2050
J. Lee et al. / Tetrahedron 68 (2012) 2045e2051
(m, 4H), 2.51 (s, 3H); 13C NMR (75 MHz, CDCl3):
136.4, 130.3, 129.7, 129.1, 126.6, 125.5, 14.1.
d
161.1, 153.3, 138.2,
1499, 1445, 1355, 1220, 1015, 923, 772, 713, 694 cmꢂ1; HRMS (EIþ):
m/z [MþH]þ calcd for C17H17N3: 263.1422; found: 263.1423.
4.3.9. 5-(4-Bromophenyl)-3-methyl-1-phenyl-1H-1,2,4-triazole
(9b). Mp: 100e102 ꢀC; 1H NMR (500 MHz, CDCl3):
7.48e7.41 (m,
5H), 7.36e7.32 (m, 4H), 2.51 (s, 3H); 13C NMR (125 MHz, CDCl3):
161.0, 153.2, 138.1, 132.0, 130.4, 129.7, 129.1, 126.9, 125.4, 124.6,
14.0; IR (KBr): 3055, 2928, 1595, 1509, 1433, 1341, 1282, 1169, 1090,
1072, 1031, 989, 922, 831 cmꢂ1; HRMS (EIþ): m/z [MþH]þ calcd for
C15H12BrN3: 313.0215; found: 313.0212.
4.3.17. 5-tert-Butyl-1,3-diphenyl-1H-1,2,4-triazole
128e131 ꢀC; 1H NMR (500 MHz, CDCl3):
8.15e8.12 (m, 2H),
7.54e7.35 (m, 8H), 1.32 (s, 9H); 13C NMR (125 MHz, CDCl3):
164.1,
160.0, 140.0, 131.1, 129.8, 129.1, 129.0, 128.5, 128.2, 126.5, 33.6, 33.0;
IR (KBr): 3060, 2967, 2928, 1594, 1447, 1354, 1215, 1071, 1014, 772,
717, 696, 612 cmꢂ1; HRMS (EIþ): m/z [MþH]þ calcd for C18H19N3:
277.1579; found: 277.1576.
(16c). Mp:
d
d
d
d
4.3.10. 3-Methyl-5-(4-nitrophenyl)-1-phenyl-1H-1,2,4-triazole
4.3.18. 1,3,5-Triphenyl-1H-1,2,4-triazole (17b).5 1H NMR (500 MHz,
CDCl3): d 8.26e8.24 (m, 2H), 7.58e7.56 (m, 2H), 7.34e7.56 (m, 11H).
(10b). Mp: 120e123 ꢀC; 1H NMR (500 MHz, CDCl3):
d
8.20e8.18 (m,
2H), 7.69e7.67 (m, 2H), 7.48e7.47 (m, 3H), 7.35e7.33 (m, 2H), 2.54
(s, 3H); 13C NMR (125 MHz, CDCl3):
161.4, 151.9, 148.3, 137.6, 133.8,
129.8, 129.7, 129.5, 125.4, 123.8, 13.8; IR (KBr): 3094, 3076, 2931,
d
4.3.19. 5-(4-Chlorophenyl)-1-(2,4-dichlorophenyl)-3-hexyl-1H-1,2,4-
triazole (18b).11 1H NMR (400 MHz, CDCl3):
7.53 (s, 1H), 7.41e7.39
d
2854, 2768, 1599, 1510, 1366, 1166, 1111, 1031, 988, 923, 859 cmꢂ1
;
(m, 4H), 7.31e7,29 (m, 2H), 2.82 (t, J¼7.8 Hz, 2H), 1.83 (quintet,
J¼7.6 Hz, 2H),1.45e1.41 (m, 2H),1,35e1.32 (m, 4H), 0.89 (t, J¼7.0 Hz,
3H).
HRMS (EIþ): m/z [MþH]þ calcd for C15H12N4O2: 280.0960; found:
280.0963.
4.3.11. 3-Methyl-5-(3-nitrophenyl)-1-phenyl-1H-1,2,4-triazole
4.3.20. 3-Methyl-5-phenyl-1-(2-pyridyl)-1H-1,2,4-triazole
(19b).
(11b). Mp: 100e102 ꢀC; 1H NMR (400 MHz, CDCl3):
d
8.37 (m, 1H),
8.24 (d, J¼4.8 Hz, 1H), 7.81 (d, J¼7.6 Hz, 1H), 7.54e7.47 (m, 4H),
7.46e7.33 (m, 1H), 2.53 (s, 3H); 13C NMR (100 MHz, CDCl3):
161.4,
Mp: 81e83 ꢀC; 1H NMR (400 MHz, CDCl3):
d 8.48 (m, 1H), 7.82 (td,
J¼8.0 Hz, 2.0 Hz, 1H), 7.51e7.32 (m, 7H), 2.53 (s, 3H); 13C NMR
d
(100 MHz, CDCl3): d 161.3, 155.1, 150.9, 149.2, 138.8, 130.2, 129.1,
152.0, 148.5, 137.8, 134.5, 130.0, 129.9, 129.8, 129.7, 125.6, 124.7,
123.9, 14.0; IR (KBr): 3089, 2931, 2855, 1595, 1351, 1076, 778,
128.6, 128.5, 123.8, 119.3, 14.1; IR (KBr): 3068, 3018, 2927, 1588,
1509, 1436, 1409, 1092, 1003, 782, 697 cmꢂ1; HRMS (EIþ): m/z
[MþH]þ calcd for C14H12N4: 236.1062; found: 236.1059.
697 cmꢂ1
;
HRMS (EIþ): m/z [MþH]þ calcd for C15H12N4O2:
280.0960; found: 280.0959.
4.3.21. 3,5-Dimethyl-1-phenyl-1H-1,2,4-triazole
(20b).30 Mp:
4.3.12. 3-Methyl-5-(2-nitrophenyl)-1-phenyl-1H-1,2,4-triazole
44e46 ꢀC; 1H NMR (400 MHz, CDCl3):
7.45e7.41 (m, 3H), 2.49 (s, 3H), 2.42 (s, 3H).
d
7.52e7.47 (m, 2H),
(12b). Mp: 118e120 ꢀC; 1H NMR (400 MHz, CDCl3):
d 8.04 (d,
J¼7.6 Hz, 1H), 7.70e7.60 (m, 2H), 7.55 (d, J¼7.5 Hz, 1H), 7.33e7.30
(m, 3H), 7.26e7.23 (m, 2H), 2.53 (s, 3H); 13C NMR (100 MHz, CDCl3):
4.3.22. 5-Ethyl-3-methyl-1-phenyl-1H-1,2,4-triazole (21b) and 3-
ethyl-5-methyl-1-phenyl-1H-1,2,4-triazole (21c) 7:3 mixture (not
d
161.4, 450.6, 148.5, 137.2, 133.6, 132.5, 131.3, 129.5, 128.8, 125.1,
124.7, 124.3, 14.1; IR (KBr): 3095, 3059, 2924, 2858, 1526, 1348,
1076, 992, 775, 695 cmꢂ1; HRMS (EIþ): m/z [MþH]þ calcd for
C15H12N4O2: 280.0960; found: 280.0963.
separable).16 1H NMR (400 MHz, CDCl3):
d 7.52e7.40 (m,10H, 5H for
21b and 5H for 21c), 2.78 (q, J¼7.6 Hz, 4H, 2H for 21b and 2H for
21c), 2.50 (s, 3H for 21c), 2.44 (s, 3H for 21b),1.36 (t, J¼7.6 Hz, 3H for
21c), 1.33 (t, J¼7.6 Hz, 3H for 21b).
4.3.13. 1,5-Diphenyl-3-ethyl-1H-1,2,4-triazole (13b).33 Mp: 41e43 ꢀC;
1H NMR (500 MHz, CDCl3):
d
7.49e7.47 (m, 2H), 7.39e7.30 (m, 8H),
4.3.23. 5-Benzyl-3-methyl-1-phenyl-1H-1,2,4-triazole (22b). Gummy
2.87 (q, J¼7.7 Hz, 2H), 1.42 (t, J¼7.5 Hz, 3H); 13C NMR (125 MHz,
solid; 1H NMR (400 MHz, CDCl3):
d
7.46e7.41 (m, 3H), 7.33e7.21 (m,
5H), 7.46e7.41 (m, 3H), 7.33e7.21 (m, 5H), 7.14e7.12 (m, 2H), 4.12 (s,
3H), 2.46 (s, 3H); 13C NMR (100 MHz, CDCl3):
160.6, 154.6, 137.5,
CDCl3): d 165.7, 154.1, 138.4, 129.4, 129.0, 128.7, 128.6, 125.4, 21.9, 12.8.
d
4.3.14. 1,5-Diphenyl-3-pentyl-1H-1,2,4-triazole
(14b). 1H
NMR
136.2, 129.5, 129.1, 128.9,128.6, 127.1, 125.4, 32.6, 14.1; IR (KBr): 3063,
3030, 2928,1599,1520,1425,1339, 1125, 1053, 764, 696 cmꢂ1; HRMS
(EIþ): m/z [MþH]þ calcd for C16H15N3: 249.1266; found: 249.1263.
(300 MHz, CDCl3): 7.49e7.47 (m, 2H), 7.40e7.28 (m, 8H), 2.82 (t,
d
J¼7.8 Hz, 2H), 1.86 (quintet, J¼7.8 Hz, 2H), 1.47e1.36 (m, 4H), 0.92 (t,
J¼6.9 Hz, 3H); 13C NMR (75 MHz, CDCl3):
d 165.0, 154.2, 138.5, 130.1,
129.5, 129.1, 128.8, 128.7, 128.3, 125.5, 32.0, 28.7, 28.5, 22.7, 14.3; IR
(KBr): 3066, 2929, 2859, 1597, 1509, 1448, 1405, 1359, 1072, 988,
765, 694, 592 cmꢂ1; HRMS (EIþ): m/z [MþH]þ calcd for C18H19N3:
291.1735; found: 291.1738.
4.3.24. 3-Benzyl-5-methyl-1-phenyl-1H-1,2,4-triazole (22c). Gummy
solid; 1H NMR (400 MHz, CDCl3):
d
7.52e7.48 (m, 2H), 7.45e7.40 (m,
5H), 7.33e7.30 (m, 2H), 7.26e2.22 (m, 2H), 4.09 (s, 2H), 2.48 (s, 3H);
13C NMR (100 MHz, CDCl3):
162.8, 152.8, 138.3, 137.6, 129.6, 129.1,
d
128.8,128.7,126.7,124.8, 34.9,13.4; IR (KBr): 3062, 3030, 2925,1599,
1511, 1454, 1363, 1028, 765, 696 cmꢂ1; HRMS (EIþ): m/z [MþH]þ
calcd for C16H15N3: 249.1266; found: 249.1264.
4.3.15. 1,5-Diphenyl-3-isopropyl-1H-1,2,4-triazole
(15b). Mp:
51e53 ꢀC; 1H NMR (400 MHz, CDCl3):
d 7.49e7.46 (m, 2H),
7.41e7.29 (m, 8H), 3.19 (septet, J¼7.0 Hz), 1.44 (d, J¼6.8 Hz, 6H); 13C
NMR (100 MHz, CDCl3):
d
169.3, 153.9, 138.4, 129.8, 129.3, 129.0,
4.3.25. 1-(4-Methoxyphenyl)-3-methyl-5-phenyl-1H-1,2,4-triazole
128.5, 128.3, 125.4, 28.3, 21.7; IR (KBr): 3060, 2961, 2924, 2869,
1596, 1505, 1404, 1357, 1268, 1160, 990, 919, 855, 763, 695, 603,
520 cmꢂ1; HRMS (EIþ): m/z [MþH]þ calcd for C17H17N3: 263.1422;
found: 263.1419.
(23b). Mp: 99e100 ꢀC; 1H NMR (400 MHz, CDCl3):
d 7.49 (d,
J¼6.8 Hz, 2H), 7.37e7.30 (m, 3H), 7.25 (d, J¼8.8 Hz, 2H), 6.91 (d,
J¼8.8 Hz, 2H), 3.84 (s, 3H), 2.50 (s, 3H); 13C NMR (100 MHz, CDCl3):
d
1605,159.7,154.1,131.3,129.8,128.7,128.5,128.0,126.7,114.5, 55.5,
13.9; IR (KBr): 3059, 2971, 2937, 1522, 1454, 1342, 1301, 1258, 1172,
1027, 834, 779, 720, 696 cmꢂ1; HRMS (EIþ): m/z [MþH]þ calcd for
C16H15N3O: 265.1215; found: 265.1212.
4.3.16. 1,3-Diphenyl-5-isopropyl-1H-1,2,4-triazole
(15c). Gummy
solid; 1H NMR (400 MHz, CDCl3):
d 8.17e8.15 (m, 2H), 7.56e7.38 (m,
8H), 3.15 (septet, J¼6.8 Hz), 1.37 (d, J¼7.2 Hz, 6H); 13C NMR
(100 MHz, CDCl3):
d
161.9, 161.5, 137.7, 131.1, 129.5, 129.1, 129.1,
4.3.26. 3-Methyl-1-(4-nitrophenyl)-5-phenyl-1H-1,2,4-triazole
128.5,126.6,125.7, 26.0, 21.7; IR (KBr): 3061, 2971, 2929, 2852,1596,
(24b). Mp: 114e115 ꢀC; 1H NMR (400 MHz, CDCl3):
d 8.25 (d,