4
82
M. Khan et al.
acidified with 6 N hydrochloric acid. The precipitated solid
was filtered, washed with cold water, and recrystallized
from aqueous EtOH.
4-Amino-5-(3-fluorophenyl)-2,4-dihydro-3H-1,2,4-triazole-
3-thione (5e, C
H FN S)
8 7 4
1
Yield 72%; m.p.: 220 °C; H NMR ((CD
) CO, 300 MHz):
3 2
d = 5.53 (s, 2H, NH ), 7.34 (m, 1H, Ar–H), 7.79 (m, 1H,
2
4-Amino-2,4-dihydro-5-(2-methylphenyl)-3H-1,2,4-
triazole-3-thione (5a, C H N S)
Ar–H), 8.01–8.04 (m, 2H, Ar–H), 12.94 (s, 1H, NH) ppm;
13
9
10
4
1
C NMR ((CD ) CO, 75 MHz): d = 114.7 (d, J =
C,F
3 2
Yield 76%; m.p.: 205–207 °C; H NMR (CDCl , 300 MHz):
3
2
4
2
1
9
1
4.7 Hz, C -arom.), 117.2 (d, J = 21.0 Hz, C -arom.),
C,F
d = 2.65 (s, 3H, CH ), 4.81 (s, 2H, NH ), 7.33–7.38 (m, 2H,
3
2
6
24.0 (d, J = 3.0 Hz, C -arom.), 128.2 (d, J
=
C,F
C,F
Ar–H), 7.47 (m, 1H, Ar–H), 7.93 (m, 1H, Ar–H), 12.93 (s,
5
.0 Hz, C -arom.), 130.6 (d, J = 8.3 Hz, C -arom.),
1
1
3
C,F
1
1
1
3
2
H, NH) ppm; C NMR (CDCl , 75 MHz): d = 22.0 (CH ),
3
3
3
48.4 (C-5), 162.4 (d, JC,F = 242.3 Hz, C -arom.), 168.6
21.1, 126.4, 128.7, 131.9, 132.1, 138.4 (6 9 C-arom.),
(
C-3) ppm; IR (KBr): vꢀ ¼ 3;288; 3;171; 1;536; 1;315;
61.9 (C-5), 177.6 (C-3) ppm; IR (KBr): vꢀ ¼ 3;285;
ꢁ
1
?ꢀ
1
1
;192cm ; MS (EI): m/z (%) = 210 (M , 100), 195 (2),
39 (25), 122 (34), 95 (23), 75 (8), 60 (12).
ꢁ
1
;118; 2;951; 1;506; 1;339; 1;194 cm ; MS (EI): m/z (%) =
?
06 (M , 100), 191 (20), 135 (45), 118 (37), 102 (15), 91
ꢀ
(
28), 65 (4), 60 (23).
-Amino-2,4-dihydro-5-(3-methylphenyl)-3H-1,2,4-
triazole-3-thione (5b, C H N S)
4-Amino-5-(4-fluorophenyl)-2,4-dihydro-3H-1,2,4-triazole-
-thione (5f, C H FN S)
3
8
7
4
4
1
Yield 75%; m.p.: 208 °C; H NMR (DMSO-d , 300 MHz):
6
9
10 4
d = 5.79 (s, 2H, NH ), 7.35–7.41 (m, 2H, Ar–H), 8.06–8.10
1
2
Yield 69%; m.p.: 206–208 °C; H NMR (CDCl , 300 MHz):
d = 2.42 (s, 3H, CH ), 5.51 (s, 2H, NH ), 7.36–7.45 (m, 2H,
Ar–H), 7.96–7.98 (m, 2H, Ar–H), 12.84 (s, 1H, NH) ppm;
1
3
13
m, 2H, Ar–H), 13.95 (s, 1H, NH) ppm; C NMR (DMSO-
(
3
2
3
d , 75 MHz): d = 116.1 (d, J = 21.7 Hz, C -arom.,
6
C,F
5
C -arom.), 122.7 (d, J = 3.0 Hz, C -arom.), 133.0 (d,
1
3
C,F
C NMR (CDCl , 75 MHz): d = 20.5 (CH ), 125.3, 126.2,
3
3
2
JC,F = 9.0 Hz, C -arom., C -arom.), 149.2 (C-5), 163.7 (d,
6
1
1
1
1
6
28.3, 128.5, 131.1, 138.1 (6 9 C-arom.), 149.7 (C-5),
4
JC,F = 246.8 Hz, C -arom.), 167.4 (C-3) ppm; IR (KBr):
66.2 (C-3) ppm; IR (KBr): vꢀ ¼ 3;287; 3;108; 2;947;
ꢁ
1
vꢀ ¼ 3;292; 3;113; 1;605; 1;309; 1;227cm ; MS (EI): m/z
ꢁ
1
?ꢀ
;532; 1;340; 1;179 cm ;; MS (EI): m/z (%) = 206 (M ,
00), 191 (20), 175 (5), 135 (38), 118 (42), 102 (12), 91 (30),
5 (10), 60 (15).
?
%) = 210 (M , 100), 195 (3), 139 (31), 122 (39), 95
ꢀ
(
(27), 75 (11), 60 (20).
4-Amino-5-(2-chlorophenyl)-2,4-dihydro-3H-1,2,4-
triazole-3-thione (5g, C H ClN S)
4-Amino-2,4-dihydro-5-(4-methylphenyl)-3H-1,2,4-
triazole-3-thione (5c, C H N S)
8
7
4
9
10 4
1
1
Yield 62%; m.p.: 170–172 °C; H NMR (DMSO-d6,
00 MHz): d = 5.52 (s, 2H, NH ), 7.50 (dd, 1H,
J = 7.2, 1.5 Hz, Ar–H), 7.57–7.66 (m, 3H, Ar–H), 13.99
Yield 72%; m.p.: 201 °C; H NMR ((CD ) CO, 300 MHz):
3
2
3
2
d = 2.41 (s, 3H, CH ), 5.49 (s, 2H, NH ), 7.83 (d, 2H,
3
2
J = 8.4 Hz, Ar–H), 8.01 (d, 2H, J = 8.4 Hz, Ar–H), 12.81
1
1
3
3
(s, 1H, NH) ppm;
C NMR (DMSO-d , 75 MHz):
6
(
s, 1H, NH) ppm; C NMR ((CD ) CO, 75 MHz):
3 2
d = 125.7, 127.6, 130.1, 132.8, 133.1, 133.9 (6 9
C-arom.), 149.4 (C-5), 167.2 (C-3) ppm; IR (KBr): vꢀ ¼
d = 20.7 (CH ), 120.2, 126.1, 129.9, 142.9 (4 9 C-arom.),
3
1
61.1 (C-5), 178.2 (C-3) ppm; IR (KBr): vꢀ ¼ 3;287; 3;116;
ꢁ
1
ꢁ
1
3;285; 3;112; 2;946; 2;564; 1;539; 1;068cm
;
m/z (%) = 228 (M ? 2, 23), 226 (M , 68), 191 (4),
MS (EI):
2
;946; 1;515; 1;352; 1;176cm ; MS (EI): m/z (%) = 206
?
ꢀ
?
ꢀ
(
M , 100), 191 (2), 160 (3), 135 (42), 118 (40), 102 (3), 91
18), 77 (3), 65(5), 60 (14).
1
1
57 (13), 155 (38), 140 (18), 138 (59), 113 (6), 111 (18),
02 (94), 89 (14), 75 (62), 60 (100).
(
4
3
-Amino-5-(2-fluorophenyl)-2,4-dihydro-3H-1,2,4-triazole-
-thione (5d, C H FN S)
4-Amino-5-(3-chlorophenyl)-2,4-dihydro-3H-1,2,4-
triazole-3-thione (5h, C ClN S)
Yield 68%; m.p.: 215–217 °C; H NMR (DMSO-d
300 MHz): d = 5.80 (s, 2H, NH ), 7.57 (dd, 1H, J = 8.1,
8
7
4
1
Yield 64%; m.p.: 170–171 °C; H NMR ((CD ) CO,
3
8
H
7
4
3
2
1
00 MHz): d = 5.35 (s, 2H, NH ), 7.34–7.43 (m, 2H,
,
6
2
Ar–H), 7.67 (m, 1H, Ar–H), 7.77 (dt, 1H, J = 7.5, 1.5 Hz,
1
Ar–H), 12.91 (s, 1H, NH) ppm; C NMR ((CD ) CO,
2
3
7.5 Hz, Ar–H), 7.62 (td, 1H, J = 8.7, 2.4 Hz, Ar–H), 7.97
(td, 1H, J = 7.5, 1.8 Hz, Ar–H), 8.14 (t, 1H, J = 1.8 Hz,
3
2
3
7
5 MHz): d = 114.4 (d, J = 19.3 Hz, C -arom.), 115.9
C,F
1
d, J = 20.2 Hz, C -arom.), 124.4 (d, J = 3.8 Hz,
13
(
Ar–H), 14.03 (s, 1H, NH) ppm; C NMR (DMSO-d ,
6
C,F
C,F
5
C -arom.), 131.7 (d, J = 2.2 Hz, C -arom.), 133.0 (d,
6
75 MHz): d = 127.0, 128.0, 128.1, 130.8, 131.0, 133.6
(6 9 C-arom.), 148.6 (C-5), 167.7 (C-3) ppm; IR (KBr):
C,F
4
JC,F = 8.25 Hz, C -arom.), 147.1 (C-5), 160.5 (d,
2
JC,F = 249.7 Hz, C -arom.), 168.2 (C-3) ppm; IR (KBr):
ꢁ1
vꢀ ¼ 3;306; 3;104; 2;928; 1;535; 1;325; 1;080cm ; MS (EI):
?
ꢀ
ꢁ
1
vꢀ ¼ 3;312; 3;171; 1;574; 1;316; 1;236cm ; MS (EI): m/z
m/z (%) = 228 (M ? 2, 35), 226 (M , 100), 157 (8), 155
(25), 140 (11), 138 (34), 113 (10), 111 (25), 102 (24), 89 (8),
75 (25), 60 (43).
?
%) = 210 (M , 100), 190 (2), 139 (13), 122 (33), 102
ꢀ
(
(
11), 95 (8), 75 (7), 60 (20).
1
23