselectivesynthesis and deprotection of 11-diacetates under eco-friendlyconditionsrdquoMonatshefte fur Chemie vol 143 no 4 pp 643ndash6522012

[24] A R Massah R J Kalbasi and N Samah ldquoHighly selectivesynthesis of 120573-amino carbonyl compounds over ZSM-5-SO

3H

under solvent-free conditionsrdquo Bulletin of the Korean ChemicalSociety vol 32 no 5 pp 1703ndash1708 2011

[25] A R Massah F Kazemi D Azadi et al ldquoA mild and chemos-elective solvent-free method for the synthesis of N-aryl and N-alkysulfonamidesrdquo Letters inOrganic Chemistry vol 3 no 3 pp235ndash241 2006

[26] A R Massah B Asadi M Hoseinpour A Molseghi R JKalbasi and H Javaherian Naghash ldquoA novel and efficientsolvent-free and heterogeneous method for the synthesis ofprimary secondary and bis-N-acylsulfonamides using metalhydrogen sulfate catalystsrdquo Tetrahedron vol 65 no 36 pp7696ndash7705 2009

[27] A R Massah H Adibi R Khodarahmi et al ldquoSynthesisin vitro antibacterial and carbonic anhydrase II inhibitoryactivities of N-acylsulfonamides using silica sulfuric acid asan efficient catalyst under both solvent-free and heterogeneousconditionsrdquo Bioorganic andMedicinal Chemistry vol 16 no 10pp 5465ndash5472 2008

[28] A R Massah M Dabagh S Shahidi H J Naghash AR Momeni and H Aliyan ldquoP

2O5SiO2as an efficient and

recyclable catalyst for N-acylation of sulfonamides under het-erogeneous and solvent-free conditionsrdquo Journal of the IranianChemical Society vol 6 no 2 pp 405ndash411 2009

[29] P Pushpaletha and M Lalithambika ldquoModified attapulgite anefficient solid acid catalyst for acetylation of alcohols usingacetic acidrdquo Applied Clay Science vol 51 no 4 pp 424ndash4302011

[30] L Osiglio G Romanelli and M Blanco ldquoAlcohol acetylationwith acetic acid using borated zirconia as catalystrdquo Journal ofMolecular Catalysis A vol 316 no 1ndash2 pp 52ndash58 2010

[31] P R Likhar R Arundhathi S Ghosh and M L KantamldquoPolyaniline nanofiber supported FeCl

3 an efficient and

reusable heterogeneous catalyst for the acylation of alcohols andamines with acetic acidrdquo Journal of Molecular Catalysis A vol302 no 1ndash2 pp 142ndash149 2009

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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International Journal ofPhotoenergy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Carbohydrate Chemistry

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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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Medicinal ChemistryInternational Journal of

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Chromatography Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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CatalystsJournal of

ISRN Organic Chemistry 5

Table 2 Continued

Entry Amine Acylating agent Products Time min(yield )

16 NH2H

3C C

O

O CO

CH3H

3C NH C

OCH

3H3C 2 (91)

17

CH3

NH2

CO

O CO

CH3

H3C NH C

OCH

3

CH3

2 (88)

18 NH CO

O CO

CH3

H3C N C

O

2CH

3 10 (78)

20 NH2 CO

O CO

CH3

H3C NH C

OCH

3 2 (86)

21 NH2

CO

Cl CO

NH 2 (90)

22 NH2H

3C Cl

CO

NH CO

H3C 2 (92)

23 NH2

CH3

ClCO

NH CO

CH3

2 (88)

24 NH2 ClC

O

NH CO

2 (90)

25 NH2 ClC

O

NH CO

2 (94)

26 NH2

H3C C

O

O CO

H3C(CH

2)3

(CH2)3CH

3

NH CO

H3C (CH

2)3CH

35 (80)

27 NH2

H3C C

O

O CO

(CH3)2HC CH(CH

3)2

NH CO

H3C CH(CH

3)2

5 (70)

28 NH2 C

O

O CO

H3C CH

3

NH CO

CH3

2 (88)

29 H3C SO

2NH

2 CO

O CO

H3C CH

3C

O

H3C CH

3SO

2NH 5 (92)

30 H3C SO

2NH

2 CO

O CO

H3C(CH

2)3 (CH

2)3CH

3

C

O

H3C (CH

2)3CH

3SO

2NH 15 (80)

a20mmol scale

(400MHz CDCl3) 120575 (ppm) 093 (t 3H 119869 = 72Hz) 149ndash

132 (m 4H) 176 (quint 2H 119869 = 68Hz) 431 (t 2H 119869 =68Hz) 741-751 (m 3H) 806 (d 2H 119869 = 76Hz) 13C NMR(100MHz CDCl

3) 120575 (ppm) 140 224 282 284 535 651

1283 1295 1305 1328 1667

n-Hexyl benzoate (Table 3 entry 3) FT-IR (KBr cmminus1)3066 2956 2931 2860 1721 1602 1453 1274 1111 711 1HNMR (400MHz CDCl

3) 120575 (ppm) 094 (t 3H 119869 = 72Hz)

151ndash130 (m 6H) 180 (quint 2H 119869 = 68Hz) 435 (t 2H 119869 =68Hz) 746ndash758 (m 3H) 808 (d 2H 119869 = 72Hz) 13CNMR

6 ISRN Organic Chemistry

Table 3 ZSM-5-SO3H catalyzed acylation of alcohols and phenols under solvent-free conditions

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

1 OH CO

O CO

CO

H3C(CH

2)3O 10 (80)

2 OH2 C

OO C

OCO

H3C(CH

2)4O 15 (81)

3 OH3 C

OO C

OCO

H3C(CH

2)5O 15 (83)

4OH C

OO C

OO C

O25 (70)

5 7OH C

OO C

OCO

H3C(CH

2)9O

10 (90)15 (89)a

6 CH2OH C

OO C

OCO

CH2O 10 (89)

7 OH3 C

O

O CO

H3C CH

3

CO

CH3

H3C(CH

2)5O 10 (88)

8 OH5 C

O

O CO

H3C CH

3CO

CH3

H3C(CH

2)7O 5 (95)

9 OH7 C

O

O CO

H3C CH

3CO

CH3

H3C(CH

2)9O 3 (95)

10 OH5 C

O

ClH3C C

OCH

3H

3C(CH

2)7O 5 (93)

11 OH7 ClC

O

H3C C

OCH

3H

3C(CH

2)9O 5 (95)

12 CH2OH

ClCO

H3C C

OCH

3CH

2O 5 (95)

13 OH CO

O CO

H3C CH

3

O CO

CH3

5 (96)

14 OH CO

O CO

O CO

5 (75)

15 OH CO

O CO

H3C(CH

2)3

(CH2)3CH

3

O CO

(CH2)3CH

35 (81)

16 OH7 OHC

OCO

H3C(CH

2)9O 3 (88)

17 OH5 OHC

OCO

H3C(CH

2)7O 4 (85)

18 OH4 OHC

OCO

H3C(CH

2)6O

4 (80)6 (75)a

ISRN Organic Chemistry 7

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

19 OH3 OHC

OCO

H3C(CH

2)6O 5 (75)

20 OH2 OHC

OCO

H3C(CH

2)4O 5 (68)

21 OH OHCO

CO

H3C(CH

2)3O 5 (61)

22 OH7 OHC

OMe C

OMeH

3C(CH

2)9O 2 (75)

23 OH5 OHMe C

OMeC

OH

3C(CH

2)7O 3 (69)

24 OH3 OHMe C

OMeC

OH

3C(CH

2)5O 3 (61)

25 OH7 OHCO

H3C C

OCH

3H

3C(CH

2)9O 1 (80)

26 OH5 OHC

O

H3C C

OCH

3H

3C(CH

2)7O 2 (75)

27 OH3 OHC

O

H3C C

OCH

3H

3C(CH

2)5O 2 (60)

28 CH2OH C

O

OHH3C C

OCH

3CH

2O 2 (82)

29 OH7 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)9O 2 (85)

30 OH5 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)7O 2 (80)

31 OHHOOHC

OCH

2C C

OO O C

OCH

2H

2

(CH2)2

5 (84)

32 OH4 OHC

OCH

2O C

OCH

2

(CH2)6H

3C 1 (68)

33 OH5 OHC

OCH

2O C

OCH

2

H3C (CH

2)7

1 (70)

34 OH7 OHC

OCH

2O C

OCH

2

H3C (CH

2)8

1 (74)

35 OH2

OHN

O

HO

O

NO

O

O

OH

3C-(H

2C)

4(CH

2)4-CH

3

5 (33)

8 ISRN Organic Chemistry

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

36 OH3

OHHON

OON

O

O

O

OH

3C-(H

2C)

5(CH

2)5-CH

3

5 (43)

37 OH4 OHHO

O O O O

H3C-(H

2C)

6-O O-(CH

2)6-CH

3

5 (70)

38 OH5 OHHO

O O O O

H3C-(H

2C)

7-O O-(CH

2)7-CH

3

5 (75)

a20mmol scale

(100MHz CDCl3) 1667 1328 1306 1295 1283 651 315

287 257 226 140n-Decyl benzoate (Table 3 entry 5) FT-IR (KBr cmminus1)

3068 2926 2856 1721 1602 1457 1274 1111 711 1H NMR(400MHz CDCl

3) 120575 (ppm) 091 (t 3H 119869 = 72Hz) 152ndash

125 (m 14H) 180 (quint 2H 119869 = 72Hz) 435 (t 2H119869 = 68Hz) 747ndash758 (m 3H) 807 (d 2H 119869 = 72Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 141 227 261 288 293

294 296 319 651 1283 1295 1306 1328 1666n-Hexyl acetate (Table 3 entry 7) FT-IR (KBr cmminus1)

2957 2933 1742 1462 1367 1240 1039 1H NMR (400MHzCDCl

3) 120575 (ppm) 084 (t 3H 119869 = 68Hz) 135ndash120 (m

6H) 156 (quint 2H 119869 = 68Hz) 199 (s 3H) 401 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 139 209

225 256 286 314 646 1712n-Octyl acetate (Table 3 entry 8) FT-IR (KBr cmminus1)

2929 2859 1743 1463 1367 1239 1040 1H NMR (400MHzCDCl

3) 120575 (ppm) 086 (t 3H 119869 = 68Hz) 138ndash121 (m 10H)

160 (m 2H) 203 (s 3H) 404 (t 2H 119869 = 68Hz) 13C NMR(400MHz CDCl

3) 120575 (ppm) 140 209 226 259 286 291

292 318 646 1711n-Decyl acetate (Table 3 entry 9) FT-IR (KBr cmminus1)

2927 2858 1743 1464 1366 1239 1041 1H NMR (400MHzCDCl

3) 120575 (ppm) 087 (t 3H 119869 = 68Hz) 139ndash121 (m

14H) 160 (quint 2H 119869 = 68Hz) 203 (s 3H) 404 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 209

226 259 286 292 293 295 319 646 1711Benzyl acetate (Table 3 entry 12) FT-IR (KBr cmminus1)

3034 2954 1742 1455 1380 1230 1027 747 698 1H NMR(400MHz CDCl

3) 120575 (ppm) 214 (s 3H) 516 (s 2H) 743ndash

735 (m 5H) 13C NMR (100MHz CDCl3) 120575 (ppm) 210

663 769 772 775 1283 1283 1286 1360 1709n-Octyl-4-methylbenzoate (Table 3 entry 23) FT-IR

(KBr cmminus1) 1719 1612 1464 1274 1107 752 1H NMR(400MHz CDCl

3) 120575 (ppm) 092 (t 3H 119869 = 68Hz) 127ndash

142 (m 10H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 68Hz) 726 (d 1H 119869 = 80Hz) 796 (d 1H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 216

227 261 288 292 293 318 649 767 770 774 1279 12901296 1434 1668

n-Hexyl-4-methylbenzoate (Table 3 entry 24) FT-IR(KBr cmminus1) 17193 16126 12742 11069 7539 1H NMR(400MHz CDCl

3) 120575 (ppm) 093 (t 3H 119869 = 72Hz) 133ndash

142 (m 6H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 64Hz) 726 (d 2H 119869 = 80Hz) 796 (d 2H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 140 217

226 257 287 315 650 770 772 1278 12904 1296 14341668

Decyl propanoate (Table 3 entry 29) IR (KBr cmminus1)1740 1464 1186 1083 749 1H NMR (400MHz CDCl

3)

120575 (ppm) 089 (t 3H 119869 = 64Hz) 115 (t 3H 119869 = 76Hz) 122ndash138 (m 14H) 158ndash167 (m 2H) 233 (q 2H 119869 = 76Hz) 407(t 2H 119869 = 68Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm)

92 141 227 259 276 287 293 293 295 319 645 1746Octyl propanoate (Table 3 entry 30) IR (KBr cmminus1)

1740 1464 1186 1083 723 1H NMR (400MHz CDCl3)

120575 (ppm) 086 (t 3H 119869 = 64Hz) 112 (t 3H 119869 = 76Hz)122ndash138 (m 10H) 159 (quint 2H 119869 = 72Hz) 230 (q 2H119869 = 76Hz) 404 (t 2H 119869 = 68Hz) 13C NMR (100MHzCDCl

3) 120575 (ppm) 91 140 226 259 276 286 292 292 318

644 1745Ethane-12-diylbis(2-phenylacetate) (Table 3 entry 31) IR

(KBr cmminus1) 1738 1454 1245 1139 726 1H NMR (400MHzCDCl

3) 120575 (ppm) 364 (s 4H) 431ndash436 (m 4H) 728ndash740

(m 10H) 13C NMR (100MHz CDCl3) 120575 (ppm) 411 624

1272 1286 1293 1338 1713n-Heptyl phenylacetate (Table 3 entry 32) IR (KBr

cmminus1) 1737 1456 1251 1155 721 1HNMR (400MHz CDCl3)

120575 (ppm) 095 (t 3H 119869 = 64Hz) 126ndash141 (m 8H) 161ndash172(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash728 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 226 258

286 289 318 415 650 768 772 775 1270 1286 12931343 1717

n-Octyl phenylacetate (Table 3 entry 33) IR (KBr cmminus1)1737 1456 1252 1154 7212 1H NMR (400MHz CDCl

3)

120575 (ppm) 095 (t 3H 119869 = 68Hz) 124ndash141 (m 10H) 162ndash171(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 227 259

286 292 318 415 650 768 771 774 1270 1286 12931343

ISRN Organic Chemistry 9

n-Decyl phenylacetate (Table 3 entry 34) IR (KBr cmminus1)1738 1456 1251 1155 721 1H NMR (400MHz CDCl

3)

120575 (ppm) 093 (t 3H 119869 = 64Hz) 127ndash138 (m 14H) 161ndash168(m 2H) 366 (s 2H) 412 (t 2H 119869 = 68Hz) 739ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 142 227 259

286 292 293 295 319 415 651 768 771 774 1270 12861293 1343

Dipentylpyridine-26-dicarboxylate (Table 3 entry 35)IR (KBr cmminus1) 1741 1465 12440 1149 759 1H NMR(400MHz CDCl

3) 120575 (ppm) 094 (t 6H 119869 = 80Hz) 136ndash

150 (m 8H) 185 (quint 4H 119869 = 68Hz) 443 (t 4H 119869 =68Hz) 802 (t 1H 119869 = 76Hz) 828 (d 2H 119869 = 80Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 224 281 283 664

767 771 773 774 1277 1381 1487 1647Dihexylpyridine-26-dicarboxylate (Table 3 entry 36) IR

(KBr cmminus1) 1722 1241 1144 753 1H NMR (400MHzCDCl

3) 120575 (ppm) 082ndash093 (m 6H) 181 (quint 4H 119869 =

72Hz) 122ndash138 (m 8H) 138-148 (m 4H) 439 (t 4H119869 = 72Hz) 799 (t 1H 119869 = 80Hz) 824 (d 2H 119869 = 76Hz)

Diheptyl glutarate (Table 3 entry 37) IR (KBr cmminus1)1738 1465 1148 1065 725 1H NMR (400MHz CDCl

3)

120575 (ppm) 088 (t 6H 119869 = 68Hz) 122ndash138 (m 16H) 160(quint 4H 119869 = 68Hz) 195 (quint 4H 119869 = 72Hz) 237 (t4H 119869 = 72Hz) 406 (t 4H 119869 = 68Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 140 202 226 259 286 289 317 334

646 1731Dioctyl glutarate (Table 3 entry 38) IR (KBr cmminus1) 1737

1465 1064 722 1H NMR (400MHz CDCl3) 120575 (ppm) 090

(t 6H 119869 = 64Hz) 124ndash140 (m 20H) 159ndash168 (m 4H)192ndash202 (m 4H) 236ndash248 (m 4H) 408 (t 4H 119869 =56Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 141 199 202

226 259 286 292 292 318 330 332 334 647 647 17301731

3 Results and Discussion

As a starting point for this work the reaction was optimizedin order to find the best conditions especially in agree-ment with green chemistry (Table 1) To find the optimumconditions for acylation of amines and sulfonamides withcarboxylic acid anhydrides and chlorides several sets of reac-tion conditions were examined (Table 1 entries 1ndash5) Thusunder the best conditions amines (2mmol) were acylated atroom temperature almost quantitatively with carboxylic acidanhydrides or chlorides (2ndash4mmol) in the presence of 0005ndash001 g of ZSM-5-SO

3H without use of any solvents (Table 1

entries 1ndash4) Acylation of sulfonamides (1mmol) occurredonly with aliphatic anhydrides (15mmol) in the presenceof 001 g of catalyst at room temperature under solvent-freeconditions (Table 1 entry 5)

Then the reactionwas exploredwith a variety of aromaticand aliphatic amines to evaluate the scope and limitations ofthis method (Table 2) The results showed that the differentaromatic amines containing various electron-donating and -withdrawing groups as well as aliphatic amines reacted withcarboxylic acid chlorides or anhydrides within 5ndash30minutesto produce the corresponding amides in 70ndash95 yield

Benzoic anhydride and benzoyl chloridewas used as aromaticacylating agents Also acylation of amines were examinedusing different aliphatic acylating agents including aceticpentanoic and isobutanoic anhydridesThe excellent activityof ZSM-5-SO

3Hwas demonstrated by the good to high yields

obtained for anilines having electron-withdrawing groupssuch as Cl and NO

2(Table 2 entries 7ndash9) However the

best yields were obtained with substrates bearing electron-donating groups such as methoxy especially in the para-position (Table 2 entries 2 and 14) Also very good resultswere obtained when secondary amines were acylated in thepresence of ZSM-5-SO

3H and the corresponding amides

were obtained in 78ndash90 yields in 10ndash30 minutes at roomtemperature under solvent-free conditions (Table 2 entries 12and 18) Finally this method was used for the acylation of 4-methylbenzenesulfonamide as a weak nucleophile with aceticand pentanoic anhydrides Interestingly the corresponding119873-acyl sulfonamides were obtained in 80 and 92 yieldsafter 5 and 15 minutes in high purity (Table 2 entries 29 and30)

To demonstrate the versatility of this protocol the acyla-tion of alcohols andphenolswas investigated using carboxylicacids carboxylic acid anhydrides and chlorides as acylatingagents At first several sets of reaction conditions wereexamined to find the best conditions for acylation of alcoholsIn the optimum conditions alcohols and phenols (1mmol)were acylated at room temperature with acetic anhydridesor chlorides (2mmol) in the presence of 001 g of ZSM-5-SO3H under the solvent-free conditions (Table 1 entry 6)

Acylation with benzoic anhydride was done at 80∘C using005 g of catalyst (Table 1 entry 7) When carboxylic acidswere used as acylating agents the reactions were done at 80ndash120∘C (Table 1 entries 8ndash10)

Using a simple experimental procedure the ZSM-5-SO3H catalyzed acylation of benzylic primary and second-

ary alcohols proceeded efficiently using carboxylic acidanhydrides and chlorides (Table 3 entries 1ndash15) Differentcarboxylic acid anhydrides and chlorides such as benzoicanhydride acetic anhydride pentanoic anhydride and acetylchloride were used as acylating agent and the correspondingesters were obtained in high isolated yields and purityafter short reaction times under the solvent-free conditionsPrimary alcohols were acylated faster than secondary ones(Table 3 entries 4) and sterically hindered alcohols such astert-butyl alcohol remained unchanged It was interesting tonote that phenols were also satisfactorily acylated generatingthe corresponding esters in 75ndash95 yields (Table 3 entries13ndash15)

In order to generalize the catalytic efficiency of ZSM-5-SO3H for direct acylating with carboxylic acids the acy-

lation of alcohols was tried with different carboxylic acid(Table 3 entries 16ndash38) while most literature methods fordirect acylation of alcohols employ only acetic acid [29ndash31] Acylation with acetic propanoic phenyl acetic benzoicacid and 4-methylbenzoic acid resulted in good yield ofthe esters under the solvent-free conditions Also pleasingresults were obtained when acylation of alcohols was donewith dicarboxylic acids such as glutaric acid and pyridine-16-dicarboxylic acid and the corresponding diester was

10 ISRN Organic Chemistry

CH3

CH3

CH3

CH3

NH2

ZSM-5-SO3H

Ac2O (2 eq)

OH

+

O

+

NHO O

1000

CH3

NH2

ZSM-5-SO3H

H3C

Ac2O (2 eq)

NH

+ +

O

0 100

HO O

O

CH3

CH3

ZSM-5-SO3H

Ac2O (2 eq)

OH

OH+

O

+7

7

7 7

7

7O

O

20 80

O

CH3

ZSM-5-SO3H

H3C

NO2

NO2

Ac2O (1 eq)

OH OH

+

O

+

O O

O

80 20

CH3

CH3

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH

OH+

O

+ O

O

0 100

O

CH3

CH3

NH2

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH+

HN

+ O

O

0 100

O

rt 5 min

rt 3 min

rt 2 min

rt 2 min

Scheme 3

obtained in high purity in absence of solvent (Table 3 entries35ndash38) It is noteworthy that in contrast to most reportedmethods that need excess of acetic acid in this methodacylation of alcohols was carried out using only 12ndash20 eqof carboxylic acid Also acylation of ethylene glycol as adiol was carried out with phenylacetic acid under solvent-free conditions and the corresponding ester was obtainedin 84 after 5 minutes It should be mentioned that several

efforts to use this method for direct acylation of amines forthe synthesis of amides were not successful

The importance of selectivity in organic chemistryencouraged us to consider the selectivity of acylation ofdifferent alcohols and amines Several reactions were car-ried out using carboxylic acid anhydrides and chlorides asacylating agents and surprisingly the excellent selectivitywas found For example aromatic amines such as 4-methyl

ISRN Organic Chemistry 11

aniline can be converted into the amide in the presence ofphenol On the other hand aromatic amines were acylatedselectively in the presence of aliphatic alcohol Furthermorethe reactions of alcohols with acylating agent were so fastin comparison to those of the phenol that the selectiveacylation of aliphatic alcohols in the presence of phenolsappeared to be a distinct possibility The result showedthat selective acylation of phenols with or without electron-donating group in the presence of phenols with electron-withdrawing group is possible with this method As wellas carboxylic acid anhydrides and chlorides the excellentselectivity was observed when carboxylic acids were usedas acylating agent Acylation of alcohols was carried outselectively in the presence of phenols Also acylation ofalcohols was done in the presence of amines selectivelywhile as mentioned above this selectivity is reversed whencarboxylic acid anhydrides were used as acylating agent(Scheme 3)

To show another advantage of the present acylationmethod and the importance of scale-up ability for laboratoryand industrial purposes a few amines and phenols wereacylated in large scale successfully without considerable lim-itation For example acylation of 4-methyl aniline (Table 2entry 4) 1-decanol with benzoic anhydride (Table 3 entry5) and 1-heptanol with benzoic acid (Table 3 entry 18) wascarried out in 20mmol scales as well as the 1mmol ones Theonly difference is the reaction time Reaction in large scaleneeds more time that is because of the difficulty in stirringthe reaction mixture under solvent-free conditions

Finally we were interested to study the reusability ofthe catalysts due to economical and environmental aspectsFor this purpose the reaction of 1-heptanol with benzoicanhydride and benzoic acid was chosen as model reactionsAt the end of each run the catalyst was recovered fromthe reaction mixture by addition of dichloromethane simplefiltration and drying at 100∘C and then reused The recycledZSM-5-SO

3H was used for further runs and its activity did

not show any significant decrease even after four runs

4 Conclusion

In conclusion we have described a highly efficient and che-moselective synthetic route for the acylation of sulfonamidesamines alcohols and phenols with carboxylic acids car-boxylic acid chlorides and anhydrides in the presence ofZSM-5-SO

3H under solvent-free conditions This method

has advantages in terms of low cost and nontoxic nature of thecatalyst high yield and purity of the products short reactiontimes operational simplicity and easy workup In additionrecyclability of this protocol is attractive and useful Directacylation of alcohols with different carboxylic acids is anotheradvantage of this protocol

Acknowledgment

The support from Islamic Azad University Shahreza Branch(IAUSH) Research Council is gratefully acknowledged

References

[1] T W Greene and P G M Wuts Protective Groups in OrganicSynthesis Wiley New York NY USA 3rd edition 1999

[2] W Steglich andGHofle ldquoNN-dimethyl-4-pyridinamine a veryeffective acylation catalystrdquo Angewandte Chemie vol 8 no 12pp 980ndash981 1969

[3] E Vedejs and S T Diver ldquoTributylphosphine a remarkableacylation catalystrdquo Journal of the American Chemical Societyvol 115 no 8 pp 3358ndash3359 1993

[4] E F V Scriven ldquo4-Dialkylaminopyridines super acylation andalkylation catalystsrdquo Chemical Society Reviews vol 12 no 2 pp129ndash161 1983

[5] K Ishihara M Kubota H Kurihara and H Yamamoto ldquoScan-dium trifluoromethanesulfonate as an extremely active Lewisacid catalyst in acylation of alcohols with acid anhydrides andmixed anhydridesrdquo The Journal of Organic Chemistry vol 61no 14 pp 4560ndash4567 1996

[6] R Alleti W S Oh M Perambuduru Z Afrasiabi E Sinn andV P Reddy ldquoGadolinium triflate immobilized in imidazoliumbased ionic liquids a recyclable catalyst and green solvent foracetylation of alcohols and aminesrdquo Green Chemistry vol 7 no4 pp 203ndash206 2005

[7] T N Parac-Vogt K Deleersnyder and K Binnemans ldquoLan-thanide(III) tosylates as new acylation catalystsrdquo EuropeanJournal of Organic Chemistry vol 2005 no 9 pp 1810ndash18152005

[8] K D Surya ldquoRuthenium(III) chloride catalyzed acylation ofalcohols phenols thiols and aminesrdquo Tetrahedron Letters vol45 no 14 pp 2919ndash2922 2004

[9] F M Shirini M A Zolfigol M Abedini and P SalehildquoAl(HSO

4)3catalyzed acetylation and formylation of alcoholsrdquo

Bulletin of the Korean Chemical Society vol 24 no 11 pp 1683ndash1685 2003

[10] A Orita C Tanahashi A Kakuda and J Otera ldquoHighly pow-erful and practical acylation of alcohols with acid anhydridecatalyzed by Bi(OTf)

3rdquo Journal of Organic Chemistry vol 66

no 26 pp 8926ndash8934 2001[11] Y Nakae I Kusaki and T Sato ldquoLithium perchlorate catalyzed

acetylation of alcohols under mild reaction conditionsrdquo Synlettvol 2001 no 10 pp 1584ndash1586 2001

[12] R Ballini G Bosica S Carloni L Ciaralli R Maggi and GSartori ldquoZeolite HSZ-360 as a new reusable catalyst for thedirect acetylation of alcohols and phenols under solventlessconditionsrdquo Tetrahedron Letters vol 39 no 33 pp 6049ndash60521998

[13] B M Choudary V Bhaskar M L Kantam K Koteswara Raoand K V Raghavan ldquoAcylation of alcohols with carboxylicacids via the evolution of compatible acidic sites in montmo-rillonitesrdquo Green Chemistry vol 2 pp 67ndash70 2000

[14] M H Sarvari and H Sharghi ldquoZinc oxide (ZnO) as a newhighly efficient and reusable catalyst for acylation of alcoholsphenols and amines under solvent free conditionsrdquo Tetrahe-dron vol 61 no 46 pp 10903ndash10907 2005

[15] J Izumi I Shiina and T Mukaiyama ldquoAn efficient esterifica-tion reaction between equimolar amounts of free carboxylicacids and alcohols by the combined use of octamethylcyclote-trasiloxane and a catalytic amount of titanium(iv) chloridetris(trifluoromethanesulfonate)rdquo Chemistry Letters vol 2 pp141ndash142 1995

[16] R Alleti M Perambuduru S Samantha and V P ReddyldquoGadolinium triflate an efficient and convenient catalyst for

12 ISRN Organic Chemistry

acetylation of alcohols and aminesrdquo Journal of Molecular Catal-ysis A vol 226 no 1 pp 57ndash59 2005

[17] F Shirini K RaMoghadam and T Naghdi ldquo13-Dichloro-55-dimethylhydantoin an efficient catalyst for the solvent freesynthesis of 18-dioxo-octahydro-xanthenesrdquo Iranian Journal ofCatalysis vol 2 pp 55ndash59 2012

[18] A DyerAn Introduction to Zeolite Molecular Sieves JohnWileyamp Sons Inc New York NY USA 1988

[19] A R Massah R J Kalbasi and M Azadi ldquoHighly selectiveoxidation of alcohols using MnO

2TiO2-ZrO2as a novel het-

erogeneous catalystrdquo Comptes Rendus Chimie vol 15 no 5 pp428ndash436 2012

[20] A R Massah R J Kalbasi and M Toghyani ldquoSulfonatedpolystyrenemontmorillonite nanocomposite as a new andefficient catalyst for the solvent-free Mannich reactionrdquo IranianJournal of Catalysis vol 2 no 1 pp 41ndash49 2012

[21] R J Kalbasi M Ghiaci and A R Massah ldquoHighly selectivevapor phase nitration of toluene to 4-nitro toluene usingmodified and unmodified H

3PO4ZSM-5rdquo Applied Catalysis A

vol 353 no 1 pp 1ndash8 2009[22] R J Kalbasi A Abbaspourrad A R Massah and F Zamani

ldquoHighly selective vapor-phase acylation of veratrole overH3PO4TiO2-ZrO2 using ethyl acetate as a green and efficient

acylating agentrdquo Chinese Journal of Chemistry vol 28 no 2 pp273ndash284 2010

[23] A R Massah R J Kalbasi and A Shafiei ldquoZSM-5-SO3H as

a novel efficient and reusable catalyst for the chemoselectivesynthesis and deprotection of 11-diacetates under eco-friendlyconditionsrdquoMonatshefte fur Chemie vol 143 no 4 pp 643ndash6522012

[24] A R Massah R J Kalbasi and N Samah ldquoHighly selectivesynthesis of 120573-amino carbonyl compounds over ZSM-5-SO

3H

under solvent-free conditionsrdquo Bulletin of the Korean ChemicalSociety vol 32 no 5 pp 1703ndash1708 2011

[25] A R Massah F Kazemi D Azadi et al ldquoA mild and chemos-elective solvent-free method for the synthesis of N-aryl and N-alkysulfonamidesrdquo Letters inOrganic Chemistry vol 3 no 3 pp235ndash241 2006

[26] A R Massah B Asadi M Hoseinpour A Molseghi R JKalbasi and H Javaherian Naghash ldquoA novel and efficientsolvent-free and heterogeneous method for the synthesis ofprimary secondary and bis-N-acylsulfonamides using metalhydrogen sulfate catalystsrdquo Tetrahedron vol 65 no 36 pp7696ndash7705 2009

[27] A R Massah H Adibi R Khodarahmi et al ldquoSynthesisin vitro antibacterial and carbonic anhydrase II inhibitoryactivities of N-acylsulfonamides using silica sulfuric acid asan efficient catalyst under both solvent-free and heterogeneousconditionsrdquo Bioorganic andMedicinal Chemistry vol 16 no 10pp 5465ndash5472 2008

[28] A R Massah M Dabagh S Shahidi H J Naghash AR Momeni and H Aliyan ldquoP

2O5SiO2as an efficient and

recyclable catalyst for N-acylation of sulfonamides under het-erogeneous and solvent-free conditionsrdquo Journal of the IranianChemical Society vol 6 no 2 pp 405ndash411 2009

[29] P Pushpaletha and M Lalithambika ldquoModified attapulgite anefficient solid acid catalyst for acetylation of alcohols usingacetic acidrdquo Applied Clay Science vol 51 no 4 pp 424ndash4302011

[30] L Osiglio G Romanelli and M Blanco ldquoAlcohol acetylationwith acetic acid using borated zirconia as catalystrdquo Journal ofMolecular Catalysis A vol 316 no 1ndash2 pp 52ndash58 2010

[31] P R Likhar R Arundhathi S Ghosh and M L KantamldquoPolyaniline nanofiber supported FeCl

3 an efficient and

reusable heterogeneous catalyst for the acylation of alcohols andamines with acetic acidrdquo Journal of Molecular Catalysis A vol302 no 1ndash2 pp 142ndash149 2009

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

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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

6 ISRN Organic Chemistry

Table 3 ZSM-5-SO3H catalyzed acylation of alcohols and phenols under solvent-free conditions

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

1 OH CO

O CO

CO

H3C(CH

2)3O 10 (80)

2 OH2 C

OO C

OCO

H3C(CH

2)4O 15 (81)

3 OH3 C

OO C

OCO

H3C(CH

2)5O 15 (83)

4OH C

OO C

OO C

O25 (70)

5 7OH C

OO C

OCO

H3C(CH

2)9O

10 (90)15 (89)a

6 CH2OH C

OO C

OCO

CH2O 10 (89)

7 OH3 C

O

O CO

H3C CH

3

CO

CH3

H3C(CH

2)5O 10 (88)

8 OH5 C

O

O CO

H3C CH

3CO

CH3

H3C(CH

2)7O 5 (95)

9 OH7 C

O

O CO

H3C CH

3CO

CH3

H3C(CH

2)9O 3 (95)

10 OH5 C

O

ClH3C C

OCH

3H

3C(CH

2)7O 5 (93)

11 OH7 ClC

O

H3C C

OCH

3H

3C(CH

2)9O 5 (95)

12 CH2OH

ClCO

H3C C

OCH

3CH

2O 5 (95)

13 OH CO

O CO

H3C CH

3

O CO

CH3

5 (96)

14 OH CO

O CO

O CO

5 (75)

15 OH CO

O CO

H3C(CH

2)3

(CH2)3CH

3

O CO

(CH2)3CH

35 (81)

16 OH7 OHC

OCO

H3C(CH

2)9O 3 (88)

17 OH5 OHC

OCO

H3C(CH

2)7O 4 (85)

18 OH4 OHC

OCO

H3C(CH

2)6O

4 (80)6 (75)a

ISRN Organic Chemistry 7

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

19 OH3 OHC

OCO

H3C(CH

2)6O 5 (75)

20 OH2 OHC

OCO

H3C(CH

2)4O 5 (68)

21 OH OHCO

CO

H3C(CH

2)3O 5 (61)

22 OH7 OHC

OMe C

OMeH

3C(CH

2)9O 2 (75)

23 OH5 OHMe C

OMeC

OH

3C(CH

2)7O 3 (69)

24 OH3 OHMe C

OMeC

OH

3C(CH

2)5O 3 (61)

25 OH7 OHCO

H3C C

OCH

3H

3C(CH

2)9O 1 (80)

26 OH5 OHC

O

H3C C

OCH

3H

3C(CH

2)7O 2 (75)

27 OH3 OHC

O

H3C C

OCH

3H

3C(CH

2)5O 2 (60)

28 CH2OH C

O

OHH3C C

OCH

3CH

2O 2 (82)

29 OH7 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)9O 2 (85)

30 OH5 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)7O 2 (80)

31 OHHOOHC

OCH

2C C

OO O C

OCH

2H

2

(CH2)2

5 (84)

32 OH4 OHC

OCH

2O C

OCH

2

(CH2)6H

3C 1 (68)

33 OH5 OHC

OCH

2O C

OCH

2

H3C (CH

2)7

1 (70)

34 OH7 OHC

OCH

2O C

OCH

2

H3C (CH

2)8

1 (74)

35 OH2

OHN

O

HO

O

NO

O

O

OH

3C-(H

2C)

4(CH

2)4-CH

3

5 (33)

8 ISRN Organic Chemistry

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

36 OH3

OHHON

OON

O

O

O

OH

3C-(H

2C)

5(CH

2)5-CH

3

5 (43)

37 OH4 OHHO

O O O O

H3C-(H

2C)

6-O O-(CH

2)6-CH

3

5 (70)

38 OH5 OHHO

O O O O

H3C-(H

2C)

7-O O-(CH

2)7-CH

3

5 (75)

a20mmol scale

(100MHz CDCl3) 1667 1328 1306 1295 1283 651 315

287 257 226 140n-Decyl benzoate (Table 3 entry 5) FT-IR (KBr cmminus1)

3068 2926 2856 1721 1602 1457 1274 1111 711 1H NMR(400MHz CDCl

3) 120575 (ppm) 091 (t 3H 119869 = 72Hz) 152ndash

125 (m 14H) 180 (quint 2H 119869 = 72Hz) 435 (t 2H119869 = 68Hz) 747ndash758 (m 3H) 807 (d 2H 119869 = 72Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 141 227 261 288 293

294 296 319 651 1283 1295 1306 1328 1666n-Hexyl acetate (Table 3 entry 7) FT-IR (KBr cmminus1)

2957 2933 1742 1462 1367 1240 1039 1H NMR (400MHzCDCl

3) 120575 (ppm) 084 (t 3H 119869 = 68Hz) 135ndash120 (m

6H) 156 (quint 2H 119869 = 68Hz) 199 (s 3H) 401 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 139 209

225 256 286 314 646 1712n-Octyl acetate (Table 3 entry 8) FT-IR (KBr cmminus1)

2929 2859 1743 1463 1367 1239 1040 1H NMR (400MHzCDCl

3) 120575 (ppm) 086 (t 3H 119869 = 68Hz) 138ndash121 (m 10H)

160 (m 2H) 203 (s 3H) 404 (t 2H 119869 = 68Hz) 13C NMR(400MHz CDCl

3) 120575 (ppm) 140 209 226 259 286 291

292 318 646 1711n-Decyl acetate (Table 3 entry 9) FT-IR (KBr cmminus1)

2927 2858 1743 1464 1366 1239 1041 1H NMR (400MHzCDCl

3) 120575 (ppm) 087 (t 3H 119869 = 68Hz) 139ndash121 (m

14H) 160 (quint 2H 119869 = 68Hz) 203 (s 3H) 404 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 209

226 259 286 292 293 295 319 646 1711Benzyl acetate (Table 3 entry 12) FT-IR (KBr cmminus1)

3034 2954 1742 1455 1380 1230 1027 747 698 1H NMR(400MHz CDCl

3) 120575 (ppm) 214 (s 3H) 516 (s 2H) 743ndash

735 (m 5H) 13C NMR (100MHz CDCl3) 120575 (ppm) 210

663 769 772 775 1283 1283 1286 1360 1709n-Octyl-4-methylbenzoate (Table 3 entry 23) FT-IR

(KBr cmminus1) 1719 1612 1464 1274 1107 752 1H NMR(400MHz CDCl

3) 120575 (ppm) 092 (t 3H 119869 = 68Hz) 127ndash

142 (m 10H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 68Hz) 726 (d 1H 119869 = 80Hz) 796 (d 1H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 216

227 261 288 292 293 318 649 767 770 774 1279 12901296 1434 1668

n-Hexyl-4-methylbenzoate (Table 3 entry 24) FT-IR(KBr cmminus1) 17193 16126 12742 11069 7539 1H NMR(400MHz CDCl

3) 120575 (ppm) 093 (t 3H 119869 = 72Hz) 133ndash

142 (m 6H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 64Hz) 726 (d 2H 119869 = 80Hz) 796 (d 2H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 140 217

226 257 287 315 650 770 772 1278 12904 1296 14341668

Decyl propanoate (Table 3 entry 29) IR (KBr cmminus1)1740 1464 1186 1083 749 1H NMR (400MHz CDCl

3)

120575 (ppm) 089 (t 3H 119869 = 64Hz) 115 (t 3H 119869 = 76Hz) 122ndash138 (m 14H) 158ndash167 (m 2H) 233 (q 2H 119869 = 76Hz) 407(t 2H 119869 = 68Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm)

92 141 227 259 276 287 293 293 295 319 645 1746Octyl propanoate (Table 3 entry 30) IR (KBr cmminus1)

1740 1464 1186 1083 723 1H NMR (400MHz CDCl3)

120575 (ppm) 086 (t 3H 119869 = 64Hz) 112 (t 3H 119869 = 76Hz)122ndash138 (m 10H) 159 (quint 2H 119869 = 72Hz) 230 (q 2H119869 = 76Hz) 404 (t 2H 119869 = 68Hz) 13C NMR (100MHzCDCl

3) 120575 (ppm) 91 140 226 259 276 286 292 292 318

644 1745Ethane-12-diylbis(2-phenylacetate) (Table 3 entry 31) IR

(KBr cmminus1) 1738 1454 1245 1139 726 1H NMR (400MHzCDCl

3) 120575 (ppm) 364 (s 4H) 431ndash436 (m 4H) 728ndash740

(m 10H) 13C NMR (100MHz CDCl3) 120575 (ppm) 411 624

1272 1286 1293 1338 1713n-Heptyl phenylacetate (Table 3 entry 32) IR (KBr

cmminus1) 1737 1456 1251 1155 721 1HNMR (400MHz CDCl3)

120575 (ppm) 095 (t 3H 119869 = 64Hz) 126ndash141 (m 8H) 161ndash172(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash728 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 226 258

286 289 318 415 650 768 772 775 1270 1286 12931343 1717

n-Octyl phenylacetate (Table 3 entry 33) IR (KBr cmminus1)1737 1456 1252 1154 7212 1H NMR (400MHz CDCl

3)

120575 (ppm) 095 (t 3H 119869 = 68Hz) 124ndash141 (m 10H) 162ndash171(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 227 259

286 292 318 415 650 768 771 774 1270 1286 12931343

ISRN Organic Chemistry 9

n-Decyl phenylacetate (Table 3 entry 34) IR (KBr cmminus1)1738 1456 1251 1155 721 1H NMR (400MHz CDCl

3)

120575 (ppm) 093 (t 3H 119869 = 64Hz) 127ndash138 (m 14H) 161ndash168(m 2H) 366 (s 2H) 412 (t 2H 119869 = 68Hz) 739ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 142 227 259

286 292 293 295 319 415 651 768 771 774 1270 12861293 1343

Dipentylpyridine-26-dicarboxylate (Table 3 entry 35)IR (KBr cmminus1) 1741 1465 12440 1149 759 1H NMR(400MHz CDCl

3) 120575 (ppm) 094 (t 6H 119869 = 80Hz) 136ndash

150 (m 8H) 185 (quint 4H 119869 = 68Hz) 443 (t 4H 119869 =68Hz) 802 (t 1H 119869 = 76Hz) 828 (d 2H 119869 = 80Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 224 281 283 664

767 771 773 774 1277 1381 1487 1647Dihexylpyridine-26-dicarboxylate (Table 3 entry 36) IR

(KBr cmminus1) 1722 1241 1144 753 1H NMR (400MHzCDCl

3) 120575 (ppm) 082ndash093 (m 6H) 181 (quint 4H 119869 =

72Hz) 122ndash138 (m 8H) 138-148 (m 4H) 439 (t 4H119869 = 72Hz) 799 (t 1H 119869 = 80Hz) 824 (d 2H 119869 = 76Hz)

Diheptyl glutarate (Table 3 entry 37) IR (KBr cmminus1)1738 1465 1148 1065 725 1H NMR (400MHz CDCl

3)

120575 (ppm) 088 (t 6H 119869 = 68Hz) 122ndash138 (m 16H) 160(quint 4H 119869 = 68Hz) 195 (quint 4H 119869 = 72Hz) 237 (t4H 119869 = 72Hz) 406 (t 4H 119869 = 68Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 140 202 226 259 286 289 317 334

646 1731Dioctyl glutarate (Table 3 entry 38) IR (KBr cmminus1) 1737

1465 1064 722 1H NMR (400MHz CDCl3) 120575 (ppm) 090

(t 6H 119869 = 64Hz) 124ndash140 (m 20H) 159ndash168 (m 4H)192ndash202 (m 4H) 236ndash248 (m 4H) 408 (t 4H 119869 =56Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 141 199 202

226 259 286 292 292 318 330 332 334 647 647 17301731

3 Results and Discussion

As a starting point for this work the reaction was optimizedin order to find the best conditions especially in agree-ment with green chemistry (Table 1) To find the optimumconditions for acylation of amines and sulfonamides withcarboxylic acid anhydrides and chlorides several sets of reac-tion conditions were examined (Table 1 entries 1ndash5) Thusunder the best conditions amines (2mmol) were acylated atroom temperature almost quantitatively with carboxylic acidanhydrides or chlorides (2ndash4mmol) in the presence of 0005ndash001 g of ZSM-5-SO

3H without use of any solvents (Table 1

entries 1ndash4) Acylation of sulfonamides (1mmol) occurredonly with aliphatic anhydrides (15mmol) in the presenceof 001 g of catalyst at room temperature under solvent-freeconditions (Table 1 entry 5)

Then the reactionwas exploredwith a variety of aromaticand aliphatic amines to evaluate the scope and limitations ofthis method (Table 2) The results showed that the differentaromatic amines containing various electron-donating and -withdrawing groups as well as aliphatic amines reacted withcarboxylic acid chlorides or anhydrides within 5ndash30minutesto produce the corresponding amides in 70ndash95 yield

Benzoic anhydride and benzoyl chloridewas used as aromaticacylating agents Also acylation of amines were examinedusing different aliphatic acylating agents including aceticpentanoic and isobutanoic anhydridesThe excellent activityof ZSM-5-SO

3Hwas demonstrated by the good to high yields

obtained for anilines having electron-withdrawing groupssuch as Cl and NO

2(Table 2 entries 7ndash9) However the

best yields were obtained with substrates bearing electron-donating groups such as methoxy especially in the para-position (Table 2 entries 2 and 14) Also very good resultswere obtained when secondary amines were acylated in thepresence of ZSM-5-SO

3H and the corresponding amides

were obtained in 78ndash90 yields in 10ndash30 minutes at roomtemperature under solvent-free conditions (Table 2 entries 12and 18) Finally this method was used for the acylation of 4-methylbenzenesulfonamide as a weak nucleophile with aceticand pentanoic anhydrides Interestingly the corresponding119873-acyl sulfonamides were obtained in 80 and 92 yieldsafter 5 and 15 minutes in high purity (Table 2 entries 29 and30)

To demonstrate the versatility of this protocol the acyla-tion of alcohols andphenolswas investigated using carboxylicacids carboxylic acid anhydrides and chlorides as acylatingagents At first several sets of reaction conditions wereexamined to find the best conditions for acylation of alcoholsIn the optimum conditions alcohols and phenols (1mmol)were acylated at room temperature with acetic anhydridesor chlorides (2mmol) in the presence of 001 g of ZSM-5-SO3H under the solvent-free conditions (Table 1 entry 6)

Acylation with benzoic anhydride was done at 80∘C using005 g of catalyst (Table 1 entry 7) When carboxylic acidswere used as acylating agents the reactions were done at 80ndash120∘C (Table 1 entries 8ndash10)

Using a simple experimental procedure the ZSM-5-SO3H catalyzed acylation of benzylic primary and second-

ary alcohols proceeded efficiently using carboxylic acidanhydrides and chlorides (Table 3 entries 1ndash15) Differentcarboxylic acid anhydrides and chlorides such as benzoicanhydride acetic anhydride pentanoic anhydride and acetylchloride were used as acylating agent and the correspondingesters were obtained in high isolated yields and purityafter short reaction times under the solvent-free conditionsPrimary alcohols were acylated faster than secondary ones(Table 3 entries 4) and sterically hindered alcohols such astert-butyl alcohol remained unchanged It was interesting tonote that phenols were also satisfactorily acylated generatingthe corresponding esters in 75ndash95 yields (Table 3 entries13ndash15)

In order to generalize the catalytic efficiency of ZSM-5-SO3H for direct acylating with carboxylic acids the acy-

lation of alcohols was tried with different carboxylic acid(Table 3 entries 16ndash38) while most literature methods fordirect acylation of alcohols employ only acetic acid [29ndash31] Acylation with acetic propanoic phenyl acetic benzoicacid and 4-methylbenzoic acid resulted in good yield ofthe esters under the solvent-free conditions Also pleasingresults were obtained when acylation of alcohols was donewith dicarboxylic acids such as glutaric acid and pyridine-16-dicarboxylic acid and the corresponding diester was

10 ISRN Organic Chemistry

CH3

CH3

CH3

CH3

NH2

ZSM-5-SO3H

Ac2O (2 eq)

OH

+

O

+

NHO O

1000

CH3

NH2

ZSM-5-SO3H

H3C

Ac2O (2 eq)

NH

+ +

O

0 100

HO O

O

CH3

CH3

ZSM-5-SO3H

Ac2O (2 eq)

OH

OH+

O

+7

7

7 7

7

7O

O

20 80

O

CH3

ZSM-5-SO3H

H3C

NO2

NO2

Ac2O (1 eq)

OH OH

+

O

+

O O

O

80 20

CH3

CH3

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH

OH+

O

+ O

O

0 100

O

CH3

CH3

NH2

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH+

HN

+ O

O

0 100

O

rt 5 min

rt 3 min

rt 2 min

rt 2 min

Scheme 3

obtained in high purity in absence of solvent (Table 3 entries35ndash38) It is noteworthy that in contrast to most reportedmethods that need excess of acetic acid in this methodacylation of alcohols was carried out using only 12ndash20 eqof carboxylic acid Also acylation of ethylene glycol as adiol was carried out with phenylacetic acid under solvent-free conditions and the corresponding ester was obtainedin 84 after 5 minutes It should be mentioned that several

efforts to use this method for direct acylation of amines forthe synthesis of amides were not successful

The importance of selectivity in organic chemistryencouraged us to consider the selectivity of acylation ofdifferent alcohols and amines Several reactions were car-ried out using carboxylic acid anhydrides and chlorides asacylating agents and surprisingly the excellent selectivitywas found For example aromatic amines such as 4-methyl

ISRN Organic Chemistry 11

aniline can be converted into the amide in the presence ofphenol On the other hand aromatic amines were acylatedselectively in the presence of aliphatic alcohol Furthermorethe reactions of alcohols with acylating agent were so fastin comparison to those of the phenol that the selectiveacylation of aliphatic alcohols in the presence of phenolsappeared to be a distinct possibility The result showedthat selective acylation of phenols with or without electron-donating group in the presence of phenols with electron-withdrawing group is possible with this method As wellas carboxylic acid anhydrides and chlorides the excellentselectivity was observed when carboxylic acids were usedas acylating agent Acylation of alcohols was carried outselectively in the presence of phenols Also acylation ofalcohols was done in the presence of amines selectivelywhile as mentioned above this selectivity is reversed whencarboxylic acid anhydrides were used as acylating agent(Scheme 3)

To show another advantage of the present acylationmethod and the importance of scale-up ability for laboratoryand industrial purposes a few amines and phenols wereacylated in large scale successfully without considerable lim-itation For example acylation of 4-methyl aniline (Table 2entry 4) 1-decanol with benzoic anhydride (Table 3 entry5) and 1-heptanol with benzoic acid (Table 3 entry 18) wascarried out in 20mmol scales as well as the 1mmol ones Theonly difference is the reaction time Reaction in large scaleneeds more time that is because of the difficulty in stirringthe reaction mixture under solvent-free conditions

Finally we were interested to study the reusability ofthe catalysts due to economical and environmental aspectsFor this purpose the reaction of 1-heptanol with benzoicanhydride and benzoic acid was chosen as model reactionsAt the end of each run the catalyst was recovered fromthe reaction mixture by addition of dichloromethane simplefiltration and drying at 100∘C and then reused The recycledZSM-5-SO

3H was used for further runs and its activity did

not show any significant decrease even after four runs

4 Conclusion

In conclusion we have described a highly efficient and che-moselective synthetic route for the acylation of sulfonamidesamines alcohols and phenols with carboxylic acids car-boxylic acid chlorides and anhydrides in the presence ofZSM-5-SO

3H under solvent-free conditions This method

has advantages in terms of low cost and nontoxic nature of thecatalyst high yield and purity of the products short reactiontimes operational simplicity and easy workup In additionrecyclability of this protocol is attractive and useful Directacylation of alcohols with different carboxylic acids is anotheradvantage of this protocol

Acknowledgment

The support from Islamic Azad University Shahreza Branch(IAUSH) Research Council is gratefully acknowledged

References

[1] T W Greene and P G M Wuts Protective Groups in OrganicSynthesis Wiley New York NY USA 3rd edition 1999

[2] W Steglich andGHofle ldquoNN-dimethyl-4-pyridinamine a veryeffective acylation catalystrdquo Angewandte Chemie vol 8 no 12pp 980ndash981 1969

[3] E Vedejs and S T Diver ldquoTributylphosphine a remarkableacylation catalystrdquo Journal of the American Chemical Societyvol 115 no 8 pp 3358ndash3359 1993

[4] E F V Scriven ldquo4-Dialkylaminopyridines super acylation andalkylation catalystsrdquo Chemical Society Reviews vol 12 no 2 pp129ndash161 1983

[5] K Ishihara M Kubota H Kurihara and H Yamamoto ldquoScan-dium trifluoromethanesulfonate as an extremely active Lewisacid catalyst in acylation of alcohols with acid anhydrides andmixed anhydridesrdquo The Journal of Organic Chemistry vol 61no 14 pp 4560ndash4567 1996

[6] R Alleti W S Oh M Perambuduru Z Afrasiabi E Sinn andV P Reddy ldquoGadolinium triflate immobilized in imidazoliumbased ionic liquids a recyclable catalyst and green solvent foracetylation of alcohols and aminesrdquo Green Chemistry vol 7 no4 pp 203ndash206 2005

[7] T N Parac-Vogt K Deleersnyder and K Binnemans ldquoLan-thanide(III) tosylates as new acylation catalystsrdquo EuropeanJournal of Organic Chemistry vol 2005 no 9 pp 1810ndash18152005

[8] K D Surya ldquoRuthenium(III) chloride catalyzed acylation ofalcohols phenols thiols and aminesrdquo Tetrahedron Letters vol45 no 14 pp 2919ndash2922 2004

[9] F M Shirini M A Zolfigol M Abedini and P SalehildquoAl(HSO

4)3catalyzed acetylation and formylation of alcoholsrdquo

Bulletin of the Korean Chemical Society vol 24 no 11 pp 1683ndash1685 2003

[10] A Orita C Tanahashi A Kakuda and J Otera ldquoHighly pow-erful and practical acylation of alcohols with acid anhydridecatalyzed by Bi(OTf)

3rdquo Journal of Organic Chemistry vol 66

no 26 pp 8926ndash8934 2001[11] Y Nakae I Kusaki and T Sato ldquoLithium perchlorate catalyzed

acetylation of alcohols under mild reaction conditionsrdquo Synlettvol 2001 no 10 pp 1584ndash1586 2001

[12] R Ballini G Bosica S Carloni L Ciaralli R Maggi and GSartori ldquoZeolite HSZ-360 as a new reusable catalyst for thedirect acetylation of alcohols and phenols under solventlessconditionsrdquo Tetrahedron Letters vol 39 no 33 pp 6049ndash60521998

[13] B M Choudary V Bhaskar M L Kantam K Koteswara Raoand K V Raghavan ldquoAcylation of alcohols with carboxylicacids via the evolution of compatible acidic sites in montmo-rillonitesrdquo Green Chemistry vol 2 pp 67ndash70 2000

[14] M H Sarvari and H Sharghi ldquoZinc oxide (ZnO) as a newhighly efficient and reusable catalyst for acylation of alcoholsphenols and amines under solvent free conditionsrdquo Tetrahe-dron vol 61 no 46 pp 10903ndash10907 2005

[15] J Izumi I Shiina and T Mukaiyama ldquoAn efficient esterifica-tion reaction between equimolar amounts of free carboxylicacids and alcohols by the combined use of octamethylcyclote-trasiloxane and a catalytic amount of titanium(iv) chloridetris(trifluoromethanesulfonate)rdquo Chemistry Letters vol 2 pp141ndash142 1995

[16] R Alleti M Perambuduru S Samantha and V P ReddyldquoGadolinium triflate an efficient and convenient catalyst for

12 ISRN Organic Chemistry

acetylation of alcohols and aminesrdquo Journal of Molecular Catal-ysis A vol 226 no 1 pp 57ndash59 2005

[17] F Shirini K RaMoghadam and T Naghdi ldquo13-Dichloro-55-dimethylhydantoin an efficient catalyst for the solvent freesynthesis of 18-dioxo-octahydro-xanthenesrdquo Iranian Journal ofCatalysis vol 2 pp 55ndash59 2012

[18] A DyerAn Introduction to Zeolite Molecular Sieves JohnWileyamp Sons Inc New York NY USA 1988

[19] A R Massah R J Kalbasi and M Azadi ldquoHighly selectiveoxidation of alcohols using MnO

2TiO2-ZrO2as a novel het-

erogeneous catalystrdquo Comptes Rendus Chimie vol 15 no 5 pp428ndash436 2012

[20] A R Massah R J Kalbasi and M Toghyani ldquoSulfonatedpolystyrenemontmorillonite nanocomposite as a new andefficient catalyst for the solvent-free Mannich reactionrdquo IranianJournal of Catalysis vol 2 no 1 pp 41ndash49 2012

[21] R J Kalbasi M Ghiaci and A R Massah ldquoHighly selectivevapor phase nitration of toluene to 4-nitro toluene usingmodified and unmodified H

3PO4ZSM-5rdquo Applied Catalysis A

vol 353 no 1 pp 1ndash8 2009[22] R J Kalbasi A Abbaspourrad A R Massah and F Zamani

ldquoHighly selective vapor-phase acylation of veratrole overH3PO4TiO2-ZrO2 using ethyl acetate as a green and efficient

acylating agentrdquo Chinese Journal of Chemistry vol 28 no 2 pp273ndash284 2010

[23] A R Massah R J Kalbasi and A Shafiei ldquoZSM-5-SO3H as

a novel efficient and reusable catalyst for the chemoselectivesynthesis and deprotection of 11-diacetates under eco-friendlyconditionsrdquoMonatshefte fur Chemie vol 143 no 4 pp 643ndash6522012

[24] A R Massah R J Kalbasi and N Samah ldquoHighly selectivesynthesis of 120573-amino carbonyl compounds over ZSM-5-SO

3H

under solvent-free conditionsrdquo Bulletin of the Korean ChemicalSociety vol 32 no 5 pp 1703ndash1708 2011

[25] A R Massah F Kazemi D Azadi et al ldquoA mild and chemos-elective solvent-free method for the synthesis of N-aryl and N-alkysulfonamidesrdquo Letters inOrganic Chemistry vol 3 no 3 pp235ndash241 2006

[26] A R Massah B Asadi M Hoseinpour A Molseghi R JKalbasi and H Javaherian Naghash ldquoA novel and efficientsolvent-free and heterogeneous method for the synthesis ofprimary secondary and bis-N-acylsulfonamides using metalhydrogen sulfate catalystsrdquo Tetrahedron vol 65 no 36 pp7696ndash7705 2009

[27] A R Massah H Adibi R Khodarahmi et al ldquoSynthesisin vitro antibacterial and carbonic anhydrase II inhibitoryactivities of N-acylsulfonamides using silica sulfuric acid asan efficient catalyst under both solvent-free and heterogeneousconditionsrdquo Bioorganic andMedicinal Chemistry vol 16 no 10pp 5465ndash5472 2008

[28] A R Massah M Dabagh S Shahidi H J Naghash AR Momeni and H Aliyan ldquoP

2O5SiO2as an efficient and

recyclable catalyst for N-acylation of sulfonamides under het-erogeneous and solvent-free conditionsrdquo Journal of the IranianChemical Society vol 6 no 2 pp 405ndash411 2009

[29] P Pushpaletha and M Lalithambika ldquoModified attapulgite anefficient solid acid catalyst for acetylation of alcohols usingacetic acidrdquo Applied Clay Science vol 51 no 4 pp 424ndash4302011

[30] L Osiglio G Romanelli and M Blanco ldquoAlcohol acetylationwith acetic acid using borated zirconia as catalystrdquo Journal ofMolecular Catalysis A vol 316 no 1ndash2 pp 52ndash58 2010

[31] P R Likhar R Arundhathi S Ghosh and M L KantamldquoPolyaniline nanofiber supported FeCl

3 an efficient and

reusable heterogeneous catalyst for the acylation of alcohols andamines with acetic acidrdquo Journal of Molecular Catalysis A vol302 no 1ndash2 pp 142ndash149 2009

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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Analytical ChemistryInternational Journal of

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Journal of

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Quantum Chemistry

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Organic Chemistry International

ElectrochemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

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CatalystsJournal of

ISRN Organic Chemistry 7

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

19 OH3 OHC

OCO

H3C(CH

2)6O 5 (75)

20 OH2 OHC

OCO

H3C(CH

2)4O 5 (68)

21 OH OHCO

CO

H3C(CH

2)3O 5 (61)

22 OH7 OHC

OMe C

OMeH

3C(CH

2)9O 2 (75)

23 OH5 OHMe C

OMeC

OH

3C(CH

2)7O 3 (69)

24 OH3 OHMe C

OMeC

OH

3C(CH

2)5O 3 (61)

25 OH7 OHCO

H3C C

OCH

3H

3C(CH

2)9O 1 (80)

26 OH5 OHC

O

H3C C

OCH

3H

3C(CH

2)7O 2 (75)

27 OH3 OHC

O

H3C C

OCH

3H

3C(CH

2)5O 2 (60)

28 CH2OH C

O

OHH3C C

OCH

3CH

2O 2 (82)

29 OH7 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)9O 2 (85)

30 OH5 OHC

O

CH3CH

2CO

CH2CH

3H

3C(CH

2)7O 2 (80)

31 OHHOOHC

OCH

2C C

OO O C

OCH

2H

2

(CH2)2

5 (84)

32 OH4 OHC

OCH

2O C

OCH

2

(CH2)6H

3C 1 (68)

33 OH5 OHC

OCH

2O C

OCH

2

H3C (CH

2)7

1 (70)

34 OH7 OHC

OCH

2O C

OCH

2

H3C (CH

2)8

1 (74)

35 OH2

OHN

O

HO

O

NO

O

O

OH

3C-(H

2C)

4(CH

2)4-CH

3

5 (33)

8 ISRN Organic Chemistry

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

36 OH3

OHHON

OON

O

O

O

OH

3C-(H

2C)

5(CH

2)5-CH

3

5 (43)

37 OH4 OHHO

O O O O

H3C-(H

2C)

6-O O-(CH

2)6-CH

3

5 (70)

38 OH5 OHHO

O O O O

H3C-(H

2C)

7-O O-(CH

2)7-CH

3

5 (75)

a20mmol scale

(100MHz CDCl3) 1667 1328 1306 1295 1283 651 315

287 257 226 140n-Decyl benzoate (Table 3 entry 5) FT-IR (KBr cmminus1)

3068 2926 2856 1721 1602 1457 1274 1111 711 1H NMR(400MHz CDCl

3) 120575 (ppm) 091 (t 3H 119869 = 72Hz) 152ndash

125 (m 14H) 180 (quint 2H 119869 = 72Hz) 435 (t 2H119869 = 68Hz) 747ndash758 (m 3H) 807 (d 2H 119869 = 72Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 141 227 261 288 293

294 296 319 651 1283 1295 1306 1328 1666n-Hexyl acetate (Table 3 entry 7) FT-IR (KBr cmminus1)

2957 2933 1742 1462 1367 1240 1039 1H NMR (400MHzCDCl

3) 120575 (ppm) 084 (t 3H 119869 = 68Hz) 135ndash120 (m

6H) 156 (quint 2H 119869 = 68Hz) 199 (s 3H) 401 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 139 209

225 256 286 314 646 1712n-Octyl acetate (Table 3 entry 8) FT-IR (KBr cmminus1)

2929 2859 1743 1463 1367 1239 1040 1H NMR (400MHzCDCl

3) 120575 (ppm) 086 (t 3H 119869 = 68Hz) 138ndash121 (m 10H)

160 (m 2H) 203 (s 3H) 404 (t 2H 119869 = 68Hz) 13C NMR(400MHz CDCl

3) 120575 (ppm) 140 209 226 259 286 291

292 318 646 1711n-Decyl acetate (Table 3 entry 9) FT-IR (KBr cmminus1)

2927 2858 1743 1464 1366 1239 1041 1H NMR (400MHzCDCl

3) 120575 (ppm) 087 (t 3H 119869 = 68Hz) 139ndash121 (m

14H) 160 (quint 2H 119869 = 68Hz) 203 (s 3H) 404 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 209

226 259 286 292 293 295 319 646 1711Benzyl acetate (Table 3 entry 12) FT-IR (KBr cmminus1)

3034 2954 1742 1455 1380 1230 1027 747 698 1H NMR(400MHz CDCl

3) 120575 (ppm) 214 (s 3H) 516 (s 2H) 743ndash

735 (m 5H) 13C NMR (100MHz CDCl3) 120575 (ppm) 210

663 769 772 775 1283 1283 1286 1360 1709n-Octyl-4-methylbenzoate (Table 3 entry 23) FT-IR

(KBr cmminus1) 1719 1612 1464 1274 1107 752 1H NMR(400MHz CDCl

3) 120575 (ppm) 092 (t 3H 119869 = 68Hz) 127ndash

142 (m 10H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 68Hz) 726 (d 1H 119869 = 80Hz) 796 (d 1H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 216

227 261 288 292 293 318 649 767 770 774 1279 12901296 1434 1668

n-Hexyl-4-methylbenzoate (Table 3 entry 24) FT-IR(KBr cmminus1) 17193 16126 12742 11069 7539 1H NMR(400MHz CDCl

3) 120575 (ppm) 093 (t 3H 119869 = 72Hz) 133ndash

142 (m 6H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 64Hz) 726 (d 2H 119869 = 80Hz) 796 (d 2H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 140 217

226 257 287 315 650 770 772 1278 12904 1296 14341668

Decyl propanoate (Table 3 entry 29) IR (KBr cmminus1)1740 1464 1186 1083 749 1H NMR (400MHz CDCl

3)

120575 (ppm) 089 (t 3H 119869 = 64Hz) 115 (t 3H 119869 = 76Hz) 122ndash138 (m 14H) 158ndash167 (m 2H) 233 (q 2H 119869 = 76Hz) 407(t 2H 119869 = 68Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm)

92 141 227 259 276 287 293 293 295 319 645 1746Octyl propanoate (Table 3 entry 30) IR (KBr cmminus1)

1740 1464 1186 1083 723 1H NMR (400MHz CDCl3)

120575 (ppm) 086 (t 3H 119869 = 64Hz) 112 (t 3H 119869 = 76Hz)122ndash138 (m 10H) 159 (quint 2H 119869 = 72Hz) 230 (q 2H119869 = 76Hz) 404 (t 2H 119869 = 68Hz) 13C NMR (100MHzCDCl

3) 120575 (ppm) 91 140 226 259 276 286 292 292 318

644 1745Ethane-12-diylbis(2-phenylacetate) (Table 3 entry 31) IR

(KBr cmminus1) 1738 1454 1245 1139 726 1H NMR (400MHzCDCl

3) 120575 (ppm) 364 (s 4H) 431ndash436 (m 4H) 728ndash740

(m 10H) 13C NMR (100MHz CDCl3) 120575 (ppm) 411 624

1272 1286 1293 1338 1713n-Heptyl phenylacetate (Table 3 entry 32) IR (KBr

cmminus1) 1737 1456 1251 1155 721 1HNMR (400MHz CDCl3)

120575 (ppm) 095 (t 3H 119869 = 64Hz) 126ndash141 (m 8H) 161ndash172(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash728 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 226 258

286 289 318 415 650 768 772 775 1270 1286 12931343 1717

n-Octyl phenylacetate (Table 3 entry 33) IR (KBr cmminus1)1737 1456 1252 1154 7212 1H NMR (400MHz CDCl

3)

120575 (ppm) 095 (t 3H 119869 = 68Hz) 124ndash141 (m 10H) 162ndash171(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 227 259

286 292 318 415 650 768 771 774 1270 1286 12931343

ISRN Organic Chemistry 9

n-Decyl phenylacetate (Table 3 entry 34) IR (KBr cmminus1)1738 1456 1251 1155 721 1H NMR (400MHz CDCl

3)

120575 (ppm) 093 (t 3H 119869 = 64Hz) 127ndash138 (m 14H) 161ndash168(m 2H) 366 (s 2H) 412 (t 2H 119869 = 68Hz) 739ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 142 227 259

286 292 293 295 319 415 651 768 771 774 1270 12861293 1343

Dipentylpyridine-26-dicarboxylate (Table 3 entry 35)IR (KBr cmminus1) 1741 1465 12440 1149 759 1H NMR(400MHz CDCl

3) 120575 (ppm) 094 (t 6H 119869 = 80Hz) 136ndash

150 (m 8H) 185 (quint 4H 119869 = 68Hz) 443 (t 4H 119869 =68Hz) 802 (t 1H 119869 = 76Hz) 828 (d 2H 119869 = 80Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 224 281 283 664

767 771 773 774 1277 1381 1487 1647Dihexylpyridine-26-dicarboxylate (Table 3 entry 36) IR

(KBr cmminus1) 1722 1241 1144 753 1H NMR (400MHzCDCl

3) 120575 (ppm) 082ndash093 (m 6H) 181 (quint 4H 119869 =

72Hz) 122ndash138 (m 8H) 138-148 (m 4H) 439 (t 4H119869 = 72Hz) 799 (t 1H 119869 = 80Hz) 824 (d 2H 119869 = 76Hz)

Diheptyl glutarate (Table 3 entry 37) IR (KBr cmminus1)1738 1465 1148 1065 725 1H NMR (400MHz CDCl

3)

120575 (ppm) 088 (t 6H 119869 = 68Hz) 122ndash138 (m 16H) 160(quint 4H 119869 = 68Hz) 195 (quint 4H 119869 = 72Hz) 237 (t4H 119869 = 72Hz) 406 (t 4H 119869 = 68Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 140 202 226 259 286 289 317 334

646 1731Dioctyl glutarate (Table 3 entry 38) IR (KBr cmminus1) 1737

1465 1064 722 1H NMR (400MHz CDCl3) 120575 (ppm) 090

(t 6H 119869 = 64Hz) 124ndash140 (m 20H) 159ndash168 (m 4H)192ndash202 (m 4H) 236ndash248 (m 4H) 408 (t 4H 119869 =56Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 141 199 202

226 259 286 292 292 318 330 332 334 647 647 17301731

3 Results and Discussion

As a starting point for this work the reaction was optimizedin order to find the best conditions especially in agree-ment with green chemistry (Table 1) To find the optimumconditions for acylation of amines and sulfonamides withcarboxylic acid anhydrides and chlorides several sets of reac-tion conditions were examined (Table 1 entries 1ndash5) Thusunder the best conditions amines (2mmol) were acylated atroom temperature almost quantitatively with carboxylic acidanhydrides or chlorides (2ndash4mmol) in the presence of 0005ndash001 g of ZSM-5-SO

3H without use of any solvents (Table 1

entries 1ndash4) Acylation of sulfonamides (1mmol) occurredonly with aliphatic anhydrides (15mmol) in the presenceof 001 g of catalyst at room temperature under solvent-freeconditions (Table 1 entry 5)

Then the reactionwas exploredwith a variety of aromaticand aliphatic amines to evaluate the scope and limitations ofthis method (Table 2) The results showed that the differentaromatic amines containing various electron-donating and -withdrawing groups as well as aliphatic amines reacted withcarboxylic acid chlorides or anhydrides within 5ndash30minutesto produce the corresponding amides in 70ndash95 yield

Benzoic anhydride and benzoyl chloridewas used as aromaticacylating agents Also acylation of amines were examinedusing different aliphatic acylating agents including aceticpentanoic and isobutanoic anhydridesThe excellent activityof ZSM-5-SO

3Hwas demonstrated by the good to high yields

obtained for anilines having electron-withdrawing groupssuch as Cl and NO

2(Table 2 entries 7ndash9) However the

best yields were obtained with substrates bearing electron-donating groups such as methoxy especially in the para-position (Table 2 entries 2 and 14) Also very good resultswere obtained when secondary amines were acylated in thepresence of ZSM-5-SO

3H and the corresponding amides

were obtained in 78ndash90 yields in 10ndash30 minutes at roomtemperature under solvent-free conditions (Table 2 entries 12and 18) Finally this method was used for the acylation of 4-methylbenzenesulfonamide as a weak nucleophile with aceticand pentanoic anhydrides Interestingly the corresponding119873-acyl sulfonamides were obtained in 80 and 92 yieldsafter 5 and 15 minutes in high purity (Table 2 entries 29 and30)

To demonstrate the versatility of this protocol the acyla-tion of alcohols andphenolswas investigated using carboxylicacids carboxylic acid anhydrides and chlorides as acylatingagents At first several sets of reaction conditions wereexamined to find the best conditions for acylation of alcoholsIn the optimum conditions alcohols and phenols (1mmol)were acylated at room temperature with acetic anhydridesor chlorides (2mmol) in the presence of 001 g of ZSM-5-SO3H under the solvent-free conditions (Table 1 entry 6)

Acylation with benzoic anhydride was done at 80∘C using005 g of catalyst (Table 1 entry 7) When carboxylic acidswere used as acylating agents the reactions were done at 80ndash120∘C (Table 1 entries 8ndash10)

Using a simple experimental procedure the ZSM-5-SO3H catalyzed acylation of benzylic primary and second-

ary alcohols proceeded efficiently using carboxylic acidanhydrides and chlorides (Table 3 entries 1ndash15) Differentcarboxylic acid anhydrides and chlorides such as benzoicanhydride acetic anhydride pentanoic anhydride and acetylchloride were used as acylating agent and the correspondingesters were obtained in high isolated yields and purityafter short reaction times under the solvent-free conditionsPrimary alcohols were acylated faster than secondary ones(Table 3 entries 4) and sterically hindered alcohols such astert-butyl alcohol remained unchanged It was interesting tonote that phenols were also satisfactorily acylated generatingthe corresponding esters in 75ndash95 yields (Table 3 entries13ndash15)

In order to generalize the catalytic efficiency of ZSM-5-SO3H for direct acylating with carboxylic acids the acy-

lation of alcohols was tried with different carboxylic acid(Table 3 entries 16ndash38) while most literature methods fordirect acylation of alcohols employ only acetic acid [29ndash31] Acylation with acetic propanoic phenyl acetic benzoicacid and 4-methylbenzoic acid resulted in good yield ofthe esters under the solvent-free conditions Also pleasingresults were obtained when acylation of alcohols was donewith dicarboxylic acids such as glutaric acid and pyridine-16-dicarboxylic acid and the corresponding diester was

10 ISRN Organic Chemistry

CH3

CH3

CH3

CH3

NH2

ZSM-5-SO3H

Ac2O (2 eq)

OH

+

O

+

NHO O

1000

CH3

NH2

ZSM-5-SO3H

H3C

Ac2O (2 eq)

NH

+ +

O

0 100

HO O

O

CH3

CH3

ZSM-5-SO3H

Ac2O (2 eq)

OH

OH+

O

+7

7

7 7

7

7O

O

20 80

O

CH3

ZSM-5-SO3H

H3C

NO2

NO2

Ac2O (1 eq)

OH OH

+

O

+

O O

O

80 20

CH3

CH3

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH

OH+

O

+ O

O

0 100

O

CH3

CH3

NH2

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH+

HN

+ O

O

0 100

O

rt 5 min

rt 3 min

rt 2 min

rt 2 min

Scheme 3

obtained in high purity in absence of solvent (Table 3 entries35ndash38) It is noteworthy that in contrast to most reportedmethods that need excess of acetic acid in this methodacylation of alcohols was carried out using only 12ndash20 eqof carboxylic acid Also acylation of ethylene glycol as adiol was carried out with phenylacetic acid under solvent-free conditions and the corresponding ester was obtainedin 84 after 5 minutes It should be mentioned that several

efforts to use this method for direct acylation of amines forthe synthesis of amides were not successful

The importance of selectivity in organic chemistryencouraged us to consider the selectivity of acylation ofdifferent alcohols and amines Several reactions were car-ried out using carboxylic acid anhydrides and chlorides asacylating agents and surprisingly the excellent selectivitywas found For example aromatic amines such as 4-methyl

ISRN Organic Chemistry 11

aniline can be converted into the amide in the presence ofphenol On the other hand aromatic amines were acylatedselectively in the presence of aliphatic alcohol Furthermorethe reactions of alcohols with acylating agent were so fastin comparison to those of the phenol that the selectiveacylation of aliphatic alcohols in the presence of phenolsappeared to be a distinct possibility The result showedthat selective acylation of phenols with or without electron-donating group in the presence of phenols with electron-withdrawing group is possible with this method As wellas carboxylic acid anhydrides and chlorides the excellentselectivity was observed when carboxylic acids were usedas acylating agent Acylation of alcohols was carried outselectively in the presence of phenols Also acylation ofalcohols was done in the presence of amines selectivelywhile as mentioned above this selectivity is reversed whencarboxylic acid anhydrides were used as acylating agent(Scheme 3)

To show another advantage of the present acylationmethod and the importance of scale-up ability for laboratoryand industrial purposes a few amines and phenols wereacylated in large scale successfully without considerable lim-itation For example acylation of 4-methyl aniline (Table 2entry 4) 1-decanol with benzoic anhydride (Table 3 entry5) and 1-heptanol with benzoic acid (Table 3 entry 18) wascarried out in 20mmol scales as well as the 1mmol ones Theonly difference is the reaction time Reaction in large scaleneeds more time that is because of the difficulty in stirringthe reaction mixture under solvent-free conditions

Finally we were interested to study the reusability ofthe catalysts due to economical and environmental aspectsFor this purpose the reaction of 1-heptanol with benzoicanhydride and benzoic acid was chosen as model reactionsAt the end of each run the catalyst was recovered fromthe reaction mixture by addition of dichloromethane simplefiltration and drying at 100∘C and then reused The recycledZSM-5-SO

3H was used for further runs and its activity did

not show any significant decrease even after four runs

4 Conclusion

In conclusion we have described a highly efficient and che-moselective synthetic route for the acylation of sulfonamidesamines alcohols and phenols with carboxylic acids car-boxylic acid chlorides and anhydrides in the presence ofZSM-5-SO

3H under solvent-free conditions This method

has advantages in terms of low cost and nontoxic nature of thecatalyst high yield and purity of the products short reactiontimes operational simplicity and easy workup In additionrecyclability of this protocol is attractive and useful Directacylation of alcohols with different carboxylic acids is anotheradvantage of this protocol

Acknowledgment

The support from Islamic Azad University Shahreza Branch(IAUSH) Research Council is gratefully acknowledged

References

[1] T W Greene and P G M Wuts Protective Groups in OrganicSynthesis Wiley New York NY USA 3rd edition 1999

[2] W Steglich andGHofle ldquoNN-dimethyl-4-pyridinamine a veryeffective acylation catalystrdquo Angewandte Chemie vol 8 no 12pp 980ndash981 1969

[3] E Vedejs and S T Diver ldquoTributylphosphine a remarkableacylation catalystrdquo Journal of the American Chemical Societyvol 115 no 8 pp 3358ndash3359 1993

[4] E F V Scriven ldquo4-Dialkylaminopyridines super acylation andalkylation catalystsrdquo Chemical Society Reviews vol 12 no 2 pp129ndash161 1983

[5] K Ishihara M Kubota H Kurihara and H Yamamoto ldquoScan-dium trifluoromethanesulfonate as an extremely active Lewisacid catalyst in acylation of alcohols with acid anhydrides andmixed anhydridesrdquo The Journal of Organic Chemistry vol 61no 14 pp 4560ndash4567 1996

[6] R Alleti W S Oh M Perambuduru Z Afrasiabi E Sinn andV P Reddy ldquoGadolinium triflate immobilized in imidazoliumbased ionic liquids a recyclable catalyst and green solvent foracetylation of alcohols and aminesrdquo Green Chemistry vol 7 no4 pp 203ndash206 2005

[7] T N Parac-Vogt K Deleersnyder and K Binnemans ldquoLan-thanide(III) tosylates as new acylation catalystsrdquo EuropeanJournal of Organic Chemistry vol 2005 no 9 pp 1810ndash18152005

[8] K D Surya ldquoRuthenium(III) chloride catalyzed acylation ofalcohols phenols thiols and aminesrdquo Tetrahedron Letters vol45 no 14 pp 2919ndash2922 2004

[9] F M Shirini M A Zolfigol M Abedini and P SalehildquoAl(HSO

4)3catalyzed acetylation and formylation of alcoholsrdquo

Bulletin of the Korean Chemical Society vol 24 no 11 pp 1683ndash1685 2003

[10] A Orita C Tanahashi A Kakuda and J Otera ldquoHighly pow-erful and practical acylation of alcohols with acid anhydridecatalyzed by Bi(OTf)

3rdquo Journal of Organic Chemistry vol 66

no 26 pp 8926ndash8934 2001[11] Y Nakae I Kusaki and T Sato ldquoLithium perchlorate catalyzed

acetylation of alcohols under mild reaction conditionsrdquo Synlettvol 2001 no 10 pp 1584ndash1586 2001

[12] R Ballini G Bosica S Carloni L Ciaralli R Maggi and GSartori ldquoZeolite HSZ-360 as a new reusable catalyst for thedirect acetylation of alcohols and phenols under solventlessconditionsrdquo Tetrahedron Letters vol 39 no 33 pp 6049ndash60521998

[13] B M Choudary V Bhaskar M L Kantam K Koteswara Raoand K V Raghavan ldquoAcylation of alcohols with carboxylicacids via the evolution of compatible acidic sites in montmo-rillonitesrdquo Green Chemistry vol 2 pp 67ndash70 2000

[14] M H Sarvari and H Sharghi ldquoZinc oxide (ZnO) as a newhighly efficient and reusable catalyst for acylation of alcoholsphenols and amines under solvent free conditionsrdquo Tetrahe-dron vol 61 no 46 pp 10903ndash10907 2005

[15] J Izumi I Shiina and T Mukaiyama ldquoAn efficient esterifica-tion reaction between equimolar amounts of free carboxylicacids and alcohols by the combined use of octamethylcyclote-trasiloxane and a catalytic amount of titanium(iv) chloridetris(trifluoromethanesulfonate)rdquo Chemistry Letters vol 2 pp141ndash142 1995

[16] R Alleti M Perambuduru S Samantha and V P ReddyldquoGadolinium triflate an efficient and convenient catalyst for

12 ISRN Organic Chemistry

acetylation of alcohols and aminesrdquo Journal of Molecular Catal-ysis A vol 226 no 1 pp 57ndash59 2005

[17] F Shirini K RaMoghadam and T Naghdi ldquo13-Dichloro-55-dimethylhydantoin an efficient catalyst for the solvent freesynthesis of 18-dioxo-octahydro-xanthenesrdquo Iranian Journal ofCatalysis vol 2 pp 55ndash59 2012

[18] A DyerAn Introduction to Zeolite Molecular Sieves JohnWileyamp Sons Inc New York NY USA 1988

[19] A R Massah R J Kalbasi and M Azadi ldquoHighly selectiveoxidation of alcohols using MnO

2TiO2-ZrO2as a novel het-

erogeneous catalystrdquo Comptes Rendus Chimie vol 15 no 5 pp428ndash436 2012

[20] A R Massah R J Kalbasi and M Toghyani ldquoSulfonatedpolystyrenemontmorillonite nanocomposite as a new andefficient catalyst for the solvent-free Mannich reactionrdquo IranianJournal of Catalysis vol 2 no 1 pp 41ndash49 2012

[21] R J Kalbasi M Ghiaci and A R Massah ldquoHighly selectivevapor phase nitration of toluene to 4-nitro toluene usingmodified and unmodified H

3PO4ZSM-5rdquo Applied Catalysis A

vol 353 no 1 pp 1ndash8 2009[22] R J Kalbasi A Abbaspourrad A R Massah and F Zamani

ldquoHighly selective vapor-phase acylation of veratrole overH3PO4TiO2-ZrO2 using ethyl acetate as a green and efficient

acylating agentrdquo Chinese Journal of Chemistry vol 28 no 2 pp273ndash284 2010

[23] A R Massah R J Kalbasi and A Shafiei ldquoZSM-5-SO3H as

a novel efficient and reusable catalyst for the chemoselectivesynthesis and deprotection of 11-diacetates under eco-friendlyconditionsrdquoMonatshefte fur Chemie vol 143 no 4 pp 643ndash6522012

[24] A R Massah R J Kalbasi and N Samah ldquoHighly selectivesynthesis of 120573-amino carbonyl compounds over ZSM-5-SO

3H

under solvent-free conditionsrdquo Bulletin of the Korean ChemicalSociety vol 32 no 5 pp 1703ndash1708 2011

[25] A R Massah F Kazemi D Azadi et al ldquoA mild and chemos-elective solvent-free method for the synthesis of N-aryl and N-alkysulfonamidesrdquo Letters inOrganic Chemistry vol 3 no 3 pp235ndash241 2006

[26] A R Massah B Asadi M Hoseinpour A Molseghi R JKalbasi and H Javaherian Naghash ldquoA novel and efficientsolvent-free and heterogeneous method for the synthesis ofprimary secondary and bis-N-acylsulfonamides using metalhydrogen sulfate catalystsrdquo Tetrahedron vol 65 no 36 pp7696ndash7705 2009

[27] A R Massah H Adibi R Khodarahmi et al ldquoSynthesisin vitro antibacterial and carbonic anhydrase II inhibitoryactivities of N-acylsulfonamides using silica sulfuric acid asan efficient catalyst under both solvent-free and heterogeneousconditionsrdquo Bioorganic andMedicinal Chemistry vol 16 no 10pp 5465ndash5472 2008

[28] A R Massah M Dabagh S Shahidi H J Naghash AR Momeni and H Aliyan ldquoP

2O5SiO2as an efficient and

recyclable catalyst for N-acylation of sulfonamides under het-erogeneous and solvent-free conditionsrdquo Journal of the IranianChemical Society vol 6 no 2 pp 405ndash411 2009

[29] P Pushpaletha and M Lalithambika ldquoModified attapulgite anefficient solid acid catalyst for acetylation of alcohols usingacetic acidrdquo Applied Clay Science vol 51 no 4 pp 424ndash4302011

[30] L Osiglio G Romanelli and M Blanco ldquoAlcohol acetylationwith acetic acid using borated zirconia as catalystrdquo Journal ofMolecular Catalysis A vol 316 no 1ndash2 pp 52ndash58 2010

[31] P R Likhar R Arundhathi S Ghosh and M L KantamldquoPolyaniline nanofiber supported FeCl

3 an efficient and

reusable heterogeneous catalyst for the acylation of alcohols andamines with acetic acidrdquo Journal of Molecular Catalysis A vol302 no 1ndash2 pp 142ndash149 2009

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

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 ISRN Organic Chemistry

Table 3 Continued

Entry Alcohol (phenol) Acylating agent Products Time min(yield )

36 OH3

OHHON

OON

O

O

O

OH

3C-(H

2C)

5(CH

2)5-CH

3

5 (43)

37 OH4 OHHO

O O O O

H3C-(H

2C)

6-O O-(CH

2)6-CH

3

5 (70)

38 OH5 OHHO

O O O O

H3C-(H

2C)

7-O O-(CH

2)7-CH

3

5 (75)

a20mmol scale

(100MHz CDCl3) 1667 1328 1306 1295 1283 651 315

287 257 226 140n-Decyl benzoate (Table 3 entry 5) FT-IR (KBr cmminus1)

3068 2926 2856 1721 1602 1457 1274 1111 711 1H NMR(400MHz CDCl

3) 120575 (ppm) 091 (t 3H 119869 = 72Hz) 152ndash

125 (m 14H) 180 (quint 2H 119869 = 72Hz) 435 (t 2H119869 = 68Hz) 747ndash758 (m 3H) 807 (d 2H 119869 = 72Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 141 227 261 288 293

294 296 319 651 1283 1295 1306 1328 1666n-Hexyl acetate (Table 3 entry 7) FT-IR (KBr cmminus1)

2957 2933 1742 1462 1367 1240 1039 1H NMR (400MHzCDCl

3) 120575 (ppm) 084 (t 3H 119869 = 68Hz) 135ndash120 (m

6H) 156 (quint 2H 119869 = 68Hz) 199 (s 3H) 401 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 139 209

225 256 286 314 646 1712n-Octyl acetate (Table 3 entry 8) FT-IR (KBr cmminus1)

2929 2859 1743 1463 1367 1239 1040 1H NMR (400MHzCDCl

3) 120575 (ppm) 086 (t 3H 119869 = 68Hz) 138ndash121 (m 10H)

160 (m 2H) 203 (s 3H) 404 (t 2H 119869 = 68Hz) 13C NMR(400MHz CDCl

3) 120575 (ppm) 140 209 226 259 286 291

292 318 646 1711n-Decyl acetate (Table 3 entry 9) FT-IR (KBr cmminus1)

2927 2858 1743 1464 1366 1239 1041 1H NMR (400MHzCDCl

3) 120575 (ppm) 087 (t 3H 119869 = 68Hz) 139ndash121 (m

14H) 160 (quint 2H 119869 = 68Hz) 203 (s 3H) 404 (t 2H119869 = 68Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 209

226 259 286 292 293 295 319 646 1711Benzyl acetate (Table 3 entry 12) FT-IR (KBr cmminus1)

3034 2954 1742 1455 1380 1230 1027 747 698 1H NMR(400MHz CDCl

3) 120575 (ppm) 214 (s 3H) 516 (s 2H) 743ndash

735 (m 5H) 13C NMR (100MHz CDCl3) 120575 (ppm) 210

663 769 772 775 1283 1283 1286 1360 1709n-Octyl-4-methylbenzoate (Table 3 entry 23) FT-IR

(KBr cmminus1) 1719 1612 1464 1274 1107 752 1H NMR(400MHz CDCl

3) 120575 (ppm) 092 (t 3H 119869 = 68Hz) 127ndash

142 (m 10H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 68Hz) 726 (d 1H 119869 = 80Hz) 796 (d 1H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 216

227 261 288 292 293 318 649 767 770 774 1279 12901296 1434 1668

n-Hexyl-4-methylbenzoate (Table 3 entry 24) FT-IR(KBr cmminus1) 17193 16126 12742 11069 7539 1H NMR(400MHz CDCl

3) 120575 (ppm) 093 (t 3H 119869 = 72Hz) 133ndash

142 (m 6H) 179 (quint 2H 119869 = 68Hz) 244 (s 3H) 433(t 2H 119869 = 64Hz) 726 (d 2H 119869 = 80Hz) 796 (d 2H119869 = 80Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm) 140 217

226 257 287 315 650 770 772 1278 12904 1296 14341668

Decyl propanoate (Table 3 entry 29) IR (KBr cmminus1)1740 1464 1186 1083 749 1H NMR (400MHz CDCl

3)

120575 (ppm) 089 (t 3H 119869 = 64Hz) 115 (t 3H 119869 = 76Hz) 122ndash138 (m 14H) 158ndash167 (m 2H) 233 (q 2H 119869 = 76Hz) 407(t 2H 119869 = 68Hz) 13C NMR (100MHz CDCl

3) 120575 (ppm)

92 141 227 259 276 287 293 293 295 319 645 1746Octyl propanoate (Table 3 entry 30) IR (KBr cmminus1)

1740 1464 1186 1083 723 1H NMR (400MHz CDCl3)

120575 (ppm) 086 (t 3H 119869 = 64Hz) 112 (t 3H 119869 = 76Hz)122ndash138 (m 10H) 159 (quint 2H 119869 = 72Hz) 230 (q 2H119869 = 76Hz) 404 (t 2H 119869 = 68Hz) 13C NMR (100MHzCDCl

3) 120575 (ppm) 91 140 226 259 276 286 292 292 318

644 1745Ethane-12-diylbis(2-phenylacetate) (Table 3 entry 31) IR

(KBr cmminus1) 1738 1454 1245 1139 726 1H NMR (400MHzCDCl

3) 120575 (ppm) 364 (s 4H) 431ndash436 (m 4H) 728ndash740

(m 10H) 13C NMR (100MHz CDCl3) 120575 (ppm) 411 624

1272 1286 1293 1338 1713n-Heptyl phenylacetate (Table 3 entry 32) IR (KBr

cmminus1) 1737 1456 1251 1155 721 1HNMR (400MHz CDCl3)

120575 (ppm) 095 (t 3H 119869 = 64Hz) 126ndash141 (m 8H) 161ndash172(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash728 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 226 258

286 289 318 415 650 768 772 775 1270 1286 12931343 1717

n-Octyl phenylacetate (Table 3 entry 33) IR (KBr cmminus1)1737 1456 1252 1154 7212 1H NMR (400MHz CDCl

3)

120575 (ppm) 095 (t 3H 119869 = 68Hz) 124ndash141 (m 10H) 162ndash171(m 2H) 367 (s 2H) 414 (t 2H 119869 = 64Hz) 740ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 141 227 259

286 292 318 415 650 768 771 774 1270 1286 12931343

ISRN Organic Chemistry 9

n-Decyl phenylacetate (Table 3 entry 34) IR (KBr cmminus1)1738 1456 1251 1155 721 1H NMR (400MHz CDCl

3)

120575 (ppm) 093 (t 3H 119869 = 64Hz) 127ndash138 (m 14H) 161ndash168(m 2H) 366 (s 2H) 412 (t 2H 119869 = 68Hz) 739ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 142 227 259

286 292 293 295 319 415 651 768 771 774 1270 12861293 1343

Dipentylpyridine-26-dicarboxylate (Table 3 entry 35)IR (KBr cmminus1) 1741 1465 12440 1149 759 1H NMR(400MHz CDCl

3) 120575 (ppm) 094 (t 6H 119869 = 80Hz) 136ndash

150 (m 8H) 185 (quint 4H 119869 = 68Hz) 443 (t 4H 119869 =68Hz) 802 (t 1H 119869 = 76Hz) 828 (d 2H 119869 = 80Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 224 281 283 664

767 771 773 774 1277 1381 1487 1647Dihexylpyridine-26-dicarboxylate (Table 3 entry 36) IR

(KBr cmminus1) 1722 1241 1144 753 1H NMR (400MHzCDCl

3) 120575 (ppm) 082ndash093 (m 6H) 181 (quint 4H 119869 =

72Hz) 122ndash138 (m 8H) 138-148 (m 4H) 439 (t 4H119869 = 72Hz) 799 (t 1H 119869 = 80Hz) 824 (d 2H 119869 = 76Hz)

Diheptyl glutarate (Table 3 entry 37) IR (KBr cmminus1)1738 1465 1148 1065 725 1H NMR (400MHz CDCl

3)

120575 (ppm) 088 (t 6H 119869 = 68Hz) 122ndash138 (m 16H) 160(quint 4H 119869 = 68Hz) 195 (quint 4H 119869 = 72Hz) 237 (t4H 119869 = 72Hz) 406 (t 4H 119869 = 68Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 140 202 226 259 286 289 317 334

646 1731Dioctyl glutarate (Table 3 entry 38) IR (KBr cmminus1) 1737

1465 1064 722 1H NMR (400MHz CDCl3) 120575 (ppm) 090

(t 6H 119869 = 64Hz) 124ndash140 (m 20H) 159ndash168 (m 4H)192ndash202 (m 4H) 236ndash248 (m 4H) 408 (t 4H 119869 =56Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 141 199 202

226 259 286 292 292 318 330 332 334 647 647 17301731

3 Results and Discussion

As a starting point for this work the reaction was optimizedin order to find the best conditions especially in agree-ment with green chemistry (Table 1) To find the optimumconditions for acylation of amines and sulfonamides withcarboxylic acid anhydrides and chlorides several sets of reac-tion conditions were examined (Table 1 entries 1ndash5) Thusunder the best conditions amines (2mmol) were acylated atroom temperature almost quantitatively with carboxylic acidanhydrides or chlorides (2ndash4mmol) in the presence of 0005ndash001 g of ZSM-5-SO

3H without use of any solvents (Table 1

entries 1ndash4) Acylation of sulfonamides (1mmol) occurredonly with aliphatic anhydrides (15mmol) in the presenceof 001 g of catalyst at room temperature under solvent-freeconditions (Table 1 entry 5)

Then the reactionwas exploredwith a variety of aromaticand aliphatic amines to evaluate the scope and limitations ofthis method (Table 2) The results showed that the differentaromatic amines containing various electron-donating and -withdrawing groups as well as aliphatic amines reacted withcarboxylic acid chlorides or anhydrides within 5ndash30minutesto produce the corresponding amides in 70ndash95 yield

Benzoic anhydride and benzoyl chloridewas used as aromaticacylating agents Also acylation of amines were examinedusing different aliphatic acylating agents including aceticpentanoic and isobutanoic anhydridesThe excellent activityof ZSM-5-SO

3Hwas demonstrated by the good to high yields

obtained for anilines having electron-withdrawing groupssuch as Cl and NO

2(Table 2 entries 7ndash9) However the

best yields were obtained with substrates bearing electron-donating groups such as methoxy especially in the para-position (Table 2 entries 2 and 14) Also very good resultswere obtained when secondary amines were acylated in thepresence of ZSM-5-SO

3H and the corresponding amides

were obtained in 78ndash90 yields in 10ndash30 minutes at roomtemperature under solvent-free conditions (Table 2 entries 12and 18) Finally this method was used for the acylation of 4-methylbenzenesulfonamide as a weak nucleophile with aceticand pentanoic anhydrides Interestingly the corresponding119873-acyl sulfonamides were obtained in 80 and 92 yieldsafter 5 and 15 minutes in high purity (Table 2 entries 29 and30)

To demonstrate the versatility of this protocol the acyla-tion of alcohols andphenolswas investigated using carboxylicacids carboxylic acid anhydrides and chlorides as acylatingagents At first several sets of reaction conditions wereexamined to find the best conditions for acylation of alcoholsIn the optimum conditions alcohols and phenols (1mmol)were acylated at room temperature with acetic anhydridesor chlorides (2mmol) in the presence of 001 g of ZSM-5-SO3H under the solvent-free conditions (Table 1 entry 6)

Acylation with benzoic anhydride was done at 80∘C using005 g of catalyst (Table 1 entry 7) When carboxylic acidswere used as acylating agents the reactions were done at 80ndash120∘C (Table 1 entries 8ndash10)

Using a simple experimental procedure the ZSM-5-SO3H catalyzed acylation of benzylic primary and second-

ary alcohols proceeded efficiently using carboxylic acidanhydrides and chlorides (Table 3 entries 1ndash15) Differentcarboxylic acid anhydrides and chlorides such as benzoicanhydride acetic anhydride pentanoic anhydride and acetylchloride were used as acylating agent and the correspondingesters were obtained in high isolated yields and purityafter short reaction times under the solvent-free conditionsPrimary alcohols were acylated faster than secondary ones(Table 3 entries 4) and sterically hindered alcohols such astert-butyl alcohol remained unchanged It was interesting tonote that phenols were also satisfactorily acylated generatingthe corresponding esters in 75ndash95 yields (Table 3 entries13ndash15)

In order to generalize the catalytic efficiency of ZSM-5-SO3H for direct acylating with carboxylic acids the acy-

lation of alcohols was tried with different carboxylic acid(Table 3 entries 16ndash38) while most literature methods fordirect acylation of alcohols employ only acetic acid [29ndash31] Acylation with acetic propanoic phenyl acetic benzoicacid and 4-methylbenzoic acid resulted in good yield ofthe esters under the solvent-free conditions Also pleasingresults were obtained when acylation of alcohols was donewith dicarboxylic acids such as glutaric acid and pyridine-16-dicarboxylic acid and the corresponding diester was

10 ISRN Organic Chemistry

CH3

CH3

CH3

CH3

NH2

ZSM-5-SO3H

Ac2O (2 eq)

OH

+

O

+

NHO O

1000

CH3

NH2

ZSM-5-SO3H

H3C

Ac2O (2 eq)

NH

+ +

O

0 100

HO O

O

CH3

CH3

ZSM-5-SO3H

Ac2O (2 eq)

OH

OH+

O

+7

7

7 7

7

7O

O

20 80

O

CH3

ZSM-5-SO3H

H3C

NO2

NO2

Ac2O (1 eq)

OH OH

+

O

+

O O

O

80 20

CH3

CH3

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH

OH+

O

+ O

O

0 100

O

CH3

CH3

NH2

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH+

HN

+ O

O

0 100

O

rt 5 min

rt 3 min

rt 2 min

rt 2 min

Scheme 3

obtained in high purity in absence of solvent (Table 3 entries35ndash38) It is noteworthy that in contrast to most reportedmethods that need excess of acetic acid in this methodacylation of alcohols was carried out using only 12ndash20 eqof carboxylic acid Also acylation of ethylene glycol as adiol was carried out with phenylacetic acid under solvent-free conditions and the corresponding ester was obtainedin 84 after 5 minutes It should be mentioned that several

efforts to use this method for direct acylation of amines forthe synthesis of amides were not successful

The importance of selectivity in organic chemistryencouraged us to consider the selectivity of acylation ofdifferent alcohols and amines Several reactions were car-ried out using carboxylic acid anhydrides and chlorides asacylating agents and surprisingly the excellent selectivitywas found For example aromatic amines such as 4-methyl

ISRN Organic Chemistry 11

aniline can be converted into the amide in the presence ofphenol On the other hand aromatic amines were acylatedselectively in the presence of aliphatic alcohol Furthermorethe reactions of alcohols with acylating agent were so fastin comparison to those of the phenol that the selectiveacylation of aliphatic alcohols in the presence of phenolsappeared to be a distinct possibility The result showedthat selective acylation of phenols with or without electron-donating group in the presence of phenols with electron-withdrawing group is possible with this method As wellas carboxylic acid anhydrides and chlorides the excellentselectivity was observed when carboxylic acids were usedas acylating agent Acylation of alcohols was carried outselectively in the presence of phenols Also acylation ofalcohols was done in the presence of amines selectivelywhile as mentioned above this selectivity is reversed whencarboxylic acid anhydrides were used as acylating agent(Scheme 3)

To show another advantage of the present acylationmethod and the importance of scale-up ability for laboratoryand industrial purposes a few amines and phenols wereacylated in large scale successfully without considerable lim-itation For example acylation of 4-methyl aniline (Table 2entry 4) 1-decanol with benzoic anhydride (Table 3 entry5) and 1-heptanol with benzoic acid (Table 3 entry 18) wascarried out in 20mmol scales as well as the 1mmol ones Theonly difference is the reaction time Reaction in large scaleneeds more time that is because of the difficulty in stirringthe reaction mixture under solvent-free conditions

Finally we were interested to study the reusability ofthe catalysts due to economical and environmental aspectsFor this purpose the reaction of 1-heptanol with benzoicanhydride and benzoic acid was chosen as model reactionsAt the end of each run the catalyst was recovered fromthe reaction mixture by addition of dichloromethane simplefiltration and drying at 100∘C and then reused The recycledZSM-5-SO

3H was used for further runs and its activity did

not show any significant decrease even after four runs

4 Conclusion

In conclusion we have described a highly efficient and che-moselective synthetic route for the acylation of sulfonamidesamines alcohols and phenols with carboxylic acids car-boxylic acid chlorides and anhydrides in the presence ofZSM-5-SO

3H under solvent-free conditions This method

has advantages in terms of low cost and nontoxic nature of thecatalyst high yield and purity of the products short reactiontimes operational simplicity and easy workup In additionrecyclability of this protocol is attractive and useful Directacylation of alcohols with different carboxylic acids is anotheradvantage of this protocol

Acknowledgment

The support from Islamic Azad University Shahreza Branch(IAUSH) Research Council is gratefully acknowledged

References

[1] T W Greene and P G M Wuts Protective Groups in OrganicSynthesis Wiley New York NY USA 3rd edition 1999

[2] W Steglich andGHofle ldquoNN-dimethyl-4-pyridinamine a veryeffective acylation catalystrdquo Angewandte Chemie vol 8 no 12pp 980ndash981 1969

[3] E Vedejs and S T Diver ldquoTributylphosphine a remarkableacylation catalystrdquo Journal of the American Chemical Societyvol 115 no 8 pp 3358ndash3359 1993

[4] E F V Scriven ldquo4-Dialkylaminopyridines super acylation andalkylation catalystsrdquo Chemical Society Reviews vol 12 no 2 pp129ndash161 1983

[5] K Ishihara M Kubota H Kurihara and H Yamamoto ldquoScan-dium trifluoromethanesulfonate as an extremely active Lewisacid catalyst in acylation of alcohols with acid anhydrides andmixed anhydridesrdquo The Journal of Organic Chemistry vol 61no 14 pp 4560ndash4567 1996

[6] R Alleti W S Oh M Perambuduru Z Afrasiabi E Sinn andV P Reddy ldquoGadolinium triflate immobilized in imidazoliumbased ionic liquids a recyclable catalyst and green solvent foracetylation of alcohols and aminesrdquo Green Chemistry vol 7 no4 pp 203ndash206 2005

[7] T N Parac-Vogt K Deleersnyder and K Binnemans ldquoLan-thanide(III) tosylates as new acylation catalystsrdquo EuropeanJournal of Organic Chemistry vol 2005 no 9 pp 1810ndash18152005

[8] K D Surya ldquoRuthenium(III) chloride catalyzed acylation ofalcohols phenols thiols and aminesrdquo Tetrahedron Letters vol45 no 14 pp 2919ndash2922 2004

[9] F M Shirini M A Zolfigol M Abedini and P SalehildquoAl(HSO

4)3catalyzed acetylation and formylation of alcoholsrdquo

Bulletin of the Korean Chemical Society vol 24 no 11 pp 1683ndash1685 2003

[10] A Orita C Tanahashi A Kakuda and J Otera ldquoHighly pow-erful and practical acylation of alcohols with acid anhydridecatalyzed by Bi(OTf)

3rdquo Journal of Organic Chemistry vol 66

no 26 pp 8926ndash8934 2001[11] Y Nakae I Kusaki and T Sato ldquoLithium perchlorate catalyzed

acetylation of alcohols under mild reaction conditionsrdquo Synlettvol 2001 no 10 pp 1584ndash1586 2001

[12] R Ballini G Bosica S Carloni L Ciaralli R Maggi and GSartori ldquoZeolite HSZ-360 as a new reusable catalyst for thedirect acetylation of alcohols and phenols under solventlessconditionsrdquo Tetrahedron Letters vol 39 no 33 pp 6049ndash60521998

[13] B M Choudary V Bhaskar M L Kantam K Koteswara Raoand K V Raghavan ldquoAcylation of alcohols with carboxylicacids via the evolution of compatible acidic sites in montmo-rillonitesrdquo Green Chemistry vol 2 pp 67ndash70 2000

[14] M H Sarvari and H Sharghi ldquoZinc oxide (ZnO) as a newhighly efficient and reusable catalyst for acylation of alcoholsphenols and amines under solvent free conditionsrdquo Tetrahe-dron vol 61 no 46 pp 10903ndash10907 2005

[15] J Izumi I Shiina and T Mukaiyama ldquoAn efficient esterifica-tion reaction between equimolar amounts of free carboxylicacids and alcohols by the combined use of octamethylcyclote-trasiloxane and a catalytic amount of titanium(iv) chloridetris(trifluoromethanesulfonate)rdquo Chemistry Letters vol 2 pp141ndash142 1995

[16] R Alleti M Perambuduru S Samantha and V P ReddyldquoGadolinium triflate an efficient and convenient catalyst for

12 ISRN Organic Chemistry

acetylation of alcohols and aminesrdquo Journal of Molecular Catal-ysis A vol 226 no 1 pp 57ndash59 2005

[17] F Shirini K RaMoghadam and T Naghdi ldquo13-Dichloro-55-dimethylhydantoin an efficient catalyst for the solvent freesynthesis of 18-dioxo-octahydro-xanthenesrdquo Iranian Journal ofCatalysis vol 2 pp 55ndash59 2012

[18] A DyerAn Introduction to Zeolite Molecular Sieves JohnWileyamp Sons Inc New York NY USA 1988

[19] A R Massah R J Kalbasi and M Azadi ldquoHighly selectiveoxidation of alcohols using MnO

2TiO2-ZrO2as a novel het-

erogeneous catalystrdquo Comptes Rendus Chimie vol 15 no 5 pp428ndash436 2012

[20] A R Massah R J Kalbasi and M Toghyani ldquoSulfonatedpolystyrenemontmorillonite nanocomposite as a new andefficient catalyst for the solvent-free Mannich reactionrdquo IranianJournal of Catalysis vol 2 no 1 pp 41ndash49 2012

[21] R J Kalbasi M Ghiaci and A R Massah ldquoHighly selectivevapor phase nitration of toluene to 4-nitro toluene usingmodified and unmodified H

3PO4ZSM-5rdquo Applied Catalysis A

vol 353 no 1 pp 1ndash8 2009[22] R J Kalbasi A Abbaspourrad A R Massah and F Zamani

ldquoHighly selective vapor-phase acylation of veratrole overH3PO4TiO2-ZrO2 using ethyl acetate as a green and efficient

acylating agentrdquo Chinese Journal of Chemistry vol 28 no 2 pp273ndash284 2010

[23] A R Massah R J Kalbasi and A Shafiei ldquoZSM-5-SO3H as

a novel efficient and reusable catalyst for the chemoselectivesynthesis and deprotection of 11-diacetates under eco-friendlyconditionsrdquoMonatshefte fur Chemie vol 143 no 4 pp 643ndash6522012

[24] A R Massah R J Kalbasi and N Samah ldquoHighly selectivesynthesis of 120573-amino carbonyl compounds over ZSM-5-SO

3H

under solvent-free conditionsrdquo Bulletin of the Korean ChemicalSociety vol 32 no 5 pp 1703ndash1708 2011

[25] A R Massah F Kazemi D Azadi et al ldquoA mild and chemos-elective solvent-free method for the synthesis of N-aryl and N-alkysulfonamidesrdquo Letters inOrganic Chemistry vol 3 no 3 pp235ndash241 2006

[26] A R Massah B Asadi M Hoseinpour A Molseghi R JKalbasi and H Javaherian Naghash ldquoA novel and efficientsolvent-free and heterogeneous method for the synthesis ofprimary secondary and bis-N-acylsulfonamides using metalhydrogen sulfate catalystsrdquo Tetrahedron vol 65 no 36 pp7696ndash7705 2009

[27] A R Massah H Adibi R Khodarahmi et al ldquoSynthesisin vitro antibacterial and carbonic anhydrase II inhibitoryactivities of N-acylsulfonamides using silica sulfuric acid asan efficient catalyst under both solvent-free and heterogeneousconditionsrdquo Bioorganic andMedicinal Chemistry vol 16 no 10pp 5465ndash5472 2008

[28] A R Massah M Dabagh S Shahidi H J Naghash AR Momeni and H Aliyan ldquoP

2O5SiO2as an efficient and

recyclable catalyst for N-acylation of sulfonamides under het-erogeneous and solvent-free conditionsrdquo Journal of the IranianChemical Society vol 6 no 2 pp 405ndash411 2009

[29] P Pushpaletha and M Lalithambika ldquoModified attapulgite anefficient solid acid catalyst for acetylation of alcohols usingacetic acidrdquo Applied Clay Science vol 51 no 4 pp 424ndash4302011

[30] L Osiglio G Romanelli and M Blanco ldquoAlcohol acetylationwith acetic acid using borated zirconia as catalystrdquo Journal ofMolecular Catalysis A vol 316 no 1ndash2 pp 52ndash58 2010

[31] P R Likhar R Arundhathi S Ghosh and M L KantamldquoPolyaniline nanofiber supported FeCl

3 an efficient and

reusable heterogeneous catalyst for the acylation of alcohols andamines with acetic acidrdquo Journal of Molecular Catalysis A vol302 no 1ndash2 pp 142ndash149 2009

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

ISRN Organic Chemistry 9

n-Decyl phenylacetate (Table 3 entry 34) IR (KBr cmminus1)1738 1456 1251 1155 721 1H NMR (400MHz CDCl

3)

120575 (ppm) 093 (t 3H 119869 = 64Hz) 127ndash138 (m 14H) 161ndash168(m 2H) 366 (s 2H) 412 (t 2H 119869 = 68Hz) 739ndash727 (m5H) 13C NMR (100MHz CDCl

3) 120575 (ppm) 142 227 259

286 292 293 295 319 415 651 768 771 774 1270 12861293 1343

Dipentylpyridine-26-dicarboxylate (Table 3 entry 35)IR (KBr cmminus1) 1741 1465 12440 1149 759 1H NMR(400MHz CDCl

3) 120575 (ppm) 094 (t 6H 119869 = 80Hz) 136ndash

150 (m 8H) 185 (quint 4H 119869 = 68Hz) 443 (t 4H 119869 =68Hz) 802 (t 1H 119869 = 76Hz) 828 (d 2H 119869 = 80Hz) 13CNMR (100MHz CDCl

3) 120575 (ppm) 140 224 281 283 664

767 771 773 774 1277 1381 1487 1647Dihexylpyridine-26-dicarboxylate (Table 3 entry 36) IR

(KBr cmminus1) 1722 1241 1144 753 1H NMR (400MHzCDCl

3) 120575 (ppm) 082ndash093 (m 6H) 181 (quint 4H 119869 =

72Hz) 122ndash138 (m 8H) 138-148 (m 4H) 439 (t 4H119869 = 72Hz) 799 (t 1H 119869 = 80Hz) 824 (d 2H 119869 = 76Hz)

Diheptyl glutarate (Table 3 entry 37) IR (KBr cmminus1)1738 1465 1148 1065 725 1H NMR (400MHz CDCl

3)

120575 (ppm) 088 (t 6H 119869 = 68Hz) 122ndash138 (m 16H) 160(quint 4H 119869 = 68Hz) 195 (quint 4H 119869 = 72Hz) 237 (t4H 119869 = 72Hz) 406 (t 4H 119869 = 68Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 140 202 226 259 286 289 317 334

646 1731Dioctyl glutarate (Table 3 entry 38) IR (KBr cmminus1) 1737

1465 1064 722 1H NMR (400MHz CDCl3) 120575 (ppm) 090

(t 6H 119869 = 64Hz) 124ndash140 (m 20H) 159ndash168 (m 4H)192ndash202 (m 4H) 236ndash248 (m 4H) 408 (t 4H 119869 =56Hz) 13CNMR (100MHzCDCl

3) 120575 (ppm) 141 199 202

226 259 286 292 292 318 330 332 334 647 647 17301731

3 Results and Discussion

As a starting point for this work the reaction was optimizedin order to find the best conditions especially in agree-ment with green chemistry (Table 1) To find the optimumconditions for acylation of amines and sulfonamides withcarboxylic acid anhydrides and chlorides several sets of reac-tion conditions were examined (Table 1 entries 1ndash5) Thusunder the best conditions amines (2mmol) were acylated atroom temperature almost quantitatively with carboxylic acidanhydrides or chlorides (2ndash4mmol) in the presence of 0005ndash001 g of ZSM-5-SO

3H without use of any solvents (Table 1

entries 1ndash4) Acylation of sulfonamides (1mmol) occurredonly with aliphatic anhydrides (15mmol) in the presenceof 001 g of catalyst at room temperature under solvent-freeconditions (Table 1 entry 5)

Then the reactionwas exploredwith a variety of aromaticand aliphatic amines to evaluate the scope and limitations ofthis method (Table 2) The results showed that the differentaromatic amines containing various electron-donating and -withdrawing groups as well as aliphatic amines reacted withcarboxylic acid chlorides or anhydrides within 5ndash30minutesto produce the corresponding amides in 70ndash95 yield

Benzoic anhydride and benzoyl chloridewas used as aromaticacylating agents Also acylation of amines were examinedusing different aliphatic acylating agents including aceticpentanoic and isobutanoic anhydridesThe excellent activityof ZSM-5-SO

3Hwas demonstrated by the good to high yields

obtained for anilines having electron-withdrawing groupssuch as Cl and NO

2(Table 2 entries 7ndash9) However the

best yields were obtained with substrates bearing electron-donating groups such as methoxy especially in the para-position (Table 2 entries 2 and 14) Also very good resultswere obtained when secondary amines were acylated in thepresence of ZSM-5-SO

3H and the corresponding amides

were obtained in 78ndash90 yields in 10ndash30 minutes at roomtemperature under solvent-free conditions (Table 2 entries 12and 18) Finally this method was used for the acylation of 4-methylbenzenesulfonamide as a weak nucleophile with aceticand pentanoic anhydrides Interestingly the corresponding119873-acyl sulfonamides were obtained in 80 and 92 yieldsafter 5 and 15 minutes in high purity (Table 2 entries 29 and30)

To demonstrate the versatility of this protocol the acyla-tion of alcohols andphenolswas investigated using carboxylicacids carboxylic acid anhydrides and chlorides as acylatingagents At first several sets of reaction conditions wereexamined to find the best conditions for acylation of alcoholsIn the optimum conditions alcohols and phenols (1mmol)were acylated at room temperature with acetic anhydridesor chlorides (2mmol) in the presence of 001 g of ZSM-5-SO3H under the solvent-free conditions (Table 1 entry 6)

Acylation with benzoic anhydride was done at 80∘C using005 g of catalyst (Table 1 entry 7) When carboxylic acidswere used as acylating agents the reactions were done at 80ndash120∘C (Table 1 entries 8ndash10)

Using a simple experimental procedure the ZSM-5-SO3H catalyzed acylation of benzylic primary and second-

ary alcohols proceeded efficiently using carboxylic acidanhydrides and chlorides (Table 3 entries 1ndash15) Differentcarboxylic acid anhydrides and chlorides such as benzoicanhydride acetic anhydride pentanoic anhydride and acetylchloride were used as acylating agent and the correspondingesters were obtained in high isolated yields and purityafter short reaction times under the solvent-free conditionsPrimary alcohols were acylated faster than secondary ones(Table 3 entries 4) and sterically hindered alcohols such astert-butyl alcohol remained unchanged It was interesting tonote that phenols were also satisfactorily acylated generatingthe corresponding esters in 75ndash95 yields (Table 3 entries13ndash15)

In order to generalize the catalytic efficiency of ZSM-5-SO3H for direct acylating with carboxylic acids the acy-

lation of alcohols was tried with different carboxylic acid(Table 3 entries 16ndash38) while most literature methods fordirect acylation of alcohols employ only acetic acid [29ndash31] Acylation with acetic propanoic phenyl acetic benzoicacid and 4-methylbenzoic acid resulted in good yield ofthe esters under the solvent-free conditions Also pleasingresults were obtained when acylation of alcohols was donewith dicarboxylic acids such as glutaric acid and pyridine-16-dicarboxylic acid and the corresponding diester was

10 ISRN Organic Chemistry

CH3

CH3

CH3

CH3

NH2

ZSM-5-SO3H

Ac2O (2 eq)

OH

+

O

+

NHO O

1000

CH3

NH2

ZSM-5-SO3H

H3C

Ac2O (2 eq)

NH

+ +

O

0 100

HO O

O

CH3

CH3

ZSM-5-SO3H

Ac2O (2 eq)

OH

OH+

O

+7

7

7 7

7

7O

O

20 80

O

CH3

ZSM-5-SO3H

H3C

NO2

NO2

Ac2O (1 eq)

OH OH

+

O

+

O O

O

80 20

CH3

CH3

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH

OH+

O

+ O

O

0 100

O

CH3

CH3

NH2

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH+

HN

+ O

O

0 100

O

rt 5 min

rt 3 min

rt 2 min

rt 2 min

Scheme 3

obtained in high purity in absence of solvent (Table 3 entries35ndash38) It is noteworthy that in contrast to most reportedmethods that need excess of acetic acid in this methodacylation of alcohols was carried out using only 12ndash20 eqof carboxylic acid Also acylation of ethylene glycol as adiol was carried out with phenylacetic acid under solvent-free conditions and the corresponding ester was obtainedin 84 after 5 minutes It should be mentioned that several

efforts to use this method for direct acylation of amines forthe synthesis of amides were not successful

The importance of selectivity in organic chemistryencouraged us to consider the selectivity of acylation ofdifferent alcohols and amines Several reactions were car-ried out using carboxylic acid anhydrides and chlorides asacylating agents and surprisingly the excellent selectivitywas found For example aromatic amines such as 4-methyl

ISRN Organic Chemistry 11

aniline can be converted into the amide in the presence ofphenol On the other hand aromatic amines were acylatedselectively in the presence of aliphatic alcohol Furthermorethe reactions of alcohols with acylating agent were so fastin comparison to those of the phenol that the selectiveacylation of aliphatic alcohols in the presence of phenolsappeared to be a distinct possibility The result showedthat selective acylation of phenols with or without electron-donating group in the presence of phenols with electron-withdrawing group is possible with this method As wellas carboxylic acid anhydrides and chlorides the excellentselectivity was observed when carboxylic acids were usedas acylating agent Acylation of alcohols was carried outselectively in the presence of phenols Also acylation ofalcohols was done in the presence of amines selectivelywhile as mentioned above this selectivity is reversed whencarboxylic acid anhydrides were used as acylating agent(Scheme 3)

To show another advantage of the present acylationmethod and the importance of scale-up ability for laboratoryand industrial purposes a few amines and phenols wereacylated in large scale successfully without considerable lim-itation For example acylation of 4-methyl aniline (Table 2entry 4) 1-decanol with benzoic anhydride (Table 3 entry5) and 1-heptanol with benzoic acid (Table 3 entry 18) wascarried out in 20mmol scales as well as the 1mmol ones Theonly difference is the reaction time Reaction in large scaleneeds more time that is because of the difficulty in stirringthe reaction mixture under solvent-free conditions

Finally we were interested to study the reusability ofthe catalysts due to economical and environmental aspectsFor this purpose the reaction of 1-heptanol with benzoicanhydride and benzoic acid was chosen as model reactionsAt the end of each run the catalyst was recovered fromthe reaction mixture by addition of dichloromethane simplefiltration and drying at 100∘C and then reused The recycledZSM-5-SO

3H was used for further runs and its activity did

not show any significant decrease even after four runs

4 Conclusion

In conclusion we have described a highly efficient and che-moselective synthetic route for the acylation of sulfonamidesamines alcohols and phenols with carboxylic acids car-boxylic acid chlorides and anhydrides in the presence ofZSM-5-SO

3H under solvent-free conditions This method

has advantages in terms of low cost and nontoxic nature of thecatalyst high yield and purity of the products short reactiontimes operational simplicity and easy workup In additionrecyclability of this protocol is attractive and useful Directacylation of alcohols with different carboxylic acids is anotheradvantage of this protocol

Acknowledgment

The support from Islamic Azad University Shahreza Branch(IAUSH) Research Council is gratefully acknowledged

References

[1] T W Greene and P G M Wuts Protective Groups in OrganicSynthesis Wiley New York NY USA 3rd edition 1999

[2] W Steglich andGHofle ldquoNN-dimethyl-4-pyridinamine a veryeffective acylation catalystrdquo Angewandte Chemie vol 8 no 12pp 980ndash981 1969

[3] E Vedejs and S T Diver ldquoTributylphosphine a remarkableacylation catalystrdquo Journal of the American Chemical Societyvol 115 no 8 pp 3358ndash3359 1993

[4] E F V Scriven ldquo4-Dialkylaminopyridines super acylation andalkylation catalystsrdquo Chemical Society Reviews vol 12 no 2 pp129ndash161 1983

[5] K Ishihara M Kubota H Kurihara and H Yamamoto ldquoScan-dium trifluoromethanesulfonate as an extremely active Lewisacid catalyst in acylation of alcohols with acid anhydrides andmixed anhydridesrdquo The Journal of Organic Chemistry vol 61no 14 pp 4560ndash4567 1996

[6] R Alleti W S Oh M Perambuduru Z Afrasiabi E Sinn andV P Reddy ldquoGadolinium triflate immobilized in imidazoliumbased ionic liquids a recyclable catalyst and green solvent foracetylation of alcohols and aminesrdquo Green Chemistry vol 7 no4 pp 203ndash206 2005

[7] T N Parac-Vogt K Deleersnyder and K Binnemans ldquoLan-thanide(III) tosylates as new acylation catalystsrdquo EuropeanJournal of Organic Chemistry vol 2005 no 9 pp 1810ndash18152005

[8] K D Surya ldquoRuthenium(III) chloride catalyzed acylation ofalcohols phenols thiols and aminesrdquo Tetrahedron Letters vol45 no 14 pp 2919ndash2922 2004

[9] F M Shirini M A Zolfigol M Abedini and P SalehildquoAl(HSO

4)3catalyzed acetylation and formylation of alcoholsrdquo

Bulletin of the Korean Chemical Society vol 24 no 11 pp 1683ndash1685 2003

[10] A Orita C Tanahashi A Kakuda and J Otera ldquoHighly pow-erful and practical acylation of alcohols with acid anhydridecatalyzed by Bi(OTf)

3rdquo Journal of Organic Chemistry vol 66

no 26 pp 8926ndash8934 2001[11] Y Nakae I Kusaki and T Sato ldquoLithium perchlorate catalyzed

acetylation of alcohols under mild reaction conditionsrdquo Synlettvol 2001 no 10 pp 1584ndash1586 2001

[12] R Ballini G Bosica S Carloni L Ciaralli R Maggi and GSartori ldquoZeolite HSZ-360 as a new reusable catalyst for thedirect acetylation of alcohols and phenols under solventlessconditionsrdquo Tetrahedron Letters vol 39 no 33 pp 6049ndash60521998

[13] B M Choudary V Bhaskar M L Kantam K Koteswara Raoand K V Raghavan ldquoAcylation of alcohols with carboxylicacids via the evolution of compatible acidic sites in montmo-rillonitesrdquo Green Chemistry vol 2 pp 67ndash70 2000

[14] M H Sarvari and H Sharghi ldquoZinc oxide (ZnO) as a newhighly efficient and reusable catalyst for acylation of alcoholsphenols and amines under solvent free conditionsrdquo Tetrahe-dron vol 61 no 46 pp 10903ndash10907 2005

[15] J Izumi I Shiina and T Mukaiyama ldquoAn efficient esterifica-tion reaction between equimolar amounts of free carboxylicacids and alcohols by the combined use of octamethylcyclote-trasiloxane and a catalytic amount of titanium(iv) chloridetris(trifluoromethanesulfonate)rdquo Chemistry Letters vol 2 pp141ndash142 1995

[16] R Alleti M Perambuduru S Samantha and V P ReddyldquoGadolinium triflate an efficient and convenient catalyst for

12 ISRN Organic Chemistry

acetylation of alcohols and aminesrdquo Journal of Molecular Catal-ysis A vol 226 no 1 pp 57ndash59 2005

[17] F Shirini K RaMoghadam and T Naghdi ldquo13-Dichloro-55-dimethylhydantoin an efficient catalyst for the solvent freesynthesis of 18-dioxo-octahydro-xanthenesrdquo Iranian Journal ofCatalysis vol 2 pp 55ndash59 2012

[18] A DyerAn Introduction to Zeolite Molecular Sieves JohnWileyamp Sons Inc New York NY USA 1988

[19] A R Massah R J Kalbasi and M Azadi ldquoHighly selectiveoxidation of alcohols using MnO

2TiO2-ZrO2as a novel het-

erogeneous catalystrdquo Comptes Rendus Chimie vol 15 no 5 pp428ndash436 2012

[20] A R Massah R J Kalbasi and M Toghyani ldquoSulfonatedpolystyrenemontmorillonite nanocomposite as a new andefficient catalyst for the solvent-free Mannich reactionrdquo IranianJournal of Catalysis vol 2 no 1 pp 41ndash49 2012

[21] R J Kalbasi M Ghiaci and A R Massah ldquoHighly selectivevapor phase nitration of toluene to 4-nitro toluene usingmodified and unmodified H

3PO4ZSM-5rdquo Applied Catalysis A

vol 353 no 1 pp 1ndash8 2009[22] R J Kalbasi A Abbaspourrad A R Massah and F Zamani

ldquoHighly selective vapor-phase acylation of veratrole overH3PO4TiO2-ZrO2 using ethyl acetate as a green and efficient

acylating agentrdquo Chinese Journal of Chemistry vol 28 no 2 pp273ndash284 2010

[23] A R Massah R J Kalbasi and A Shafiei ldquoZSM-5-SO3H as

a novel efficient and reusable catalyst for the chemoselectivesynthesis and deprotection of 11-diacetates under eco-friendlyconditionsrdquoMonatshefte fur Chemie vol 143 no 4 pp 643ndash6522012

[24] A R Massah R J Kalbasi and N Samah ldquoHighly selectivesynthesis of 120573-amino carbonyl compounds over ZSM-5-SO

3H

under solvent-free conditionsrdquo Bulletin of the Korean ChemicalSociety vol 32 no 5 pp 1703ndash1708 2011

[25] A R Massah F Kazemi D Azadi et al ldquoA mild and chemos-elective solvent-free method for the synthesis of N-aryl and N-alkysulfonamidesrdquo Letters inOrganic Chemistry vol 3 no 3 pp235ndash241 2006

[26] A R Massah B Asadi M Hoseinpour A Molseghi R JKalbasi and H Javaherian Naghash ldquoA novel and efficientsolvent-free and heterogeneous method for the synthesis ofprimary secondary and bis-N-acylsulfonamides using metalhydrogen sulfate catalystsrdquo Tetrahedron vol 65 no 36 pp7696ndash7705 2009

[27] A R Massah H Adibi R Khodarahmi et al ldquoSynthesisin vitro antibacterial and carbonic anhydrase II inhibitoryactivities of N-acylsulfonamides using silica sulfuric acid asan efficient catalyst under both solvent-free and heterogeneousconditionsrdquo Bioorganic andMedicinal Chemistry vol 16 no 10pp 5465ndash5472 2008

[28] A R Massah M Dabagh S Shahidi H J Naghash AR Momeni and H Aliyan ldquoP

2O5SiO2as an efficient and

recyclable catalyst for N-acylation of sulfonamides under het-erogeneous and solvent-free conditionsrdquo Journal of the IranianChemical Society vol 6 no 2 pp 405ndash411 2009

[29] P Pushpaletha and M Lalithambika ldquoModified attapulgite anefficient solid acid catalyst for acetylation of alcohols usingacetic acidrdquo Applied Clay Science vol 51 no 4 pp 424ndash4302011

[30] L Osiglio G Romanelli and M Blanco ldquoAlcohol acetylationwith acetic acid using borated zirconia as catalystrdquo Journal ofMolecular Catalysis A vol 316 no 1ndash2 pp 52ndash58 2010

[31] P R Likhar R Arundhathi S Ghosh and M L KantamldquoPolyaniline nanofiber supported FeCl

3 an efficient and

reusable heterogeneous catalyst for the acylation of alcohols andamines with acetic acidrdquo Journal of Molecular Catalysis A vol302 no 1ndash2 pp 142ndash149 2009

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

10 ISRN Organic Chemistry

CH3

CH3

CH3

CH3

NH2

ZSM-5-SO3H

Ac2O (2 eq)

OH

+

O

+

NHO O

1000

CH3

NH2

ZSM-5-SO3H

H3C

Ac2O (2 eq)

NH

+ +

O

0 100

HO O

O

CH3

CH3

ZSM-5-SO3H

Ac2O (2 eq)

OH

OH+

O

+7

7

7 7

7

7O

O

20 80

O

CH3

ZSM-5-SO3H

H3C

NO2

NO2

Ac2O (1 eq)

OH OH

+

O

+

O O

O

80 20

CH3

CH3

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH

OH+

O

+ O

O

0 100

O

CH3

CH3

NH2

ZSM-5-SO3H

AcOH (12 eq)

120∘C

OH+

HN

+ O

O

0 100

O

rt 5 min

rt 3 min

rt 2 min

rt 2 min

Scheme 3

obtained in high purity in absence of solvent (Table 3 entries35ndash38) It is noteworthy that in contrast to most reportedmethods that need excess of acetic acid in this methodacylation of alcohols was carried out using only 12ndash20 eqof carboxylic acid Also acylation of ethylene glycol as adiol was carried out with phenylacetic acid under solvent-free conditions and the corresponding ester was obtainedin 84 after 5 minutes It should be mentioned that several

efforts to use this method for direct acylation of amines forthe synthesis of amides were not successful

The importance of selectivity in organic chemistryencouraged us to consider the selectivity of acylation ofdifferent alcohols and amines Several reactions were car-ried out using carboxylic acid anhydrides and chlorides asacylating agents and surprisingly the excellent selectivitywas found For example aromatic amines such as 4-methyl

ISRN Organic Chemistry 11

aniline can be converted into the amide in the presence ofphenol On the other hand aromatic amines were acylatedselectively in the presence of aliphatic alcohol Furthermorethe reactions of alcohols with acylating agent were so fastin comparison to those of the phenol that the selectiveacylation of aliphatic alcohols in the presence of phenolsappeared to be a distinct possibility The result showedthat selective acylation of phenols with or without electron-donating group in the presence of phenols with electron-withdrawing group is possible with this method As wellas carboxylic acid anhydrides and chlorides the excellentselectivity was observed when carboxylic acids were usedas acylating agent Acylation of alcohols was carried outselectively in the presence of phenols Also acylation ofalcohols was done in the presence of amines selectivelywhile as mentioned above this selectivity is reversed whencarboxylic acid anhydrides were used as acylating agent(Scheme 3)

To show another advantage of the present acylationmethod and the importance of scale-up ability for laboratoryand industrial purposes a few amines and phenols wereacylated in large scale successfully without considerable lim-itation For example acylation of 4-methyl aniline (Table 2entry 4) 1-decanol with benzoic anhydride (Table 3 entry5) and 1-heptanol with benzoic acid (Table 3 entry 18) wascarried out in 20mmol scales as well as the 1mmol ones Theonly difference is the reaction time Reaction in large scaleneeds more time that is because of the difficulty in stirringthe reaction mixture under solvent-free conditions

Finally we were interested to study the reusability ofthe catalysts due to economical and environmental aspectsFor this purpose the reaction of 1-heptanol with benzoicanhydride and benzoic acid was chosen as model reactionsAt the end of each run the catalyst was recovered fromthe reaction mixture by addition of dichloromethane simplefiltration and drying at 100∘C and then reused The recycledZSM-5-SO

3H was used for further runs and its activity did

not show any significant decrease even after four runs

4 Conclusion

In conclusion we have described a highly efficient and che-moselective synthetic route for the acylation of sulfonamidesamines alcohols and phenols with carboxylic acids car-boxylic acid chlorides and anhydrides in the presence ofZSM-5-SO

3H under solvent-free conditions This method

has advantages in terms of low cost and nontoxic nature of thecatalyst high yield and purity of the products short reactiontimes operational simplicity and easy workup In additionrecyclability of this protocol is attractive and useful Directacylation of alcohols with different carboxylic acids is anotheradvantage of this protocol

Acknowledgment

The support from Islamic Azad University Shahreza Branch(IAUSH) Research Council is gratefully acknowledged

References

[1] T W Greene and P G M Wuts Protective Groups in OrganicSynthesis Wiley New York NY USA 3rd edition 1999

[2] W Steglich andGHofle ldquoNN-dimethyl-4-pyridinamine a veryeffective acylation catalystrdquo Angewandte Chemie vol 8 no 12pp 980ndash981 1969

[3] E Vedejs and S T Diver ldquoTributylphosphine a remarkableacylation catalystrdquo Journal of the American Chemical Societyvol 115 no 8 pp 3358ndash3359 1993

[4] E F V Scriven ldquo4-Dialkylaminopyridines super acylation andalkylation catalystsrdquo Chemical Society Reviews vol 12 no 2 pp129ndash161 1983

[5] K Ishihara M Kubota H Kurihara and H Yamamoto ldquoScan-dium trifluoromethanesulfonate as an extremely active Lewisacid catalyst in acylation of alcohols with acid anhydrides andmixed anhydridesrdquo The Journal of Organic Chemistry vol 61no 14 pp 4560ndash4567 1996

[6] R Alleti W S Oh M Perambuduru Z Afrasiabi E Sinn andV P Reddy ldquoGadolinium triflate immobilized in imidazoliumbased ionic liquids a recyclable catalyst and green solvent foracetylation of alcohols and aminesrdquo Green Chemistry vol 7 no4 pp 203ndash206 2005

[7] T N Parac-Vogt K Deleersnyder and K Binnemans ldquoLan-thanide(III) tosylates as new acylation catalystsrdquo EuropeanJournal of Organic Chemistry vol 2005 no 9 pp 1810ndash18152005

[8] K D Surya ldquoRuthenium(III) chloride catalyzed acylation ofalcohols phenols thiols and aminesrdquo Tetrahedron Letters vol45 no 14 pp 2919ndash2922 2004

[9] F M Shirini M A Zolfigol M Abedini and P SalehildquoAl(HSO

4)3catalyzed acetylation and formylation of alcoholsrdquo

Bulletin of the Korean Chemical Society vol 24 no 11 pp 1683ndash1685 2003

[10] A Orita C Tanahashi A Kakuda and J Otera ldquoHighly pow-erful and practical acylation of alcohols with acid anhydridecatalyzed by Bi(OTf)

3rdquo Journal of Organic Chemistry vol 66

no 26 pp 8926ndash8934 2001[11] Y Nakae I Kusaki and T Sato ldquoLithium perchlorate catalyzed

acetylation of alcohols under mild reaction conditionsrdquo Synlettvol 2001 no 10 pp 1584ndash1586 2001

[12] R Ballini G Bosica S Carloni L Ciaralli R Maggi and GSartori ldquoZeolite HSZ-360 as a new reusable catalyst for thedirect acetylation of alcohols and phenols under solventlessconditionsrdquo Tetrahedron Letters vol 39 no 33 pp 6049ndash60521998

[13] B M Choudary V Bhaskar M L Kantam K Koteswara Raoand K V Raghavan ldquoAcylation of alcohols with carboxylicacids via the evolution of compatible acidic sites in montmo-rillonitesrdquo Green Chemistry vol 2 pp 67ndash70 2000

[14] M H Sarvari and H Sharghi ldquoZinc oxide (ZnO) as a newhighly efficient and reusable catalyst for acylation of alcoholsphenols and amines under solvent free conditionsrdquo Tetrahe-dron vol 61 no 46 pp 10903ndash10907 2005

[15] J Izumi I Shiina and T Mukaiyama ldquoAn efficient esterifica-tion reaction between equimolar amounts of free carboxylicacids and alcohols by the combined use of octamethylcyclote-trasiloxane and a catalytic amount of titanium(iv) chloridetris(trifluoromethanesulfonate)rdquo Chemistry Letters vol 2 pp141ndash142 1995

[16] R Alleti M Perambuduru S Samantha and V P ReddyldquoGadolinium triflate an efficient and convenient catalyst for

12 ISRN Organic Chemistry

acetylation of alcohols and aminesrdquo Journal of Molecular Catal-ysis A vol 226 no 1 pp 57ndash59 2005

[17] F Shirini K RaMoghadam and T Naghdi ldquo13-Dichloro-55-dimethylhydantoin an efficient catalyst for the solvent freesynthesis of 18-dioxo-octahydro-xanthenesrdquo Iranian Journal ofCatalysis vol 2 pp 55ndash59 2012

[18] A DyerAn Introduction to Zeolite Molecular Sieves JohnWileyamp Sons Inc New York NY USA 1988

[19] A R Massah R J Kalbasi and M Azadi ldquoHighly selectiveoxidation of alcohols using MnO

2TiO2-ZrO2as a novel het-

erogeneous catalystrdquo Comptes Rendus Chimie vol 15 no 5 pp428ndash436 2012

[20] A R Massah R J Kalbasi and M Toghyani ldquoSulfonatedpolystyrenemontmorillonite nanocomposite as a new andefficient catalyst for the solvent-free Mannich reactionrdquo IranianJournal of Catalysis vol 2 no 1 pp 41ndash49 2012

[21] R J Kalbasi M Ghiaci and A R Massah ldquoHighly selectivevapor phase nitration of toluene to 4-nitro toluene usingmodified and unmodified H

3PO4ZSM-5rdquo Applied Catalysis A

vol 353 no 1 pp 1ndash8 2009[22] R J Kalbasi A Abbaspourrad A R Massah and F Zamani

ldquoHighly selective vapor-phase acylation of veratrole overH3PO4TiO2-ZrO2 using ethyl acetate as a green and efficient

acylating agentrdquo Chinese Journal of Chemistry vol 28 no 2 pp273ndash284 2010

[23] A R Massah R J Kalbasi and A Shafiei ldquoZSM-5-SO3H as

a novel efficient and reusable catalyst for the chemoselectivesynthesis and deprotection of 11-diacetates under eco-friendlyconditionsrdquoMonatshefte fur Chemie vol 143 no 4 pp 643ndash6522012

[24] A R Massah R J Kalbasi and N Samah ldquoHighly selectivesynthesis of 120573-amino carbonyl compounds over ZSM-5-SO

3H

under solvent-free conditionsrdquo Bulletin of the Korean ChemicalSociety vol 32 no 5 pp 1703ndash1708 2011

[25] A R Massah F Kazemi D Azadi et al ldquoA mild and chemos-elective solvent-free method for the synthesis of N-aryl and N-alkysulfonamidesrdquo Letters inOrganic Chemistry vol 3 no 3 pp235ndash241 2006

[26] A R Massah B Asadi M Hoseinpour A Molseghi R JKalbasi and H Javaherian Naghash ldquoA novel and efficientsolvent-free and heterogeneous method for the synthesis ofprimary secondary and bis-N-acylsulfonamides using metalhydrogen sulfate catalystsrdquo Tetrahedron vol 65 no 36 pp7696ndash7705 2009

[27] A R Massah H Adibi R Khodarahmi et al ldquoSynthesisin vitro antibacterial and carbonic anhydrase II inhibitoryactivities of N-acylsulfonamides using silica sulfuric acid asan efficient catalyst under both solvent-free and heterogeneousconditionsrdquo Bioorganic andMedicinal Chemistry vol 16 no 10pp 5465ndash5472 2008

[28] A R Massah M Dabagh S Shahidi H J Naghash AR Momeni and H Aliyan ldquoP

2O5SiO2as an efficient and

recyclable catalyst for N-acylation of sulfonamides under het-erogeneous and solvent-free conditionsrdquo Journal of the IranianChemical Society vol 6 no 2 pp 405ndash411 2009

[29] P Pushpaletha and M Lalithambika ldquoModified attapulgite anefficient solid acid catalyst for acetylation of alcohols usingacetic acidrdquo Applied Clay Science vol 51 no 4 pp 424ndash4302011

[30] L Osiglio G Romanelli and M Blanco ldquoAlcohol acetylationwith acetic acid using borated zirconia as catalystrdquo Journal ofMolecular Catalysis A vol 316 no 1ndash2 pp 52ndash58 2010

[31] P R Likhar R Arundhathi S Ghosh and M L KantamldquoPolyaniline nanofiber supported FeCl

3 an efficient and

reusable heterogeneous catalyst for the acylation of alcohols andamines with acetic acidrdquo Journal of Molecular Catalysis A vol302 no 1ndash2 pp 142ndash149 2009

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

ISRN Organic Chemistry 11

aniline can be converted into the amide in the presence ofphenol On the other hand aromatic amines were acylatedselectively in the presence of aliphatic alcohol Furthermorethe reactions of alcohols with acylating agent were so fastin comparison to those of the phenol that the selectiveacylation of aliphatic alcohols in the presence of phenolsappeared to be a distinct possibility The result showedthat selective acylation of phenols with or without electron-donating group in the presence of phenols with electron-withdrawing group is possible with this method As wellas carboxylic acid anhydrides and chlorides the excellentselectivity was observed when carboxylic acids were usedas acylating agent Acylation of alcohols was carried outselectively in the presence of phenols Also acylation ofalcohols was done in the presence of amines selectivelywhile as mentioned above this selectivity is reversed whencarboxylic acid anhydrides were used as acylating agent(Scheme 3)

To show another advantage of the present acylationmethod and the importance of scale-up ability for laboratoryand industrial purposes a few amines and phenols wereacylated in large scale successfully without considerable lim-itation For example acylation of 4-methyl aniline (Table 2entry 4) 1-decanol with benzoic anhydride (Table 3 entry5) and 1-heptanol with benzoic acid (Table 3 entry 18) wascarried out in 20mmol scales as well as the 1mmol ones Theonly difference is the reaction time Reaction in large scaleneeds more time that is because of the difficulty in stirringthe reaction mixture under solvent-free conditions

Finally we were interested to study the reusability ofthe catalysts due to economical and environmental aspectsFor this purpose the reaction of 1-heptanol with benzoicanhydride and benzoic acid was chosen as model reactionsAt the end of each run the catalyst was recovered fromthe reaction mixture by addition of dichloromethane simplefiltration and drying at 100∘C and then reused The recycledZSM-5-SO

3H was used for further runs and its activity did

not show any significant decrease even after four runs

4 Conclusion

In conclusion we have described a highly efficient and che-moselective synthetic route for the acylation of sulfonamidesamines alcohols and phenols with carboxylic acids car-boxylic acid chlorides and anhydrides in the presence ofZSM-5-SO

3H under solvent-free conditions This method

has advantages in terms of low cost and nontoxic nature of thecatalyst high yield and purity of the products short reactiontimes operational simplicity and easy workup In additionrecyclability of this protocol is attractive and useful Directacylation of alcohols with different carboxylic acids is anotheradvantage of this protocol

Acknowledgment

The support from Islamic Azad University Shahreza Branch(IAUSH) Research Council is gratefully acknowledged

References

[1] T W Greene and P G M Wuts Protective Groups in OrganicSynthesis Wiley New York NY USA 3rd edition 1999

[2] W Steglich andGHofle ldquoNN-dimethyl-4-pyridinamine a veryeffective acylation catalystrdquo Angewandte Chemie vol 8 no 12pp 980ndash981 1969

[3] E Vedejs and S T Diver ldquoTributylphosphine a remarkableacylation catalystrdquo Journal of the American Chemical Societyvol 115 no 8 pp 3358ndash3359 1993

[4] E F V Scriven ldquo4-Dialkylaminopyridines super acylation andalkylation catalystsrdquo Chemical Society Reviews vol 12 no 2 pp129ndash161 1983

[5] K Ishihara M Kubota H Kurihara and H Yamamoto ldquoScan-dium trifluoromethanesulfonate as an extremely active Lewisacid catalyst in acylation of alcohols with acid anhydrides andmixed anhydridesrdquo The Journal of Organic Chemistry vol 61no 14 pp 4560ndash4567 1996

[6] R Alleti W S Oh M Perambuduru Z Afrasiabi E Sinn andV P Reddy ldquoGadolinium triflate immobilized in imidazoliumbased ionic liquids a recyclable catalyst and green solvent foracetylation of alcohols and aminesrdquo Green Chemistry vol 7 no4 pp 203ndash206 2005

[7] T N Parac-Vogt K Deleersnyder and K Binnemans ldquoLan-thanide(III) tosylates as new acylation catalystsrdquo EuropeanJournal of Organic Chemistry vol 2005 no 9 pp 1810ndash18152005

[8] K D Surya ldquoRuthenium(III) chloride catalyzed acylation ofalcohols phenols thiols and aminesrdquo Tetrahedron Letters vol45 no 14 pp 2919ndash2922 2004

[9] F M Shirini M A Zolfigol M Abedini and P SalehildquoAl(HSO

4)3catalyzed acetylation and formylation of alcoholsrdquo

Bulletin of the Korean Chemical Society vol 24 no 11 pp 1683ndash1685 2003

[10] A Orita C Tanahashi A Kakuda and J Otera ldquoHighly pow-erful and practical acylation of alcohols with acid anhydridecatalyzed by Bi(OTf)

3rdquo Journal of Organic Chemistry vol 66

no 26 pp 8926ndash8934 2001[11] Y Nakae I Kusaki and T Sato ldquoLithium perchlorate catalyzed

acetylation of alcohols under mild reaction conditionsrdquo Synlettvol 2001 no 10 pp 1584ndash1586 2001

[12] R Ballini G Bosica S Carloni L Ciaralli R Maggi and GSartori ldquoZeolite HSZ-360 as a new reusable catalyst for thedirect acetylation of alcohols and phenols under solventlessconditionsrdquo Tetrahedron Letters vol 39 no 33 pp 6049ndash60521998

[13] B M Choudary V Bhaskar M L Kantam K Koteswara Raoand K V Raghavan ldquoAcylation of alcohols with carboxylicacids via the evolution of compatible acidic sites in montmo-rillonitesrdquo Green Chemistry vol 2 pp 67ndash70 2000

[14] M H Sarvari and H Sharghi ldquoZinc oxide (ZnO) as a newhighly efficient and reusable catalyst for acylation of alcoholsphenols and amines under solvent free conditionsrdquo Tetrahe-dron vol 61 no 46 pp 10903ndash10907 2005

[15] J Izumi I Shiina and T Mukaiyama ldquoAn efficient esterifica-tion reaction between equimolar amounts of free carboxylicacids and alcohols by the combined use of octamethylcyclote-trasiloxane and a catalytic amount of titanium(iv) chloridetris(trifluoromethanesulfonate)rdquo Chemistry Letters vol 2 pp141ndash142 1995

[16] R Alleti M Perambuduru S Samantha and V P ReddyldquoGadolinium triflate an efficient and convenient catalyst for

12 ISRN Organic Chemistry

acetylation of alcohols and aminesrdquo Journal of Molecular Catal-ysis A vol 226 no 1 pp 57ndash59 2005

[17] F Shirini K RaMoghadam and T Naghdi ldquo13-Dichloro-55-dimethylhydantoin an efficient catalyst for the solvent freesynthesis of 18-dioxo-octahydro-xanthenesrdquo Iranian Journal ofCatalysis vol 2 pp 55ndash59 2012

[18] A DyerAn Introduction to Zeolite Molecular Sieves JohnWileyamp Sons Inc New York NY USA 1988

[19] A R Massah R J Kalbasi and M Azadi ldquoHighly selectiveoxidation of alcohols using MnO

2TiO2-ZrO2as a novel het-

erogeneous catalystrdquo Comptes Rendus Chimie vol 15 no 5 pp428ndash436 2012

[20] A R Massah R J Kalbasi and M Toghyani ldquoSulfonatedpolystyrenemontmorillonite nanocomposite as a new andefficient catalyst for the solvent-free Mannich reactionrdquo IranianJournal of Catalysis vol 2 no 1 pp 41ndash49 2012

[21] R J Kalbasi M Ghiaci and A R Massah ldquoHighly selectivevapor phase nitration of toluene to 4-nitro toluene usingmodified and unmodified H

3PO4ZSM-5rdquo Applied Catalysis A

vol 353 no 1 pp 1ndash8 2009[22] R J Kalbasi A Abbaspourrad A R Massah and F Zamani

ldquoHighly selective vapor-phase acylation of veratrole overH3PO4TiO2-ZrO2 using ethyl acetate as a green and efficient

acylating agentrdquo Chinese Journal of Chemistry vol 28 no 2 pp273ndash284 2010

[23] A R Massah R J Kalbasi and A Shafiei ldquoZSM-5-SO3H as

a novel efficient and reusable catalyst for the chemoselectivesynthesis and deprotection of 11-diacetates under eco-friendlyconditionsrdquoMonatshefte fur Chemie vol 143 no 4 pp 643ndash6522012

[24] A R Massah R J Kalbasi and N Samah ldquoHighly selectivesynthesis of 120573-amino carbonyl compounds over ZSM-5-SO

3H

under solvent-free conditionsrdquo Bulletin of the Korean ChemicalSociety vol 32 no 5 pp 1703ndash1708 2011

[25] A R Massah F Kazemi D Azadi et al ldquoA mild and chemos-elective solvent-free method for the synthesis of N-aryl and N-alkysulfonamidesrdquo Letters inOrganic Chemistry vol 3 no 3 pp235ndash241 2006

[26] A R Massah B Asadi M Hoseinpour A Molseghi R JKalbasi and H Javaherian Naghash ldquoA novel and efficientsolvent-free and heterogeneous method for the synthesis ofprimary secondary and bis-N-acylsulfonamides using metalhydrogen sulfate catalystsrdquo Tetrahedron vol 65 no 36 pp7696ndash7705 2009

[27] A R Massah H Adibi R Khodarahmi et al ldquoSynthesisin vitro antibacterial and carbonic anhydrase II inhibitoryactivities of N-acylsulfonamides using silica sulfuric acid asan efficient catalyst under both solvent-free and heterogeneousconditionsrdquo Bioorganic andMedicinal Chemistry vol 16 no 10pp 5465ndash5472 2008

[28] A R Massah M Dabagh S Shahidi H J Naghash AR Momeni and H Aliyan ldquoP

2O5SiO2as an efficient and

recyclable catalyst for N-acylation of sulfonamides under het-erogeneous and solvent-free conditionsrdquo Journal of the IranianChemical Society vol 6 no 2 pp 405ndash411 2009

[29] P Pushpaletha and M Lalithambika ldquoModified attapulgite anefficient solid acid catalyst for acetylation of alcohols usingacetic acidrdquo Applied Clay Science vol 51 no 4 pp 424ndash4302011

[30] L Osiglio G Romanelli and M Blanco ldquoAlcohol acetylationwith acetic acid using borated zirconia as catalystrdquo Journal ofMolecular Catalysis A vol 316 no 1ndash2 pp 52ndash58 2010

[31] P R Likhar R Arundhathi S Ghosh and M L KantamldquoPolyaniline nanofiber supported FeCl

3 an efficient and

reusable heterogeneous catalyst for the acylation of alcohols andamines with acetic acidrdquo Journal of Molecular Catalysis A vol302 no 1ndash2 pp 142ndash149 2009

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

12 ISRN Organic Chemistry

acetylation of alcohols and aminesrdquo Journal of Molecular Catal-ysis A vol 226 no 1 pp 57ndash59 2005

[17] F Shirini K RaMoghadam and T Naghdi ldquo13-Dichloro-55-dimethylhydantoin an efficient catalyst for the solvent freesynthesis of 18-dioxo-octahydro-xanthenesrdquo Iranian Journal ofCatalysis vol 2 pp 55ndash59 2012

[18] A DyerAn Introduction to Zeolite Molecular Sieves JohnWileyamp Sons Inc New York NY USA 1988

[19] A R Massah R J Kalbasi and M Azadi ldquoHighly selectiveoxidation of alcohols using MnO

2TiO2-ZrO2as a novel het-

erogeneous catalystrdquo Comptes Rendus Chimie vol 15 no 5 pp428ndash436 2012

[20] A R Massah R J Kalbasi and M Toghyani ldquoSulfonatedpolystyrenemontmorillonite nanocomposite as a new andefficient catalyst for the solvent-free Mannich reactionrdquo IranianJournal of Catalysis vol 2 no 1 pp 41ndash49 2012

[21] R J Kalbasi M Ghiaci and A R Massah ldquoHighly selectivevapor phase nitration of toluene to 4-nitro toluene usingmodified and unmodified H

3PO4ZSM-5rdquo Applied Catalysis A

vol 353 no 1 pp 1ndash8 2009[22] R J Kalbasi A Abbaspourrad A R Massah and F Zamani

ldquoHighly selective vapor-phase acylation of veratrole overH3PO4TiO2-ZrO2 using ethyl acetate as a green and efficient

acylating agentrdquo Chinese Journal of Chemistry vol 28 no 2 pp273ndash284 2010

[23] A R Massah R J Kalbasi and A Shafiei ldquoZSM-5-SO3H as

a novel efficient and reusable catalyst for the chemoselectivesynthesis and deprotection of 11-diacetates under eco-friendlyconditionsrdquoMonatshefte fur Chemie vol 143 no 4 pp 643ndash6522012

[24] A R Massah R J Kalbasi and N Samah ldquoHighly selectivesynthesis of 120573-amino carbonyl compounds over ZSM-5-SO

3H

under solvent-free conditionsrdquo Bulletin of the Korean ChemicalSociety vol 32 no 5 pp 1703ndash1708 2011

[25] A R Massah F Kazemi D Azadi et al ldquoA mild and chemos-elective solvent-free method for the synthesis of N-aryl and N-alkysulfonamidesrdquo Letters inOrganic Chemistry vol 3 no 3 pp235ndash241 2006

[26] A R Massah B Asadi M Hoseinpour A Molseghi R JKalbasi and H Javaherian Naghash ldquoA novel and efficientsolvent-free and heterogeneous method for the synthesis ofprimary secondary and bis-N-acylsulfonamides using metalhydrogen sulfate catalystsrdquo Tetrahedron vol 65 no 36 pp7696ndash7705 2009

[27] A R Massah H Adibi R Khodarahmi et al ldquoSynthesisin vitro antibacterial and carbonic anhydrase II inhibitoryactivities of N-acylsulfonamides using silica sulfuric acid asan efficient catalyst under both solvent-free and heterogeneousconditionsrdquo Bioorganic andMedicinal Chemistry vol 16 no 10pp 5465ndash5472 2008

[28] A R Massah M Dabagh S Shahidi H J Naghash AR Momeni and H Aliyan ldquoP

2O5SiO2as an efficient and

recyclable catalyst for N-acylation of sulfonamides under het-erogeneous and solvent-free conditionsrdquo Journal of the IranianChemical Society vol 6 no 2 pp 405ndash411 2009

[29] P Pushpaletha and M Lalithambika ldquoModified attapulgite anefficient solid acid catalyst for acetylation of alcohols usingacetic acidrdquo Applied Clay Science vol 51 no 4 pp 424ndash4302011

[30] L Osiglio G Romanelli and M Blanco ldquoAlcohol acetylationwith acetic acid using borated zirconia as catalystrdquo Journal ofMolecular Catalysis A vol 316 no 1ndash2 pp 52ndash58 2010

[31] P R Likhar R Arundhathi S Ghosh and M L KantamldquoPolyaniline nanofiber supported FeCl

3 an efficient and

reusable heterogeneous catalyst for the acylation of alcohols andamines with acetic acidrdquo Journal of Molecular Catalysis A vol302 no 1ndash2 pp 142ndash149 2009

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