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A. FEKRI AND E. M. KESHK
307 (100), 273 (47), 251 (39), 229 (58), 77 (82). Analysis for C20H19N3O2S (365.45): Calcd.:
C, 65.73; H, 5.24; N, 11.50; Found: C, 65.57; H, 5.34; N, 11.38.
2-Benzoyl-3-methyl-5-phenylamino-4-(p-tolylazo)-thiophene (16a): Red crystals, m.p.
=164–165°C. Yield = 81%. IR (ν¯/cm−1): 3282 (NH), 1654 (C O), 1596 (C C), 1542
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(N N). H NMR (DMSO-d6): 2.35 (s, 3H, CH3), 2.40 (s, 3H, CH3), 7.25–7.75 (m, 14H,
Ar-H), 13.60 (s, 1H, NH). MS (M+; EI): m/z (%) = 411 (65), 398 (31), 385 (26), 372 (53),
358 (47), 320 (58), 292 (28), 267 (66), 243 (38), 228 (44), 215 (100), 91 (52), 77 (78). Analy-
sis for C25H21N3OS (411.52): Calcd.: C, 72.97; H, 5.14; N, 10.21; Found: C, 72.85; H, 5.19;
N, 10.14.
2-Benzoyl-3-methyl-4-(p-methoxyphenylazo)-5-phenylamino-thiophene (16b): Red
crystals, m.p. = 177–179°C. Yield = 78%. IR (ν¯/cm−1): 3294 (NH), 1651 (C O), 1597
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(C C), 1558 (N N). H NMR (DMSO-d6): 2.35 (s, 3H, CH3), 3.85 (s, 3H, OCH3),
7.05–7.85 (m, 14H, Ar-H), 12.95 (s, 1H, NH). MS (M+; EI): m/z (%) = 427 (62), 414 (73),
388 (22), 307 (18), 292 (42), 280 (79), 277 (48), 244 (39), 228 (53), 215 (100), 92 (58), 77
(85). Analysis for C25H21N3O2S (427.52): Calcd.: C, 70.24; H, 4.95; N, 9.83; Found: C,
70.13; H, 4.86; N, 9.92.
2-Ethoxycarbonyl-3-methyl-5-phenylamino-4-(p-tolylazo)-thiophene (17a): Reddish
brown crystals, m.p. = 145–146°C. Yield = 78%. IR (ν¯/cm−1): 3203 (NH), 1695 (C O),
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1595 (C C), 1550 (N=N). H NMR (DMSO-d6): 1.30 (t, 3H, CH3, J = 7.15 Hz), 2.35 (s,
3H, CH3), 2.60 (s, 3H, CH3), 4.30 (q, 2H, CH2, J = 7.15 Hz), 7.20–7.65 (m, 9H, Ar-H),
13.75 (s, 1H, NH). 13C NMR (DMSO-d6): 14.28, 14.59, 21.14, 60.25, 115.46 (2C), 125.42,
128.61 (2C), 129.76 (2C), 131.84 (2C), 135.18, 137.68, 140.62, 142.37, 145.43, 149.74,
154.28, 163.37. MS (M+; EI): m/z (%) = 379 (51), 349 (36), 334 (29), 262 (54), 258 (48),
242 (61), 229 (38), 211 (100), 77 (83). Analysis for C21H21N3O2S (379.48): Calcd.: C, 66.47;
H, 5.58; N, 11.07; Found: C, 66.58; H, 5.56; N, 11.13.
2-Ethoxycarbonyl-3-methyl-4-(p-methoxyphenylazo)-5-phenylamino-thiophene (17b):
Reddish brown crystals, m.p. = 174–175°C. Yield = 74%. IR (ν¯/cm−1): 3214 (NH), 1691
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(C O), 1593 (C C), 1531 (N N). H NMR (DMSO-d6): 1.30 (t, 3H, CH3, J = 7.15 Hz),
2.35 (s, 3H, CH3), 3.85 (s, 3H, OCH3), 4.30 (q, 2H, CH2, J = 7.15 Hz), 7.05–7.70 (m,
9H, Ar-H), 13.65 (s, 1H, NH). 13C NMR (DMSO-d6): 14.16, 14.63, 55.62, 60.21, 116.22
(2C), 122.74, 128.71 (2C), 129.41 (2C), 129.73 (2C), 135.22, 137.34, 141.73, 144.94, 149.08,
154.13, 161.36, 163.32. MS (M+; EI): m/z (%) = 395 (43), 364 (93), 326 (54), 319 (73), 274
(22), 245 (29), 212 (100), 77 (85). Analysis for C21H21N3O3S (395.47): Calcd.: C, 63.78; H,
5.35; N, 10.63; Found: C, 63.92; H, 5.30; N, 10.54.
2-Cyano-3-methyl-5-phenylamino-4-(p-tolylazo)-thiophene (18a): Red crystals, m.p. =
168–170°C. Yield = 81%. IR (ν¯/cm−1): 3284 (NH), 2194 (C≡N), 1594 (C C), 1540
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(N N). H NMR (DMSO-d6): 2.35 (s, 3H, CH3), 2.45 (s, 3H, CH3), 7.30–7.75 (m, 9H,
Ar-H), 13.75 (s, 1H, NH). 13C NMR (DMSO-d6): 14.17, 21.14, 105.83, 111.60, 115.82
(2C), 122.69, 125.41, 128.61 (2C), 129.68 (2C), 131.24 (2C), 135.14, 138.52, 142.46, 147.83,
155.06. MS (M+; EI): m/z (%) = 332 (100), 318 (35), 306 (66), 279 (52), 267 (71), 255 (55),
241 (19), 227 (38), 199 (51), 77 (66). Analysis for C19H16N4S (332.42): Calcd.: C, 68.65; H,
4.85; N, 16.85; Found: C, 68.53; H, 4.78; N, 16.89.
2-Cyano-3-methyl-4-(p-methoxyphenylazo)-5-phenylamino-thiophene (18b): Red crys-
tals, m.p. = 184–186°C. Yield = 78%. IR (ν¯/cm−1): 3277 (NH), 2198 (C≡N), 1597
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(C C), 1558 (N N). H NMR (DMSO-d6): 2.35 (s, 3H, CH3), 3.85 (s, 3H, OCH3),
7.05–7.85 (m, 9H, Ar-H), 13.05 (s, 1H, NH). 13C NMR (DMSO-d6): 14.15, 55.58, 105.65,