Molecules 2017, 22, 268
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3.7. (E)-5-Benzylidene-2-((E)-2-(1-(5-methyl-1-(p-tolyl)-1H-1,2,3-triazol-4-yl)ethylidene)-
hydrazinyl)thiazol-4(5H)-one (16)
A mixture of 15 (1.6 g, 5 mmol) and benzaldehyde (0.53 g, 5 mmol) in ethanol and catalytic amount
of piperidine (5 drops) was refluxed for 3 h. The resulting solid was collected and recrystallized from
◦
acetic acid affording white crystals of 16, Yield: 80%, m.p.: 283 C. FT-IR (KBr, cm−1): 3124 (NH), 2974
(CH), 1705 (CO), 1624 (C=N). 1H-NMR (300 MHz, DMSO-d6):
3.30 (s, 3H, CH3), 7.42–7.51 (m, 10H, ArH’s and = CH) and 11.91 (s, br, 1H, NH). 13C-NMR (DMSO-d6)
= 8.1, 19.1, 20.8, 123.9, 129.2, 129.7, 129.9, 130.7, 132.5, 138.2, 139.3, 139.6, 146.2, 159.8, 167.8, 174.1.
δ = 2.49 (s, 3H, CH3), 2.54 (s, 3H, CH3),
δ
Anal. Calcd. For C22H20N6SO (416.51), C, 63.44; H, 4.84; N, 20.18; S, 7.70 Found: C, 63.50; H, 4.90; N,
20.20; S, 7.75.
3.8. 5-(Aryldiazenyl)-4-substituted-2-(3-(5-methyl-1-(p-tolyl)-1H-1,2,3-triazol-4-yl)-5-phenyl-4,5-
dihydro-1H-pyrazole-1-yl)thiazole 20a–d, 21
Method A: A mixture of 17 (1.9 g, 5 mmol), the appropriate hydrazonoyl halides 3a,c,e,f or 3b
(5 mmol) and triethyl amine (0.5 mg, 0.75 mL, 5 mmol) in ethanol (20 mL) was heated under reflux for
4 h. The resulting solid was collected and recrystallized, giving thiazole derivatives 20a–d and 21.
Method B: Benzenediazonium chloride (5 mmol) which was prepared via reaction of aniline
(0.55 g, 5mmol), hydrochloric acid (3 mL, 6 M), and sodium nitrite (0.35 g, 5 mmol) was added
dropwise, with stirring, to a cold solution of 21. The reaction mixture was stirred for 3 h .The resulting
solid was collected, washed with water and crystallized from ethanol, giving 20b.
(E)-4-Methyl-2-(3-(5-methyl-1-(p-tolyl)-1H-1,2,3-triazol-4-yl)-5-phenyl-4,5-dihydro-1H-pyrazol-1-yl)-5-
(phenyldiazenyl)thiazole (20a). Orange crystals from acetic acid, Yield: 75%, m.p.: 235 ◦C; FT-IR (KBr,
cm−1): 3045, 2926, 2860 (CH), 1653 (C=N), 1587 (C=C); 1H-NMR
(
300 MHz, DMSO-d6):
CH3), 2.56 (s, 3H, CH3), 2.70 (s, 3H, CH3), 3.72–3.74 (dd, 1H, Hb), 3.78 (dd, 1H, Ha), 5.78 (dd, 1H, Hx)
and 7.26–7.76 (m, 14H, ArH’s). 13C-NMR (DMSO-d6)
= 8.1, 12.82, 21.0, 33.2, 63.6, 114.8, 121.7, 123.8,
δ = 2.49 (s, 3H,
δ
127.5, 129.1, 129.5, 129.8, 130.1, 130.7, 130.9, 139.2, 139.7, 144.8, 149.6, 154.1, 161.1. MS (El, m/z (%)): 518
(M+, 100), 489 (5), 413 (2), 273 (15), 184 (20), 170 (15), 144 (25), 91 (35%), 77 (70), 65 (17). Anal. Calcd.
For C29H26N8S (518.65), C, 67.16; H, 5.05; N, 21.61; S, 6.18 Found C, 67.26; H, 5.10; N, 21.69; S, 6.28.
(E)-2-(3-(5-Methyl-1-(p-tolyl)-1H-1,2,3-triazol-4-yl)-5-phenyl-4,5-dihydro-1H-pyrazol-1-yl)-4-phenyl-5-
◦
(phenyldiazenyl)thiazole (20b). Red crystals from acetic acid, Yield: 70%, m.p.: 275 C; FT-IR (KBr, cm−1):
3043, 2924 (CH), 1666 (C=N); 1H-NMR (300 MHz, CDCl3):
δ = 2.49 (s, 3H, CH3), 2.71 (s, 3H, CH3),
3.73–3.78 (dd, 1H, Hb), 4.18 (dd, 1H, Ha) 5.82 (dd, 1H, Hx), and 7.33–8.18 (m, 19H, ArH’s), 13C-NMR
(DMSO-d6)
δ = 8.1, 12.82, 21.0, 33.2, 63.6, 108.7, 121.7, 123.8, 126.7, 127.4, 128.2, 128.7, 128.2, 129.8, 129.9,
130.1, 130.4, 130.9, 133.1, 136.2, 139.1, 139.7, 144.7, 154.7, 168.0 MS (El, m/z (%): 580 (M+, 85), 551 (30),
447 (10), 367 (30), 133 (40), 91(50), 77(100), 65(20). Anal. Calcd. For C34H28N8S (580.72), C, 70.32; H,
4.86; N, 19.30; S, 5.52 Found C, 70.22; H, 4.75; N, 19.20; S, 5.56.
(E)-4-Methyl-2-(3-(5-methyl-1-(p-tolyl)-1H-1,2,3-triazol-4-yl)-5-phenyl-4,5-dihydro◦-1H-pyrazol-1-yl)-5-
(p-tolyldiazenyl)thiazole (20c). Red crystals from acetic acid, Yield: 70%, m.p.: 240 C; FT-IR (KBr, cm−1):
3039, 2926 (CH), 1658 (C=N); 1H-NMR (300 MHz, CDCl3):
δ = 2.40 (s, 3H, CH3), 2.46 (s, 3H, CH3),
2.60 (s, 3H, CH3), 2.72 (s, 3H, CH3), 3.5–3.6 (dd, 1H, Hb), 4.1–4.2 (dd, 1H, Ha), 5.61–5.64 (dd, 1H, Hx)
and 6.81–8.17 (m, 13H, ArH’s). Anal. Calcd. For C30H28N8S (532.68), C, 67.65; H, 5.30; N, 2.04; S, 6.02
Found C, 67.72; H, 5.34; N, 2.14; S, 6.12.
(E)-5-((4-Chlorophenyl)diazenyl)-4-methyl-2-(3-(5-methyl-1-(p-tolyl)-1H-1,2,3-triazol-4-yl)-5-phenyl-4,5-
dihydro-1H-pyrazol-1-yl)thiazole (20d). Red crystals from ethanol, Yield:65%, m.p.: 220 ◦C; FT-IR (KBr,
cm−1): 3037, 2926 (CH), 1670 (C=N); 1H-NMR (300 MHz, CDCl3):
δ
= 2.48 (s, 3H, CH3), 2.56 (s, 3H,
CH3), 2.69 (s, 3H,CH3), 3.63–3.72 (dd, 1H, Hb), 4.11–4.21 (dd, 1H, Ha), 5.64–5.70 (dd, 1H, Hx) and