Molecules 2012, 17
8838
IR (KBr, cm−1) ν 3480, 3417, 2945, 2867, 1738, 1641, 1454, 1372, 1244, 1160, 1038, 885, 756;
1H-NMR (CDCl3, 300 MHz) δ 0.80, 0.88, 0.91, 0.96, 1.68 (3H each, s, 24, 25, 26, 27, 30-CH3), 2.01,
2.06 (3H each, s, 3 and 23-OCOCH3), 2.65 (4H, m, 17-COOCH2(CH2)4CH2OCOCH2CH2), 2.99 (1H,
m, 19-CH), 3.68 (1H, d, J = 11.5 Hz, 23-CH2), 3.86 (1H, d, J = 11.5 Hz, 23-CH2), 4.05 (4H, m,
17-COOCH2(CH2)4CH2), 4.60 (1H, s, 29=CH2), 4.72 (1H, s, 29=CH2), 4.74 (1H, m, 3-CH); HR-MS
(ESI, M+H) m/z: calcd for C44H69O10 757.4734, found 757.4738.
Pentanedioic acid, 1-[6-[(3β,23-diacetoxylup-20(29)-en-28-oyl)oxy]ethyl] ester (6i). From 1,6-hexanediol
(106 mg, 0.9 mmol) and glutaric anhydride (48.0 mg, 0.42 mmol); column chromatography with
petroleum ether/ethyl acetate = 1:2 (v:v). Yield: 55.0 mg (68%) as a yellow oil; IR (KBr, cm−1) ν 3454,
2943, 2866, 1731, 1642, 1454, 1378, 1247, 1157, 1054, 771; 1H-NMR (CDCl3, 300 MHz) δ 0.80, 0.87,
0.91, 0.96, 1.68 (3H each, s, 24, 25, 26, 27, 30-CH3), 1.98, 2.06 (3H each, s, 3 and 23-OCOCH3), 2.41
(4H, m, 28-COOCH2(CH2)4CH2OCOCH2CH2CH2), 2.99 (1H, m, 19-CH), 3.69 (1H, d, J = 10.2 Hz,
23-CH2), 3.83 (1H, d, J = 10.2 Hz, 23-CH2), 4.06 (4H, m, 28-COOCH2(CH2)4 CH2), 4.60 (1H, s,
29=CH2), 4.72 (1H, s, 29=CH2), 4.74 (1H, m, 3-CH); HR-MS (ESI, M+H) m/z: calcd for C45H71O10
771.4891, found 771.4896.
1,2-Xylenedioic acid, 1-[6-[(3β,23-diacetoxylup-20(29)-en-28-oyl)oxy]ethyl] ester (6j). From
1,6-hexanediol (106.0 mg, 0.9 mmol) and phthalic anhydride (62.0 mg, 0.42 mmol); column
chromatography with petroleum ether/ethyl acetate/acetic acid = 50:50:1 (v:v:v). Yield: 50.0 mg (59%)
as a yellow oil; IR (KBr, cm−1) ν 3479, 2946, 2866, 1735, 1704, 1591, 1384, 1369, 1246, 1130, 1040,
1
652; H-NMR (CDCl3, 300 MHz) δ 0.79, 0.87, 0.91, 0.95, 1.68 (3H each, s, 24, 25, 26, 27, 30-CH3),
2.01, 2.05 (3H each, s, 3 and 23-OCOCH3), 2.99 (1H, m, 19-CH), 3.68(1H, d, J = 11.6 Hz, 23-CH2),
3.84 (1H, d, J = 11.6 Hz, 23-CH2), 4.07 (4H, m, 28-COOCH2(CH2)4CH2), 4.60 (1H, s, 29=CH2), 4.73
(1H, s, 29=CH2), 4.76 (1H, m, 3-CH), 7.48 (4H, m, 17-COO(CH2)6OCOC6H4COOH); HR-MS (ESI,
M+H) m/z: calcd for C48H69O10 805.4734, found 805.4739.
Butanedioic acid, 1-[4-[(3β,23-diacetoxylup-20(29)-en-28-oyl)oxy]butynyl] ester (6k). Butyne-1,4-diol
(77.0 mg, 0.9 mmol) and succinic anhydride (37.0 mg, 0.37 mmol); column chromatography with
petroleum ether/ethyl acetate/acetic acid = 50:50:1 (v:v:v). Yield: 50.0 mg (64%) as a yellow solid, mp
99 °C–101 °C; IR (KBr, cm−1) ν 3450, 2929, 2870, 1736, 1649, 1427, 1370, 1246, 1148, 1041, 971,
1
803, 641; H-NMR (CDCl3, 300 MHz) δ 0.80, 0.87, 0.90, 0.96, 1.68(3H each, s, 24, 25, 26, 27,
30-CH3), 2.01, 2.06 (3H each, s, 3 and 23-OCOCH3), 2.69 (4H, t, 17- 17-COOCH2C≡CCH2O
COCH2CH2COOH), 2.99 (1H, m, 19-CH), 3.68 (1H, d, J = 11.7 Hz, 23-CH2), 3.85 (1H, d, J = 11.7
Hz, 23-CH2), 4.69 (7H, m, 29=CH2, 3-CH and 17-COOCH2C≡CCH2); HR-MS (ESI, M+H) m/z: calcd
for C42H61O10 725.4108, found 725.4102.
Pentanedioic acid, 1-[4-[(3β,23-diacetoxylup-20(29)-en-28-oyl)oxy]butynyl] ester (6l). From
butyne-1,4-diol (77.0 mg, 0.9 mmol) and glutaric anhydride (42.0 mg, 0.37 mmo); column
chromatography with petroleum ether/ethyl acetate/acetic acid = 50:50:1 (v:v:v). Yield: 50.0 mg (67%)
as a yellow solid, mp 90 °C–92 °C; IR (KBr, cm−1) ν 3438, 2946, 2871, 1737, 1643, 1582, 1451, 1369,
1245, 1146, 1123, 1041, 973; 1H-NMR (DMSO, 300 MHz) δ 0.76, 0.83, 0.87, 0.94, 1.65 (3H each, s,
24, 25, 26, 27, 30-CH3), 1.96, 1.99 (3H each, s, 3 and 23-OCOCH3), 2.19 (4H, m, 17-COOCH2