982
Chem. Pharm. Bull.
Vol. 63, No. 12 (2015)
another 50min at room temperature to complete the reaction, 2H, H-2′, 6′, J=6.9Hz), 6.90 (d, 1H, H-5″, J=9Hz), 6.77 (d,
which forms the second stage. The reaction conditions for 1H, H-6,″ J=8.4Hz), 7.50 (m, 3H, H-3′, 4′, 5′).
various derivatives are depicted in Table 4. The precipitated
dicyclohexyl urea was filtered off and the filtrate was con- yl)thiazolidin-4-one (6e)
centrated to dryness under reduced pressure. The residue ob- Yield 47.1%. Colorless microcrystalline powder. mp 162°C.
2-(3,4-Dimethoxyphenyl)3-(4-oxo-2-phenyl-4H-chromen-6-
tained was taken up in chloroform and the organic layer was Rf value 0.347. UV λmax (MeOH) nm: 260, 298. IR (KBr)
washed successively with 5% NaHCO3 and then finally with cm−1: 3404, 3313, 1674, 1629, 1139, 709, MS (ESI) m/z: 416.1
1
brine. The organic layer was dried over sodium sulphate and (M+1). H-NMR (CDCl3, 300MHz) δ: 6.98 (s, 1H, H-Ar-CH-
the solvent was removed under reduced pressure to get crude of thiazolidinone ring), 4.00 (dd, 2H, H-CH2 of thiazolidinone
product, which was then purified by column chromatography ring, J=15.6Hz, J=15.9Hz), 6.52 (s, 1H, H-3), 7.887 (s, 1H,
on silica gel using CHCl3–MeOH (8:2) as the mobile phase H-5), 7.77 (s, 2H, H-7, 8) 8.04 (d, 2H, H-2′, 6′, J=6.3Hz), 7.2
to obtain the title compounds [6a–e, 12a–e, and 18a–e]. The (d, 2H, H-2″, 6″, J=8.4Hz), 6.60 (d, 2H, H-3″, 5″, J=8.4Hz),
novel analogues were characterized by a combination of spec- 7.53 (m, 3H, H-3′, 4′, 5′).
tral techniques.
3-(3-Methoxy-4-oxo-2-phenyl-4H-chromen-6-yl)-2-
3-(4-Oxo-2-phenyl-4H-chromen-6-yl)-2-phenylthiazolidin-4- phenylthiazolidin-4-one (12a)
one (6a)
Yield 64.1%. White powder. mp 185°C. Rf value 0.596. UV
Yield 44.1% as micro-crystalline powder. mp 225°C. Rf λmax (MeOH) nm: 306, 258. IR (KBr) cm−1: 1679, 1631, 1452,
value 0.439. UV λmax (MeOH) nm: 298. IR (KBr) cm−1: 1159, 690. MS (EI) m/z: 428 (M+), 410, 354, 292, 178, 251,
1
1
1670, 1654, 1132, 692. MS (ESI) m/z: 400 (M+1). H-NMR 222, 135. H-NMR (DMSO-d6, 400MHz) δ: 3.80 (s, 3H, H-
(CDCl3, 400MHz) δ: 7.00 (s, 1H, H-Ar-CH- of thiazolidinone OCH3), 4.00 (dd, 2H, H- CH2 of thiazolidinone ring, J=18Hz,
ring), 4.00 (dd, 2H, H-CH2 of thiazolidinone ring, J=14.3Hz, J=15.6Hz), 6.7 (s, 1H, H-CH of thiazolidinone ring), 8.00 (m,
J=14.5Hz), 6.70 (s, 1H, H-3), 7.94 (s, 1H, H-5), 7.80 (dd, 2H, 3H, H-5, 2″, 6″), 7.68 (d, 1H, H-8, J=8.7Hz), 7.70 (d, 1H, H-7,
H-7, 8, J=9.3Hz, J=8.7Hz), 7.40 (d, 2H, H-2′, 6′, J=6.6Hz), J=9.3Hz), 7.50 (d, 3H, H-3″, 4″, 5″), 7.41 (d, 2H, H-2′, 6′), 7.29
8.10 (d, 2H, H-2″, 6″, J=6.3Hz), 7.30 (m, 3H, H-3′, 4′, 5′), 7.50 (m, 3H, H-3′, 4′, 5′). 13C-NMR (DMSO, 300MHz) δ: 173.33
(m, 3H, H-3″, 4″, 5″). 13C-NMR (300MHz, CDCl3) δ: 162.65 (C-4), 170.85 (C-4*), 155.2 (C-2), 152.5 (C-9), 140.6 (C-3),
(C-2), 106.68 (C-3), 176.47 (C-4), 119.27 (C-5), 134.9 (C-6), 139.6 (C-1″), 134.5 (C-6), 131.3 (C-1′), 130.9 (C-4′), 130.3
128.64 (C-7), 119.27 (C-8), 153.35 (C-9), 123.4 (C-10), 130.96 (C-4″), 128.8 (C-7), 128.65 (C-3″, C-5″), 128.3 (C-3′, C-5′),
(C-1′), 126.37 (C-2′, C-6′), 128.7 (C-3′, C-5′), 131.44 (C-4′), 128.1 (C-2″, C-6″), 127.2 (C-2′, C-6′), 123.63 (C-10), 121.1
63.43 (C-2*), 170.80 (C-4*), 32.96 (C-5*), 139.5 (C-1″), 129.07 9C-5), 119.25 (C-8), 63.42 (C-2*), 59.82 (C-OCH3), 33.0 (C-5*).
(C-2″, C-6″), 128.77 (C-5″, C-3″), 127.2 (C-4″).
3-(3-Methoxy-4-oxo-2-phenyl-4H-chromen-6-yl)-2-(4-
H-chromen-6-yl)- methoxyphenyl)thiazolidin-4-one (12b)
2-(4-Methoxyphenyl)3-(4-oxo-2-phenyl-4
thiazolidin-4-one (6b)
Yield 80.0%. Off white powder. mp 171°C. Rf value 0.553.
Yield 40.3%. Colorless microcrystalline powder. mp 225°C. UV λmax (MeOH) nm; 306, 258. IR (KBr) cm−1: 1687, 1626,
1
Rf value 0.469. UV λmax (MeOH) nm: 260, 298. IR (KBr) 1491, 1161, 688. MS (ESI) m/z: 459 (M+1). H-NMR (DMSO-
cm−1: 1670, 1642, 1143, 777, 1452, 1442. MS (ESI) m/z: 430 d6, 300MHz) δ: 3.65 (s, 3H, H-OCH3 at C4″), 3.76 (s, 3H,
1
(M+1). H-NMR (CDCl3, 300MHz) δ: 3.65 (s, 3H, H-OCH3 at H-OCH3 at C3), 4.00 (dd, 2H, H-CH2 of thiazolidinone ring,
C-4″), 6.99 (s, 1H, H-Ar-CH- of thiazolidinone ring), 4.00 (dd, J=15.6Hz, J=15.6Hz), 6.60 (s, 1H, H-CH of thiazolidinone
2H, H-CH2 of thiazolidinone ring, J=13.34Hz, J=13.51Hz), ring), 7.99 (s, 3H, H-5, 7, 8), 7.50 (s, 3H, H-3′, 4′, 5′), 7.36 (d,
6.60 (s, 1H, H-3), 7.91 (s, 1H, H-5), 7.73–7.86 (d, 2H, H-7, 8, 2H, H-2′, 6′, J=8.7Hz), 6.80 (d, 2H, H-2″, 6″, J=24.9Hz), 7.70
J=26.7Hz), 8.03 (d, 2H, H-2″, 6″, J=5.4Hz), 7.32 (d, 2H, H-2′, (d, 2H, H-3″, 5″).
6′, J=7.2Hz), 6.8 (d, 2H, H-3′, 5″, J=7.2Hz), 7.56 (m, 3H, H-3′,
4′, 5′).
2-(3,4-Dichlorophenyl)3-(4-oxo-2-phenyl-4H-chromen-6-yl)
thiazolidin-4-one (6c)
2-(3,4-Dichlorophenyl)-3-(3-methoxy-4-oxo-2-phenyl-4H-
chromen-6-yl)thiazolidin-4-one (12c)
-
Yield 90.3%. White fine powder. mp 169°C. Rf value 0.617.
UV λmax (MeOH) nm: 306, 246. IR (KBr) cm−1: 1672, 1640,
Yield 49.0%. Colorless microcrystalline powder. mp 200°C. 1481, 1155, 680, 819. MS (ESI) m/z: 498 (M+1). 1H-NMR
Rf value 0.551. UV λmax (MeOH) nm: 260, 288. IR (KBr) (DMSO-d6, 400MHz) δ: 3.90 (s, 3H, H-OCH3), 4.00 (dd, 2H,
cm−1: 1672, 1641, 1134, 677, 813. MS (ESI) m/z: 469 (M+1). H-CH2 of thiazolidinone ring, J=18Hz, J=15.7Hz), 6.98 (s,
1H-NMR (CDCl3, 300MHz) δ: 6.99 (s, 1H, H-Ar-CH- of thia- 1H, H-CH of thiazolidinone ring), 7.86 (s, 1H, H-5), 8.01 (d,
zolidinone ring), 4.00 (dd, 2H, H-CH2 of thiazolidinone ring, 2H, H-2′, 6′, J=6.2Hz), 7.43 (d, 1H, H-4′, J=8.3Hz), 7.70 (m,
J=15.9Hz, J=15.6Hz), 6.98 (s, 1H, H-3), 7.97 (s, 1H, H-5), 3H, H-7, 8, 2″), 7.40 (m, 4H, H-3′, 5′, 5″, 6″).
8.05 (d, 2H, H-2′, 6′, J=6.3Hz), 7.46 (d, 1H, H-4′, J=8.4Hz),
7.80 (m, 3H, H-7, 8, 2″), 7.5 (m, 4H, H-3′, 5′, 5″, 6″).
2-(3,4-Dimethoxyphenyl)-3-(3-methoxy-4-oxo-2-phenyl-4H-
chromen-6-yl)thiazolidin-4-one (12d)
2-(3,4-Dimethoxyphenyl)3-(4-oxo-2-phenyl-4
H
-chromen-6-
Yield 68.4%. Off white fine powder. mp 203°C. Rf value
yl)thiazolidin-4-one (6d)
0.51. UV λmax (MeOH) nm: 306, 246. IR (KBr) cm−1: 1678,
1
Yield 38.4%. Off white powder. mp 186°C. Rf value 0.429. 1640, 1481, 1148, 698. MS (ESI) m/z: 490 (M+1). H-NMR
UV λmax (MeOH) nm: 262, 296. IR (KBr) cm−1: 1693, 1649, (DMSO, 300MHz) δ: 3.64 (s, 3H, H- of OCH3 at C4″), 3.69
1
1141, 700, 1454. MS (ESI) m/z: 460 (M+1). H-NMR (CDCl3, (s, 6H, H-OCH3 at C3 & C3″), 4.00 (dd, 2H, H-CH2 of thia-
300MHz) δ: 3.66 (d, 6H, H-OCH3, J=14.4Hz), 7.00 (d, 2H, zolidinone ring, J=15.6Hz, J=15.6Hz), 6.70 (s, 1H, H-CH
H-Ar-CH- of thiazolidinone ring, H-2″, J=9.3Hz), 4.00 (dd, of thiazolidinone ring), 6.77 (d, 1H, H-6″, J=8.4Hz), 6.90
2H, H-CH2 of thiazolidinone ring, J=12.9Hz, J=12.6Hz), 6.57 (d, 1H, H-5″, J=7.8Hz), 7.02 (s, 1H, H-2″), 7.68 (d, 1H, H-8,
(s, 1H, H-3), 7.94 (s, 1H, H-5), 7.7–7.8 (m, 2H, H-7, 8), 8.00 (d, J=8.7Hz), 7.77 (d, 1H, H-7, J=10.2Hz), 8.00 (m 3H, H- 5′, 6′),