Molecules 2014, 19
2999
115.53 (3 Ar-C), 123.97 (1 Ar-C), 124.80 (2 Ar-C), 127.35 (1 Ar-C), 128.20 (3 Ar-C), 129.27 (1 Ar-C),
129.53 (3 Ar-C), 129.82 (1 Ar-C), 130.09 (3 Ar-C), 131.54 (2 Ar-C), 131.59 (1 Ar-C), 134.54 (1 Ar-C),
140.75 (CN-C=N-NH in hydrazone form), 141.81 (2 Ar-C), 148.47 (triazole C-3), 148.60 (triazole C-3),
154.14 (triazole C-5), 154.97 (triazole C-5); MS m/z (rel. int. %) 349 (M+ + 1, 10), 348 (M+, 38), 347
(22), 320 (9), 319 (7), 290 (4), 244 (3), 243 (4), 242 (6), 215 (9), 204 (2), 155 (6), 149 (6), 143 (3), 129
(6), 128 (5), 105 (19), 92 (6), 91 (8), 77 (100), 76 (67), 65 (20), 64 (14), 63 (7), 61 (6), 52 (5), 51 (26),
50 (14); Anal. Calcd. for C18H16N6S (348.42): C, 62.05; H, 4.63; N, 24.16; S, 9.20. Found: C, 61.91;
H, 4.78; N, 24.35; S, 9.06.
2-(5-Ethylthio-4-phenyl-4H-1,2,4-triazol-3-yl)-2-(4-methylphenyldiazenyl)acetonitrile (5A). Yellow
crystals. Yield (1.22 g, 82%); m.p.: 169–170 °C. IR (KBr): v = 2980, 2920 (aliph. CH), 2217 (CN),
1594 (C=N), 1547 (-N=N-) cm−1; 1H-NMR: δ = 1.43 (t, 3H, J = 7.2 Hz, CH3), 1.47 (t, 3H, J = 7.2 Hz,
CH3), 2.26 (s, 3H, CH3), 2.34 (s, 3H, CH3), 3.28-3.34 (m, 4H, 2 CH2), 6.27 (d, 2H, J = 8.4 Hz, ArH),
6.94 (d, 2H, J = 8.4 Hz, ArH), 7.18 (d, 2H, J = 8.4 Hz, ArH), 7.30-32 (m, 5H, ArH), 7.35–7.37 (m, 3H,
ArH), 7.59–7.63 (m, 3H, ArH), 7.65–7.67 (m, 1H, ArH), 8.78 (s, 0.20H, hydrazone NH); 13.70 (s,
0.80H, triazole NH); 13C-NMR: δ = 14.66 (CH3), 14.68 (CH3), 20.70 (CH3), 20.92 (CH3), 26.60 (CH2),
26.76 (CH2), 98.34 (=C-CN in azo-enamine form), 114.21 (CN), 114.50 (CN), 115.48 (4 Ar-C),
127.37 (1 Ar-C), 128.22 (3 Ar-C), 129.78 (2 Ar-C), 130.04 (2 Ar-C), 130.07 (4 Ar-C), 131.50 (2 Ar-C),
131.64 (1 Ar-C), 133.75 (1 Ar-C), 134.58 (1 Ar-C), 134.64 (2 Ar-C), 138.48 (1 Ar-C), 139.57
(CN-C=N-NH in hydrazone form), 148.55 (triazole C-3), 148.73 (triazole C-3), 153.97 (triazole C-5),
154.75 (triazole C-5); MS m/z (rel. int. %) 363 (M+ + 1, 11), 362 (M+, 40), 361 (21), 348 (5), 347 (6),
346 (8), 345 (6), 335 (6), 334 (16), 333 (10), 306 (9), 305 (11), 274 (4), 273 (5), 257 (5), 243 (4), 242 (6),
231 (4), 230 (5), 215 (14), 188 (4), 157 (8), 156 (11), 149 (11), 148 (7), 144 (6), 143 (6), 128 (8), 119 (14),
118 (13), 117 (9), 106 (8), 105 (22), 104 (13), 103 (11), 97 (6), 92 (14), 91 (100), 90 (26), 77 (49), 76 (17),
66 (6), 65 (27), 64 (21), 63 (12), 61 (6), 60 (9), 59 (13), 56 (9), 51 (26); Anal. Calcd. for C19H18N6S
(362.45): C, 62.96; H, 5.01; N, 23.19; S, 8.85. Found: C, 63.14; H, 4.87; N, 23.30; S, 9.01.
2-(4-Chlorophenyldiazenyl)-2-(5-ethylthio-4-phenyl-4H-1,2,4-triazol-3-yl)acetonitrile (7A). Yellow
crystals. Yield (0.785 g, 50%); m.p.: 118–120 °C. IR (KBr): v = 2925 (aliph. CH), 2217 (CN),
1597 (C=N), 1547 (-N=N-) cm−1; 1H-NMR: δ = 1.43 (t, 3H, J = 7.2 Hz, CH3), 1.48 (t, 3H, J = 7.2 Hz,
CH3), 3.27–3.35 (m, 4H, 2 CH2), 6.30 (d, 2H, J = 9 Hz, ArH), 7.10 (d, 2H, J = 9 Hz, ArH), 7.30–7.36
(m, 8H, ArH), 7.57–7.68 (m, 6H, ArH), 8.91 (s, 0.60H, hydrazone NH), 13.74 (s, 0.40H, triazole NH);
13C-NMR: δ = 14.65 (2 CH3), 26.62 (CH2), 26.76 (CH2), 99.68 (=C-CN in azo-enamine form), 108.93
(CN), 114.02 (CN), 115.46 (2 Ar-C), 116.65 (2 Ar-C), 127.33 (3 Ar-C), 128.17 (2 Ar-C), 128.99 (1 Ar-C),
129.28 (4 Ar-C), 129.61 (1 Ar-C), 129.85 (1 Ar-C), 130.12 (4 Ar-C), 131.48 (1 Ar-C), 131.61 (1 Ar-C),
134.54 (1 Ar-C), 139.48 (1 Ar-C), 140.44 (CN-C=N-NH in hydrazone form), 148.30 (triazole C-3),
148.49 (triazole C-3), 154.37 (triazole C-5), 155.11 (triazole C-5); MS m/z (rel. int. %) 384 (M+, 27),
382 (M+, 78), 381 (20), 356 (4), 355 (7), 354 (13), 353 (15), 352 (5), 328 (7), 327 (10), 326 (13), 325 (17),
324 (7), 293 (7), 244 (4), 243 (9), 242 (15), 241 (7), 232 (3), 231 (3), 215 (15), 214 (10), 213 (7), 192 (3),
191 (8), 183 (4), 182 (6), 181 (7), 167 (5), 157 (10), 156 (25), 155 (13), 149 (12), 148 (5), 143 (3), 142 (6),
141 (9), 140 (4), 139 (17), 138 (11), 129 (13), 128 (12), 127 (10), 126 (11), 125 (9), 119 (5), 118 (17),
113 (32), 112 (17), 111 (100), 110 (78), 105 (23), 104 (15), 103 (12), 102 (13), 100 (6), 99 (16), 92 (8),