Printer Friendly

Synthesis and studies of fused/isolated thiophene derivatives.

Introduction

Thiophene, thiazole, pyrazole, isoxazole and pyrimidine derivatives isolated and fused being an integral part of DNA and RNA which play an essential role in several biological processes and have considerable chemical and pharmacological importance, particularly, the pyrimidine ring can be found in nucleoside antibiotics, antibacterials, cardio: vascular as well as agro chemical and vetcer products [1] In addition, many of these derivatives were found to possess a variety of pronounced activities such as an anti-inflammatory [2-6], antimalarial [7-9], anti-allergic [10-11], antimicrobial [12-17]. Recently, some new substituted pyrimidine derivatives have been synthesized, which exhibit analgesic, anti-inflammatory, antiparkinsonian and androgenic-anabolic activities [18-23]. In view of these observation and as continuation of our work [24-26] on synthesis and studies on some heterocyclic compounds, we synthesized some new compounds containing thiophene, thiazole, pyrazole, isoxazole and pyrimidine derivatives.

Result and Discussion

Starting 2-(2-mercapto-1-phenylethylidene)malononitrile 1 was obtained from reaction of acetophenone with malononitrile which reacts with elemental sulfur to give thiono derivative 1. The structure of compound 1 was confirmed by IR spectra, which revealed the presence of peaks at [gamma] 2200 [cm.sup.-1] (C[equivalent to]N), also [sup.1]H NMR spectra revealed the presence of signal peaks at [delta] 1.3(s, H, sH), at [delta] 3.8(s, 2H, C[H.sub.2]S), 7-8(m. 5H, Ar-[H.sup.+]). The mass spectra showed the molecular ion peak at m/z [M.sup.+](199). Compound 1 boils with a mixture of acetic acid/acetic anhydride gives the intermediate compound 2 which cyclizes to 5-acetyl-2-amino-4-phenylthiophene-3-carbonitrile 3. The structure of compound 3 was confirmed by IR spectra, which revealed the presence of peaks at [gamma] 3400-3200 [cm.sup.-1] (N[H.sub.2]), at [gamma] 2200 [cm.sup.-1] (C[equivalent to]N), [gamma] 1700-1680 [cm.sup.-1] (C=O), also [sup.1]H NMR spectra revealed the presence of signal peaks at [delta] 2.3 (s, 3H, C[H.sub.3]-CO), at [delta] 6.9-7.1(br, 2H, N[H.sub.2]), at [delta] 7.5-7.8(m. 5H, Ar-[H.sup.+]). The mass spectra showed the molecular ion peak at m/z (242).

Boiling of compound 3 in a mixture of acetic acid/acetic anhydride give N-(5-acetyl-3-cyano-4-phenylthiophene-2-yl)acetamide 4. The structure of compound 4 was confirmed by IR spectra, which revealed the presence of peaks at [gamma] 2200 [cm.sup.-1] (C[equivalent to]N), [gamma] 1700 1680 [cm.sup.-1] (C=O), at [gamma] 3100-3300 [cm.sup.-1] (NH) also [sup.1]H NMR spectra revealed the presence of signal peaks at [delta] 2.5(s, 6H, 2C[H.sub.3]CO), at [delta] 6.9-7.1(br, IH, NH), at [delta] 7.5-8 (m. 5H, Ar-[H.sup.+]). The mass spectra showed the molecular ion peak at m/z (283). Boiling of compound 4 in the presence of ethanol as a solvent and piperidine as a catalyst converts it to compound 3, Scheme 1.

[FORMULA NOT REPRODUCIBLE IN ASCII]

The synthesis of 6-(1-formylvinyloxy)-5-phenylthieno[2,3-d]pyrimidine-2,4-dicarboxylic acid 5 and 6-(1-formylvinyloxy)-1,2-dihydro-5-phenylthieno [2,3-d]pyrimidine-2,4-dicarboxylic acid 6 taken place by reacting of compounds 3 and 4 with formic acid. The structure of compounds 5 and 6 were confirmed by IR spectra, which revealed the presence of peaks at [gamma] 3100-3300 [cm.sup.-1] (NH, OH), at [gamma] 1690-1700 [cm.sup.-1] (C=O), at [gamma] 1560 [cm.sup.-1] (C=N), also [sup.1]H NMR spectra revealed the presence of signal peaks at [delta] 9-9.5 (s, 3H, 2COOH, CHO), at [delta] 7.5-8 (m. 5H, Ar-[H.sup.+]), at [delta] 3-3.5 (br, 1H, NH), at [delta] 2.5 3(s, 2H, C[H.sub.2]). The mass spectra showed the molecular ion peaks at m/z (370), (372) for 5 and 6 respectively, Scheme 2.

[FORMULA NOT REPRODUCIBLE IN ASCII]

Reaction of compounds 3 and 4 with elemental sulfur under catalyst triethyl amine afforded 1-(3-amino-4-phenylthieno[2,3-c]isothiazole-5-yl)ethanone 7. The structure of compound 7 was confirmed by IR spectra, which revealed the presence of peaks at [gamma] 3000 3300 [cm.sup.-1] (N[H.sub.2]), at [gamma] 1680-1700 [cm.sup.-1] (C=O), at [gamma] 1540-1560 [cm.sup.-1] (C=N), also, [sup.1]H NMR spectra revealed the presence of signal peaks at [delta] 7.8 (m. 5H, Ar-[H.sup.+]), at o[delta] 3.2-3.5 (br, 2H, N[H.sub.2]), at [delta] 2(s, 3H, C[H.sub.3]-C=O). The mass spectra showed the molecular ion peak at m/z (274), Scheme 3.

[FORMULA NOT REPRODUCIBLE IN ASCII]

The compound 1 was coupled with aromatic diazonium chloride to yield the 2-(2-mercapto-2-hydrazone-1-phenylethylidene)malononitrile derivatives 8a-c. The structure of compound 8a was confirmed by IR spectra, which revealed the presence of peaks at [gamma] 3180-3300 [cm.sup.-1] (NH), at [gamma] 2200 [cm.sup.-1] (C[equivalent to]N), at [gamma] 1630 [cm.sup.-1] (C=N), also [sup.1]H NMR spectra showed the molecular ion revealed the presence of signal peaks at [delta] 3.2-3.6(br, 2H, NH & SH), at [delta] 7.8 (m. 10H, Ar-[H.sup.+]). The mass spectra showed the ion peak at m/z (303), cyclization of compound 8a was occurred by heating in acetic acid to give 5-hydrazone-2,5-dihydro-2-imino-4-phenylthiophene-3-carbonitrile derivatives 9a-c. The structure of compound 9a was confirmed by IR spectra, which revealed the presence of peaks at [gamma] 3200-3300 [cm.sup.-1] (NH), at [gamma] 2200 [cm.sup.-1] (C[equivalent to]N), at [gamma] 1620-1640 [cm.sup.-1] (C=N), also [sup.]1H NMR spectra showed the molecular ion revealed the presence of signal peaks at [delta] 7.4 8.8 (m. 10H, Ar-[H.sup.+]), at [delta] 3.5(br, 1H, NH aromatic), at [delta] 1.9 (br, 1H, NH aliphatic). The mass spectra showed the ion peak at m/z (303). Reaction of compound 9a with acetic acid and zinc dust afforded to N-(4-cyano-2,5-dihydro-5-oxo-3-phenylthiophene-2yl)acetamide 10. The structure of compo-und 10 was confirmed by IR spectra, which revealed the presence of peaks at [gamma] 3200-3400 [cm.sup.-1] (NH), at [gamma] 2200 [cm.sup.-1] (C[equivalent to]N), at [gamma] 1650-1720 [cm.sup.-1] (C=O), also [sup.1]H NMR spectra revealed the presence of signal peaks at [delta] 8.8 (s, 1H, OH), at [delta] 7.4-8.8 (m. 5H, Ar-[H.sup.+]), at [delta] 3.5(s, 1H, CH cyclic), at [delta] 1.9(s, 3H, C[H.sub.3]CO). The mass spectra showed the molecular ion peak at m/z (258) Scheme 4.

When compound 10 was interacted with one mole of hydrazine hydrate in the presence of acetic acid as a catalyst or one mole of phenyl hydrazine in the presence of piperidine as a catalyst gave 1-(3,5-diamino-4-phenyl-3H-thieno[2,3-c]pyrazole-2(5H)-yl)ethanone 11 and 3,5-dihydro-2,4-diphenyl-2H-thieno[2,3-c]pyrazole-3,5-diamine 12 respectively. The structure of compound (11) was confirmed by IR spectra, which revealed the presence of peaks at [gamma] 3000-3300 [cm.sup.-1] (N[H.sub.2]), at [gamma] 1680-1700 [cm.sup.-1] (C=O), at [gamma] 1540-1560 [cm.sup.-1] (C=N). also [sup.1]H NMR spectra revealed the presence of signal peaks at [delta] 7-8(m, 5H, Ar-[H.sup.+]), at [delta] 5.8(s, 1H, CH cyclic), at [delta] 3.2-3.5(br, 4H, 2N[H.sub.2]), at [delta] 2.5(s, 3H, C[H.sub.3]CO). The mass spectra showed the molecular ion peak at m/z (274), Scheme 4.

When the compound 10 was interacted with one mole of urea or thiourea in the presence of piperidine as catalyst gave 4,6-diamino-5-phenylthieno[2,3-d]pyrimidine-2(6H)-one (13) and 4,6-diamino-5-phenylthieno[2,3-d]pyrimidine-2(6H)-thione 14, respectively. The structure of compound (13) was confirmed by IR spectra, which revealed the presence of peaks at [gamma] 3000-3300 [cm.sup.-1] (N[H.sub.2]), at [gamma] 1540-1560 [cm.sup.-1] (C=N), at [gamma] 1650-1720 [cm.sup.-1] (C=O). also [sup.1]H NMR spectra revealed the presence of signal peaks at [delta] 7-8(m, 5H, Ar-[H.sup.+]), at [delta] 5.8(s, 1H, CH cyclic), at [delta] 3.2-3.5(br, 4H, 2N[H.sub.2]). The mass spectra showed the molecular ion peak at m/z (258), Scheme 4.

When the compound 10 was interacted with one mole of hydroxyl amine hydrochloride gave 3,5-dihydro-4-phenylthieno[2,3-c]isoxazole-3,5-diamine (15). The structure of compound (15) was confirmed by IR spectra, which revealed the presence of peaks at [gamma] 3000-3300 [cm.sup.-1] (N[H.sub.2]), at [gamma] 1540-1560 [cm.sup.-1] (C=N), also [sup.1]H NMR spectra revealed the presence of signal peaks at [delta] 7-8(m, 5H, Ar-[H.sup.+]), at [delta] 3.2-3.5 (br, 4H, 2N[H.sub.2]), at [delta] 5.8(s, 1H, CH cyclic). The mass spectra showed the molecular ion peak at m/z (233), Scheme 4

[FORMULA NOT REPRODUCIBLE IN ASCII]

Adding of compound 1 to ylidene malononitrile would yielded polyfunctionally intermediate compound 16, which is anticipated to cyclize into 5-(2,2-dicyano-1-phenylvinyl)-2,5-dihydro-2-aminothiophene-3-carbonitrile derivatives 17a-c. The structure of the compound 17c were confirmed by IR spectra, which revealed the presence of signal peaks at [gamma] 3200-3500 [cm.sup.-1] (N[H.sub.2]), at [gamma] 2200 [cm.sup.-1] (C[equivalent to]N), also [sup.1]H NMR spectra showed the presence of signal peaks at [delta] 7-8 (m. 5H, Ar-[H.sup.+]), at [delta] 1.7 (br, 2H, N[H.sub.2]). The mass spectra of the compound 17c showed the molecular ion peak at m/z (352) which is in agreement with its molecular formula ([C.sub.21]1[H.sub.12][N.sub.4]S), Scheme 5.

[FORMULA NOT REPRODUCIBLE IN ASCII]

The compound 1 was condensed with acetophenone, p-methoxyacetophenone or p-nitroacetophenone using piperidine as a catalyst in the presence of ethanol as a solvent afforded polyfunctionally substituted intermediate compound 18, which is anticipated to cyclize into 2,5-dihydro-2-imino-4-phenyl-5-(1-phenylethylidene)thiophene-3-carbonitrile derivatives 19a-c. The structure of the compound 19a was confirmed by IR spectra, which showed absorption band at [gamma] 3000-3500 [cm.sup.-1] attributed to (NH), at [gamma] 2200 [cm.sup.-1] attributed to (C[equivalent to]N), at [gamma] 1620 [cm.sup.-1] (C=N). [sup.1]H NMR spectrum in DMSO for compound 19a as signals at [delta] 7-8 (m. 10H, Ar-[H.sup.+]), at [delta] 1.9(br, 1H, NH), at [delta] 2.6(s, 3H, C[H.sub.3]). The mass spectra of compound 19a showed molecular ion peak at m/z (302) which is in agreement with its molecular formula ([C.sub.19][H.sub.14][N.sub.2]S), Scheme 6.

[FORMULA NOT REPRODUCIBLE IN ASCII]

Also, compound 1 was condensed with aromatic aldehydes such as benzaldehyde, o-hydroxy benzaldehyde, p-methoxy benzaldehyde using piperidine as a catalyst and ethanol as a solvent afforded polyfunctionally substituted intermediate 20 which is anticipated to cyclise into 5-benzylidene-2,5-dihydro-2-imino-4-phenylthiophene-3-carbonitrile derivatives 21a-e. The structure of compound 21d was confirmed by IR spectrum, which showed absorption band at [gamma] 3200-3400 [cm.sup.-1] (NH), at [gamma] 2200 [cm.sup.-1] (C[equivalent to]N), at [gamma] 1600 [cm.sup.-1] (C=N), also [sup.1]H NMR spectra of compound 21d as example revealed the presence of signal peaks at [delta] 7-8.5 (m. 9H, Ar-[H.sup.+]), at [delta] 4(s, 3H, C[H.sub.3]O), at [delta] 1.2 (br, 1H, NH). The mass spectra showed the molecular ion peak at m/z (318) which is in agreement with its molecular formula ([C.sub.19][H.sub.14][N.sub.2]SO) Scheme 7.

[FORMULA NOT REPRODUCIBLE IN ASCII]

Alternatively compound 1 reacts with arylidine derivatives to gives the intermediate compound (22) which cyclizes to ethyl-5-(2,2-dicyano-1-phenyl-vinyl)-2,5-dihydro-2-aminothiophene-3-carboxylate derivatives (23a-c). The structure of compound 23a was confirmed by IR spectrum which showed absorption band at [gamma] 3300-3500 [cm.sup.-1] attributed to (N[H.sub.2]), at [gamma] 2200 [cm.sup.-1] attributed to (C[equivalent to]N), at [gamma] 1705 [cm.sup.-1] attributed to (C=O),. [sup.1]H NMR spectrum in DMSO for compound 23a revealed the presence of signal peaks at [delta] 7-8 (m, 5h, Ar-[H.sup.+]), at [delta] 1.9 (br, 2H, N[H.sub.2]), at [delta] 2.4 (t, 3H, C[H.sub.3]), at [delta] 4.2 (quartet, 2H, C[H.sub.2]). The mass spectra showed the molecular ion peak at m/z (323) which is in agreement with its molecular formula ([C.sub.17][H.sub.13][N.sub.3]S[O.sub.2]), Scheme 8.

[FORMULA NOT REPRODUCIBLE IN ASCII]

Experimental

All melting points were uncorrected. IR spectra were recorded on a Pye Unicam SP-II00 Spectrophotometer using KBr disc. [sup.1]H NMR spectra were recorded on a Varian EM-390 MHz spectrophotometer using DMSO [d.sub.6] as a solvent and TMS as an internal standard. Chemical shifts are expressed as ppm units..

Synthesis of 2-(2-mercapto-1-phenylethylidene)malononitrile 1

Equimolar amount of 2-(1-phenylethylidene)malononitrile (0.01 mol) (1.68 gm) and sulfur (0.01 mol) (0.32 gm) in ethanol in the presence of triethyl amine (about 0.5 ml) were heated under reflux for 3 hours. Then the reaction mixture was filtered on hot to remove unreacted sulfur. The filtrate was concentrated, cooled, amount of water was added and the solid so formed was collected by filtration and then recrystallized from ethanol to give (1) (c.f. Table 1).

Synthesis of 5-acetyl-2-amino-4-phenylthiophene-3-carbonitrile 3

Equimolar amount of compound (1) (0.01 mol) (2 gm), acetic acid (about 15 ml) and acetic anhydride (about 15 ml) were refluxed for 2 hours. Then the reaction mixture was concentrated, cooled, amount of water was added and the solid so formed was collected by filtration and then recrystallized from ethanol to give (3) (c.f. Table 1).

Synthesis of N-(5-acetyl-3-cyano-4-phenylthiophene-2-yl)acetamide 4

Equimolar amount of compound (3) (0.01 mol) (2.42 gm), acetic acid (about 15 ml) and acetic anhydride (about 15 ml) were heated under reflux for 2 hrs. Then the reaction mixture was concentrated, cooled, amount of water was added and the solid so formed was collected by filtration and then recrystallized from ethanol to give (4) (c.f. Table 1).

Synthesis of 6-(1-formylvinyloxy)-5-phenylthieno[2,3-d]pyrimidine-2,4 dicarboxylic acid 5

Equimolar amount of compound (3) (0.01 mol) (2.42 gm), and formic acid (about 20 ml) were heated under reflux for 3 hrs. The reaction mixture was cooled and the solid so formed by water addition was collected by filtration and then recrystallized from ethanol to give (5) (c.f. Table 1).

Synthesis of 6-(1-formylvinyloxy)-1,2-dihydro-5-phenylthieno[2,3-d]pyri-midine-2,4-dicarboxylic acid 6

Equimolar amount of compound (4) (0.01 mol) (3.84 gm) and formic acid (about 20 ml) were heated under reflux for 3 hrs. The reaction mixture was cooled and the solid so formed by water addition was collected by filtration and then recrystallized from ethanol to give (6) (c.f. Table 1).

Synthesis of 1-(3-amino-4-phenylthieno[2,3-c]isothiazole-5-yl) ethanone 7

Equimolar amount of compound (3 or 4) (0.01 mol) (2.42-3.84 gm), respectively) and sulfur (0.01 mol) (0.32 gm) in ethanol in the presence of triethyl amine (about 0.5 ml) were heated under reflux for 3 hrs. Then the reaction mixture was filtered on hot to remove unreacted sulfur. The filterate was concentrated, cooled, amount of water was added and the solid so formed was collected by filtration and then recrystallized from ethanol to give (7) (c.f. Table 1).

Synthesis of 2-(2-mercapto-2-hydrazone-1-phenylethylidene)malononitrile derivatives (8a:c)

General procedure 1

Equimolar amount of sod. nitrite (0.01 mol) (0.79 gm) was added to about 5 ml of HCl with shaking and then was diluted by little amount of water and then was added to equimolar amount of aniline derivative (such as aniline, p-methoxy aniline, p-bromo aniline) (0.01 mol) (0.63 gm, 1.23 gm, 1.72 gm, respectively). The formed aromatic diazonium chloride was added drop wisely with shaking to a solution in ethanol of equimolar amount of compound (1) (0.01 mol) (2 gm) in ice bath and the dye so formed was collected by filtration and then recrystallized from ethanol to give (8a-c) (c.f. Table 1).

Synthesis of 5-hydrazone-2,5-dihydro-2-imino-4-phenylthiophene-3-carbo-nitrile derivatives (9a:c).

General procedure 2

A solution of compound (8a-c) (2gm) in acetic acid (about 40 ml) was heated under reflux for 1.5 hrs. The reaction mixture was concentrated, cooled, filtrated and the solid so formed was collected by filtration and then recrystallized from ethanol to give (9a-c) (c.f. Table 1).

Synthesis of N-(4-cyano-2,5-dihydro-5-oxo-3-phenylthiophene-2yl)aceta-mide 10

General procedure 3

To a solution of compound (9a-c) (1 gm), zinc dust was added with stirring. The reaction mixture was refluxed for 15 min. and then left to cool. The solid product so formed on dilution was collected by filtration and recrystallized from ethanol to give (10) (c.f. Table 1).

Synthesis of 1-(3,5-diamino-4-phenyl-3H-thieno[2,3-c]pyrazole-2(5H)-yl) ethanone 11

Equimolar amount of compound (10) (0.01 mol) (2.58 gm), hydrazine hydrate (0.01 mol) (0.5 gm) and 10 ml of acetic acid were refluxed for 8 hours. The reaction mixture was concentrated, cooled and the solid so formed by water addition was collected by filtration and then recrystallized from ethanol to give (11) (c.f. Table 1). Synthesis of 3,5-dihydro-2,4-diphenyl-2H-thieno [2,3-c]pyrazole-3,5-diami-ne (12). Equimolar amount of compound (10) (0.01 mol) (2.58 gm), phenyl hydrazine (0.01 mol) (1.08 gm) and few drops of piperidine as a catalyst were refluxed for 8 hours. Then the reaction mixture was concentrated, cooled and the solid so formed by water addition was collected by filtration and then recrystallized from ethanol to give (12) (c.f. Table 1).

Synthesis of 4,6-diamino-5-phenylthieno[2,3-d]pyrimidine-2(6H)-one 13

Equimolar amount of compound (10) (0.01 mol) (2.58 gm), urea (0.01 mol) (0.6 gm) and few drops of piperidine as a catalyst were refluxed for 8 hours. Then the reaction mixture was concentrated, cooled and the solid so formed by water addition was collected by filtration and then recrystallized from ethanol to give (13) (c.f. Table 1).

Synthesis of 4,6-diamino-5-phenylthieno[2,3-d]pyrimidine-2(6H)thione 14

Equimolar amount of compound (10) (0.01 mol) (2.58 gm), thiourea (0.01 mol) (0.76 gm) and few drops of piperidine as a catalyst were refluxed for 8 hours. Then the reaction mixture was concentrated, cooled and the solid so formed by water addition was collected by filtration and then recrystallized from ethanol to give (14) (c.f. Table 1).

Synthesis of 3,5-dihydro-4-phenylthieno[2,3-c]isoxazole-3,5-diamine (15)

Equimolar amount of compound (10) (0.01 mol) (2.58 gm), hydroxyl amine hydrochloride (0.01 mol) (0.695 gm) and few drops of piperidine as a catalyst were refluxed for 8 hours. Then the reaction mixture was concentrated, cooled and the solid so formed by water addition was collected by filtration and then recrystallized from ethanol to give (15) (c.f. Table 1).

Synthesis of 5-(2,2-dicyano-1-phenylvinyl)-2,5-dihydro-2-aminothiophene-3-carbonitrile derivatives (17a:c)

General procedure 4

Equimolar amount of malononitril (0.01 mol) (0.66 gm) and aldehyde (0.01 mol) such as (formaldehyde, acetaldehyde, benzaldehyde) (0.3 gm, 0.44 gm, 1.06 gm, respectively) in ethanol and few drops of piperidine as a catalyst were refluxed for 1 hr. then equimolar amount of compound (1) (0.01 mol) (2 gm) was added to the reaction mixture and refluxed for 5 hrs., then the reaction mixture was concentrated, cooled and the solid so formed by adding amount of water was collected by filtration and then recrystallized from ethanol to give (17a-c) (c.f. Table 1).

Synthesis of 2,5-dihydro-2-imino-4-phenyl-5-(1-phenylethylidene)thiophe-ne-3-carbonitrile derivatives (19a-c).

General procedure 5

Equimolar amount of compound (1) (0.01 mol) (2 gm) and acetophenone derivatives (0.01 mol) such as (acetophenone, p-methoxyacetophenone, p-nitroacetophenone) (1.2 gm, 1.5 gm, 1.65 gm, respectively) in ethanol and few drops of piperidine were heated under reflux for 8 hrs. The reaction mixture was concentrated, cooled and the solid product so formed by water addition was collected by filtration and recrystallized from ethanol to give (19a-c) (c.f. Table 1).

Synthesis of 5-benzylidene-2,5-dihydro-2-imino-4-phenylthiophene-3-carbonitrile derivatives (21a-c).

General procedure 6

Equimolar amount of compound (1) (0.01 mol) (2 gm) and aromatic aldehyde (benzaldehyde, p-methoxybenzaldehyde, p-chlorobenzaldehyde) (0.01 mol) (1.06 gm, 1.36 gm, 1.4 gm, respectively) in ethanol and few drops of piperidine were refluxed for 8 hrs. The reaction mixture was concentrated, cooled and the solid product so formed by water addition was collected by filtration and recrystallized from ethanol to give (21a-c) (c.f. Table 1).

Synthesis of ethyl-5-(2,2-dicyano-1-phenylvinyl)-2,5-dihydro-2-aminothiophene-3-carboxylate derivatives (23a-c).

General procedure 7

Equimolar amount of ethylcyanoacetate (0.01 mol) (1.13 gm) and aldehyde such as (formaldehyde, acetaldehyde, benzaldehyde) (0.01 mol) (0.3 gm, 0.44 gm, 1.06 gm, respectively) in ethanol and few drops of piperidine were refluxed for 1 hr. The equimolar amount of compound (1) (0.01 mol) (2 gm) was added to the reaction mixture and refluxed for 5 hrs., then the reaction mixture was concentrated, cooled and the solid product so formed by water addition was collected by filtration and then recrystallized from ethanol to give (23a-c) (c.f. Table 1).

References

[1] Fayed, A.A.; Hosni, H.M., Flefel, E.M., Amr, A.E., 2009. World 1. of Chemistry, 4(1): 58-65.

[2] Santagati, N.A., A. Caruso, V.M.C Cutuli and F. Caccamo, 1995 Farmaco Rome., 50(10): 689-692.

[3] Nakanishi, M and M. Shiraki, 1972 Japan, 73 42,271 (CCI. CI7D), Chem. Abstr., 78: 29795j.

[4] Devni, MB., C.I. Shishoo, U.S. Pathak, S.H. Parikh, A V. Radhakrishnan and A C. Padhya, 1976. Indian J. Chem., 14B: 537-542.

[5] Manhas, M.S., MS. Sharma and S.G. Arnin, 1972J. Med Chem., 15: 106107.

[6] Perrisin, M., M Faver, C. Luu Due, F. Huguet, C. Gaultier and C. Narcisse, 1988. Eur. J. Med. Chem., 23: 453-456.

[7] Rosowsky, A, M Chaykovsky, K.K.N. Chen, M. Lin and RJ. Medest, 1973. J. Med. Chem., 16(3): 185-188.

[8] Rosowsky, A, K.K.N. Chen and M. Lin, 1973. J. Med. Chem., 16(3): 191194.

[9] Chaykovsky, M., M. Lin A. Rosowsky and E.I. Medest, 1973. J. Med. Chem., 16(3): 188-191.

[10] Gillespie, E., K.W. Dungan, AW. Gomoll and RJ. Seideharnel, 1985. Int. 1. Irnmunopharmaco., 7(5): 655-660; Chem. Abstr., 103: 189379q.

[11] Temple, D.L., J.P. Yevich, R.R Covington, C.A. Hannrng, R.I. Seideharnel, H.K Mackey and M.I. Bartek, 1979. J. Med. Chern., 22(5): 505-510.

[12] Blaszkiewicz, P., H. Vorbruggen and H.J. Kessler, 1976. Ger. Offen. 2, 411,274, Chem. Abstr., 84: 17412t.

[13] Chambhare, R.V. and B.G. Khadse, 2003 Eur. J. Med. Chem., 38(1): 89- 100..

[14] Dave, C.G. and RD. Shah, 2002. Molecules, 7: 554-565.

[15] Ram, V.I., 1979. Arch. Pharm., 31(1): 19-25.

[16] Abdel-Rahman, AE., E.A. Bakhite and E.A. Al-Taifi, 2002. 1. Chin Chem. Soc., 49: 223-227.

[17] Cox, J.M, J.H.E. Marsden, RA Burrell, N. Elmore and M.C. Shephard, 1977. Ger. Offen. 2, 654, 090 Chern. Abstr., 87, 128906p.

[18] Amr, AE., M.J. Hegab, AA Ibrahim and M.M. Abdalah, 2003. Monatsh. Chem., 134: 1395-1409.

[19] Amr, AE. and MM. Abdalah, 2002. Ind. J. Heterocycl. Chem., 12: 129-134.

[20] Nehad, AA, A.E. Amr and AI. A1husien, 2007. Monatsh. Chem., 138: 559567.

[21] Amr, AB., M.S. Nermien and M.M Abdalah, 2007. Monatsh. Chem., 138: 699-707.

[22] Amr, AB., M.M. Ashraf, F.M Salwa, AA Nagla and AG. Hammam, 2006. Bioorg. Med Chem., 14: 5481-4588.

[23] Amr, AB., H.H. Sayed and M.M. Abdalah, 2005. Arch. Pharma. Chem. Life Sci., 338: 433-440.

[24] N.A.A. E1-Kanzi, H.A. Soleiman and A.K. Khalafallah, Phosphorus, salfur and silicon. 182, 1459-1473 (2007).

[25] H.A. Soleiman and N.A.A. E1-Kanzi, Phosphorus, salfur and silicon, 183, 1679-1690 (2008).

[26] H.A. Soleiman, F.M. Abdel-Latif, M.A. Khalil and I.H. E1azab, Phosphorus, salfur and silicon, 177, 1001 (2002).

(1) H.A. Soleiman, (2) M.A. Barsy, (3) A.K. Khalafallah and (4) A.A. Reda

Chemistry Department, Aswan Faculty of Science, South Valley University, Aswan, Egypt.
Table 1: Characterization of the Compounds.

Comp Yield Colour
No. %

1 86 Pale yellow

3 50 Yellow

4 79 Pale brown

5 57 Brown

6 51 Brown

7 79 Brown

8a 81 Deep red

8b 56 Deep brown

8c 95 Deep brown

9a 42 Deep red

9b 90 Deep red

9c 56 Deep red

10 31 Yellowish
 green

11 68 Brown

12 50 Brown

13 83 Brown

14 77 Brown

15 73 Brown

17a 81 Brown

17b 69 Brown

17c 83 Deep brown

19a 66 Brown

19b 64 Brown

19c 63 Brown

21a 74 Deep brown

21b 75 Brown

21c 32 Brown

21d 60 Brown

21e 54 Deep brown

23a 83 Brown

23b 82 Brown

23c 77 Brown

Comp M.P. Solvent
No. [degrees]C of cryst.

1 98 Ethanol

3 122 Ethanol

4 198 Ethanol

5 138 Ethanol

6 130 Ethanol

7 208 Ethanol

8a 260 Ethanol

8b 83 Ethanol

8c 260 Ethanol

9a 300 Ethanol

9b 120 Ethanol

9c 250 Ethanol

10 120 Ethanol

11 Ethanol
 186
12 Ethanol
 170
13 Ethanol
 175
14 Ethanol
 172
15 Ethanol
 166
17a Ethanol
 135
17b Ethanol
 95
17c Ethanol
 100
19a Ethanol
 92
19b Ethanol
 96
19c Ethanol
 101
21a Ethanol
 132
21b Ethanol
 180
21c Ethanol
 238
21d Ethanol
 150
21e Ethanol
 160
23a Ethanol
 130
23b Ethanol
 135
23c Ethanol
 142

Comp M. formula M. Wt. Elemental Analysis
No.

 C H N

1 [C.sub.11][H.sub.8] 66.05 4.00 14.00
 [N.sub.2]S (200) 66.05 4.01 14.05

3 [C.sub.13][H.sub.10] 64.46 4.13 11.57
 [N.sub.2]SO (242) 64.41 4.08 11.55

4 [C.sub.15][H.sub.12] 46.87 3.13 7.29
 [N.sub.2]S[O.sub.2] 46.81 3.12 7.30
 (384)

5 [C.sub.17][H.sub.10] 55.13 2.70 7.57
 [N.sub.2]S[O.sub.6] 55.09 2.77 7.51
 (370)

6 [C.sub.17][H.sub.12] 54.83 3.23 7.53
 [N.sub.2]S[O.sub.6] 54.82 3.19 7.48
 (372)

7 [C.sub.13][H.sub.10] 56.39 3.65 10.22
 [N.sub.z][S.sub.2]O 56.90 3.68 10.20
 (274)

8a [C.sub.17][H.sub.12] 67.11 3.95 18.42
 [N.sub.2]S (304) 67.09 3.94 18.42

8b [C.sub.18][H.sub.14] 64.64 4.19 16.77
 [N.sub.4]SO (334) 64.60 4.11 16.80

8c [C.sub.17][H.sub.11] 53.26 2.87 14.62
 [N.sub.4]SBr (383) 53.23 2.82 14.69

9a [C.sub.17][H.sub.12] 67.11 3.95 18.42
 [N.sub.4]S (304) 67.07 3.94 18.55

9b C18H14N4SO (334) 64.67 4.19 16.77
 64.60 4.18 16.65
9c [C.sub.17][H.sub.11] 53.26 2.87 14.62
 [N.sub.4]SBr (383) 53.25 2.80 14.60

10 [C.sub.13][H.sub.10] 60.46 3.88 10.85
 [N.sub.2]S[O.sub.2] 60.45 3.88 10.71
 (258)

11 [C.sub.13][H.sub.14] 56.9 5.10 20.44
 [N.sub.4]SO (274) 65.11 5.05 20.43

12 [C.sub.17][H.sub.16] 66.23 5.19 18.18
 [N.sub.4]S (308) 66.22 5.18 18.23

13 [C.sub.12][H.sub.10] 55.81 3.87 21.70
 [N.sub.4]SO (258) 55.77 3.86 21.78

14 [C.sub.12][H.sub.10] 52.55 3.65 20.44
 [N.sub.4][S.sub.2] 52.57 3.57 20.51
 (274)

15 [C.sub.11][H.sub.11] 56.65 4.72 18.03
 [N.sub.3]SO (233) 56.51 4.83 18.01

17a [C.sub.18][H.sub.8] 65.28 2.90 20.29
 [N.sub.4]S (276) 65.20 2.96 20.21

17b [C.sub.16][H.sub.10] 66.21 3.45 19.31
 [N.sub.4]S (290) 66.19 3.41 19.35

17c [C.sub.21][H.sub.12] 71.59 3.41 15.91
 [N.sub.4]S (352) 71.48 3.45 15.22

19a [C.sub.19][H.sub.14] 75.49 4.64 9.27
 [N.sub.2]S (302) 75.40 4.68 9.25

19b [C.sub.20][H.sub.16] 72.29 4.82 8.43
 [N.sub.2]SO (332) 72.22 4.80 8.48

19c [C.sub.19][H.sub.13] 65.71 3.75 12.10
 [N.sub.3]S[O.sub.2] 65.67 3.70 12.18
 (347)

21a [C.sub.18][H.sub.12] 75.00 4.71 9.72
 [N.sub.2]S (288) 75.13 4.78 9.70

21b [C.sub.18][H.sub.12] 71.05 3.95 9.21
 [N.sub.2]SO (304) 70.98 3.90 9.81

21c [C.sub.18][H.sub.12] 71.05 3.95 9.21
 [N.sub.2]SO (304) 71.00 3.90 9.22

21d [C.sub.19][H.sub.14] 71.70 4.40 8.80
 [N.sub.2SO (318) 71.75 4.00 8.78

21e [C.sub.18][H.sub.11] 66.98 3.14 8.68
 [N.sub.2]SCl (322.5) 66.87 3.19 8.65

23a [C.sub.17][H.sub.13] 63.16 4.02 13.00
 [N.sub.3]S[O.sub.2] 63.14 4.08 13.01
 (323)

23b [C.sub.18][H.sub.15] 64.10 4.45 12.46
 [N.sub.3]SO (337) 64.15 4.19 12.40

23c [C.sub.23][H.sub.17] 69.17 4.26 10.52
 [N.sub.3]S[O.sub.2] 69.22 4.26 10.55
 (399)

Comp Elemental Analysis Mass
No. spectra

 S Cl Br

1 16.00 -- -- 200
 16.02

3 13.22 -- -- 242
 13.21

4 8.33 -- -- 384
 8.29

5 8.64 -- -- 368
 8.61

6 8.60 -- -- 369
 8.68

7 23.36 -- -- 274
 23.25

8a 10.53 -- -- 304
 10.50

8b 9.58 -- -- 334
 9.57

8c 8.35 -- 20.88 383
 8.32 20.81

9a 10.53 -- -- 304
 10.56

9b 9.58 -- -- 334
 9.60

9c 8.35 20.88 383
 8.41 20.85

10 12.40 -- -- 258
 12.43

11 11.68 -- -- 276
 11.65

12 10.38 -- -- 304
 10.42

13 12.40 -- -- 258
 12.38

14 23.36 -- -- 274
 23.30

15 13.73 -- -- 233
 13.69

17a 11.59 -- -- 276
 11.66

17b 11.03 -- -- 290
 10.98

17c 9.09 -- -- 352
 9.02

19a 10.60 -- -- 302
 10.53

19b 9.64 -- -- 332
 9.60

19c 9.22 -- -- 347
 9.18

21a 11.11 -- -- 288
 11.00

21b 10.25 -- -- 304
 10.25

21c 10.25 -- -- 304
 10.28

21d 10.06 -- 318
 10.11

21e 9.92 11.00 322.5
 9.90 10.86

23a 9.91 -- 323
 9.92

23b 9.49 -- 337
 9.53

23c 8.02 -- 399
 7.97
COPYRIGHT 2012 Research India Publications
No portion of this article can be reproduced without the express written permission from the copyright holder.
Copyright 2012 Gale, Cengage Learning. All rights reserved.

Article Details
Printer friendly Cite/link Email Feedback
Author:Soleiman, H.A.; Barsy, M.A.; Khalafallah, A.K.; Reda, A.A.
Publication:International Journal of Applied Chemistry
Date:May 1, 2012
Words:5360
Previous Article:Metabolism of halogenated hydroxyquinolines.
Next Article:Design and fabrication of polysilicon Nanowire.
Topics:

Terms of use | Privacy policy | Copyright © 2021 Farlex, Inc. | Feedback | For webmasters |