J.A. Kumar et al. / European Journal of Medicinal Chemistry 65 (2013) 389e402
399
(75 MHz, CDCl3): 164.24, 161.55, 160.94, 159.48, 154.24, 146.86,
141.74, 136.74, 132.01, 130.44, 130.33, 128.34, 124.50, 120.85, 120.07,
119.03, 116.82, 116.26, 115.59, 112.55, 112.22, 62.53, 61.13, 14.14,
13.89; EI-MS (m/z): 451, 473 [M þ H]þ, [M þ Na]þ.
2OCH2), 3.83 (s, 3H, OCH3), 2.43 (s, 3H, CH3), 1.28 (t, 6H, J ¼ 6.9 Hz,
2CH3); 13C NMR (75 MHz, CDCl3): 161.80, 159.74, 159.38, 156.14,
148.65, 146.53, 141.54, 139.28, 139.02, 129.86, 128.92, 125.24,121.54,
121.36, 119.71, 119.37, 117.74, 110.17, 62.30, 61.01, 55.68, 21.42, 14.13,
13.88; EI-MS (m/z): 477 [M þ H]þ, 499 [M þ Na]þ.
7.7.10. Dimethyl-1-(3-fluorophenyl)-3-(2-oxo-2H-chromene-3-yl)-
1H-pyrazole-4,5-dicarboxylate (12j)
7.7.16. Diethyl-1-(3-chlorophenyl)-3-(6-methoxy-2-oxo-2H-
chromene-3-yl)-1H-pyrazole-4,5-dicarboxylate (12p)
Yield: 70%; pale yellow solid; m.p: 202e203 ꢀC; IR (KBr): 2949,
1728, 1606, 1554, 1473, 1444, 1323, 1244, 1162, 1102, 987 cmꢁ1
;
1H
Yield: 74%; pale yellow solid; m.p: 152e154 ꢀC; IR (KBr): 2926,
NMR (CDCl3):
d
8.04 (s, 1H aromatic), 7.59e7.27 (m, 7H, aromatic),
1713, 1586, 1548, 1492, 1455, 1269, 1216, 1166, 1106, 1015, 970 cmꢁ1
;
7.21e7.12 (m, 1H, aromatic), 3.88 (s, 3H, OCH3), 3.82 (s, 3H, OCH3);
1H NMR (300 MHz, CDCl3):
d 7.96 (s, 1H, aromatic), 7.56 (s, 1H, ar-
EI-MS (m/z): 423 [M þ H]þ, 445 [M þ Na]þ.
omatic), 7.45e7.39 (m, 3H, aromatic), 7.20 (d, 1H, J ¼ 8.75, aro-
matic), 7.10 (dd, 1H, J ¼ 8.75, 2.18 Hz, aromatic), 6.93 (d, 1H,
J ¼ 2.18 Hz, aromatic), 4.28 (q, 4H, J ¼ 7.17 Hz, 2OCH2), 3.84 (s, 3H,
OCH3), 1.30 (t, 6H, J ¼ 6.9 Hz, 2CH3); 13C NMR (75 MHz, CDCl3):
161.46, 159.30, 159.00, 156.13, 146.88, 141.41, 140.04, 136.49, 134.92,
129.98, 129.08, 124.94, 122.59, 121.10, 119.80, 119.30, 117.73, 110.13,
62.38, 61.02, 55.59, 14.13, 13.93; EI-MS (m/z): 497 [M þ H]þ, 519
[M þ Na]þ.
7.7.11. Diethyl-1-(4-chlorophenyl)-3-(2-oxo-2H-chromen-3-yl)-
1H-pyrazole-4,5-dicarboxylate (12k)
Yield: 74%; pale yellow solid; m.p: 110e112 ꢀC; IR (KBr): 2924,
2856,1737,1603,1547,1494,1456,1373,1308,1249,1217,1173,1094,
954 cmꢁ1 1H NMR (CDCl3):
; d 8.00 (s, 1H, aromatic), 7.52 (d, 2H,
J ¼ 8.75 Hz, aromatic), 7.50e7.42 (m, 4H, aromatic), 7.37 (d, 1H,
J ¼ 8.75 Hz, aromatic), 7.28 (d,1H, J ¼ 7.77 Hz, aromatic), 4.30 (q, 4H,
J ¼ 7.17 Hz, 2OCH2), 1.28 (t, 6H, J ¼ 6.80 Hz, 2CH3); 13C NMR
(75 MHz, CDCl3): 161.50, 159.40, 158.80, 154.33, 146.74, 141.50,
137.67, 136.57, 135.11, 131.89, 129.33, 128.32, 125.94, 124.41, 121.04,
119.13, 116.84, 62.39, 61.04, 14.20, 13.97; EI-MS (m/z): 467 [M þ H]þ,
489 [M þ Na]þ.
7.7.17. Diethyl-3-(7-methoxy-2-oxo-2H-chromene-3-yl)-1-phenyl-
1H-pyrazole-4,5-dicarboxylate (12q)
Yield: 72%; pale yellow solid; m.p: 136e138 ꢀC; IR (KBr): 2975,
2931, 1729, 1617, 1548, 1502, 1466, 1359, 1309, 1229, 1181, 1092,
1022, 939 cmꢁ1; 1H NMR (300 MHz, CDCl3):
d 7.96 (s, 1H, aromatic),
7.53e7.45 (m, 5H, aromatic), 7.40 (d, 1H, J ¼ 8.49 Hz, aromatic),
6.85e6.80 (m, 2H, aromatic), 4.28 (q, 4H, J ¼ 7.17 Hz, 2OCH2), 3.90
(s, 3H, OCH3), 1.30 (t, 6H, J ¼ 6.9 Hz, 2CH3); 13C NMR (75 MHz,
CDCl3): 163.09, 159.71, 159.55, 156.12, 146.83, 141.88, 139.19, 129.24,
129.16, 129.05, 124.70, 117.37, 112.98, 112.73, 100.58, 62.30, 61.02,
55.71, 14.17, 13.88; EI-MS (m/z): 473 [M þ H]þ.
7.7.12. Diethyl-1-(4-bromophenyl)-3-(2-oxo-2H-chromene-3-yl)-
1H-pyrazole-4,5-dicarboxylate (12l)
Yield: 75%; pale yellow solid; m.p: 142e144 ꢀC; IR (KBr): 2922,
2855,1734,1604,1542,1491,1450,1367,1311,1262,1218,1166,1096,
952 cmꢁ1; 1H NMR (300 MHz, CDCl3):
d 8.00 (s, 1H, aromatic), 7.61
(d, 2H, J ¼ 8.89 Hz, aromatic), 7.57e7.51 (m, 2H, aromatic), 7.41 (d,
2H, J ¼ 8.89 Hz, aromatic), 7.38 (d, 1H, J ¼ 8.89 Hz, aromatic), 7.27 (t,
1H, J ¼ 7.91 Hz, aromatic), 4.30 (q, 4H, J ¼ 7.17 Hz, 2OCH2), 1.30 (t,
6H, 2CH3); 13C NMR (75 MHz, CDCl3): 159.54, 153.98, 142.14, 137.86,
136.55, 132.35, 132.16, 128.32, 126.11, 124.59, 123.17, 118.84, 116.65,
62.63, 61.23,13.93,13.73; EI-MS (m/z): 330 [M þ H]þ, 331 [Mþ2H]þ.
7.7.18. Diethyl-3-(7-methoxy-2-oxo-2H-chromene-3-yl)-1-m-
tolyl-1H-pyrazole-4,5-dicarboxylate (12r)
Yield: 79%; pale yellow solid; m.p: 162e164 ꢀC; IR (KBr): 2978,
2925, 2852, 1729, 1613, 1460, 1267, 1232, 1151, 1096, 1025,
925 cmꢁ1; 1H NMR (300 MHz, CDCl3):
d 7.95 (s, 1H, aromatic), 7.43e
7.20 (m, 5H, aromatic), 6.86e6.80 (m, 2H, aromatic), 4.28 (2q, 4H,
J ¼ 7.17 Hz, 2OCH3), 3.89 (s, 3H, OCH3), 2.43 (s, 3H, CH3), 1.28 (2t, 6H,
2CH3); 13C NMR (CDCl3): 163.02, 161.79, 159.75, 159.39, 156.08,
146.72, 141.75, 139.18, 139.06, 136.73, 129.72, 129.18, 128.85, 125.22,
121.52, 117.45, 115.96, 112.85, 112.69, 100.56, 62.18, 60.88, 55.64,
21.37, 14.12, 13.85; EI-MS (m/z): 477 [M þ H]þ, 499 [M þ Na]þ;
HRMS-ESI calcd for C26H24N2O7Na [M þ Na]þ 499.1481; found
499.1462.
7.7.13. Dimethyl-1-(4-bromophenyl)-3-(2-oxo-2H-chromene-3-
yl)-1H-pyrazole-4,5-dicarboxylate (12m)
Yield: 72%; pale yellow solid; m.p: 215e217 ꢀC; IR (KBr): 2923,
2855, 1739, 1712, 1612, 1542, 1490, 1446, 1378, 1254, 1095,
974 cmꢁ1; 1H NMR (300 MHz, CDCl3):
d 8.04 (s, 1H, aromatic), 7.65
(d, 2H, J ¼ 8.89 Hz, aromatic), 7.58e7.52 (m, 2H, aromatic), 7.43e
7.36 (m, 3H, aromatic), 7.30 (t, 1H, J ¼ 8.2 Hz, aromatic), 3.88 (s, 3H,
OCH3), 3.82 (s, 3H, OCH3); EI-MS (m/z): 483, 485 [M þ H]þ, 505, 507
[M þ Na]þ.
7.7.19. Diethyl-1-(3-chlorophenyl)-3-(7-methoxy-2-oxo-2H-
chromene-3-yl)-1H-pyrazole-4,5-dicarboxylate (12s)
7.7.14. Diethyl-3-(6-methoxy-2-oxo-2H-chromene-3-yl)-1-phenyl-
1H-pyrazole-4,5-dicarboxylate (12n)
Yield: 69%; pale yellow solid; m.p: 143e145 ꢀC; IR (KBr): 2976,
2931, 2191, 1726, 1618, 1549, 1463, 1360, 1317, 1285, 1231, 1117, 1094,
Yield: 76%; pale yellow solid; m.p: 102e104 ꢀC; IR (KBr): 2976,
2929, 1730, 1617, 1548, 1502, 1464, 1363, 1308, 1229, 1091, 1020,
1024, 949 cmꢁ1; 1H NMR (300 MHz, CDCl3):
d 7.95 (s, 1H, aromatic),
7.55 (s, 1H, aromatic), 7.47e7.38 (m, 4H, aromatic), 6.86e6.80 (m,
2H, aromatic), 4.30 (q, 4H, J ¼ 7.17 Hz, 2OCH2), 3.90 (s, 3H, OCH3),
1.30 (t, 6H, J ¼ 6.9 Hz, 2CH3); 13C NMR (75 MHz, CDCl3): 163.14,
161.71, 159.41, 156.07, 147.11, 141.96, 139.96, 134.90, 130.04, 129.24,
129.10, 124.92, 122.59, 116.93, 116.65, 112.96, 112.55, 100.54, 62.45,
61.06, 55.68, 14.07, 13.84; EI-MS (m/z): 497 [M þ H]þ.
835 cmꢁ1; 1H NMR (300 MHz, CDCl3):
d 7.98 (s, 1H, aromatic), 7.53e
7.44 (m, 5H, aromatic), 7.30 (d, 1H, J ¼ 9.06 Hz, aromatic), 7.10 (dd,
1H, J ¼ 9.06, 3.02 Hz, aromatic), 6.92 (d, 1H, J ¼ 3.02, Hz, aromatic),
4.30 (q, 4H, J ¼ 7.17 Hz, 2OCH2), 3.83 (s, 3H, OCH3), 1.26 (t, 6H,
J ¼ 6.9 Hz, 2CH3); EI-MS (m/z): 463 [M þ H]þ, 485 [M þ Na]þ.
7.7.15. Diethyl-3-(6-methoxy-2-oxo-2H-chromene-3-yl)-1-m-
tolyl-1H-pyrazole-4,5-dicarboxylate (12o)
7.7.20. Diethyl-3-(7-(3-methylbut-2-enyloxy-2-oxo-2H-chromene-
3-yl)-1-phenyl-1H-pyrazole-4,5-dicarboxylate (12t)
Yield: 80%; pale yellow solid; m.p: 107e109 ꢀC; IR (KBr): 2924,
2855, 1713, 1585, 1546, 1497, 1459, 1377, 1269, 1223, 1160, 1105,
Yield: 68%; pale yellow solid; m.p: 109e110 ꢀC; IR (KBr): 2925,
2860, 1726, 1610, 1618, 1550, 1502, 1456, 1359, 1305, 1226, 1169,
1016, 970 cmꢁ1; 1H NMR (300 MHz, CDCl3):
d
7.96 (s, 1H, aromatic),
1092, 1003 cmꢁ1 1H NMR (300 MHz, CDCl3):
; d 7.95 (s, 1H, aro-
7.38e7.22 (m, 5H, aromatic), 7.09 (dd, 1H, J ¼ 2.64, 8.87 Hz, aro-
matic), 7.56e7.34 (m, 6H, aromatic), 6.88e6.76 (m, 2H, aromatic),
5.45 (t,1H, J ¼ 6.23 Hz, CH), 4.58 (d, 2H, CH2), 4.28 (q, 4H, J ¼ 7.17 Hz,
matic), 6.92 (d, 1H, J ¼ 2.64 Hz, aromatic), 4.28 (q, 4H, J ¼ 7.17 Hz,