Med Chem Res (2012) 21:3568–3580
3577
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COOH), 1620 (C=O, COON), 1500 (C=S, thiazole). H
NMR (400 MHz, DMSO-d6) d: 0.76 (s, 3H, CH3), 0.88 (s,
6H, 2 9 CH3), 0.96 (s, 3H, CH3), 0.98 (s, 3H, CH3), 1.08
(s, 6H, 2 9 CH3), 1.10 (s, 3H, CH3), 1.17 (s, 3H, CH3),
2.00–2.08 (m, 2H, CH2CH-thiazole), 2.74–2.86 (m, 1H,
C18–H), 4.81–4.88 (m, 3H, CH2COO, Et–CH-thiazole),
5.18 (br.s, 1H, C12–H), 12.06 (br.s 1H, COOH). 13C NMR
(100 MHz, DMSO-d6) d: 202.0 (C=S), 179.0 (C-28), 176.7
(C=O, thiazole), 176.3 (C=O, COON), 165.3 (C-3), 144.4
(C-13), 121.8 (C-12), 46.9 (C-17). DEPT: 8 9 CH3,
12 9 CH2, 5 9 CH, 37 9 C at. Anal. calcd. for
C37H54N2O5S2: C, 66.23; H, 8.11; N, 4.17; Found: C,
66.39; H, 8.22; N, 4.30%.
4.14 (t, J = 7.4 Hz, 2H, NCH2CH2), 4.24 (s, 2H, CH2–
thiazol) 5.21 (br.s, 1H, C12–H). 13C NMR (100 MHz,
DMSO-d6) d: 201.5 (C=S), 177.8 (C-28), 175.5 (C=O, thi-
azole), 174.7 (C=O, COON), 169.2 (C-3), 144.1 (C-13).
122.4 (C-12), 52.1 (COOCH3), 46.7 (C-17). DEPT:
8 9 CH3, 13 9 CH2, 4 9 CH, 37 9 C at. Anal. calcd. for
C37H54N2O5S2: C, 66.23; H, 8.11; N, 4.17; Found: C, 66.40;
H, 8.23; N, 4.21%.
3-(Rhodanine-3-hexanoyloxyimino)-olean-12-en-28-oic acid
methyl ester (IVf) Yield 87%, mp 134–138ꢁC. IR (m,
cm-1): 1720 (C=O, COOCH3), 1695 (C=O, thiazole), 1640
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(C=O, COON), 1500 (C=S). H NMR (400 MHz, DMSO-
d6) d: 0.69 (s, 3H, CH3), 0.88 (s, 6H, 2 9 CH3), 0.98 (s, 3H,
CH3), 1.07 (s, 3H, CH3), 1.10 (s, 3H, CH3), 1.16 (s, 3H, CH3),
1.42–1.62 (m), 1.98 (m), 2.24 (t, J = 7.2 Hz), 2.41 (t,
J = 7.2 Hz), 3.85 (t, J = 7.3 Hz) (10H, (CH2)5), 2.73–2.85
(m, 1H, C18–H), 3.55 (s, 3H, COOCH3), 4.25 (s, 2H, CH2-
thiazole), 5.21 (br.s, 1H, C12–H). 13C NMR (100 MHz,
DMSO-d6) d: 203.1 (C=S), 177.8 (C-28), 175.1 (C=O, thi-
azole), 171.3 (C=O, COON), 170.1 (C-3), 144.1 (C-13),
122.5 (C-12), 52.1 (COOCH3), 46.7 (C-17). DEPT:
8 9 CH3, 16 9 CH2, 4 9 CH, 40 9 C at. Anal. calcd. for
C40H60N2O5S2: C, 67.38; H, 8.48; N, 3.93; Found: C, 67.17;
H, 8.34; N, 4.19%.
3-(Rhodanine-5-acetyloxyimino)-olean-12-en-28-oic acid
methyl ester (IVc) Yield 90%, mp 128–130ꢁC. IR (m,
cm-1): 1720 (C=O, COOCH3), 1705 (C=O, thiazole), 1635
(C=O, COON), 1505 (C=O, thiazole). 1H NMR (300 MHz,
CDCl3) d: 0.76 (s, 3H, CH3), 0.90 (s, 3H, CH3), 0.93 (s,
3H, CH3), 1.03 (s, 3H, CH3), 1.13 (s, 6H, 2 9 CH3), 1.24
(s, 3H, CH3), 2.88 (dd, J1 = 4.2, 13.8 Hz, 1H, C18–H),
3.63 (s, 3H, COOCH3), 4.09 (s, 2H, CH2COON), 4.96 (s,
2H, CH2-thiazole), 5.29 (t, 1H, J = 3.6 Hz, C12–H). 13C
NMR (75 MHz, CDCl3) d: 200.1 (C=S), 178.0 (C-28),
175.9 (C=O, thiazole), 172.9 (C=O, COON), 165.5 (C-3),
143.8 (C-13), 121.9 (C-12), 51.6 (COOCH3), 46.7 (C-17).
DEPT: 8 9 CH3, 12 9 CH2, 4 9 CH, 36 9 C at. Anal.
calcd. for C36H52N2O5S2: C, 65.82; H, 7.98; N, 4.26;
Found: C, 66.05; H, 8.15; N, 4.14%.
3-(5-Ethylrhodanine-3-acetyloxyimino)-olean-12-en-28-oic
acid methyl ester (IVg) Yield 81%, mp 183–185ꢁC. IR (m,
cm-1): 1720 (C=O, COOCH3), 1700 (C=O, thiazole), 1620
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(C=O, COON), 1495 (C=S). H NMR (400 MHz, DMSO-
3-(2,4-Thiazolidinedione-3-acetyloxyimino)-olean-12-en-28-
oic acid methyl ester (IVd) Yield 91%, mp 192–194ꢁC. IR
(m, cm-1): 1725 (C=O, COOCH3), 1705 (C=O, thiazole),
1680 (C=O, thiazole), 1630 (C=O, COON). 1H NMR
(400 MHz, DMSO-d6) d: 0.70 (s, 3H, CH3), 0.89 (s, 6H,
2 9 CH3), 0.99 (s, 3H, CH3), 1.09 (s, 3H, CH3), 1.10 (s, 3H,
CH3), 1.18 (s, 3H, CH3), 2.77–2.88 (m, 1H, C18–H), 3.55 (s,
3H, COOCH3), 4.37 (s, 2H, CH2COON), 4.51 (s, 2H, CH2-
thiazole), 5.19–5.23 (m, 1H, C12–H). 13C NMR (100 MHz,
DMSO-d6) d: 177.8 (C-28), 176.6 (C=O, NHCOCH-thia-
zole), 172.4 (C=O, SCONH-thiazole), 172.0, (C=O,
COON), 166.3 (C-3), 144.2 (C-13), 122.3 (C-12), 52.1
(COOCH3), 46.7 (C-17); DEPT: 8 9 CH3, 12 9 CH2,
4 9 CH, 36 9 C at. Anal. calcd. for C36H52N2O6S: C,
67.47; H, 8.18; N, 4.37; Found: C, 67.57; H, 8.30; N, 4.51%.
d6) d: 0.70 (s, 3H, CH3), 0.89 (s, 6H, 2 9 CH3), 0.98 (s, 3H,
CH3), 1.08 (s, 3H, CH3), 1.10 (s, 3H, CH3), 1.17 (s, 3H, CH3),
2.01–2.10 (m, 2H, CH2CH-thiazole), 2.77–2.87 (m, 1H,
C18–H), 3.55 (s, 3H, COOCH3), 4.79–4.93 (m, 3H,
CH2COO, EtCH-thiazole), 5.18–5.24 (m, 1H, C12–H). 13C
NMR (100 MHz, DMSO-d6) d: 202.6 (C=S), 177.8 (C-28),
176.7 (C=O, thiazole), 176.6 (C=O, COON), 165.5 (C-3),
144.2 (C-13), 122.3 (C-12), 52.1 (C-31), 46.7 (C-17). DEPT:
9 9 CH3, 12 9 CH2, 5 9 CH, 38 9 C at. Anal. calcd. for
C38H56N2O5S2: C, 66.63; H, 8.24; N, 4.09; Found: C, 66.78;
H, 8.32; N, 4.25%.
3-[5-(4-Methoxyphenylmethylidene)-rhodanine-3-acetylox-
yimino)-olean-12-en-28-oic acid methyl ester (IVi)
Yield 95%, mp 102–109ꢁC. IR (m, cm-1): 1725 (C=O,
COOCH3), 1695 (C=O, thiazole), 1620 (C=O, COON),
1500 (C=S), 1270 (Ar-OCH3). 1H NMR (400 MHz,
DMSO-d6) d: 0.72 (s, 3H, CH3), 0.90 (s, 6H, 2 9 CH3),
0.98 (s, 3H, CH3), 1.11 (s, 6H, 2 9 CH3), 1.20 (s, 3H,
CH3), 2.77–2.87 (m, 1H, C18–H), 3.57 (s, 3H, COOCH3),
3.87 (s, 3H, CH3O), 5.05 (s, 2H, NCH2COO), 5.21 (s, 1H,
C12–H), 7.14 (d, J = 8.3 Hz, 2H, Ar), 7.64 (d, J = 8.3 Hz,
2H, Ar), 7.81 (s, 1H, Ar–CH). 13C NMR (100 MHz,
3-(Rhodanine-3-propionyloxyimino)-olean-12-en-28-oic acid
methyl ester (IVe) Yield 82%, mp 152–154ꢁC. IR (m,
cm-1): 1720 (C=O, COOCH3), 1700 (C=O, thiazole), 1635
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(C=O, COON), 1490 (C=S). H NMR (400 MHz, DMSO-
d6) d: 0.69 (s, 3H, CH3), 0.88 (s, 6H, 2 9 CH3), 0.97 (s, 3H,
CH3), 1.07 (s, 3H, CH3), 1.10 (s, 3H, CH3), 1.16 (s, 3H, CH3),
2.77 (t, J = 7.4, 2H, NCH2CH2), 3.55 (s, 3H, COOCH3),
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