Synthesis, Characterization and Antimicrobial Activity of Some Schiff Bases of 2-amino-4-(4-chlorophenyl)–n-(3-furan-2-ylmethyl carboxamido) thiophenes

 

Monica Arora*, J. Saravanan, S. Mohan, Shivaji Bhattacharjee

Department of Pharmaceutical Chemistry, PES College of Pharmacy, Bangalore-50, Karnataka, India.

*Corresponding Author E-mail: monicaarora15@gmail.com

 

 

ABSTRACT:

2-amino-4-(4-chlorophenyl)-N-(3-furan-2-ylmethyl carboxamido) thiophenes was synthesized using versatile Gewald reaction .First step is preparation of  furfuryl cyanoacetamide which was carried out by condensation of furfuryl amine and ethyl cyano acetate which was then reacted with p-chloro  acetophenone, sulphur, diethyl amine to give 2-amino-4-(4-chlorophenyl)-N-(3-furan-2-yl methyl carboxamido) thiophene (SM-4) later the compound was treated with twelve different substituted aryl aldehydes to yield twelve new Schiff bases(SM 4a-4l). The compounds were characterized IR, 1H NMR and mass spectral data and screened for antimicrobial activity.

 

KEYWORDS: Synthesis, Thiophenes, Schiff bases, Spectral analysis, Antimicrobial activity.

 


INTRODUCTION:

A large number of medicinal compounds which have been discovered belong to heterocycles containing Nitrogen and Sulphur. Various pharmacological activity of these heterocycles has helped the implementation of new approaches towards the discovery of novel drugs. Thiophenes and its derivatives are an important class of heterocyclic compounds specifically, the benzo[b] thiophenes reported to possess wide spectrum of biological properties such as antimicrobial1, anti- inflammatory2, CNS depressant activity3, antifungal activity4, analgesic5, anti-tumor6, alkaline phosphatase inhibitor7.

 

Similarly Schiff Bases derivatives also have been reported to possess an array of biological activities therefore attracts interest both for synthetic and biological point of view. Schiff base exhibits antimicrobial8, ulcerogenic9, anticonvulsant10, CNS depressant activities11. Generally, In Pharmaceutical field new drugs are discovered by molecular modification of the lead compound of established activity. So far, a range of new thiophenes have been synthesized and screened for their biological activity.

 

The encouraging results prompted us design and prepare new 2-amino benzo[b] thiophenes by adaptation of well known and versatile Gewald reaction13 and their Schiff bases where in two moieties incorporating heterocycles are linked together through azomethine (-CH=N-) grouping and to study their anti microbial activity.

 

MATERIAL AND METHODS:

Chemicals:

Furfuryl amine, ethyl cyanoacetate, , p-chloro  acetophenone, acetic anhydride, sulphur, diethyl amine, 4’-dimethyl amino benzaldehyde, 3’,4’5’-trimethoxy benzaldehyde, 3’,4’-dimethoxy benzaldehyde, 2’-nitro benzaldehyde,3’-nitro benzaldehyde, 2’-chloro benzaldehyde, 4’–chloro benzaldehyde,  4’-hydroxy benzaldehyde, 4’-hydroxy 3’-methoxy benzaldehyde, 2’-hydroxy  benzaldehyde, 4’-methoxy benzaldehyde, 4’-dimethyl amino bezaldehyde, 4’methyl benzaldehyde were obtained from local dealer. All other chemical used were of laboratory grade.

 

EXPERIMENTAL:

Melting points were taken in open capillary tubes and are uncorrected. The purity of compounds was confirmed by thin layer chromatography using Merck silica gel 60 F254 coated aluminium plates. IR spectra were recorded on Shimadzu-FTIR Infrared spectrometer in KBr (νmax in cm−1). 1H NMR spectra were recorded in CDCl3 and DMSO-d6 on a Varian (300 MHz) spectrometer using TMS as internal standard and 13C NMR spectra were recorded in CDCl3 and in DMSO-d6 on a Varian (75 MHz) spectrometer. FABMS spectra were recorded on a JEOL SX 102/DA-6000 Mass spectrometer using argon/xenon (6 kv,10 mA) as the FAB gas.

 

Preparation of 3-(4-chlorophenyl)-2-cyano-N-(furan-2-ylmethyl) but-2-enamide:

Furfuryl cyanoacetamide was prepared by condensation of furfuryl amine and ethyl cyano acetate (1:1) by heating for 2 hours at 160o C. Furfuryl cyanoacetamide is further reacted with p-chloro acetophenone in presence of ammonium acetate (1gm) and glacial acetic acid (2ml) in benzene (100 ml) for 12 hours in dean stark apparatus with continuous separation of water. After 12 hours the reaction mixture was cooled, diluted with 10 ml of benzene and washed with sodium carbonate solution (10%w/v in water) and water successively and dried over anhydrous sodium sulphate. The solvent was removed under vacuum and the intermediate crude product obtained was immediately processed for the next step.

Preparation of 2-amino-4-(4-chlorophenyl)-N-(3-furan-2-ylmethyl carboxamido) thiophenes (SM-4):

To a mixture of 3-(4-chlorophenyl)-2-cyano-N-(furan-2-ylmethyl) but-2-enamide in alcohol (40ml) and sulfur (1.28gm) at 50oC, diethyl amine (7ml) was added dropwise with stirring. The reaction mixture was stirred for further 3 hours at same temperature. The reaction mixture was directly used for further derivatization.

 

Preparation of 2-[(substituted benzylidene) amino] 4-(4-chlorophenyl)-N-(3-furan-2-ylmethyl carboxamido) thiophenes. (SM-4a-4l):

A mixture of equimolar amount (0.01) of 2-amino thiophenes, benzaldehyde derivatives (a-l) in ethanol (40ml) along with catalytic amount of glacial acetic acid was refluxed for 4 hours. The reaction mixture was concentrated cooled, the solid obtained was filtered and recrystallized from ethanol to give Schiff base (SM-4a-4l). It was obtained 55-60% yield.

 


 

Scheme

 

Table -1 Physical data of 2-amino-4-(4-chlorophenyl)-N-(3-furan-2-ylmethyl carboxamido) thiophene. (SM-4)

 

Comp Code

Molecular

Formula

M.W(g)

Recrystalization

Solvent

M.P(OC)

%Yield

TLC Solvent

Rf Value

SM-4

C16H13ClN2O2S

332

2-propanol

   181

45

Methanol: Chloroform(9:1)

0.64

 

Table-2 Physical data of 2-[(substituted benzylidene) amino] 4-(4-chlorophenyl)-N-(3-furan-2-ylmethyl carboxamido) thiophenes.(SM-4a-4l)

Comp Code

X

Molecular Formula

M.W (g)

M.P (oC)

% Yield

T.L.C Solvent

Rf Value

SM-4a

3’4’5’–trimethoxy benzaldehyde

C26H23ClN2O5S

510

206

69

Methanol: Chloroform (9:1)

0.51

SM-4b

3’4’–dimethoxy benzaldehyde

C25H21ClN2O4S

480.3

197

63

Methanol: Chloroform (9:1)

0.71

SM-4c

2’–nitro benzaldehyde

C23H16ClN3O4S

465.6

184

58

Methanol: Chloroform (9:1)

0.63

SM-4d

3’-nitro benzaldehyde

C23H16ClN3O4S

465.6

192

52

Methanol: Chloroform (9:1)

0.58

SM-4e

2’-chloro benzaldehyde

C23H16Cl2N2O2S

455.3

185

55

Methanol: Chloroform (9:1)

0.70

SM-4f

4’-chloro benzaldehyde

C23H16Cl2N2O2S

455.3

223

57

Methanol: Chloroform (9:1)

0.49

SM-4g

4’-hydroxy benzaldehyde

C23H17ClN2O3S

436.9

208

50

Methanol: Chloroform (9:1)

0.50

SM-4h

4’hydroxy 3’methoxy benzaldehyde

C24H19ClN2O4S

467.4

212

59

Methanol: Chloroform (9:1)

0.41

SM-4i

2’hydroxy benzaldehyde

C23H17ClN2O3S

436.9

214

47

Methanol: Chloroform (9:1)

0.33

SM-4j

4’- methoxy benzaldehyde

C24H19ClN2O3S

450.1

177

70

Methanol: Chloroform (9:1)

0.75

SM-4k

4’ –dimethyl amino benzaldehyde

C25H22ClN3O2S

463.1

192

55

Methanol: Chloroform (9:1)

0.59

SM-4l

4’ –methyl

benzaldehyde

C25H22ClN3O2S

435.0

183

48

Methanol: Chloroform (9:1)

0.66

 

Table-3 Spectral data of 2-amino-4-(4-chlorophenyl)-N-(3-furan-2-ylmethyl carboxamido) thiophene.(SM-4)

Comp Code

λ  max.(nm)

IR

1 H NMR

SM-4

159

3303.46 cm-1(NH stretch of amide);3092.12 cm-1(Ar-CH );2776.9 cm-1(Ali-CH);1672.9 cm-1(C=O of amide);1620.30(-NH bend); 1524.65 (Ar C=C);1648.61 (HC=N);1148.14 cm-1(C-O of furan);871.09 (C-N);751.89 (C-S);721.85 (C-Cl)

8.0(s,1H of CONH-)7.3-7.5(m,2H of aromatic H)7.2-7.4(m,2H of aromatic )7.1(d,1H of furfuryl ring)6.4(s,1H of  thiophene)6.2(d,2H of furfuryl ring) 4.1(d,2H of –CH2of furfuryl ring 5.5(s,2H of NH2)

 


Antimicrobial studies

All the synthesized compounds were screened for their antibacterial and antifungal activity by agar diffusion method 12 at a conc of 50µg/ml against Staphylococcus aureus, Bacillus subtilis, Escherichia coli, Klebsiella pneumonia, Aspergillus niger and Candida albicans .After 24 hours of drug addition, zone of inhibition was measured and recorded. Ampicillin, Norfloxacin and Mecanazole nitrate at 50µg/ml were used as standards in the experiment

 

RESULTS:

From the antibacterial activity results it was observed that both electron donating and electron withdrawing groups on the aldehydic phenyl ring of the compounds influenced the activity. Among the drugs tested for antimicrobial activities Table 5, Table 6 showed that compounds SM-4a, SM-4e, SM-4f, SM-4g, SM-4i exhibited potent activity by showing zone of inhibition ranging from 15mm-23mm.All these drugs showed potent activity against Staphylococcus aureus with high zone of inhibition. All other drug showed drugs showed moderate inhibitory properties against the test organism. Against Candida albicans none of the test drugs showed significant activity. Standard drugs, Ampicillin, Norfloxacin and Mecanazole nitrate exhibited potent inhibitory properties against all the test organism.

 

DISCUSSION:

From the IR, 1H, NMR and mass spectrum obtained, characterization of data has been done and given in table 1, 2, 3 and 4. The IR spectrum of  2-amino-4-(4-chlorophenyl)-N-(3-furan-2-ylmethylcarboxamido)thiophene. (SM-4) shows NH2 peak at3306.46 cm-1.The NMR spectrum shows a broad peak at δ =5.5 of NH2.

 

The IR spectra of all the Schiff bases shows the disappearance of NH2 peak and the appearance of –N=CH (Imine) peak at the range of 1640-1680 cm-1 which clearly suggest the formation of expected compounds. The NMR spectra of the compounds SM-4b,SM-4c,SM-4e,SM-4g and SM-4l shows sharp singlet peak at the range of δ =8.2-8.7 of –N=CH (Imine)  which also further confirms the formation of the compounds of the series. The compounds SM-4b, SM-4c and SM-4e, SM-4g, SM-4l were also confirmed by Mass spectrum.

 

 


Table-4 Spectral data of 2-[(substituted benzylidene) amino] 4-(4-chlorophenyl)-N-(3-furan-2-ylmethyl carboxamido) thiophenes.(SM-4a-4l)

X

λ  max. (nm)

 IR

1 H NMR

Mass

3’4’5’–trimethoxy benzaldehyde

275

3393.41 cm-1(NH stretch of amide);3100.21cm-1(Ar-CH );2779.5 cm-1(Ali-CH);1670.0 cm-1(C=O of amide);1621.21(-NH bend); 1525.45 (Ar C=C);1647.01 (HC=N); 1257.95

(Ar C-O of OCH3);1148.41 cm-1(C-O of furan);870.00 (C-N);752.88 (C-S);721.06 (C-Cl)

 

 

3’4’–dimethoxy benzaldehyde

271

3396.32 cm-1(NH stretch of amide);3165.29cm-1(Ar-CH );2780.32 cm-1(Ali-CH);1674.96cm-1(C=O of amide);1622.22(-NH bend); 1524.44 (Ar C=C);1646.00 (HC=N); 1251.76

(Ar C-O of OCH3);1142.65 cm-1(C-O of furan);870.00 (C-N);750.34 (C-S);724.32(C-Cl)

8.2(s,2H 1H of CONH- ,1H of N=CH)7.4-7.6(m,4H of aromatic H)7.3-7.5(m,3H of aromatic )7.1(d,1H of furfuryl ring)6.5(s,1H of  thiophene)6.0(d,2H of furfuryl ring) 3.5(s,6H of –OCH3)4.1(d,2H of –CH2of furfuryl ring

480

2’-nitro benzaldehyde

249

3389.30 cm-1(NH stretch of amide);3159.78cm-1(Ar-CH );2789.01 cm-1(Ali-CH);1677.69cm-1(C=O of amide);1654.98(-NH bend); 1521.32 (Ar C=C);1647.43 (HC=N);1381.34 (N-O of NO2);1141.62 cm-1(C-O of furan);875.52 (C-N);754.33 (C-S);724.22(C-Cl)

8.6(s,2H 1H of CONH-,1H of N=CH) 8.0(1H of  aromatic H)  7.4-7.6(m,3H of aromatic H) 7.7-7.8(m,4H of aromatic H) 7.1(d,1H of furfuryl ring) 6.5(s,1H of thiophene)6.0(d,2H of furfuryl ring)4.1(d,2H of –CH2 of furfuryl ring)

423

3’-nitro benzaldehyde

263

3370.40 cm-1(NH stretch of amide);3161.77cm-1(Ar-CH );2791.31 cm-1(Ali-CH);1640.21cm-1(C=O of amide);1649.47(-NH bend); 1522.89 (Ar C=C);1647.40 (HC=N);1379.21 (N-O of NO2);1142.60 cm-1(C-O of furan);875.65 (C-N);752.21 (C-S);743.31(C-Cl)

 

 

2’ -chloro benzaldehyde

269

3350.45 cm-1(NH stretch of amide);3201.32cm-1(Ar-CH );2798.36 cm-1(Ali-CH);1642.21cm-1(C=O of amide);1650.34(-NH bend); 1530.84 (Ar C=C);1646.32 (HC=N);1148.43 cm-1(C-O of furan);877.21 (C-N);749.61 (C-S);747.62(C-Cl)

8.5(s,2H 1H of CONH- ,1H of N=CH)7.5-7.7((m,4H aromatic H) 7.8-7.9(m,4H aromatic H) 7.1(d,1H of furfuryl ring)   6.9 (s,1H of thiophene)6.1(d,2H of furfuryl ring) 4.3(d,2H of –CH2 of furfuryl ring)

455

4’-chloro benzaldehyde

245

3345.45 cm-1(NH stretch of amide);3279.43cm-1(Ar-CH);2794.33cm-1(Ali-CH);1650.09cm-1(C=O of amide);1665.06(-NH bend); 1521.62(Ar C=C);1644.32 (HC=N);1146.03 cm-1(C-O of furan);879.12 (C-N);750.03 (C-S);749.32(C-Cl)

 

 

4’-hydroxy benzaldehyde

250

 3354 cm-1  (OH); 3342.45 cm-1(NH stretch of amide);3200.21cm-1(Ar-CH );2766.23 cm-1(Ali-CH);1640.20cm-1(C=O of amide);1643.32(-NH bend); 1524.67(ArC=C);1642.65(HC=N);1148.43 cm-1(C-O of furan);877.21 (C-N);744.61 (C-S);748.22(C-Cl)

8.3(s,2H 1H of CONH- ,1H of N=CH)7.3-7.5((m,4H aromatic H) 7.6-7.9(m,4H aromatic H) 7.0(d,1H of furfuryl ring)   6.6 (s,1H of thiophene)6.2(d,2H of furfuryl ring) 5.2(s,1Hof OH)  4.2(d,2H of –CH2 of furfuryl ring)

436

4’ –hydroxy 3-methoxy benzaldehyde

220

3400.07 cm-1  (OH); 3343.51 cm-1(NH stretch of amide);3165.29cm-1(Ar-CH );2780.32 cm-1(Ali-CH);1674.96cm-1(C=O of amide);1622.22(-NH bend); 1523.99 (Ar C=C);1654.16 (HC=N); 1255.77

(Ar C-O of OCH3);1144.55 cm-1(C-O of furan);875.01 (C-N);757.36 (C-S);729.32(C-Cl)

 

 

2’ -hydroxy benzaldehyde

237

3360.03 cm-1  (OH); 3347.44 cm-1(NH stretch of amide);3276.27cm-1(Ar-CH );2769.27 cm-1(Ali-CH);1651.23cm-1(C=O of amide);1639.27(-NH bend); 1532.23(ArC=C);1651.05(HC=N);1154.34 cm-1(C-O of furan);878.22 (C-N);745.69 (C-S);750.27(C-Cl)

 

 

4’–methoxy benzaldehyde

274

3400.26 cm-1(NH stretch of amide);3208.64cm-1(Ar-CH );2780.32 cm-1(Ali-CH);1674.96cm-1(C=O of amide);1622.22(-NH bend); 1524.44 (Ar C=C);1646.00 (HC=N); 1251.76

(Ar C-O of OCH3);1142.65 cm-1(C-O of furan);870.00 (C-N);750.34 (C-S);724.32(C-Cl)

 

 

4’–dimethyl amino benzaldehyde

236

3396.32 cm-1(NH stretch of amide); 3165.29cm-1(Ar-CH); 2780.32 cm-1(Ali-CH); 2959.13 (CH of CH3).  1674.96cm-1(C=O of amide);1622.22(-NH bend); 1524.44 (Ar C=C);1646.00 (HC=N); 1251.76

(Ar C-O of OCH3);1142.65 cm-1(C-O of furan);870.00 (C-N);750.34 (C-S);724.32(C-Cl)

 

 

4’ –methyl benzaldehyde

227

3246.01 cm-1 (NH); 3043.00 cm-1   (Ar-CH,Str); 2876.06cm-1(Ali-CH); 2948.13 (CH of CH3).   1622.21 cm-1  (C-N, imine, Str);(C=C,Ar, Str);1321.21 cm-1  (C=N); 1609.06cm-1   (C=O);741cm-1 (C-Cl);776.03 cm-1 (C-S)

8.1(s,2H 1H of CONH- ,1H of N=CH)7.3-7.5((m,4H aromatic H) 7.6-7.7(m,4H aromatic H) 7.1(d,1H of furfuryl ring)   6.8 (s,1H of thiophene)6.0(d,2H of furfuryl ring) 4.2(d,2H of –CH2 of furfuryl ring) 2.1(s,3H of CH3)

435

 

Table-5 Antimicrobial activity of 2-amino-4-(4-chlorophenyl)-N-(3-furan-2-ylmethyl carboxamido) thiophene. (SM-4)

Comp Code

S.aureus

B.subtilus

E.coli

K.pneumonia

A.niger

C.albicans

SM-4

16

14

13

13

16

--

Ampicillin

23

17

23

17

--

--

Norfloxacin

24

27

26

27

--

--

Miconazole

--

--

--

--

30

27

 

Table -6 Antimicrobial activity of 2-[(substituted benzylidene) amino] 4-(4-chlorophenyl)-N-(3-furan-2-ylmethyl carboxamido) thiophenes.(SM-4a-4l)

Comp Code

S.aureus

B.subtilus

E.coli

K.pneumonia

A.niger

C.albicans

3’4’5’–trimethoxy benzaldehyde

21

18

--

14

14

--

3’4’–dimethoxy benzaldehyde

16

15

--

14

15

--

2’-nitro benzaldehyde

14

13

11

10

13

--

3’-nitro benzaldehyde

13

11

10

10

12

--

2’ chloro benzaldehyde

22

19

19

18

18

10

4’-chloro benzaldehyde

23

19

20

18

19

11

4’-hydroxy benzaldehyde

22

18

17

18

17

10

4’-hydroxy 3’-   methoxy

benzaldehyde

20

16

19

16

18

09

2’ –hydroxy benzaldehyde

22

16

19

17

18

09

4’ –methoxy benzaldehyde

14

14

15

18

18

08

4’ –dimethyl amino benzaldehyde

12

13

14

--

15

--

4’ –methyl benzaldehyde

16

15

14

14

13

--

Ampicillin

22

18

24

18

--

--

Norfloxacin

33

28

26

28

--

--

Miconazole

--

--

--

--

30

27

 


ACKNOWLEDGEMENTS:

The authors are thankful to Management, PES college of Pharmacy for providing necessary facilities.

 

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Received on 04.12.2012         Modified on 14.12.2012

Accepted on 20.12.2012         © AJRC All right reserved

Asian J. Research Chem. 6(1):  January 2013; Page 24-28