8
F. M. SALEH ET AL.
2H, CH2), 2.85 (t, 2H, CH2), 2.98 (t, 2H, CH2) and MS (EI, 70 eV) m/z (%): 438 (Mþ, 13.9), 105 (24.35), 77
7.16–8.38 (m, 14H); 13C NMR (75 MHz, CDCl3) d 20.8,
(100); Anal. Calcd. for C23H14N6S2 (438.5): C, 63.00; H,
24.3, 29.6, 120.5, 122.5, 123.3, 124.4, 126.2, 128.1, 128.4,
128.5, 128.7, 129.7, 131.4, 138.5, 138.9, 147.8, 158.7, 164.7,
166.6; Anal. Calcd. for C24H20N6S (424.5): C, 67.90; H, 4.75;
N, 19.80; S, 7.55. Found: C, 67.97; H, 4.68; N, 19.87; S, 7.59.
2-((3,4-Dihydronaphthalen-1(2H)-ylidene)hydrazono)-3-
(p-tolyl)-5-(p-tolyldiazenyl)-2,3-di-hydro-1,3,4-thiadiazole
(29) Dark red crystals, mp 198–200 ꢁC (DMF), Yield (81%);
1H NMR (300 MHz, CDCl3) d 1.94–1.98 (m, 2H, CH2), 2.43
(s, 3H, CH3), 2.47 (s, 3H, CH3), 2.84 (t, 2H, CH2), 2.97 (t,
2H, CH2) and 7.17–8.37 (m, 12H); 13C NMR (75 MHz,
CDCl3) d 21.1, 21.7, 22.2, 28.1, 30.0, 122.0, 122.3, 123.9,
125.8, 126.4, 128.6, 129.9, 130.1, 132.2, 136.5, 137.2, 140.7,
144.1, 150.0, 160.8, 162.2, 163.4; MS (EI, 70 eV) m/z (%):
452 (Mþ, 51.4), 91 (100), 65 (19.5); Anal. Calcd. for
C26H24N6S (452.6): C, 69.00; H, 5.35; N, 18.57; S, 7.08.
Found: C, 69.08; H, 5.41; N, 18.49; S, 7.16.
3.22; N, 19.16; S, 14.62. Found: C, 63.09; H, 3.16; N, 19.08;
S, 14.55.
2,5-Diphenyl-4-(3-phenyl-5-(phenyldiazenyl)-1,3,4-thia-
diazol-2(3H)-ylidene)-2,4-dihydro-3H-pyrazol-3-one (34D)
Black crystals, mp 229–231 ꢁC (DMF), yield (80%); IR (ꢀmax
,
cmꢀ1) ꢀ 1636 (CO); 1H NMR (300 MHz, CDCl3) d
7.16–8.19 (m, 20H); 13C NMR (75 MHz, CDCl3) d 104.3,
118.7, 119.4, 120.9, 122.1, 128.1, 128.5, 128.6, 128.7, 128.9,
129.4, 129.7, 131.2, 137.8, 140.4, 142.3, 146.4, 147.7, 155.4,
165.6, 166.7; MS (EI, 70 eV) m/z (%): 500 (Mþ, 23.8), 337
(14.0), 105 (15.2), 91 (15.4), 77 (100); Anal. Calcd. for
C29H20N6OS (500.6): C, 69.58; H, 4.03; N, 16.79; S, 6.40.
Found: C, 69.49; H, 3.93; N, 16.70; S, 6.32.
5-Methyl-2-phenyl-4-(3-phenyl-5-(phenyldiazenyl)-1,3,4-
thiadiazol-2(3H)-ylidene)-2,4-dihydro-3H-pyrazol-3-one
(34E) Black crystals, mp 178–180 ꢁC (DMF), yield (82%); IR
1
(ꢀmax, cmꢀ1) ꢀ 1633 (CO); H NMR (300 MHz, CDCl3) d
2.33 (s, 3H, CH3) and 7.15–8.07 (m, 15H); 13C NMR
(75 MHz, CDCl3) d 14.5, 104.3, 118.7, 119.5, 120.9, 122.6,
128.2, 128.6, 128.7, 128.9, 129.7, 140.5, 142.3, 146.4, 147.7,
147.9, 165.7, 166.5; MS (EI, 70 eV) m/z (%): 438 (Mþ, 30.7),
275 (11.2), 105 (14.6), 91 (13.5), 77 (100); Anal. Calcd. for
C24H18N6OS (438.5): C, 65.74; H, 4.14; N, 19.17; S, 7.31.
Found: C, 65.64; H, 4.07; N, 19.08; S, 7.23.
Synthesis of 1,3,4-thiadiazol-2(3H)-ylidene deriva-
tives (34–36)
These compounds were prepared by the same procedure
described for the preparation of thiadiazole derivatives 10, 11,
13, 14 and 22–29 (Method A) using thioanilides 31A–E
(5 mmol) in place of 2-((methylthio)carbonthioyl)hydrazones 7,
12 and 18–21 in acetonitrile (50 mL). The resulting solid prod-
uct that precipitated was collected, washed with ethanol and
crystallized from a suitable solvent to afford the corresponding
1,3,4-thiadiazole derivatives 34–36. The products 34–36 pre-
pared together with their physical constants are listed below:
5,5-Dimethyl-2-(3-phenyl-5-(phenyldiazenyl)-1,3,4-thia-
diazol-2(3H)-ylidene)cyclohexane-1,3-dione (34A) Red crys-
tals, mp 188–190 ꢁC (EtOH), yield (70%); IR (ꢀmax, cmꢀ1) ꢀ
5,5-Dimethyl-2-(3-(p-tolyl)-5-(p-tolyldiazenyl)-1,3,4-thia-
diazol-2(3H)-ylidene)cyclohexane-1,3-dione (35A) Red crys-
tals, mp 216–218 ꢁC (CH3CN), yield (74%); IR (ꢀmax, cmꢀ1
)
1
ꢀ 1668 (CO); H NMR (300 MHz, DMSO-d6) d 0.98 (s, 6H,
2CH3), 2.30 (s, 4H, 2CH2), 2.50 (s, 3H, CH3), 2.52 (s, 3H,
CH3) and 7.27–7.95 (m, 8H); 13C NMR (75 MHz, DMSO-
d6) d 21.2, 21.9, 28.5, 30.9, 51.1, 105.1, 123.1, 124.5, 129.8,
131.1, 138.3, 141.1, 146.5, 149.9, 162.0, 168.4, 191.5; Anal.
Calcd. for C24H24N4O2S (432.5): C, 66.64; H, 5.59; N, 12.95;
S, 7.41. Found: C, 66.73; H, 5.68; N, 13.04; S, 7.51.
1
1664 (CO); H NMR (300 MHz, DMSO-d6) d 0.97 (s, 6H,
2CH3), 2.30 (s, 4H, 2CH2) and 7.20–7.95 (m, 10H); 13C
NMR (75 MHz, DMSO-d6) d 27.9, 30.7, 50.9, 105.3, 123.2,
124.6, 129.7, 131.3, 138.5, 141.4, 146.8, 149.5, 162.6, 167.4,
192.6; MS (EI, 70 eV) m/z (%): 404 (Mþ,9.9),105 (47.0), 77
(100); Anal. Calcd. for C22H20N4O2S (404.5): C, 65.33; H,
4.98; N, 13.85; S, 7.93. Found: C, 65.42; H, 4.87; N, 13.92;
S, 8.02.
2-(3-(p-Tolyl)-5-(p-tolyldiazenyl)-1,3,4-thiadiazol-2(3H)-
ylidene)-1H-indene-1,3(2H)-dione (35B) Red crystals, mp
296–298 ꢁC (DMF), yield (80%); IR (ꢀmax, cmꢀ1) ꢀ 1650
1
(CO); H NMR (300 MHz, DMSO-d6) d 2.50 (s, 3H, CH3),
2.52 (s, 3H, CH3) and 7.34–7.99 (m, 12H); 13C NMR
(75 MHz, DMSO-d6) d 21.2, 21.4, 112.1, 119.5, 121.6, 126.9,
128.5, 129.2, 129.9, 131.3, 135.2, 138.2, 143.4, 144.8, 149.4,
166.6, 190.5; MS (EI, 70 eV) m/z (%): 438 (Mþ, 10.7), 119
(9.9), 91 (100), 65 (22.1); Anal. Calcd. for C25H18N4O2S
(438.5): C, 68.48; H, 4.14; N, 12.78; S, 7.31. Found: C, 68.39;
H, 4.03; N, 12.69; S, 7.22.
2-(3-Phenyl-5-(phenyldiazenyl)-1,3,4-thiadiazol-2(3H)-
ylidene)-1H-indene-1,3(2H)-dione (34B) Red crystals, mp
284–286 ꢁC (DMF), yield (82%); IR (ꢀmax, cmꢀ1) ꢀ 1648
(CO); 1H NMR (300 MHz, CDCl3) d 7.27–8.07 (m, 14H);
13C NMR (75 MHz, CDCl3) d 112.3, 119.6, 120.6, 122.7,
127.1, 128.6, 128.9, 129.8, 135.3, 140.2, 146.4, 147.7, 149.6,
166.7, 190.6; MS (EI, 70 eV) m/z (%): 410 (Mþ, 27.7), 248
(3.2), 105 (28.19), 77 (100); Anal. Calcd. for C23H14N4O2S
(410.5): C, 67.30; H, 3.44; N, 13.65; S, 7.81. Found: C, 67.22;
H, 3.35; N, 13.56; S, 7.70.
2-(Benzo[d]thiazol-2-yl)-2-(3-(p-tolyl)-5-(p-tolyldiazenyl)-
1,3,4-thiadiazol-2(3H)-ylidene)-acetonitrile (35C) Black crys-
tals, mp 310–312 ꢁC (DMF), yield (78%); IR (ꢀmax, cmꢀ1) ꢀ
1
2189 (CN); H NMR (300 MHz, CDCl3) d 2.49 (s, 3H, CH3),
2.52 (s, 3H, CH3) and 7.27–8.02 (m, 12H); 13C NMR
(75 MHz, CDCl3) d 20.8, 21.2, 83.6, 118.8, 121.4, 121.7, 124.4,
124.5, 125.5, 128.5, 128.9, 129.2, 129.9, 136.4, 138.6, 143.3,
145.1, 149.5, 153.6, 160.7, 166.5; MS (EI, 70eV) m/z (%): 466
(Mþ, 56.1), 119 (12.5), 91 (100), 65 (37.4); Anal. Calcd. for
2-(Benzo[d]thiazol-2-yl)-2-(3-phenyl-5-(phenyldiazenyl)-
1,3,4-thiadiazol-2(3H)-ylidene)-acetonitrile (34C) Dark
brown crystals, mp 340–342 ꢁC (DMF), yield (81%); IR
1
(ꢀmax, cmꢀ1) ꢀ 2186 (CN); H NMR (300 MHz, CDCl3) d
7.12–8.14 (m, 14H); 13C NMR (75 MHz, CDCl3) d 83.3,
118.9, 119.6, 120.5, 121.4, 122.7, 124.6, 124.7, 125.1, 128.7, C25H18N6S2 (466.6): C, 64.36; H, 3.89; N, 18.01; S, 13.74.
128.8, 129.9, 136.4, 146.5, 147.7, 149.6, 153.7, 160.6, 166.8; Found: C, 64.30; H, 3.81; N, 18.10; S, 13.67.