Natural Product Research
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extract was then suspended in distilled water and partitioned successively with
petroleum ether, CHCl3, EtOAc and n-BuOH. The n-BuOH-soluble (250 g) fraction
was chromatographed over silica gel and eluted with CHCl3–MeOH gradient solvent
(5:1 ꢁ 0:5). Combination of similar fractions on the basis of thin-layer chromatog-
raphy analysis afforded five fractions. Fraction 3 was subjected to polyamide
chromatography and eluted with H2O–EtOH (3:1), and then to sephadex LH-20 by
elution with MeOH–H2O (1:9) to yield 1 (22 mg) and 2 (35 mg).
Compound 1. yellowish solid, its HCl/Mg and Molish reaction are positive, m.p.
20
172–174ꢂC. ½ꢀꢃD ꢀ 10.7ꢂ (c ¼ 0.056, H2O). UV ꢃmax (MeOH) nm: 225, 267 and 348.
IR (KBr) ꢄmax cmꢀ1: 3400, 1655, 1610, 1508, 1448, 1363, 1178, 1076 and 841. ESI–
MS, m/z (negativꢀe mode): 917.5 [M–H]ꢀꢀ and 953.2 [MþCl]ꢀ; ESI–MSꢀ2, m/z
(M0 ¼ 917.5[M–H] ): 755.2 [(M–H)ꢀ162] , 771.2 [(M–H) –146]ꢀ, 593.1 [(M–H)–
162-162]ꢀ, 575.2 [(M – H)–162-162-H2O]ꢀ and 285 [aglycone-H]ꢀ. ESI–MS, m/z (pos-
itive mode): 919.3 [MþH]þ, 941.3 [MþNa]þ and 957.3 [MþK]þ; ESI–MSþ2 m/z
(M0 ¼ 941.3 [MþNa]þ): 655.2 [MþNa – 286 (aglyþcone)]þ; ESI–MSþ3 m/þz
(M00 ¼ 655.2 [MþNa – 286]þ): 509.1 [MþNa – 286 – 146] , 493.1 [MþNa-286-162]
and 347.1 [MþNa – 286-162-162]þ. FAB-MS: m/z 941.2 [MþNa]þ and 963.3 [M–
Hþ2Na]þ. HR-ESI–MS, m/z: 919.2702 [MþH]þ (calculated for C39H51O25,
1
919.2720). H-NMR (CD3OD) ꢂ 8.02 (2H, d, J ¼ 8.4 Hz, H-20, 60), 6.91 (2H, d,
J ¼ 8.4 Hz, H-30, 50), 6.31 (1H, br.s, H-8), 6.13 (1H, br.s, H-6), glucose: ꢂ 5.34 (1H, d,
J ¼ 8.0 Hz, H-100), 3.61 (1H, H-200), 3.69 (1H, H-300), 3.32 (1H, H-400), 3.57 (1H, H-500),
3.73 (1H, H-6a00) and 3.34 (1H, H-6b00); galactose: ꢂ 4.71 (1H, d, J ¼ 7.6 Hz, H-1000),
3.83 (1H, H-2000), 3.73 (1H, H-3000), 3.88 (1H, H-4000), 3.51 (1H, H-5000) and 3.64 ꢀ 3.60
(2H, H-6a000 and H-6b000); glucose: ꢂ 4.65 (1H, d, J ¼ 7.2 Hz, H-10000), 3.29 (1H, H-20000),
3.35 (1H, H-30000), 3.31 (1H, H-40000), 3.42 (1H, H-50000), 3.85 (1H, H-6a0000) and 3.70
(1H, H-6b0000); rhamnose: ꢂ 4.49 (1H, br.s, H-100000), 3.57 (1H, H-200000), 3.44 (1H, H-
3
00000), 3.25 (1H, H-400000), 3.37 (1H, H-500000) and 1.09 (3H, d, J ¼ 6.0 Hz, H-600000).
13C-NMR (CD3OD) ꢂ 179.1 (C-4), 165.1 (C-7), 162.1 (C-5), 160.8 (C-40), 159.0 (C-9),
158.5 (C-2), 134.2 (C-3), 132.3 (C-20, 60), 122.9 (C-10), 116.4 (C-30, 50), 104.7 (C-10),
99.8 (C-6) and 96.0 (C-8); glucose: ꢂ 100.6 (C-100), 84.3 (C-200), 77.1 (C-300), 70.8
(C-400), 71.7 (C-500) and 68.0 (C-600); galactose: ꢂ 104.4 (C-1000), 82.5 (C-2000),
74.6 (C-3000), 69.6 (C-4000), 76.1 (C-5000) and 61.6 (C-6000); glucose: ꢂ 105.6 (C-10000),
75.9 (C-20000), 78.3 (C-30000), 70.8 (C-40000), 77.1 (C-50000) and 62.1 (C-60000); rhamnose: ꢂ
101.9 (C-100000), 71.1 (C-200000), 72.0 (C-300000), 73.5 (C-400000), 69.7 (C-500000) and 17.7 (C-600000).
Compound 2. yellowish solid, its HCl/Mg reaction and Molish reaction are
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positive, m.p. 152–154ꢂC; ½ꢀꢃD ꢀ 21.5ꢂ (c ¼ 0.065, MeOH). UV ꢃmax (MeOH) nm:
225, 267 and 348. IR (KBr) ꢄmax cmꢀ1: 3386, 1655, 1608, 1506, 1441, 1361, 1178,
1074, and 843. FAB-MS: m/z 795.1 [MþNa]þ and 817.2 [M–Hþ2Na]þ. H-NMR
1
(CD3OD) ꢂ 8.05 (2H, d, J ¼ 8.0 Hz, H-20, 60), 6.92 (2H, d, J ¼ 8.0 Hz, H-30, 50), 6.37
(1H, br.s, H-8), 6.17 (1H, br.s, H-6), 5.40 (1H, d, J ¼ 7.2 Hz, H-100), 4.72 (1H, d,
J ¼ 7.6 Hz, H-1000) and 4.64 (1H, d, J ¼ 7.6 Hz, H-10000). 13C-NMR (CD3OD) ꢂ 179.8
(C-4), 165.9 (C-7), 163.2 (C-5), 161.6 (C-40), 158.9 (C-9), 158.5 (C-2), 135.0 (C-3),
132.5 (C-20, 60), 122.8 (C-10), 116.4 (C-30, 50), 105.9 (C-10), 99.9 (C-6) and 94.7 (C-8),
glucose: ꢂ 101.0 (C-100), 85.1 (C-200), 78.9 (C-300), 70.5 (C-400), 78.4 (C-500) and; 62.4
(C-600); galactose: ꢂ 104.9 (C-1000), 83.5 (C-2000), 75.0 (C-3000), 69.9 (C-4000), 76.3 (C-5000)
and 62.0 (C-6000); glucose: ꢂ 106.4 (C-10000), 76.3 (C-20000), 77.6 (C-30000), 71.1 (C-40000),
77.4 (C-50000) and 62.4 (C-60000).