Journal of the Iranian Chemical Society
General procedure for the preparation
1557, 1471, 1361, 1293, 1068, 950, 864, 791, 729, 682, 620,
−
1 1
of 1,2,4‑triazol‑5(3)‑amines 4a–j
479 cm ; H NMR (400 MHz, DMSO-d ) δ: 11.81 (1H,
6
br, NH), 7.45 (1H, m, H-6ʹ), 7.42 (1H, m, H-2ʹ), 7.33 (1H,
A suspension oꢀ thiourea (1) (0.076 g, 1 mmol), hydrazides
m, H-5ʹ), 7.01 (1H, d, J=5.6 Hz, H-4ʹ), 6.64 (2H, br, NH ),
2
1
3
3
a-j (1 mmol), dimethyl sulꢀate (2) (0.063 g, 0.5 mmol) and
3.79 (3H, s, CH ) ppm; C NMR (100 MHz, DMSO-d ) δ:
3
6
potassium carbonate (0.069 g, 0.5 mmol) in 4 mL water
was heated at 50 °C ꢀor 15–20 h. The reaction progress was
checked with TLC. The mixture was cooled in an ice bath in
order to increase in total precipitation. The solid was ꢁltered
oꢂ, washed with cold water and ethanol, and dried in an
oven at 60 °C without need ꢀor ꢀurther puriꢁcation.
160.0, 148.3 (C-3, C-5), 136.1 (C-3ʹ), 130.4 (C-5ʹ), 130.1
(C-1ʹ), 117.9 (C-6ʹ), 113.3 (C-4ʹ), 111.6 (C-2ʹ), 55.7 (CH )
3
ppm. Anal. Calcd ꢀor C H BrN : C 40.19, H 2.95, N 23.44;
8
7
4
ꢀound: C 40.21, H 2.93, N 23.40.
3(5)-(5(3)-Amino-1H-1,2,4-triazol-3-yl)phenol (4f):
Brown solid; FTIR (KBr) ν: 3323, 2987, 2375, 1636, 1578,
1486, 1449, 1340, 1293, 1237, 1166, 1086, 996, 954, 855,
3
(5)-Phenyl-1H-1,2,4-triazol-5(3)-amine (4a): White
−
1 1
solid; FTIR (KBr) ν: 3415, 2981, 2364, 1643, 1551, 1364,
784, 749, 683, 612 cm ; H NMR (400 MHz, DMSO-d ) δ:
6
−
1 1
1
1
290, 1142, 694 cm ; H NMR (400 MHz, DMSO-d ) δ:
11.69 (1H, br, NH), 9.62 (1H, br, OH), 7.29 (1H, m, H-6ʹ),
6
1.86 (1H, br, NH), 7.91–7.78 (2H, m, H-2ʹ,6ʹ), 7.53–7.25
7.16 (1H, m, H-5ʹ), 7.07 (1H, m, H-2ʹ), 6.95 (1H, m, H-4ʹ),
1
3
13
(
(
(
3H, m, H-3ʹ,4ʹ,5ʹ), 6.80 (2H, br, NH ) ppm; C NMR
6.62 (2H, s, NH ) ppm; C NMR (100 MHz, DMSO-d ) δ:
2
2
6
100 MHz, DMSO-d ) δ: 161.6, 163.6 (C-3, C-5), 132.2
163.5, 158.1 (C-3, C-5), 148.2 (C-3ʹ), 130.2 (C-1ʹ), 129.9
(C-5ʹ), 119.2 (C-6ʹ), 117.8 (C-4ʹ), 113.0 (C-2ʹ) ppm. Anal.
Calcd ꢀor C H N O: C 54.54, H 4.58, N 31.80; ꢀound: C
6
C-1ʹ), 128.4 (C-3ʹ,5ʹ), 128.0 (C-4ʹ), 127.1 (C-2ʹ,6ʹ) ppm.
Anal. Calcd ꢀor C H N : C 59.99, H 5.03, N 34.98; ꢀound:
8
8
4
8
8
4
C 60.02, H 5.04, N 34.94.
(5)-(4-Nitrophenyl)-1H-1,2,4-triazol-5(3)-amine (4b):
Orange solid; FTIR (KBr) ν: 3412, 2974, 2361, 1650, 1544,
54.50, H 4.55, N 31.84.
3
3(5)-(Pyridin-4-yl)-1H-1,2,4-triazol-5(3)-amine (4 g):
White solid; FTIR (KBr) ν: 3369, 3082, 2363, 1662, 1604,
−1
1
−1
1
388, 1337, 1146, 855, 618, 475 cm ; H NMR (400 MHz,
1488, 1414, 1347, 1115, 1051, 994, 838, 749, 681, 462 cm ;
1
DMSO-d ) δ: 12.11 (1H, br, NH), 8.34 (2H, d, J =8.3 Hz,
H NMR (400 MHz, DMSO-d ) δ: 12.37 (1H, br, NH), 8.57
6
6
H-3ʹ,5ʹ), 8.13 (2H, d, J = 8.3 Hz, H-2ʹ,6ʹ), 6.87 (2H, br,
(2H, d, J=4.5 Hz, H-3ʹ,5ʹ), 7.75 (2H, d, J=4.5 Hz, H-2ʹ,6ʹ),
13
13
NH ) ppm; C NMR (100 MHz, DMSO-d ) δ: 159.9, 147.5
6.18 (2H, s, NH ) ppm; C NMR (100 MHz, DMSO-d ) δ:
2
6
2
6
(
(
C-3, C-5), 138.9 (C-4ʹ), 130.4 (C-1ʹ), 128.2 (C-2ʹ,6ʹ), 123.0
157.8, 155.8 (C-3, C-5), 150.4 (C-3ʹ,5ʹ), 138.2 (C-1ʹ), 120.0
C-3ʹ,5ʹ) ppm. Anal. Calcd ꢀor C H N O : C 46.83, H 3.44,
(C-2ʹ,6ʹ) ppm. Anal. Calcd ꢀor C H N : C 52.17, H 4.38, N
8
7
5
2
7
7
5
N 34.13; ꢀound: C 46.88, H 3.42, N 34.16.
43.45; ꢀound: C 52.16, H 4.39, N 43.50.
3
(5)-(4-(tert-Butyl)phenyl)-1H-1,2,4-triazol-5(3)-amine
3(5)-(Furan-2-yl)-1H-1,2,4-triazol-5(3)-amine (4 h):
Brown solid; FTIR (KBr) ν: 3417, 3107, 2361, 1642, 1590,
1531, 1467, 1336, 1292, 1177, 1080, 1016, 932, 856, 756,
(
4c): White solid; FTIR (KBr) ν: 3414, 3231, 2961, 2361,
1
1
646, 1614, 1549, 1503, 1463, 1361, 1278, 1143, 1067,
−
1
1
−1 1
023, 916, 847, 770, 624, 472 cm ; H NMR (400 MHz,
601 cm ; H NMR (400 MHz, DMSO-d ) δ: 11.89 (1H, br,
6
DMSO-d ) δ: 11.70 (1H, br, NH), 7.84 (2H, d, J =7.5 Hz,
NH), 6.67 (1H, d, J=3.2 Hz, H-3ʹ), 6.61 (1H, d, J=3.2 Hz,
6
1
3
H-2ʹ,6ʹ), 7.44 (2H, d, J=7.5 Hz, H-3ʹ,5ʹ), 5.94 (2H, s, NH ),
H-4ʹ), 6.52 (1H, s, H-5ʹ), 6.41 (2H, br, NH ) ppm; C NMR
2
2
13
1
.28 (9H, s, 3×CH ) ppm; C NMR (100 MHz, DMSO-d )
(100 MHz, DMSO-d ) δ: 156.4, 152.8 (C-3, C-5), 147.2
3
6
6
δ: 155.0, 153.2 (C-3, C-5), 147.9 (C-4ʹ), 132.1 (C-1ʹ), 127.3
(C-2ʹ), 142.4 (C-5ʹ), 111.2 (C-4ʹ), 106.4 (C-3ʹ) ppm. Anal.
(
C-2ʹ,6ʹ), 126.0 (C-3ʹ,5ʹ), 35.0 (C(CH ) ), 31.3 (3 × CH )
Calcd ꢀor C H N O: C 48.00, H 4.03, N 37.32; ꢀound: C
3
3
3
6
6
4
ppm. Anal. Calcd ꢀor C H N : C 66.64, H 7.46, N 25.90;
48.03, H 4.05, N 37.28.
1
2
16
4
ꢀound: C 66.60, H 7.47, N 25.93.
3(5)-(4-Methyl-1,2,3-thiadiazol-5-yl)-1H-1,2,4-tria-
zol-5(3)-amine (4i): Yellow solid; FTIR (KBr) ν: 3441,
3206, 2363, 1660, 1568, 1447, 1388, 1353, 1284, 1208,
3
(5)-(3-Methoxyphenyl)-1H-1,2,4-triazol-5(3)-amine
(
4d): Dark cream solid; FTIR (KBr) ν: 3416, 3042, 2364,
−
1 1
1
646, 1560, 1474, 1428, 1364, 1295, 1162, 1075, 1037, 865,
1148, 1031, 824, 744, 696, 672, 609, 526, 473 cm ; H
−
1 1
8
11, 751, 691, 476 cm ; H NMR (400 MHz, DMSO-d )
NMR (400 MHz, DMSO-d ) δ: 10.22 (1H, br, NH), 6.71
6
6
1
3
δ: 11.81 (1H, br, NH), 7.45 (1H, m, H-6ʹ), 7.42 (1H, m,
(2H, s, NH ), 2.79 (3H, s, CH ) ppm; C NMR (100 MHz,
2
3
H-2ʹ), 7.33 (1H, m, H-5ʹ), 7.01 (1H, d, J=5.6 Hz, H-4ʹ), 6.64
DMSO-d ) δ: 155.9, 151.4 (C-3, C-5), 153.2 (C-5ʹ), 137.5
6
1
3
(
2H, br, NH ), 3.79 (3H, s, CH ) ppm; C NMR (100 MHz,
(C-4ʹ), 14.1 (CH ) ppm. Anal. Calcd ꢀor C H N S: C 32.96,
2
3
3
5
6
6
DMSO-d ) δ: 160.0, 148.3 (C-3, C-5), 136.1 (C-3ʹ), 130.4
H 3.32, N 46.12, S 17.60; ꢀound: C 32.99, H 3.30, N 46.08,
6
(C-5ʹ), 130.1 (C-1ʹ), 117.9 (C-6ʹ), 113.3 (C-4ʹ), 111.6 (C-2ʹ),
S 17.63.
5
5
5.7 (CH ) ppm. Anal. Calcd ꢀor C H N O: C 56.83, H
3(5)-(5-Chlorothiophen-2-yl)-1H-1,2,4-triazol-5(3)-
amine (4j): White solid; FTIR (KBr) ν: 3415, 2921, 2361,
1649, 1528, 1427, 1386, 1296, 1207, 1158, 999, 924, 789,
3
9
10
4
.30, N 29.46; ꢀound: C 56.81, H 5.33, N 29.41.
(
5)-(3-Bromophenyl)-1H-1,2,4-triazol-5(3)-amine (4e):
−
1 1
Light cream solid; FTIR (KBr) ν: 3413, 3062, 2362, 1649,
722, 626, 496, 466 cm ; H NMR (400 MHz, DMSO-d ) δ:
6
1
3