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Synthesis, Reactions and Characterization of bis-thieno[2,3-b]- pyridine-2-carbohydrazide Derivative

Fawzy A. Attaby and Ahmed A. M. Elreedy

Abstract: Reaction of diethyl 4,4'(1,4-phenylene)bis(3-amino-5-acetyl-6-methylthieno[2,3-b]pyridine-2-carboxylate (1) with hydrazine hydrate afforded the 4,4’-benzene-1,4-diylbis(5-acetyl-3-amino-6-methylthieno[2,3-b]pyridine-2-carbohydrazide) (3). The structure of 2 was inferred through independent synthetic reaction of diethyl 2,2’-{1,4-phenylenebis[3-cyano-5-acetyl-6-methylpyridine-4,2- diyl)thio]}diacetate 2 under the same applied reaction conditions. On the other hand, reaction of 3 with formic acid, acetic anhydride, triethylorthoformate, acetic acid, ethyl acetoacetate, diethylmalonate, phenylisothiocyante and acetylacetone aiming to build up pyrimidine, pyrazole or oxadiazole on the ring system of 3. Structures of all newly synthesized heterocyclic compounds in the

present study were confirmed by considering the data of IR, 1H NMR, mass spectra as well as that of elemental analyses.

Index Terms: bis-thienopyridine-2-carboxylate; bis-thienopyridine-2-carbohydrazide; bis-pyridothienopyrimidin-4(3H)-one); bis- pyridothienopyrimidin-3(4H)-yl)imidoformate; bis-pyrazolothienopyridin-3-one)

1 INTRODUCTION

The biological importance of both bis-compounds [1-5] and 2-thioxopyridine-3-carbonitriles [6-11] as well as a conjunction to our previous work [12-18] stimulated our interest to synthesize several derivatives of these ring systems that are required for several chemical transformations and for our medicinal chemistry programs.

2 RESULTS AND DISCUSSION

An unequivocal support for the structure of compound 1 [19] came from the series of reactions concerning the presence of the ester group at 2- position of the thienyl moiety. Thus, it has been found that diethyl 4,4'(1,4-phenylene)bis(3-amino-5- acetyl-6-methylthieno[2,3-b]pyridine-2-carboxylate 1 reacted with hydrazine hydrate in ethanol (20 mL) under reflux for 10 hours to give a reaction product
3 that corresponding to the loss of two molecules of ethanol. The IR spectrum (cm-1) of 3 showed the absorption bands of the NH2 and NH groups at
---------------------------------------

Fawzy A. Attaby: Professor of Organic Chemistry,

Cairo University, Faculty of Science, Chemistry Department, Giza 12613, Egypt; E- mail: fattaby@hotmail.com; Ahmed A. M. El- Reedy: Basic-Applied Sci. Dept., Faculty of Oral and Dental Medicine, Nahda University, Beni-Suef, Egypt
3454, 3322 and 3219. Its mass spectrum gave the peaks at m/z = 603, 0.5% which corresponding to the parent peak of the molecular ion [M+H]+ in addition to other peaks which gave a further confirmation of 3 structure (cf. Exp. Part and Scheme 1). Based on the above data, in addition to that of elemental analysis, this compound could be formulated as 4,4’-benzene-1,4-diylbis(5-acetyl-3- amino-6-meth-ylthieno[2,3-b]pyridine-2-carbohyd- razide) 3. An authentic sample of compound 3 was obtained by the reaction of compound 2 with hydrazine hydrate under reflux for 10 hours. It important to report here that compound 3 obtained by the two pathways was indentical in all physical and chemical properties (cf. Exp. Part). The isolation of compound 3 with their adjacent NH2 and CONHNH2 groups stimulated our interest to utilize it as a versatile starting material for the synthesis of several heterocyclic derivatives. This goal was achieved via its reactions with a variety of activated reagents aiming to build up the pyrimidine nucleus on the thienopyridine skeleton. Thus, it has been found that compound 3 reacted with formic acid under reflux to give the corresponding 4,4’-benzene-1,4-diylbis(8-acetyl-3- amino-7-methylpyrido[3’,2’:4,5]thieno[3,2-d]pyrimi- din-4-(3H)-one) 4. The reaction most probably proceeded through the formylation of NH2 group at the thiophene ring to give the non-isolable intermediate [I] which converted to the enol form [II] followed by elimination of two molecules of

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COOEt

S CN

CH3

NH2NH2.H2O

N N

Reflux

H3C

O H3C

COOEt

NC S COOEt

H2N

NH O

S NH2

CH3

NH2NH2.H2O

NH2

CH3

N N N N

Reflux

H3C

O H3C

H2N

COOEt

H3C

O H3C

H2N

NH2

1 3

HCOOH -H2O Reflux

O NHNH2

S N

OH H3C

CH3

O NHNH2

CHO S NH

H3C

CH3

N N N N

H3C

O N S HO

O NHNH2

H3C

OHC

O NHNH2

II I

NH2

O N

-H2O

S H3C

CH3

N N

H3C

O S N

H3C

N O

Scheme 1

H2N

water to afford the final isolable reaction product 4 (cf. Scheme 1). The IR spectrum (cm-1) of 3 showed the absorption bands of NH2 group at 3452, 3326 and acetyl CO group at 1736 beside ring CO group at 1678. The mass spectrum of 4 gave m/z = 623 (0.2%, [M+H]+) which corresponded to the
molecular formula C30 H22 N8 O4 S2 of the assigned structure (cf. Exp. Part). In a further investigation, compound 3 reacted with acetic anhydride under reflux for 5 hours to give the corresponding 4,4’- benzene-1,4-diylbis(8-acetyl-3-amino-2,7-dimethyl- pyrido[3’,2’:4,5]thieno[3,2-d]pyrimidin-4(3H)-one)

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5. The reaction most probably proceeded by the acetylation of NH2 group at the thiophene ring through the intermediate [I] followed by enolization and elimination of two molecules of water from the intermediate [II] to afford the final isolable reaction product 5 (cf. Scheme 2). The IR spectrum (cm-1) of this reaction product showed
the absorption bands of NH2 group at 3454, 3326 and CO groups at 1748 and 1697 and its mass spectrum gave m/z = 651 (7.7%, [M+H]+) which corresponded to the molecular formula C32 H26 N8 O4 S2 of the assigned structure (cf. Exp. Part and Scheme 2).

NHNH2

COCH3

N H

CH3

(CH3CO)2O

Reflux 5hrs.

-CH3COOH

S CH3CO

N N

H3C

COCH3

H N CH3CO

O NHNH2

NH2

O N

CH3

H2N

O NH

CH3

S H3C

CH3

-2H2O

S CH3CO

CH3

N N N N

H3C

S H3C N

N O

COCH3

H3C

N S

O OH HN

5 H2N

II NH2

Scheme 2

Moreover, compound 3 reacted with triethylorthoformate under reflux for 5 hours to afford the corresponding 6. The IR spectrum (cm-1) of 6 neither showed absorption bands of NH nor NH2 groups while absorption bands at 1691 cm-1 was detected. Thus we concluded that two molecules of triethylortho-formate reacted with 3 to afford the non-isolable intermediate [I] which in turn, reacted with another two molecules of triethylorthoformate to afford the final isolable 6 via the non-isolable product [II] (cf. Scheme 3). Moreover, its mass spectrum gave the parent peak at m/z = 735 which corresponding to the molecular weight of the assigned structure in
addition to other peaks that gave further confirmation of the structure 6 (cf. Exp. Part). As a further continuation of the interest of exploring the synthetic potential of compound 3 it was thus of value to investigate its reaction with β-dicarbonyl compounds such as ethyl aceto-acetate, acetylacetone and diethylmalonate 7a-c to afford a new heterocyclic derivatives. Thus, it has been found that compound 3 reacted with ethyl acetoacetate 7a in glacial acetic acid under reflux for 5 hours to give 5,5'-diacetyl-3,3'-diamino-2-(3- methyl-5-hydroxy-1H-pyrazole-1-carbonyl)-6,6'-dimeth- yl-4,4'-benzene-1,4-diylbisthieno[2,3-b]pyridine 8a.

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HC(OEt)3

3 Reflux

-4 C2H5OH

NH2

O N

N S

H3C

CH3

NHNH2

O EtO

S N

O H3C

CH3

N N N N

H C O

-2 C2H5OH

3 S N

H3C

O S N

H3C

N O H2N

H O OEt

H2NHN

II I

OEt

-4 C2H5OH

N O N

O N

S H3C

CH3

HC(OEt)3 N N

H3C

O S N

H3C

N O N

Scheme 3

EtO

The reaction most probably proceeded via the nucleophilic addition of hydrazidic NH2 of 3 on the carbonyl group of 7a to give the non-isolable intermediate Ia . The formation of Ia followed by elimination of two water molecules of to afford the non-isolable intermediates IIa which in turn, underwent cyclization via the elimination of two ethanol molecules to afford the final isolable reaction product 8a rather than 8`a whose structure was elucidated by considering the data of IR, mass spectral data as well as that of elemental analysis (cf. Exp. Part, Equation 1 and Scheme 3). Similarly, compound 3 reacted with acetylacetone 7b under reflux for 5 hours in glacial acetic acid to afford the corresponding 5,5'-diacetyl-3,3'-diamino-2-(3,5-di- methyl-1H-pyrazole-1-carbonyl)-6,6'-dimethyl-4,4'-
benzene-1,4-diylbisthieno[2,3-b]pyridine 8b. The IR spectrum (cm-1) of 8b showed the absorption bands of NH2 group at 3454, 3382 and CO group at
1684 and its mass spectrum gave m/z = 731 (0.5%, [M+H]+) which corresponded to the molecular weight of the molecular formula C38 H34 N8 O4 S2 of the assigned structure. Several peaks at m/z = 636 (100%, 731- dimethylpyrazole ring), 608 = (0.1%,
731- one O=C – di methyl pyrazole ring), 511 =
(4.6%, 731- one O=C - two dimethylpyrazole ring – two H), and 483 = (0.2%, 731- two dimeth- ylpyrazole – two C=O – two H) gave further confirmation of the structure 8b. The reaction most probably proceeded via the addition followed by elimination of two molecules of water through the non-isolable intermediate Ib and IIb followed by

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cyclization through the elimination of another two molecules of water to afford the final isolable reaction product 8b (cf. Scheme 4 and Equation 1). In a similar manner, compound 3 reacted with diethylmalonate 7c under reflux to afford the corresponding 4,4'-benzene-1,4-diylbis-5-acetyl-3- amino-2-(1H-pyrazol-3,5-dione-1-carbonyl)-6-methyl- thieno[2,3-b]pyridine 8c whose structure was confirmed via the elemental analysis and spectral data (cf. Exp. Part and Scheme 4). 7,7'-Diacetyl-6,6'- dimethyl-8,8'-benzene-1,4-diylbis(1,2-dihydro-3H-

R -CO-CH -R

pyrazolo[3',4':4,5]thieno[2,3-b]pyridin-3-one) 9 obtained via the reaction of compound 3 with glacial acetic acid under reflux for 5 hours. The IR (cm-1) of compound 9 showed the absorption bands of acetyl CO, ring CO as well as NH groups and its mass spectrum gave the parent peak at m/z = 684, (0.3%, [M+H]+) which corresponding to the molecular weight of the assigned structure (cf. Exp. Part and Scheme 5). 4,4'-Benzene-1,4-diylbis-5- acetyl-3-amino-6-methyl-2-(N-phenyl-1,3,4-oxadiazol-

R1-CO-CH2-R2

1 2 2

(7a-c)

-2 H2O

a, c

-2 EtOH (in a)

-4 EtOH (in c)

H3C N O

CH3

S N

O NH2

H2N O

N S N

8a-c

CH3

Scheme 4

2-amine-5-yl)thieno[2,3-b]pyridine 10 obtained through the reaction of compound 3 with phenyl isothiocyanate under reflux in pyridine for 5 hours. The IR (cm-1) of this reaction product showed the absorption bands of NH2 and C=O functional groups as well as its mass spectrum gave the parent peak at m/z = 805 which corresponding to the molecular weight of the assigned structure 10 (cf. Exp. Part and Scheme 5). Compound 3 reacted with 2-cyano-3-(4- methoxy-phenyl)prop-2-enethioamide 11 in pyridine under reflux to give a reaction product
which formulated as 4,4'-benzene-1,4-diylbis-5- acetyl-3-amino-6-methyl-N’-(4-methoxyphenylmeth- ylidene)thieno[2,3-b]pyridine-2-carbohydrazide 13 (cf. Scheme 5). The IR spectrum (cm-1) of 13 showed the absorption bands of NH2 groups at
3460, 3317 and C=O at 1666 cm-1. Its mass spectrum gave m/z = 838 which corresponded to the molecular formula C44 H38 N8 O6 S2 of the assigned structure (cf. Exp. Part). An unequivocal support for the structure of 13 was achieved via its
synthesis by another route, via using anisaldehyde

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12 to give a reaction product which was found completely identical in all aspects with 13 obtained from the first route (cf. Scheme 5 and Exp. Part). Therefore, we concluded that the reaction between

3 and 2-cyano-3-(4-methoxyphenyl)prop-2-enethio-

amide 11 most properly proceeded via the ylidine group exchange with the loss of one molecule of 2- cyanoethanethioamide to afford the corresponding reaction product 13.

H3C N O

H3C R

NH2

NH NH

CH3

- 2 H2O

H3C N O

H3C

NH2

NH N

H3C R

H3C

H2N O

CH3

H2N O

NH NH

O S

CH3

N CH3

R N NH

O S

CH3

N CH3

[I]a,b [II]a,b

Ia, IIa Ib, IIb

R, CO2Et COCH3

Addition

R1-CO-CH2-R2

-2 H2O (in IIb)

-2 EtOH (in IIa)

3 H3C

H3C

H3C N O

CH3

S N

O NH2

H3C N O

CH3

S N

O NH2

H2N O

CH3

H2N O

CH3

20a, R' = OH

20b, R' = CH3

CH3

S N

7a,b

CH3

S N

6a,b

CH3

Equation 1

3 EXPERIMENTAL

All melting points were uncorrected. I.R. (KBr discs) spectra were recorded on a Shimadzu FTIR-
8201PC Spectrophotometer. 1H-NMR spectra were recorded on a Varian Mercury 300 MHz., and a Varian Gemini 200 MHz. Spectrometers using TMS as an internal standard and CDCl3 , DMSO-d6 , and (CD3 )2 CO as solvents. Chemical shifts were expressed as δ (ppm) units. Mass spectra were recorded on Agilent LC 1200/MS Ion Trap 6320 using APCI ionization source and the spectra is enhanced using acidified water/acetonitril mobile
phase and measured in the positive mode of the ion trap (Molecular weights of most compounds are Protonated ([M+H]+).

Synthesis of (3): A solution of 1 or 2 (1g, 0.63 mol) in hydrazine hydrate (15mL) and ethanol (20 mL) was heated under reflux for 10 hrs., the excess solvents were evaporated and the reaction mixture then cooled and the solid so formed was collected by filtration, dried, and crystallized from ethanol to give 3.

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CH3COOH

O NH2

S Ac O

CH3

N N

H3C

H2N O

H5C6HN

O N

C6H5NCS

S NH2

CH3

N N

(12)

H3C

O H3C

H2N S

MeOH4C6

O N

10 N H5C6HN

NH O

OMe-p-C6H4-CH=C(CN)CSNH2 (11)

NH2

CH3

N N

H3C

O H3C

S H2N

13 O

C6H4OMe

Scheme 5

4,4'-Benzene-1,4-diylbis(5-acetyl-3-amino-6-meth- ylthieno[2,3-b]pyridi-ne-2-carbohydrazide) (3): as yellow crystals yielded by (83%); m.p>3300C; IR υ(cm-

1): 3454.1,3322.6 (NH2 ), 3219.7 (NH), 2984.1,2920.4 (aliphatic-CH), 1691.6 (Acetyl-CO), 1642.4 (Amide-

CO); MS: 603 ([M+H]+, 0.5% which corresponding to the molecular weight of the molecular formula C28 H26 N8 O4 S2 of the assigned structure) 585 (603- H2 O, 0.4%), 572 (603-NHNH2 , 42.9%), 571 (603-
NHNH2 , H, 100%), 544 (572-CO, 17.9%), 543 (571- CO, 60.2%), 513 (544-NHNH2 , 2.6%), 512 (543- NHNH2 , 0.6%), 485 (513-CO, 0.3%), 484 (512-CO,
0.8%); 1H NMR(DMSO) (δppm): 1.952(s, 6H,
2CH3 ), 2.521(s, 6H, 2COCH3 ), 4.487(br, 4H, 2NH2 ),
5.793(br, 4H, 2NH2 ), 7.606(m, 4H, ArH`S), 9.171(br,
2H, 2NH); Anal, for C28 H26 N8 O4 S2 (602) Calcd./Found(%): C(55.80/55.83%) H(4.35/4.38%)
N(18.59/18.62%) S(10.64 /10.67%).

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Synthesis of 4, 5, 6, and 9 (General method): A solution of 3 (0.6g, 1mmole) and each of15ml of (Formic acid, Acetic anhydride, Triethylortho- formate, and Acetic acid), was heated under reflux for 5 hrs. The excess solvent was evaporated and cooled. The solid was collected by filtration, dried, and crystallized from the ethanol to give 4, 5, 6, and 9 respectively.

4,4'-Benzene-1,4-diylbis(8-acetyl-3-amino-7-meth- ylpyrido[3',2':4,5]thieno[3,2-d]pyrimidin-4(3H)- one) 4: as yellow crystals yielded by (93%); m.p>3300C; IR υ(cm-1): 3452.7, 3326.4 (NH2 ),
2923.3,2852.4 (aliphatic-CH), 1736.1 (CO), 1678.6 (CO); MS: 623 ([M+H]+, 0.2% which corresponding to the molecular weight of the molecular formula
C30 H22 N8 O4 S2 of the assigned structure), 607 (623- NH2 , 7.2%), 606 (623-OH, 9.6%), 605 (623-H2 O,
29.2%), 590 (605-NH, 7.4%), 589 (605-NH2 , 21.6%),
587 (605-H2 O, 100%), 563 (590-HCN, 1.6%); 1H NMR (DMSO) (δppm): 2.172 (s, 6H, 2CH3 ), 2.504 (s, 6H, 2COCH3 ), 6.082 (br, 4H, 2NH2 ), 7.471 (m,
4H, ArH`S); Anal for C30 H22 N8 O4 S2 (622) Calcd./Found(%): C(57.87/57.90%) H(3.56/3.59%)
N(18.00/18.03%) S(10.30/10.33%).

4,4'-Benzene-1,4-diylbis(8-acetyl-3-amino-2,7-di-

methylpyrido[3',2':4,5]thieno[3,2-d]pyrimidin-4- (3H)-one) 5: as white crystals yielded by (78%); m.p>3300C; IR υ(cm-1): 3454.4,3326.3 (NH2 ), 1748.3 (CO), 1697.8 (CO); MS: 651 ([M+H]+, 7.7% which corresponding to the molecular weight of the molecular formula C32 H26 O4 N8 S2 of the assigned structure), 636 (651-CH3 , 4.5%), 635 (651-NH2 ,
30.4%), 634 (651-OH, 54.5%), 633 (651-H2 O, 100%),
620 (636-NH2 , 34.9%), 619 (633-CH3 , 23.6%), 618 (634-NH2 , 17.1%), 615 (634-H2 O, 77.3%), 603 (618- CH3 , 4.9%),; Anal, for C32 H26 O4 N8 S2 (650) Calcd./Found(%): C(59.06/59.09%) H(4.03/4.06%) N(17.22/17.25%) S(9.86/9.89%).

4,4'-Benzene-1,4-diylbis(ethyl(8-acetyl-7-methyl-

4-oxopyrido[3',2':4,5]thieno[3,2-d]pyrimidin-3(4-

H)-yl)imidoformate) 6: as yellow crystals yielded by (83.7%); m.p > 3300C; IR υ(cm-1): 2921.1,2852.4 (aliphatic-CH), 1691.6 (Acetyl-CO); MS: 735 ([M+H]+, 0.1% which corresponding to the molecular weight of the molecular formula C36 H28 N8 O6 S2 of the assigned structure), 690 (735- OEt, 1%), 677 (735-2Et, 0.6%), 663 (690-HCN, 2.3%),
661 (690-Et, 4.5%), 643 (735-2EtOH, 0.3%), 621 (677-

2CO, 100%), 606 (621-NH, 0.8%);1H NMR (DMSO) (δppm): 1.031 (t, 6H, 2CH2CH3 ), 2.018 (s, 6H, 2CH-

3 ), 2.163 (s, 2H, 2CH), 2.504 (s, 6H, 2COCH3 ), 4.322 (q, 4H, 2CH2 CH3 ), 7.563 (m, 4H, ArH`S); Anal, for C36 H28 N8 O6 S2 (734) Calcd./Found(%): C(58.84/58.87%) H(4.12/4.15%) N(15.25/15.28%) S(8.73/ 8.76%).

7,7'-Diacetyl-6,6'-dimethyl-8,8'-benzene-1,4-diylbis- (1,2-dihydro-3H-pyrazolo[3',4':4,5]thieno[2,3-b]pyrid-

in-3-one) 9: as yellow crystals yielded by (82%); m.p

>3300C; IR υ(cm-1): 2997.5,2884.2 (aliphatic-CH),
1695.6 (Acetyl-CO), 1673.3 (pyrazol-CO); MS: 684
([M+H]+, 0.3% which corresponding to the molecular weight of the molecular formula C32 H26 N8 O6 S2 of the assigned structure), 641 (684- COCH3 , 7.2%), 640 (684-CH3 CHO, 15.3%), 638 (640-H2, 100%), 626 (641-NH, 18.4%), 596 (640- CH3 CHO, 3.6%), 595 (638-CH3 CO, 2.4%), 594 (638- CH3 CHO, 4.6%), 582 (626-CH3 CO, 3.8%), 580 (596- NH2, 3.5%), 563 (595-2NH2 , 1.6%); Anal, for C32 H26 N8 O6 S2 (682.7) Calcd./Found(%): C(56.30/56.33%) H(3.84/3.87%) N(16.41/16.44%) S(9.39/9.42%).

Synthesis of 8a-c (General method): A solution of each of 3 (0.6g 1mmole) and 15ml of Ethyl 3- oxobutanoate, acetylacetone and diethylmalonate, (0.26g, 0.2g, 0.32g 2 mmole) was heated in 20ml of acetic acid under reflux for 5 hrs. The excess

solvent was evaporated and cooled. The solid was collected by filtration, dried, and crystallized from the ethanol to give 8a-c respectively.

5,5'-Diacetyl-3,3'-diamino-2-(3-methyl-5-hydroxy-

1H-pyrazole-1-carbonyl)-6,6'-dimethyl-4,4'-benz- ene-1,4-di-ylbisthieno[2,3-b]pyridine (8a): as yellow crystals yielded by (67%); m.p>3300C; IR υ(cm-1): 3482.1,3392.4 (NH2 ), 1684.8 (CO); MS: 733 (M-H, 0.1% which corresponding to the molecular weight of the molecular formula C36 H30 N8 O6 S2 of the assigned structure), 716 (733-OH, 10.6%), 715 (733-H2 O, 25.5%), 697 (715-H2 O, 14.1%), 680 (697- OH, 10.8%), 636 (733-C4 H5 ON2 , 28.4%), 635 (715- C4 H4 N2 , 8.8%), 619 (636-OH, 100%), 607 (635-CO,
30.1%), 600 (680-C4 H4 N2 , 9.9%); Anal for
C36 H30 N8 O6 S2 (734) Calcd./Found(%): C(58.84-
/58.87) H(4.12/4.15) N(15.25/15.28) S(8.73/8.76).

5,5'-Diacetyl-3,3'-diamino-2-(3,5-dimethyl-1H-

pyrazole-1-carbonyl)-6,6'-dimethyl-4,4'-benzene-

1,4-diylbis-thieno[2,3-b]pyridine (8b): as Brown

crystals yielded by (76%); m.p = 2600C; IR υ(cm-1):
3454.3,3382.2 (NH2 ), 1684.5 (CO); MS: 731 ([M+H]+, 0.5% which corresponding to the
molecular weight of the molecular formula C38 H34 N8 O4 S2 of the assigned structure), 637 (731- C5 H6 N2 , 46.8%), 636 (731-C5 H7 N2 , 100%), 635 (731-C5 H8 N2 , 34.5%), 621 (637-NH2 , 0.8%), 608 (636-CO, 0.1%), 607 (635-CO, 2.1%), 512 (608- C5 H8 N2 , 2.8%), 511 (607-C5 H8 N2 , 4.6%), 484 (512- CO, 0.7%), 483 (511-CO, 0.2%); Anal, for C38 H34 N8 O4 S2 (730) Calcd./Found(%): C(62.45/62.48%) H(4.69/4.72%) N(15.33/15.37%) S(8.77/ 8.8%).

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4,4'-Benzene-1,4-diylbis-5-acetyl-3-amino-2-(1H- pyrazol-3,5-dione-1-car-bonyl)-6-methylthieno[2,3- b]pyridine (8c): as Brown crystals yielded by (76%); m.p>3300C; IR υ(cm-1): 3479.4,3389.6 (NH2 ), 1691.7 (CO); MS: 739 ([M+H]+, 0.2% which corresponding to the molecular weight of the molecular formula C34 H26 N8 O8 S2 of the assigned structure), 723 (739- NH2 , 1.3%), 721 (739-H2 O, 11.5), 703 (721-H2 O,
3.1%), 697 (739-CH2 CO, 100%), 696 (739- CH3 CO,
13%), 679 (697-H2 O, 17.3%), 661 (679-H2 O, 8.7%),
640 (739-C3 H3 O2 N2 , 8.7%), 639 (721-C3 H2 ON2 ,
4%), 622 (721-C3 H3 O2 N2 , 2.1%); Anal, for
C34 H26 N8 O8 S2 (738) Calcd./Found(%): C(55.28/55.31%) H(3.55/3.58%) N(15.17/15.2%)
S(8.68 /8.71%).

Synthesis of 10: A solution of each of 3 (0.6g,

1mmole) and phenyl isothiocyanate, (0.27g,
2mmol) in pyridine (15 mL) was heated under
reflux for 5 hrs, cooled, poured onto ice-cold water,
and neutralized with drops acetic acid the solid was collected by filtration, dried, and crystallized from the ethanol to give 10.

4,4'-Benzene-1,4-diylbis-5-acetyl-3-amino-6-meth-

yl-2-(N-phenyl-1,3,4-oxadiazol-2-amine-5-yl)thieno- [2,3-b]-pyridine (10): as Brown crystals yielded by (81%); m.p = 2250C; IR υ(cm-1): 3464.4,3378.2 (NH2 ),
3055.5 (aromatic-CH), 1688.2 (Acetyl-CO); MS: 805 (M, 0.1% which corresponding to the molecular weight of the molecular formula C42 H32 N10 O4 S2 of
the assigned structure), 790 (805-NH, 37.2%), 789 (805-NH2 , 100%), 773 (789-NH2 , 4%), 771 (789- H2 O, 34%), 755 (773-H2 O, 5.9%), 754 (771-OH,
5.8%), 635 (789-2Ph, 7.2%); Anal, for C42 H32 N10 O4 S2 (804) Calcd./Found(%): C(62.67/62.7%) H(4.01/4.04%) N(17.40/17.43%) O(7.95/7.98%) S(7.97/ 8.00%).

Synthesis of 13 (Method A): A solution of each of

3 (0.6g, 1mmole) and 2-cyano-3-(4-methoxy

phenyl)prop-2-enethioamide 11 (0.44g, 2mmol) in
pyridine (15 mL) was heated under reflux for 5 hrs, cooled, poured onto ice-cold water, and neutralized with drops acetic acid the solid was collected by filtration, dried, and crystallized from the ethanol to give 13.

Method B: A solution of each of 3 (0.6g, 1mmole)

and 4-methoxybenzaldehyde 12 (0.27g, 2mmol) in pyridine (15 mL) was heated under reflux for 5 hrs, cooled, poured onto ice-cold water, and neutralized with drops of acetic acid the solid was collected by filtration, dried, and crystallized from the ethanol to give 13.

4,4'-Benzene-1,4-diylbis-5-acetyl-3-amino-6- methyl-N’-(4-

methoxyphenylmethylidene)thieno[2,3-

b]pyridine-2-carbohydrazide (13): as yellow crystals

yielded by (77%); m.p >3300C; IR υ(cm-1):
3460.4,3317.5 (NH2 ), 1666.5 (Amide-CO); MS: 838 (M, 0.4% which corresponding to the molecular
weight of the molecular formula C44 H38 N8 O6 S2 of the assigned structure), 731 (838-PhOCH3 , 100%),
713 (731-H2 O, 36.4%), 705 (731-CN, 7.2%), 688 (731- CH3 CO, 9.8%), 662 (705-NH,CO, 17.1%), 624 (731- PhOCH3 , 5.6%), 606 (624-H2 O, 15.3%); Anal, for
C44 H38 N8 O6 S2 (838) Calcd./Found(%): C(62.99/63.02%) H(4.57/4.60%) N(13.36/13.39%)
O(11.44/11.47%) S(7.64/ 7.67%).

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International Journal of Scientific & Engineering Research, Volume 5, Issue 4, April-2014

ISSN 2229-5518

671

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