ꢀ
2980
T. Cimbora-Zovko et al. / European Journal of Medicinal Chemistry 46 (2011) 2971e2983
1049, 978, 783, 740 cmꢃ1
;
1H NMR (DMSO-d6):
d
5.22 (1H, d,
130.5 (q, J ¼ 33.0 Hz), 132.3, 133.0, 133.5, 140.1 (q, J ¼ 1.8 Hz), 147.4,
148.5, 148. 9 (q, J ¼ 0.9 Hz), 170.5; MS (ESI) m/z 562 ([MCl]ꢃ, 15), 422
(100). Anal. for C21H11F6N5O5: Calcd C: 47.83; H: 2.10; N: 13.28.
Found C: 47.88; H: 2.15; N: 13.02.
J ¼ 14.9Hz), 5.44 (1H, d, J¼ 14.9Hz), 7.85(1H, d, J¼ 8.7 Hz), 7.99 (1H, d,
J ¼ 8.9 Hz), 8.31 (1H, dd, J1 ¼ 8.9 Hz, J2 ¼ 2.5 Hz) 8.40e8.44 (2H, m),
8.58 (1H, d, J ¼ 2.5 Hz); 13C NMR (DMSO-d6):
d 43.5, 120.9, 123.42,
123.43,124.8,125.6,131.3,132.4,133.3,138.5,147.8,148.4,148.8,167.9;
MS (FAB) m/z 432 (MHþ,1),184 (32),107 (24). Anal. for C14H8Cl3N5O5:
Calcd C, 38.87; H, 1.86; N, 16.19. Found C, 38.49; H, 1.86; N, 16.43.
5.1.3.32. 3-(2-Fluorobenzoyl)-1,3-bis[4-nitro-2-(trifluoromethyl)
phenyl]triazene (9d). Method D, reaction time: 3.5 h; yield 90%; mp
153e155 ꢄC (EtOAc/petroleum ether); IR (KBr): 3095, 1710, 1616,
1539, 1487, 1457, 1426, 1358, 1292, 1211, 1179, 1146, 1119, 1050, 936,
5.1.3.27. 3-(Acetoxyacetyl)-1,3-bis(2-chloro-4-nitrophenyl)triazene
(8k). Method C, reaction time: 10 min; yield 77%; mp 139e142 ꢄC
(EtOH); IR (KBr): 1738, 1527, 1485, 1391, 1354, 1230, 1173, 1137, 1048,
855, 801, 738 cmꢃ1 1H NMR (CDCl3):
; d 7.26 (m, 1H), 7.37 (dt, 1H,
J1 ¼1.0 Hz, J2 ¼ 7.6 Hz), 7.43 (d, 1H, J ¼ 8.9 Hz), 7.58 (d, 1H, J ¼ 8.6 Hz),
7.61e7.75 (m, 2H,), 8.37 (dd, 1H, J1 ¼ 2.4 Hz, J2 ¼ 8.9 Hz), 8.52 (d, 1H,
J ¼ 2.4 Hz), 8.62 (dd, 1H, J1 ¼ 2.5 Hz, J2 ¼ 8.6 Hz), 8.75 (d, 1H,
J ¼ 2.5 Hz); MS (ESI) m/z 580 ([MCl], 26), 422 (100). Anal. for
C21H10F7N5O5: Calcd C, 46.25; H, 1.85; N, 12.84. Found C, 46.22; H,
1.81; N, 12.75.
975 cmꢃ1; 1H NMR (CDCl3):
d 2.25 (3H, s), 5.37 (1H, s), 5.48 (1H, s),
7.48 (1H, d, J ¼ 8.7 Hz), 7.59 (1H, d, J ¼ 8.7 Hz), 8.20 (1H, dd,
J1 ¼ 2.5 Hz, J2 ¼ 8.7 Hz), 8.28 (1H, dd, J1 ¼ 2.5 Hz, J2 ¼ 8.7 Hz), 8.34 (1H,
d, J ¼ 2.5 Hz), 8.44 (1H, d, J ¼ 2.5 Hz); 13C NMR (CDCl3):
d 20.4, 61.9,
120.0, 122.76, 122.80, 125.5, 126.3, 131.7, 132.8, 134.5, 138.2, 148.2,
148.7, 149.1, 168.0, 170.5; MS (FAB) m/z 456 (MHþ, 0.8), 154 (100), 137
(77), 71 (56), 55 (56). Anal. for C16H11Cl2N5O7: Calcd C, 42.13; H, 2.43;
N, 15.35. Found C, 42.30; H, 2.48; N, 15.06.
5.1.3.33. 3-[2-(Trifluoromethyl)benzoyl]-1,3-bis[4-nitro-2-(trifluoro-
methyl)phenyl]triazene (9e). Method D, reaction time: 5 h; yield
92%; mp 176e177 ꢄC (EtOAc/petroleum ether); IR (KBr): 3102, 1726,
1622, 1539, 1486, 1425, 1357, 1321, 1291, 1217, 1150, 1116, 1047, 934,
5.1.3.28. 3-Methoxycarbonyl-1,3-bis(2-chloro-4-nitrophenyl)triazene
(8l). Method C, reaction time: 1.5 h; yield 86%; mp 139e140 ꢄC
(MeOH); IR (KBr): 3103, 1764, 1528, 1476, 1441, 1351, 1327, 1267,
829, 800, 772, 740 cmꢃ1; 1H NMR (CDCl3):
d
7.15 (d, 1H, J ¼ 8.9 Hz),
7.55 (d, 1H, J ¼ 8.6 Hz), 7.64 (m, 1H), 7.71e7.86 (m, 3H), 8.29 (dd, 1H,
J1 ¼ 2.4 Hz, J2 ¼ 8.9 Hz), 8.50 (d, 1H, J ¼ 2.4 Hz), 8.64 (dd, 1H,
J1 ¼ 2.4 Hz, J2 ¼ 8.6 Hz), 8.76 (d, 1H, J ¼ 2.4 Hz); 13C NMR (CDCl3):
1233, 1133, 1093, 956, 907, 779, 760 cmꢃ1 1H NMR (DMSO-d6):
;
d
3.96 (3H, s), 7.72 (1H, d, J ¼ 8.8 Hz), 7.95 (1H, d, J ¼ 8.8 Hz), 8.31
(1H, dd, J1 ¼ 8.9 Hz, J2 ¼ 2.5 Hz), 8.37e8.41 (2H, m), 8.56 (1H d,
d
118.9, 121.2 (q, J ¼ 272.0 Hz), 121.7 (q, J ¼ 272.0 Hz), 122.8 (q,
J ¼ 2.5 Hz); 13C NMR (DMSO-d6):
d
55.0, 120.6, 123.4, 123.7, 124.8,
J ¼ 5.8 Hz), 123.1 (q, J ¼ 5.0 Hz), 123.7 (q, J ¼ 271.9 Hz), 126.7 (q,
J ¼ 4.3 Hz),127.5 (q, J ¼ 32.1 Hz), 127.86,127.90 (q, J ¼ 0.8 Hz), 128.18
(q, J ¼ 0.9 Hz), 128.22 (q, J ¼ 33.0 Hz), 130.86, 130.93 (q, J ¼ 33.2 Hz),
132.3 (q, J ¼ 1.1 Hz), 132.5 (q, J ¼ 2.3 Hz), 132.9, 138.8 (q, J ¼ 1.8 Hz),
147.6, 148.5 (q, J ¼ 0.9 Hz), 148.8, 169.6; MS (ESI) m/z 630 ([MCl]ꢃ,
11), 422 (100). Anal. for C22H10F9N5O5: Calcd C, 44.38; H, 1.69; N,
11.76. Found C, 44.08; H, 1.72; N, 11.62.
125.6, 130.6, 132.5, 133.2, 139.5, 147.6, 148.69, 148.73, 151.8; MS (EI)
m/z 385 (Mþ e N2, 1.5), 350 (3), 230 (30), 195 (75), 184 (100), 156
(97). Anal. for C14H9Cl2N5O6: Calcd C, 40.60; H, 2.19; N, 16.91. Found
C, 40.90; H, 2.17; N, 16.85.
5.1.3.29. 1,3-Bis[4-nitro-2-(trifluoromethyl)phenyl]triazene (9a). Met-
hod B, reaction time: 2 days; yield 68%; mp 171e172 ꢄC (acetone); IR
(KBr): 3332, 3303, 1622, 1595, 1545, 1513, 1336, 1308, 1287, 1262, 1154,
5.1.3.34. 3-[3-(Trifluoromethyl)benzoyl]-1,3-bis[4-nitro-2-(trifluoro-
methyl)phenyl]triazene (9f). Method D, reaction time: 30 min; yield
82%; mp 118e121 ꢄC (EtOAc/petroleum ether); IR (KBr): 3104, 1715,
1619, 1538, 1484, 1426, 1356, 1328, 1290, 1207, 1150, 1118, 1048, 945,
1119, 1050, 897 cmꢃ1; 1H NMR (DMSO-d6):
d
7.96 (2H, d, J ¼ 8.9 Hz),
8.53 (2H, d, J ¼ 2.6 Hz), 8.57 (2H, dd, J1 ¼ 2.6 Hz, J2 ¼ 8.9 Hz),13.61 (1H,
broad); MS (FAB) m/z 424 (MHþ, 1.9), 154 (100), 136 (75), 71 (52). Anal.
for C14H7F6N5O4: Calcd C, 39.73; H, 1.67; N, 16.55. Found C, 39.71; H,
1.72; N, 16.62.
914, 800, 740 cmꢃ1; 1H NMR (CDCl3):
d
7.48 (d,1H, J ¼ 8.9 Hz), 7.59 (d,
1H, J ¼ 8.6 Hz), 7.73 (t, 1H, J ¼ 7.8 Hz), 7.94 (d, 1H, J ¼ 7.8 Hz), 8.07 (d,
1H, J ¼ 7.8 Hz), 8.14 (s,1H), 8.39 (dd,1H, J1 ¼ 2.4 Hz, J2 ¼ 8.9 Hz), 8.55
(d, 1H, J ¼ 2.4 Hz), 8.64 (dd, 1H, J1 ¼ 2.4 Hz, J2 ¼ 8.6 Hz), 8.76 (d, 1H,
5.1.3.30. 3-Acetyl-1,3-bis[4-nitro-2-(trifluoromethyl)phenyl]triazene
(9b). Method D, reaction time: 45 min; yield 79%; mp 171.8e174 ꢄC
(EtOAc/petroleum ether); IR (KBr): 3115, 3097, 1737, 1619, 1595,
1536, 1478, 1426, 1355, 1287, 1192, 1145, 1048, 965, 917, 799, 741,
J ¼ 2.4 Hz); 13C NMR (CDCl3):
119.0,121.77 (q, J ¼ 272.5 Hz),121.8 (q,
d
J ¼ 272.9 Hz), 122.9 (q, J ¼ 5.5 Hz), 123.2 (q, J ¼ 5.1 Hz), 123.5 (q,
J ¼ 271.0 Hz), 127.3 (q, J ¼ 4.0 Hz), 127.9 (q, J ¼ 0.8 Hz), 128.0 (q,
J ¼ 0.8 Hz),128.4 (q, J ¼ 32.3 Hz),129.3,129.4 (q, J ¼ 3.8 Hz),130.6 (q,
J ¼ 33.0 Hz),131.2 (q, J ¼ 33.0 Hz),133.1,133.36 (q, J ¼ 1.2 Hz),133.43,
139.4 (q, J ¼ 1.8 Hz), 147.7, 148.6 (q, J ¼ 0.9 Hz), 148.7, 169.1; MS (ESI)
m/z 630 ([MCl]ꢃ, 3), 422 (100). Anal. for C22H10F9N5O5 ꢂ 0.25 EtOAc:
Calcd C, 44.74; H, 1.96; N, 11.34. Found C, 44.77; H, 1.94; N, 11.28.
613 cmꢃ1
;
1H NMR (CDCl3):
d
2.78 (s, 3H), 7.42 (d, 1H, J ¼ 8.6 Hz),
7.78 (d, 1H, J ¼ 8.8 Hz), 8.49 (dd, 1H, J1 ¼ 2.4 Hz, J2 ¼ 8.8 Hz),
8.55e8.59 (m, 2H), 8.69 (d, 1H, J ¼ 2.5 Hz); 13C NMR (CDCl3):
d 22.4,
119.3, 121.5 (q, J ¼ 272.6 Hz), 121.9 (q, J ¼ 272.8 Hz), 122.9 (q,
J ¼ 5.5 Hz), 123.96 (q, J ¼ 5.1 Hz), 127.8 (q, J ¼ 0.9 Hz), 127.9
(q, J ¼ 32.9 Hz), 128.0 (q, J ¼ 0.75 Hz), 130.6 (q, J ¼ Hz), 133.10, 139.7
(q, J ¼ 1.9 Hz), 147.5, 148.5, 149.2 (q, J ¼ 0.9 Hz), 171.9; MS (ESI) m/z
500 ([MCl]ꢃ, 11), 422 (100). Anal. for C16H9F6N5O5: Calcd C: 41.30;
H: 1.95; N: 15.05. Found C: 41.51; H: 2.08; N: 14.95.
5.1.3.35. 3-[4-(Trifluoromethyl)benzoyl]-1,3-bis[4-nitro-2-(trifluoro-
methyl)phenyl]triazene (9g). Method D, reaction time: 1 h; yield
86%; mp 145e147 ꢄC (EtOAc/petroleum ether); IR (KBr): 3117, 3099,
1717, 1622, 1597, 1538,1482, 1426,1354, 1325, 1290,1217, 1149,1123,
5.1.3.31. 3-Benzoyl-1,3-bis[4-nitro-2-(trifluoromethyl)phenyl]triazene
(9c). Method D, reaction time: 1.5 h; yield 80%; mp 142e144 ꢄC
(EtOAc/petroleum ether); IR (KBr): 3095, 1693, 1622, 1598, 1545,
1067, 1048, 934, 850, 739 cmꢃ1 1H NMR (CDCl3):
; d 7.46 (d, 1H,
J ¼ 8.9 Hz), 7.59 (d,1H, J ¼ 8.6 Hz), 7.84 in 7.98 (AA’XX’, 4H, J ¼ 8.2 Hz),
8.41 (dd,1H, J1 ¼2.4 Hz, J2 ¼ 8.9 Hz), 8.55 (d,1H, J ¼ 2.4 Hz), 8.64 (dd,
1H, J1 ¼ 2.4 Hz, J2 ¼ 8.6 Hz), 8.76 (d, 1H, J ¼ 2.4 Hz); MS (ESI) m/z 630
([MCl]ꢃ, 12), 422 (100). Anal. for C22H10F9N5O5: Calcd C, 44.38; H,
1.69; N, 11.76. Found C, 44.50; H, 1.72; N, 11.56 3-(3-Fluorobenzoyl)-
1,3-bis[4-nitro-2-(trifluoromethyl)phenyl] triazene (9h). Method D,
reaction time: 1.5 h; yield 74%; mp 146e148 ꢄC (EtOAc/petroleum
ether); IR (KBr): 3095, 1710, 1591, 1539, 1481, 1441, 1424,1356, 1292,
1535, 1481, 1426, 1354, 1290, 1216, 1144, 1118, 1048, 934 cmꢃ1 1H
;
NMR (CDCl3):
d
7.51 (d, 1H, J ¼ 8.9 Hz), 7.57 (m, 3H) 7.68 (m, 1H),
7.87 (m, 2H), 8.38 (dd, 1H, J1 ¼ 2.4 Hz, J2 ¼ 8.9 Hz), 8.53 (d, 1H,
J ¼ 2.4 Hz), 8.62 (dd, 1H, J1 ¼ 2.4 Hz, J2 ¼ 8.6 Hz), 8.75 (d, 1H,
J ¼ 2.4 Hz); 13C NMR (CDCl3):
d
119.2, 121.8 (q, J ¼ 272.5 Hz), 121.9
(q, J ¼ 272.9 Hz), 122.8 (q, J ¼ 5.5 Hz), 123.0 (q, J ¼ 5.0 Hz), 127.8 (q,
J ¼ 0.7 Hz), 128.0 (q, J ¼ 0.9 Hz), 128.2 (q, J ¼ 32.9 Hz), 128.5, 130.2,
1176, 1148, 1118, 1048, 962, 904, 799, 739 cmꢃ1 1H NMR (CDCl3):
;