314 A.S. Shawali et al.
3.2.1. 2,2ꢀ-Bis-(4-phenyl-5-phenylimino-1,3,4-thiadiazole) (5)
1
Yellow brown solid (1.26 g, 50%), mp 310 ◦C. IR (KBr) ν 1600, 1560 cm−1; H NMR δ 7.07–
7.79 (m); MS m/z (%) 505 (M+ + 1, 7), 504 (M+, 19), 252 (3), 135 (10), 91 (100), 77 (57). Anal.
Calcd. C28H20N6S2 (504.6): C, 66.64; H, 3.99; N, 16.65; found: C, 66.54; H, 3.84; N, 16.53%.
3.2.2. 2,2ꢀ-Bis-[4-phenyl-5-(cyanobenzoylmethylene)-1,3,4-thiadiazole] (7a)
Brown solid (1.22 g, 40%), mp. 170 ◦C (EtOH). IR (KBr) ν 2191, 1640 cm−1; 1H NMR δ 6.72–
7.65 (m); MS m/z (%) 609 (M+ + 1, 5), 608 (M+, 7), 278 (2), 143 (2), 105 (100), 77 (98). Anal.
Calcd. C34H20N6O2S2 (608.7): C, 67.09; H, 3.31; N, 13.81; found: C, 67.20; H, 3.41; N, 13.75%.
3.2.3. 2,2ꢀ-Bis-[4-phenyl-5-(ethoxycarbonylcyanomethylene)-1,3,4-thiadiazole] (7b)
Brown solid (1.36 g, 50%), mp. 195◦C (EtOH). IR (KBr) ν 2206, 1659 cm−1; 1H NMR δ 1.24 (t,
J = 7 Hz, 6H), 4.23 (q, J = 7 Hz, 4H), 7.03–7.97 (m, 10H); 13C NMR δ 14.9, 15.0, 62.1, 62.2,
113.6, 120.9, 123.6, 125.4, 128.1, 128.4, 128.5, 129.7, 129.9, 130.1, 130.6, 131.8, 132.0, 138.2,
139.0, 147.7, 167.3, 167.4; MS m/z (%) 545 (M+ + 1, 52), 544 (M+, 100), 271 (2), 246 (2), 155
(2), 91 (16, 77 (43). Anal. Calcd. C26H20N6O4S2 (544.6): C, 57.41; H, 3.82; N, 15.38; found: C,
57.34; H, 3.70; N, 15.43%.
3.2.4. 2,2ꢀ-Bis-[4-phenyl-5-(2-thenoylcyanomethylene)-1,3,4-thiadiazole] (7c)
Brown solid (1.39 g, 45%), mp. 215 ◦C (EtOH). IR (KBr) ν 2207, 1660 cm−1; 1H NMR δ 7.42–
8.99 (m); MS m/z (%) 621 (M+ + 1, 3), 620 (M+, 12), 310 (14), 284 (15), 207 (100), 110 (13).
Anal. Calcd. C30H16N6O2S4 (620.7): C, 57.05; H, 2.60; N, 13.54; found: C, 58.34; H, 2.41; N,
13.50%.
3.3. Alternate synthesis of (5)
To a stirred solution of methyl N-phenyldithiocarbamate (3.20 g, 0.02 mol) in ethanol (60 ml)
containing triethylamine (2.8 ml, 0.02 mol), the bis-hydrazonoyl chloride 1 (3.07 g, 0.01 mol)
was added and the mixture was stirred for 7 h at room temperature. The precipitated solid was
filtered off, washed with water, dried and finally crystallized from EtOH–DMF to give 5 (1.89 g,
75%) as yellow brown solid which proved identical in all respects with that one obtained above
from 1 and 2.
References
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