L.-R. Wen et al. / Tetrahedron 65 (2009) 1287–1293
1291
J¼16.0 Hz), 3.41 (1H, dd, J¼7.0,16.0 Hz), 3.71 (3H, s, OCH3), 4.81 (1H,
4.2.12. 7-Chloro-4-(3-nitrophenyl)-1-phenyl-3,4-dihydro-1H-
thiochromeno[2,3-b]pyridine-2,5-dione (4l)
d, J¼6.5 Hz), 6.90 (2H, d, J¼8.5 Hz, ArH), 7.25 (3H, d, J¼8.5 Hz, ArH),
7.50 (1H, s, ArH), 7.58–7.62 (4H, m, ArH), 8.02 (1H, d, J¼1.5 Hz, ArH),
8.26 (1H, d, J¼8.5 Hz, ArH); dC (125 MHz; DMSO-d6) 35.1, 38.9, 55.5,
114.6, 118.0, 126.8, 127.3, 128.2, 128.8, 129.6, 130.2, 130.3, 130.4,
130.6, 130.9, 133.0, 135.5, 136.4, 137.3, 151.5, 158.6, 168.8, 177.0; IR
(KBr, cmꢂ1) 1712, 1608, 1582, 1539, 1391, 1269, 1120, 830, 778, 692.
Anal. Calcd for C25H18ClNO3S: C, 67.04; H, 4.05; N, 3.13. Found: C,
67.09; H, 4.04; N, 3.14. MS (ESI) m/z: 448.2 [MþH]þ.
Primrose yellow solid, Rf¼0.30 (petroleum ether–ethyl acetate,
5:1); mp 234–235 ꢀC. dH (500 MHz; DMSO-d6) 3.00 (1H, dd, J¼2.0,
16.5 Hz), 3.54 (1H, dd, J¼7.5, 16.5 Hz), 5.04 (1H, d, J¼6.5 Hz), 7.33
(1H, s, ArH), 7.54 (1H, s, ArH), 7.59 (3H, d, J¼5.0 Hz, ArH), 7.67 (1H, t,
J¼8.0 Hz, ArH), 7.75 (1H, dd, J¼2.5, 9.0 Hz, ArH), 7.84 (1H, d,
J¼8.0 Hz, ArH), 7.88 (1H, d, J¼8.5 Hz, ArH), 8.13 (1H, d, J¼8.0 Hz,
ArH), 8.22 (2H, t, J¼2.5 Hz, ArH); dC (125 MHz; DMSO-d6) 35.7, 38.3,
116.5, 121.9, 122.6, 127.3, 129.8, 130.0, 130.6, 130.8, 131.0, 132.4,
132.5, 133.5, 134.1, 136.3, 143.6, 148.6, 153.1, 168.4, 176.6; IR (KBr,
cmꢂ1) 1713, 1610, 1580, 1538, 1393, 1359, 1224, 833, 732, 693. Anal.
Calcd for C24H15ClN2O4S: C, 62.27; H, 3.27; N, 6.05. Found: C, 62.45;
H, 3.29; N, 6.09.
4.2.8. 8-Chloro-1-phenyl-4-p-tolyl-3,4-dihydro-1H-
thiochromeno[2,3-b]pyridine-2,5-dione (4h)
Primrose yellow solid, Rf¼0.30 (petroleum ether–ethyl acetate,
4:1); mp 223–225 ꢀC. dH (500 MHz; DMSO-d6) 2.24 (3H, s, CH3),
2.90 (1H, d, J¼16.0 Hz), 3.41 (1H, dd, J¼2.0, 16.0 Hz), 4.83 (1H, d,
J¼7.0 Hz), 7.15 (2H, d, J¼8.0 Hz, ArH), 7.22 (3H, d, J¼8.0 Hz, ArH),
7.51 (1H, s, ArH), 7.58 (4H, d, J¼9.5 Hz, ArH), 8.00 (1H, s, ArH), 8.24
(1H, d, J¼9.0 Hz, ArH); dC (125 MHz; DMSO-d6) 21.0, 35.5, 38.9,
117.8, 126.7, 127.0, 127.3, 128.7, 129.6, 129.8, 130.2, 130.4, 130.6,
130.8, 135.5, 136.4, 136.5, 137.3, 138.2, 151.5, 168.7, 177.0; IR (KBr,
cmꢂ1) 1713, 1607, 1571, 1536, 1269, 1218, 1129, 832, 778, 691. Anal.
Calcd for C25H18ClNO2S: C, 69.52; H, 4.20; N, 3.24. Found: C, 69.43;
H, 4.16; N, 3.21.
4.2.13. 7-Chloro-1,4-diphenyl-3,4-dihydro-1H-thiochromeno[2,3-
b]pyridine-2,5-dione (4m)
Primrose yellow solid, Rf¼0.27 (petroleum ether–ethyl acetate,
5:1); mp 243–244 ꢀC. dH (500 MHz; DMSO-d6) 2.90 (1H, d,
J¼16.0 Hz), 3.43 (1H, dd, J¼7.0,16.5 Hz), 4.85 (1H, d, J¼7.0 Hz), 7.20–
7.23 (2H, m, ArH), 7.31 (4H, d, J¼4.0 Hz, ArH), 7.48 (1H, s, ArH), 7.54
(3H, s, ArH), 7.69 (1H, dd, J¼2.0, 8.5 Hz, ArH), 7.81 (1H, d, J¼9.0 Hz,
ArH), 8.18 (1H, d, J¼2.5 Hz, ArH); dC (125 MHz; DMSO-d6) 36.0, 38.8,
117.5,127.2,127.4,127.5,129.4,129.6,129.8,130.1,130.2,130.5, 130.6,
130.8, 132.3, 132.5, 133.5, 136.5, 141.3, 152.4, 168.8, 176.7; IR (KBr,
cmꢂ1) 1705, 1616, 1574, 1539, 1406, 1359, 1266, 1208, 823, 718, 692,
555. Anal. Calcd for C24H16ClNO2S: C, 68.98; H, 3.86; N, 3.35. Found:
C, 68.80; H, 3.88; N, 3.39. MS (ESI) m/z: 418.2 [MþH]þ.
4.2.9. 7-Chloro-4-(2,5-dichlorophenyl)-1-phenyl-3,4-dihydro-1H-
thiochromeno[2,3-b]pyridine-2,5-dione (4i)
Primrose yellow solid, Rf¼0.40 (petroleum ether–ethyl acetate,
4:1); mp 225–226 ꢀC. dH (500 MHz; DMSO-d6) 2.80 (1H, dd, J¼1.0,
15.5 Hz), 3.58 (1H, dd, J¼8.0, 16.5 Hz), 5.12 (1H, d, J¼6.5 Hz), 7.20
(1H, d, J¼2.5 Hz, ArH), 7.33 (1H, s, ArH), 7.43 (1H, dd, J¼2.5,
8.5 Hz, ArH), 7.59–7.65 (5H, m, ArH), 7.76 (1H, dd, J¼2.5, 8.5 Hz,
ArH), 7.91 (1H, d, J¼8.5 Hz, ArH), 8.19 (1H, d, J¼2.0 Hz, ArH); dC
(125 MHz; DMSO-d6) 33.8, 36.4, 114.9, 126.8, 126.9, 128.8, 129.1,
129.4, 129.6, 129.9, 130.2, 130.3, 131.4, 131.9, 132.0, 132.3, 132.4,
133.0, 135.8, 139.5, 153.4, 167.4, 176.1; IR (KBr, cmꢂ1) 1714, 1614,
1588, 1548, 1359, 1270, 1127, 745, 693, 616. Anal. Calcd for
C24H14Cl3NO2S: C, 59.22; H, 2.90; N, 2.88. Found: C, 59.41; H, 2.93;
N, 2.83.
4.2.14. 7-Chloro-4-(3,4-dimethoxyphenyl)-1-phenyl-3,4-dihydro-
1H-thiochromeno[2,3-b]pyridine-2,5-dione (4n)
Primrose yellow solid, Rf¼0.25 (petroleum ether–ethyl acetate,
4:1); mp 227–228 ꢀC. dH (500 MHz; DMSO-d6) 2.94 (1H, d,
J¼16.0 Hz), 3.42 (1H, dd, J¼7.5,16.0 Hz), 3.71 (3H, s, OCH3), 3.76 (3H,
s, OCH3), 4.83 (1H, d, J¼6.5 Hz), 6.76 (1H, dd, J¼2.0, 8.5 Hz, ArH),
6.88 (1H, d, J¼8.0 Hz, ArH), 7.00 (1H, d, J¼2.0 Hz, ArH), 7.27 (1H, s,
ArH), 7.51 (1H, s, ArH), 7.58 (3H, d, J¼5.5 Hz, ArH), 7.74 (1H, dd,
J¼2.0, 8.5 Hz, ArH), 7.86 (1H, d, J¼9.0 Hz, ArH), 8.23 (1H, d, J¼2.0 Hz,
ArH); dC (125 MHz; DMSO-d6) 34.9, 38.4, 55.4, 55.5, 111.0, 111.7,
117.2, 117.8, 126.9, 128.8, 129.3, 129.6, 130.0, 130.3, 131.8, 132.0, 133.1,
136.0, 147.8, 148.9, 151.6, 168.5, 176.2; IR (KBr, cmꢂ1) 1711, 1605,
1535, 1517, 1405, 1267, 1217, 1135, 1028, 813, 730, 695. Anal. Calcd
for C26H20ClNO4S: C, 65.34; H, 4.22; N, 2.93. Found: C, 65.22; H,
4.20; N, 2.89. MS (ESI) m/z: 500.1 [MþNa]þ.
4.2.10. 7-Chloro-4-(4-chlorophenyl)-1-phenyl-3,4-dihydro-1H-
thiochromeno[2,3-b]pyridine-2,5-dione (4j)
Primrose yellow solid, Rf¼0.30 (petroleum ether–ethyl acetate,
5:1); mp 221–222 ꢀC. dH (500 MHz; CDCl3) 3.15 (1H, dd, J¼2.0,
16.5 Hz), 3.24 (1H, dd, J¼7.0, 16.5 Hz), 5.04 (1H, d, J¼6.0 Hz), 7.09
(1H, s, ArH), 7.24–7.34 (6H, m, ArH), 7.47 (1H, dd, J¼2.0, 8.5 Hz,
ArH), 7.54 (3H, d, J¼1.5 Hz, ArH), 8.44 (1H, d, J¼2.5 Hz, ArH); dC
(125 MHz; CDCl3) 35.0, 37.6, 117.9, 127.7, 128.1, 128.6, 129.1, 129.7,
130.2, 130.3, 131.8, 131.9, 133.1, 134.3, 135.8, 139.1, 151.7, 168.3,
177.3; IR (KBr, cmꢂ1) 1713, 1311, 1571, 1537, 1409, 1268, 1217, 832,
731, 694, 538. Anal. Calcd for C24H15Cl2NO2S: C, 63.73; H, 3.34; N,
3.10. Found: C, 63.87; H, 3.37; N, 3.12. MS (ESI) m/z: 452.4
[MþH]þ.
4.2.15. 7-Chloro-4-(4-methoxyphenyl)-1-phenyl-3,4-dihydro-1H-
thiochromeno[2,3-b]pyridine-2,5-dione (4o)
Primrose yellow solid, Rf¼0.20 (petroleum ether–ethyl acetate,
4:1); mp 202–203 ꢀC. dH (500 MHz; DMSO-d6) 2.90 (1H, dd, J¼1.5,
16.0 Hz), 3.41 (1H, dd, J¼7.0,16.0 Hz), 3.71 (3H, s, OCH3), 4.82 (1H, d,
J¼6.0 Hz), 6.91 (2H, d, J¼8.5 Hz, ArH), 7.25 (3H, d, J¼8.5 Hz, ArH),
7.51 (1H, s, ArH), 7.58 (3H, s, ArH), 7.72 (1H, dd, J¼2.5, 8.5 Hz, ArH),
7.83 (1H, d, J¼8.5 Hz, ArH), 8.21 (1H, d, J¼2.5 Hz, ArH); dC (125 MHz;
DMSO-d6) 35.1, 38.9, 55.5, 117.8, 127.4, 128.2, 129.6, 129.8, 130.0,
130.1, 130.5, 130.7, 130.8, 132.2, 132.5, 133.0, 133.4, 136.5, 152.1,
158.7, 168.8, 176.6; IR (KBr, cmꢂ1) 1705, 1605, 1537, 1511, 1247, 1222,
1134, 1034, 849, 735, 695. Anal. Calcd for C25H18ClNO3S: C, 67.04; H,
4.05; N, 3.13. Found: C, 67.23; H, 4.01; N, 3.11. MS (ESI) m/z: 448.2
[MþH]þ.
4.2.11. 7-Chloro-4-(2,4-dichlorophenyl)-1-phenyl-3,4-dihydro-1H-
thiochromeno[2,3-b]pyridine-2,5-dione (4k)
Primrose yellow solid, Rf¼0.32 (petroleum ether–ethyl acetate,
5:1); mp 246–247 ꢀC. dH (500 MHz; DMSO-d6) 2.80 (1H, d,
J¼16.0 Hz), 3.56 (1H, dd, J¼2.5, 15.5 Hz), 5.11 (1H, d, J¼7.0 Hz), 7.30
(1H, d, J¼8.0 Hz, ArH), 7.38 (1H, d, J¼7.5 Hz, ArH), 7.52 (2H, s, ArH),
7.61 (3H, s, ArH), 7.74 (2H, d, J¼12.0 Hz, ArH), 7.88 (1H, d, J¼8.5 Hz,
ArH), 8.18 (1H, s, ArH); dC (125 MHz; DMSO-d6) 33.9, 36.9, 115.6,
127.3, 128.6, 129.3, 129.8, 129.9, 130.0, 130.1, 130.3, 130.6, 130.7,
130.8, 132.5, 132.6, 133.2, 133.6, 134.2, 136.3, 137.0, 153.8, 168.0,
176.4; IR (KBr, cmꢂ1) 1719, 1608, 1539, 1537, 1405, 1264, 1211, 1129,
818, 733, 691. Anal. Calcd for C24H14Cl3NO2S: C, 59.22; H, 2.90; N,
2.88. Found: C, 59.07; H, 2.89; N, 2.92.
4.2.16. 7-Chloro-1-phenyl-4-p-tolyl-3,4-dihydro-1H-
thiochromeno[2,3-b]pyridine-2,5-dione (4p)
Primrose yellow solid, Rf¼0.35 (petroleum ether–ethyl acetate,
4:1); mp 223–224 ꢀC. dH (500 MHz; DMSO-d6) 2.26 (3H, s, CH3),
2.90 (1H, dd, J¼1.5, 16.0 Hz), 3.43 (1H, dd, J¼7.0, 16.0 Hz), 4.84 (1H,
d, J¼7.0 Hz), 7.15 (2H, d, J¼8.0 Hz, ArH), 7.22 (3H, t, J¼8.5 Hz, ArH),