Month 2019
One-pot Synthesis of 3-Amino-1,2,4-triazoles
1
mp 173–175°C; H-NMR (300 MHz, DMSO-d ): δ 8.13
(1 H, d, J = 9.1 Hz), 7.44 (1 H, d, J = 2 8 Hz), 7.39
6
(
(
1 H, d, J = 2.4 Hz), 7.86 (1 H, dd, J = 8.6, 2.4 Hz), 7.66
1 H, d, J = 8.6 Hz), 6.57 (2 H, s); C-NMR (100 MHz,
(1 H, dd, J = 9.1, 2.8 Hz), 6.55 (2 H, s), 3.95 (3 H, s);
1
3
13
C-NMR (75 MHz, DMSO-d ): δ 170.90, 169.24,
6
DMSO-d ): δ 170.79, 169.20, 136.64, 134.13, 133.60,
163.21, 141.32, 128.00, 122.16, 118.16, 116.79, 57.12;
6
+
1
31.82, 125.70, 120.75. HRMS (ESI-Q-TOF, m/z) calcd
HRMS (ESI-Q-TOF, m/z) calcd for C H N O [M + H] :
9
8 5 3
+
+
+
for C H BrClN [M + H] : 272.5091, found [M + H] :
235.1915, found [M + H] : 235.1919.
8
5
4
2
72.5095.
5-Methyl-4H-1,2,4-triazol-3-amine (17). This compound
was obtained as white solid, yield: 59%; mp 146–148°C;
5
-(2,4-Difluorophenyl)-1,2,4-triazol-3-amine (11).
This
À1
compound was obtained as pale yellow solid, yield: 77%;
mp 164–165°C; H-NMR (300 MHz, DMSO-d ): δ 8.09
IR (KBr, cm ): 1041, 1289, 1468, 1581, 1657, 2984,
1
1
3257; H-NMR (300 MHz, DMSO-d ): δ 6.67 (bs, 2H,
6
6
13
(
(
(
1 H, dd, J = 15.1, 8.6 Hz), 7.62–7.54 (1 H, m), 7.34
1 H, dd, J = 10.5, 8.6 Hz), 6.52 (2 H, s); C-NMR
75 MHz, DMSO-d ): δ 169.45, 169.02, 164.99, 160.74,
NH2), 2.15 (s, 3H, CH3);
C-NMR (75 MHz,
1
3
DMSO-d ): δ 165.85, 148.82, 10.81; HRMS (ESI-
6
+
Q-TOF, m/z) calcd for C H N [M + H] : 99.1065, found
6
3 6 4
+
1
32.42, 113.23, 109.62, 106.06; HRMS (ESI-Q-TOF, m/
[M + H] : 99.1069.
+
z) calcd for C H F N [M + H] : 196.1201, found
5-Propyl-4H-1,2,4-triazol-3-amine (18). This compound
8
5 2 4
+
was obtained as white solid, yield: 65%; mp 143°C; IR
[
M + H] : 196.1205.
-(2,4,5-Trifluorophenyl)-1,2,4-triazol-3-amine (12). This
compound was obtained as pale yellow solid, yield:
À1
5
(KBr, cm ): 1091, 1267, 1360, 1461, 1588, 1644, 2949,
1
3266; H-NMR (300 MHz, DMSO-d ): δ 6.56 (bs, 2H,
6
1
7
1%; mp 164–165°C; H-NMR (300 MHz, DMSO-d6):
NH ), 2.42 (t, 2H, CH ), 1.52–1.58 (q, 2H, CH ), 0.82
2
2
2
13
δ 8.08 (1 H, dd, J = 15.5, 10.4 Hz), 7.90 (1 H, dd,
J = 17.2, 10.6 Hz), 6.56 (2 H, s); C-NMR (75 MHz,
DMSO-d ): δ 169.32, 168.78, 118.57, 118.47, 108.85,
(t, 3H, CH3); C-NMR (75 MHz, DMSO-d ): δ 165.31,
6
1
3
151.81, 26.31, 20.61, 12.71; HRMS (ESI-Q-TOF, m/z)
+
+
calcd for C H N [M + H] : 126.1597, found [M + H] :
6
5 10 4
1
08.63, 108.57, 108.35; HRMS (ESI-Q-TOF, m/z) calcd
126.1596.
+
+
for C H F N [M + H] : 214.1393, found [M + H] :
8
4 3 4
2
14.1396.
5
-(3-Fluoro-4-methylphenyl)-1,2,4-triazol-3-amine (13).
Acknowledgments. Prof. Dr. Taoufik Rohand is grateful to the
Cadi Ayyad University and especially to the Polydisciplinary
Faculty of Safi for the professorship and financial support for
the LACM laboratory.
This compound was obtained as pale grey solid, yield:
1
7
7
7
4%; mp 171–172°C; H-NMR (300 MHz, DMSO-d ): δ
6
.71 (1 H, d, J = 7.9 Hz), 7.66 (1 H, d, J = 10.0 Hz),
.51 (1 H, t, J = 7.8 Hz), 6.43 (2 H, s), 2.31 (3 H, s):
1
3
C-NMR (75 MHz, DMSO-d ): δ 172.50, 169.45,
6
1
62.25, 159.82, 133.25, 130.22, 123.84, 114.20, 14.86.
REFERENCES AND NOTES
+
HRMS (ESI-Q-TOF, m/z) calcd for C H FN [M + H] :
9
8
4
+
[1] Jha, M.; Guy, S.; Ting, Y. C. Tetrahedron Lett 2011, 52, 4337.
2] Sagar, R.; Moon-Ju, K.; Park, S. B. Tetrahedron Lett 2008, 49,
192.1850, found [M + H] : 192.1854.
[
5
-(2-Nitrophenyl)-1,2,4-triazol-3-amine
(14).
This
5
080.
[3] Rai, U. S.; Isloor, A. M.; Shetty, P.; Vijesh, A. M.; Prabhu, N.;
Isloor, S.; Thiageeswaran, M.; Hoong-Kun, F. Eur J Med Chem 2010, 45,
695.
4] Abdel-Rahman, A. H.; Keshk, E. M.; Hanna, M. A.; El-Bady,
S. M. Bioorg Med Chem 2004, 12, 2483.
5] Salameh, S.; Abul-Haj, M.; Quirós, M.; Salas, J. M. Inorg
Chim Acta 2005, 358, 824.
6] Salgado, A.; Varela, C.; Collazo, A. M. G.; Pevarello, P. Magn
Reson Chem 2010, 48, 614.
[7] Shaaban, M. R.; Saleh, T. S.; Farag, A. M. Heterocycles 2007,
71, 1765.
8] Fischer, G. Adv Heterocycl Chem 2008, 95, 143.
9] Moulin, A.; Bibian, M.; Blayo, A. L.; Habnouni, S. E.;
Martinez, J.; Fehrentz, J. A. Chem Rev 2010, 110, 1809.
compound was obtained as pale yellow solid, yield: 80%;
mp 200–202°C; H-NMR (300 MHz, DMSO-d ): δ 8.14
1
6
2
(1 H, dd, J = 5.9, 3.3 Hz), 8.04 (1 H, dd, J = 5.5,
[
1
3
3.6 Hz), 7.95–7.89 (2 H, m), 6.59 (2 H, s); C-NMR
[
(75 MHz, DMSO-d ): δ 161.96, 158.39, 149.32, 132.37,
6
1
30.60, 127.69, 117.51, 106.35, 55.53; HRMS (ESI-Q-
[
+
TOF, m/z) calcd for C H N O [M + H] : 205.1655,
found [M + H] : 205.1658.
8
6
5
2
+
5
-(3-Methyl-2-nitrophenyl)-1,2,4-triazol-3-amine (15).
[
[
This compound was obtained as white solid, yield: 83%;
mp 173–174°C; H-NMR (300 MHz, DMSO-d ): δ 7.98
1
6
(
1 H, d, J = 7.5 Hz), 7.80 (1 H d, J = 7.4 Hz), 7.73 (1 H,
[10] Hameed, S.; Akhtar, T. Curr Org Chem 2011, 15, 694.
[
11] Al-Masoudi, I. A.; Al-Soud, Y. A.; Al-Salihi, N. J.;
Al-Masoudi, N. A. Chem Heterocycl Compd 2006, 42, 1377.
12] Lamttina, J. L.; Lipinski, C. A. Indian, I. N. 1987; 159, 834;
t, J = 7.7 Hz), 6.58 (1 H, s), 4.14 (1 H, s), 2.34 (3 H, s);
1
3
C-NMR (75 MHz, DMSO-d ): δ 169.41, 148.95,
6
[
1
(
2
36.33, 131.75, 131.10, 128.21, 116.27, 16.92. HRMS
ChemAbstr 1988, 108, 112455g.
+
ESI-Q-TOF, m/z) calcd for C H N O [M + H] :
[13] Tanano, S.; Imaizumi, H.; Kajita, T.; Takashima, K.;
Takewaza, K.; Yotsutsuji, M.; Yasuda, T.; Yotustsuji, A.; Sakai, H.;
Saikawa, I. Jpn. Kokai Tokkyo Koho JP 62 1987, 178, 590 ChemAbstr
9
8 5 2
+
19.1921, found [M + H] : 219.1915.
5-(5-Methoxy-2-nitrophenyl)-1,2,4-triazol-3-amine (16).
1
988, 108, 112450b.
14] Shridhar, D. R.; Jogibhukta, M.; Joshi, P. P.; Reddy, P. G.
Indian J Chem 1981, 20B, 132.
This compound was obtained as yellow solid, yield: 86%;
mp 141–142°C; H-NMR (300 MHz, DMSO-d ): δ 8.20
[
1
6
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet