全 文 :中草药 Chinese Traditional and Herbal Drugs 第 43 卷 第 11 期 2012 年 11 月
• 2141 •
汉桃叶中苷类成分研究
张 桥 1, 2,沈 娟 1, 2,赵祎武 1, 2,王振中 1, 2,萧 伟 1, 2*
1. 江苏康缘药业股份有限公司,江苏 连云港 222001
2. 中药制药过程新技术国家重点实验室,江苏 连云港 222001
摘 要:目的 研究鹅掌属植物汉桃叶(广西鹅掌柴 Schefflera kwangsiensis)茎枝的苷类成分。方法 采用硅胶柱色谱、
凝胶柱色谱等方法进行分离纯化,通过光谱分析和理化性质鉴定化合物的结构。结果 从汉桃叶中分离得到 10 个化合物,
分别鉴定为野木瓜苷 C(1)、3-O-β-D-吡喃葡萄糖基常春藤苷元-28-O-α-L-吡喃鼠李糖基-(1→4)-β-D-吡喃葡萄糖基-(1→6)-β-
D-吡喃葡萄糖苷(2)、3-O-β-D-吡喃木糖基常春藤苷元-28-O-α-L-吡喃鼠李糖基-(1→4)-O-β-D-吡喃葡萄糖基-(1→6)-O-β-D-
吡喃葡萄糖苷(3)、刺楸皂苷 B(4)、3-O-β-D-吡喃木糖基-(1→3)-O-α-L-吡喃鼠李糖基-(1→2)-O-α-L-吡喃阿拉伯糖-常春藤
苷元-28-O-α-L-吡喃鼠李糖基-(1→4)-β-D-吡喃葡萄糖基-(1→6)-O-β-D-吡喃葡萄糖酯苷(5)、3-O-[O-吡喃阿拉伯糖基-(1→4)-
O-吡喃阿拉伯糖基-(1→3)-O-吡喃鼠李糖基-(1→2)-吡喃阿拉伯糖基]-齐墩果酸-O-吡喃鼠李糖基-(1→4)-O-β-吡喃葡萄糖基-(1→
6)-β-吡喃葡萄糖基酯(6)、刺楸皂苷 G(7)、3-O-[O-吡喃阿拉伯糖基-(1→4)-O-吡喃阿拉伯糖基-(1→3)-O-吡喃鼠李糖基-(1→2)-
吡喃阿拉伯糖基]常春藤苷(8)、3-O-β-D-吡喃葡萄糖基-(1→4)-O-β-D-吡喃木糖基 l-(1→3)-O-α-L-吡喃鼠李糖基-(1→2)-O-α-L-
吡喃阿拉伯糖-齐墩果酸-28-O-α-L-吡喃鼠李糖基-(1→4)-β-D-吡喃葡萄糖基-(1→6)-O-β-D-吡喃葡萄糖酯苷(9)、3-O-β-D-吡喃
葡萄糖基-(1→4)-O-β-D-吡喃木糖基 l-(1→3)-O-α-L-吡喃鼠李糖基-(1→2)-O-α-L-吡喃阿拉伯糖-齐墩果酸-28-O-α-L-吡喃鼠李糖
基-(1→4)-β-D-吡喃葡萄糖基-(1→6)-O-6-O-乙酰基-β-D-吡喃葡萄糖酯苷(10)。结论 化合物 1、4、5、7、9、10 为首次从
该植物中分离得到。
关键词:汉桃叶;鹅掌属;野木瓜苷 C;刺楸皂苷 B;刺楸皂苷 G
中图分类号:R284.1 文献标志码:A 文章编号:0253 - 2670(2012)11 - 2141 - 05
Study on glycosides from stems of Schefflera kwangsiensis
ZHANG Qiao1, 2, SHEN Juan1, 2, ZHAO Yi-wu1, 2, WANG Zhen-zhong1, 2, XIAO Wei1, 2
1. Jiangsu Kanion Pharmaceutical Co., Ltd., Lianyungang 222001, China
2. State Key Laboratory of New-Tech for Chinese Medicine Pharmaceutical Process, Lianyungang 222001, China
Key words: stems of Schefflera kwangsiensis Merr. ex Li; Schefflera J. R. & G. Forst; staunoside C; kalopanaxsaponin B; kalopanaxsaponin G
汉桃叶为五加科鹅掌属植物广西鹅掌柴
Schefflera kwangsiensis Merr. ex Li 的茎枝,又名鹅
掌藤、七叶莲。主产于广西、福建,其味微苦、温。
有祛风止痛、舒筋活络功能。用于三叉神经痛、神
经性头痛、坐骨神经痛、风湿关节痛及胃、肠、胆
道疼痛等症[1]。汉桃叶是中药痛安注射液中的主要
药味,其化学成分研究报道较少[2-3],为进一步研究
汉桃叶药效物质基础,本实验对其水溶性成分进行
研究,共分离得到 10 个苷类化合物,分别鉴定为野
木瓜苷 C(staunoside C,1)、3-O-β-D-吡喃葡萄糖
基常春藤苷元-28-O-α-L-吡喃鼠李糖基-(1→4)-β-D-
吡喃葡萄糖基-(1→6)-β-D-吡喃葡萄糖苷(tauroside
St-H1,2)、3-O-β-D-吡喃木糖基常春藤苷元-28-
O-α-L-吡喃鼠李糖基-(1→4)-O-β-D-吡喃葡萄糖基-
(1→6)-O-β-D-吡喃葡萄糖苷(saponins HCS-B,3)、
刺楸皂苷 B(kalopanaxsaponin B,4)、3-O-β-D-吡
喃木糖基 -(1→3)-O-α-L-吡喃鼠李糖基 -(1→2)-O-
α-L-吡喃阿拉伯糖-常春藤苷元-28-O-α-L-吡喃鼠李
糖基-(1→4)-β-D-吡喃葡萄糖基-(1→6)-O-β-D-吡喃葡
萄糖酯苷 [hederagenin 3-O-β-D-xylopyranosyl-(1→3)-
O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyrano-
side-28-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyra-
收稿日期:2012-01-05
基金项目:国家科技部“973 计划”资助项目(2010CB735604)
作者简介:张 桥,男,硕士,高级工程师,从事中药新药研究与开发。Tel: (0518)85521949 E-mail: dafuyuan_hubei@163.com
*通讯作者 萧 伟 Tel: (0518)85521956 E-mail: wzhzh-nj@tom.com
中草药 Chinese Traditional and Herbal Drugs 第 43 卷 第 11 期 2012 年 11 月
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nosyl-(1→6)-O-β-D-glucopyranosyl ester,5]、3-O-[O-
吡喃阿拉伯糖基-(1→4)-O-吡喃阿拉伯糖基-(1→3)-
O-吡喃鼠李糖基-(1→2)-吡喃阿拉伯糖基]-齐墩果
酸 -O-吡喃鼠李糖基 -(1→4)-O-β-吡喃葡萄糖基 -
(1→6)-β-吡喃葡萄糖基酯(scheffarboside D,6)、
刺楸皂苷 G(kalopanaxsaponin G,7)、3-O-[O-吡喃
阿拉伯糖基-(1→4)-O-吡喃阿拉伯糖基-(1→3)-O-吡
喃鼠李糖基 -(1→2)-吡喃阿拉伯糖基 ]常春藤苷
(scheffarboside C,8)、3-O-β-D-吡喃葡萄糖基 -
(1→4)-O-β-D-吡喃木糖基 l-(1→3)-O-α-L-吡喃鼠李
糖基-(1→2)-O-α-L-吡喃阿拉伯糖-齐墩果酸-28-O-
α-L- 吡喃鼠李糖基 -(1→4)-β-D- 吡喃葡萄糖基 -
(1→6)-O-β-D-吡喃葡萄糖酯苷 [oleanolicacid 3-O-β-
D-glucopyranosyl-(1→4)-O-β-D-xylopyranosyl-(1→3)-
O-α-L-rhamnopyranosy-(1→2)-O-α-L-arabinopyrano-
side-28-O-α-L-rhamnopyranosyl-(1→4)-O-β-D-gluco-
pyranosyl-(1→6)-O-β-D-glucopyranosyl ester,9]、3-
O-β-D-吡喃葡萄糖基 -(1→4)-O-β-D-吡喃木糖基
l-(1→3)-O-α-L-吡喃鼠李糖基-(1→2)-O-α-L-吡喃阿
拉伯糖-齐墩果酸-28-O-α-L-吡喃鼠李糖基-(1→4)-
β-D-吡喃葡萄糖基-(1→6)-O-6-O-乙酰基-β-D-吡喃
葡萄糖酯苷 [oleanolic acid-3-O-β-D-glucopyranosyl-
(1→4)-O-β-D-xylopyranosyl-(1→3)-O-α-L-rhamnopy-
ranosyl-(1→2)-O-α-L-arabinopyranoside-28-O-α-L-
rhamnopyrnosyl-(1→4)-O-6-O-acetyl-β-D-glucopyra-
nosyl-(1→6)-O-β-D-glucopyranosyl ester,10]。其中
化合物 1、4、5、7、9、10 为首次从该植物中分得。
1 仪器与材料
Finnigan LC—10Advp 高效液相色谱仪,电喷
雾离子化接口,三重四极杆质谱仪(Finnigan TSQ
Quantum Discovery MAX);Bruker AV—300 型核磁
共振仪(Bruker 公司);Agilent 1100 型制备 HPLC,
Zorbax SB C18(250 mm×9.4 mm,5 μm)柱。凝胶
Sephadex LH-20(Pharmacia 公司生产);D-101 型
大孔吸附树脂(天津农药总厂);R30030B 反相 C18
填料(40~63 μm,上海安普科学仪器有限公司);
柱色谱用硅胶(200~300 目)和硅胶 GF254 均为青
岛海洋化工厂生产。所用试剂均为分析纯或色谱纯。
汉桃叶药材由南京中医药大学吴启南教授鉴定为
广西鹅掌柴Schefflera kwangsiensis Merr. ex Li的茎枝。
2 提取与分离
汉桃叶茎枝 8 kg,水煎煮提取 2 次,每次 2 h,
提取液减压浓缩的浸膏经乙醇处理 2 次,第 1 次为
65%乙醇,第 2 次为 80%乙醇。醇沉浓缩液调节 pH
值至中性,加乙醇使含醇量达 85%,滤过,滤液减
压浓缩,真空干燥,得提取物 208 g。
取汉桃叶提取物 200 g 加 800 mL 水溶解,醋酸
乙酯提取(800 mL×3),合并提取液,减压浓缩得
浸膏 16 g;醋酸乙酯提取母液用水饱和正丁醇提取
(800 mL×3),合并提取液,减压浓缩得浸膏 43 g。
水饱和正丁醇提取后母液备用。
正丁醇提取物经硅胶柱色谱分离,氯仿-甲醇
(100∶0→10∶90)梯度洗脱,得 5 个组分(Fr. 1~
5)。Fr. 5 经硅胶柱色谱,氯仿-甲醇-水(4∶1∶0.1)
洗脱得到化合物 1(49 mg);Fr. 3 经硅胶柱色谱,
氯仿-甲醇-水(5∶1∶0.1→2∶1∶0.1)洗脱,再经
反相 C18 柱(30%~100%甲醇)、凝胶 Sephadex
LH-20 纯化得化合物 2(61 mg)、3(53 mg)、4(48
mg)、5(30 mg);Fr. 4 经硅胶柱色谱,氯仿-甲醇-
水(5∶1∶0.1→2∶1∶0.1)梯度洗脱,再经反相
C18 柱(30%~100%甲醇)、凝胶 Sephadex LH-20
纯化得化合物 6(40 mg)、7(57 mg)、8(68 mg)。
水饱和正丁醇提取后母液通过 D-101 大孔树
脂,分别用水、30%、80%乙醇洗脱,收集 80%乙
醇洗脱部分浓缩除醇,水溶解,经 C18柱,水-甲醇
梯度洗脱,收集甲醇洗脱部分;经凝胶 Sephadex
LH-20 纯化,收集 1~4 流分;再经硅胶柱色谱,氯
仿-甲醇-水(65∶35∶10)洗脱,100 mL 为 1 流分,
合并 19~35 流分,浓缩,水溶解,经高效液相色谱
制备,得化合物 9(152 mg)、10(75 mg)。
3 结构鉴定
化合物 1:白色粉末。ESI-MS m/z: 1 215 [2M+
Na]+, 619 [M+Na]+。1H-NMR (300 MHz, pyridine-
d5) δ: 7.26 (2H, s, H-2′, 6′), 7.23 (2H, s, H-2″, 6″),
5.43 (1H, d, J = 7.8 Hz, Glc-H-1), 3.85 (6H, s, 3′,
5′-OCH3), 3.76 (6H, s, 3″, 5″-OCH3);13C-NMR (75
MHz, pyridine-d5) δ: 98.6 (C-1), 88.1 (C-2), 70.9
(C-4), 60.4 (C-5), 87.7 (C-6), 74.7 (C-8), 127.2 (C-1′),
131.4 (C-1″), 107.7 (C-2′), 104.8 (C-2″), 148.0 (C-3′),
148.5 (C-3″), 137.3 (C-4′), 137.3 (C-4″), 148.0 (C-5′),
148.8 (C-5″), 107.7 (C-6′), 104.9 (C-6″), 56.3 (3′,
5′-OCH3), 56.3 (3″, 5″-OCH3), 100.4 (Glc-C-1), 74.9
(Glc-C-2), 79.0 (Glc-C-3), 71.5 (Glc-C-4), 78.8
(Glc-C-5), 62.7 (Glc-C-6)。以上数据与文献报道一
致[4],故鉴定化合物 1 为野木瓜苷 C。
化合物 2:白色粉末。ESI-MS m/z: 1 127 [M+
中草药 Chinese Traditional and Herbal Drugs 第 43 卷 第 11 期 2012 年 11 月
• 2143 •
Na]+, 1 103 [M-H]−。1H-NMR (300 MHz, pyridine-
d5) δ: 6.21 (1H, d, J = 9.0 Hz, 28-O-Glc-H-1), 5.11
(1H, d, J = 9.0 Hz, 3-O-Glc-H-1), 0.84~1.16 (18H, s,
6×-CH3);13C-NMR (75 MHz, pyridine-d5) δ: 38.6
(C-1), 26.0 (C-2), 82.2 (C-3), 43.4 (C-4), 47.6 (C-5),
18.2 (C-6), 32.4 (C-7), 39.9 (C-8), 48.1 (C-9), 36.9
(C-10), 23.3 (C-11), 122.8 (C-12), 144.1 (C-13), 42.1
(C-14), 28.2 (C-15), 23.8 (C-16), 46.1 (C-17), 41.6
(C-18), 46.9 (C-19), 30.7 (C-20), 33.9 (C-21), 32.7
(C-22), 64.7 (C-23), 13.6 (C-24), 16.2 (C-25), 17.5
(C-26), 25.8 (C-27), 176.5 (C-28), 33.0 (C-29), 23.6
(C-30), 105.8 (3-O-Glc-C-1), 75.8 (3-O-Glc-C-2),
78.6 (3-O-Glc-C-3), 71.5 (3-O-Glc-C-4), 78.1 (3-O-
Glc-C-5), 62.7 (3-O-Glc-C-6), 95.6 (28-O-Glc-C-1),
73.9 (28-O-Glc-C-2), 78.3 (28-O-Glc-C-3), 70.7 (28-
O-Glc-C-4), 78.0 (28-O-Glc-C-5), 69.1 (28-O-Glc-
C-6), 104.8 (Glc′-C-1), 75.3 (Glc′-C-2), 76.4 (Glc′-C-3),
78.3 (Glc′-C-4), 77.1 (Glc′-C-5), 61.2 (Glc′-C-6),
102.7 (Rha-C-1), 72.5 (Rha-C-2), 72.7 (Rha-C-3),
73.8 (Rha-C-4), 70.3 (Rha-C-5), 18.5 (Rha-C-6)。以上
数据与文献报道一致[5],故鉴定化合物2为3-O-β-D-
吡喃葡萄糖基常春藤苷元-28-O-α-L-吡喃鼠李糖基-
(1→4)-β-D-吡喃葡萄糖基-(1→6)-β-D-吡喃葡萄糖苷。
化合物 3:白色粉末。ESI-MS m/z: 1 097 [M+
Na]+, 1 073 [M-H]−。1H-NMR (300 MHz, pyridine-d5)
δ: 6.23 (1H, d, J = 9.0 Hz, 28-O-Glc-H-1), 4.97 (1H,
d, J = 9.0 Hz, Glc′-H-1), 0.86~1.15 (18H, s, 6×
-CH3);13C-NMR (75 MHz, pyridine-d5) δ: 38.7 (C-1),
26.0 (C-2), 81.8 (C-3), 43.4 (C-4), 47.5 (C-5), 18.1
(C-6), 32.7 (C-7), 39.8 (C-8), 48.1 (C-9), 36.9 (C-10),
23.8 (C-11), 122.8 (C-12), 144.0 (C-13), 42.0 (C-14),
28.2 (C-15), 23.3 (C-16), 47.5 (C-17), 41.6 (C-18),
46.1 (C-19), 30.7 (C-20), 33.9 (C-21), 32.4 (C-22),
64.3 (C-23), 13.6 (C-24), 16.2 (C-25), 17.5 (C-26),
26.0 (C-27), 176.5 (C-28), 33.0 (C-29), 23.6 (C-30),
106.7 (3-O-Xyl-C-1), 75.3 (3-O-Xyl-C-2), 78.0 (3-O-
Xyl-C-3), 70.2 (3-O-Xyl-C-4), 67.0 (3-O-Xyl-C-5),
95.6 (28-O-Glc-C-1), 74.0 (28-O-Glc-C-2), 78.7 (28-
O-Glc-C-3), 70.7 (28-O-Glc-C-4), 78.1 (28-O-Glc-C-5),
69.1 (28-O-Glc-C-6), 104.8 (Glc′-C-1), 75.3 (Glc′-C-2),
76.4 (Glc′-C-3), 78.7 (Glc′-C-4), 77.1 (Glc′-C-5), 61.2
(Glc′-C-6), 102.7 (Rha-C-1), 72.5 (Rha-C-2), 72.7
(Rha-C-3), 73.8 (Rha-C-4), 70.7 (Rha-C-5), 18.5
(Rha-C-6)。以上数据与文献报道一致[6],故鉴定化
合物 3 为 3-O-β-D-吡喃木糖基常春藤苷元-28-O-α-
L-吡喃鼠李糖基 -(1→4)-O-β-D-吡喃葡萄糖基 -
(1→6)-O-β-D-吡喃葡萄糖苷。
化合物 4:白色粉末。ESI-MS m/z: 1 244 [M+
Na]+, 1 220 [M-H]−。1H-NMR (300 MHz, pyridine-d5)
δ: 6.23 (1H, d, J = 9.0 Hz, 28-O-Glc-H-1), 0.84~1.14
(18H, s, 6×-CH3);13C-NMR (75 MHz, pyridine-d5) δ:
39.0 (C-1), 26.1 (C-2), 80.9 (C-3), 43.4 (C-4), 47.6
(C-5), 18.1 (C-6), 32.4 (C-7), 39.8 (C-8), 48.1 (C-9),
36.8 (C-10), 23.7 (C-11), 123.0 (C-12), 144.0 (C-13),
42.0 (C-14), 28.2 (C-15), 23.3 (C-16), 46.9 (C-17),
41.6 (C-18), 46.1 (C-19), 30.7 (C-20), 34.0 (C-21),
32.7 (C-22), 63.8 (C-23), 13.9 (C-24), 16.1 (C-25),
17.5 (C-26), 26.1 (C-27), 176.5 (C-28), 33.0 (C-29),
23.7 (C-30), 104.3 (3-O-Ara-C-1), 75.7 (3-O-Ara-
C-2), 74.6 (3-O-Ara-C-3), 69.5 (3-O-Ara-C-4), 65.9
(3-O-Ara-C-5), 101.5 (Rha-C-1), 72.3 (Rha-C-2), 72.5
(Rha-C-3), 74.1 (Rha-C-4), 69.6 (Rha-C-5), 18.5
(Rha-C-6), 95.6 (28-O-Glc-C-1), 75.3 (28-O-Glc-C-
2), 78.4 (28-O-Glc-C-3), 70.2 (28-O-Glc-C-4), 76.4
(28-O-Glc-C-5), 70.9 (28-O-Glc-C-6), 104.8 (Glc′-C-
1), 73.9 (Glc′-C-2), 78.1 (Glc′-C-3), 78.6 (Glc′-C-4),
77.1 (Glc′-C-5), 61.2 (Glc′-C-6), 102.6 (Rha-C-1),
72.5 (Rha-C-2), 72.5 (Rha-C-3), 74.0 (Rha-C-4), 69.1
(Rha-C-5), 18.4 (Rha-C-6)。以上数据与文献报道一
致[7],故鉴定化合物 4 为刺楸皂苷 B。
化合物 5:白色粉末。ESI-MS m/z: 1 375 [M+
Na]+, 1 351 [M-H]−。1H-NMR (300 MHz, pyridine-
d5) δ: 6.21 (1H, d, J = 9.0 Hz, 28-O-Glc-H-1), 0.84~
1.16 (18H, s, 6×-CH3);13C-NMR (75 MHz, pyridine-
d5) δ: 39.0 (C-1), 26.3 (C-2), 81.0 (C-3), 43.5 (C-4),
47.5 (C-5), 18.0 (C-6), 32.7 (C-7), 39.8 (C-8), 48.1
(C-9), 36.8 (C-10), 23.8 (C-11), 122.8 (C-12), 144.0
(C-13), 42.0 (C-14), 28.2 (C-15), 23.3 (C-16), 46.9
(C-17), 41.6 (C-18), 46.1 (C-19), 30.7 (C-20), 33.9
(C-21), 32.4 (C-22), 63.9 (C-23), 14.2 (C-24), 16.1
(C-25), 17.4 (C-26), 26.0 (C-27), 176.5 (C-28), 33.0
(C-29), 23.6 (C-30), 104.8 (3-O-Ara-C-1), 75.3
(3-O-Ara-C-2), 75.3 (3-O-Ara-C-3), 69.5 (3-O-Ara-
C-4), 66.3 (3-O-Ara-C-5), 101.2 (Rha-C-1), 71.9
(Rha-C-2), 82.8 (Rha-C-3), 72.9 (Rha-C-4), 69.8
(Rha-C-5), 18.5 (Rha-C-6), 107.5 (Xyl-C-1), 75.6
中草药 Chinese Traditional and Herbal Drugs 第 43 卷 第 11 期 2012 年 11 月
• 2144 •
(Xyl-C-2), 78.1 (Xyl-C-3), 71.0 (Xyl-C-4), 67.3
(Xyl-C-5), 95.6 (28-O-Glc-C-1), 73.8 (28-O-Glc-C-2),
78.6 (28-O-Glc-C-3), 70.7 (28-O-Glc-C-4), 77.9
(28-O-Glc-C-5), 69.1 (28-O-Glc-C-6), 104.8 (Glc′-C-
1), 75.3 (Glc′-C-2), 76.4 (Glc′-C-3), 78.4 (Glc′-C-4),
77.1 (Glc′-C-5), 61.2 (Glc′-C-6), 102.6 (Rha-C-1),
72.5 (Rha-C-2), 72.7 (Rha-C-3), 73.9 (Rha-C-4), 70.2
(Rha-C-5), 18.4 (Rha-C-6)。以上数据与文献报道一
致[8],故鉴定化合物 5 为 3-O-β-D-吡喃木糖基-
(1→3)-O-α-L-吡喃鼠李糖基-(1→2)-O-α-L-吡喃阿拉
伯糖-常春藤苷元-28-O-α-L-吡喃鼠李糖基-(1→4)-
β-D-吡喃葡萄糖基-(1→6)-O-β-D-吡喃葡萄糖酯苷。
化合物 6:白色粉末。ESI-MS m/z: [M+H]+
1 491。1H-NMR (300 MHz, pyridine-d5) δ: 6.1 (1H,
brs, Rha-H-1), 0.76~1.16 (18H, s, 6×-CH3);13C-
NMR (75 MHz, pyridine-d5) δ: 38.5 (C-1), 26.1 (C-2),
88.4 (C-3), 39.4 (C-4), 55.5 (C-5), 17.9 (C-6), 31.9
(C-7), 39.1 (C-8), 47.6 (C-9), 36.5 (C-10), 23.2
(C-11), 122.4 (C-12), 143.8 (C-13), 41.7 (C-14), 27.7
(C-15), 22.8 (C-16), 45.8 (C-17), 41.2 (C-18), 45.8
(C-19), 30.3 (C-20), 33.5 (C-21), 32.7 (C-22), 27.7
(C-23), 16.7 (C-24), 15.2 (C-25), 17.0 (C-26), 25.6
(C-27), 176.5 (C-28), 32.7 (C-29), 23.2 (C-30), 104.6
(3-O-Ara-C-1), 75.0 (3-O-Ara-C-2), 73.5 (3-O-Ara-C-
3), 68.6 (3-O-Ara-C-4), 64.7 (3-O-Ara-C-5), 100.8
(Rha-C-1), 71.1 (Rha-C-2), 81.6 (Rha-C-3), 72.0
(Rha-C-4), 69.2 (Rha-C-5), 17.9 (Rha-C-6), 106.0
(Ara′-C-1), 74.5 (Ara′-C-2), 75.8 (Ara′-C-3), 76.0
(Ara′-C-4), 64.0 (Ara′-C-5), 102.6 (Ara″-C-1), 70.9
(Ara″-C-2), 73.5 (Ara″-C-3), 68.6 (Ara″-C-4), 66.6
(Ara″-C-5), 95.1 (28-O-Glc-C-1), 73.1 (28-O-Glc-
C-2), 77.9 (28-O-Glc-C-3), 69.9 (28-O-Glc-C-4), 77.5
(28-O-Glc-C-5), 68.6 (28-O-Glc-C-6), 104.6 (Glc′-C-1),
74.5 (Glc′-C-2), 76.0 (Glc′-C-3), 77.9 (Glc′-C-4), 76.3
(Glc′-C-5), 60.6 (Glc′-C-6), 102.1 (Rha-C-1), 71.7
(Rha-C-2), 72.0 (Rha-C-3), 73.5 (Rha-C-4), 69.9 (Rha-
C-5), 17.9 (Rha-C-6)。以上数据与文献报道一致[9],故
鉴定化合物 6 为 3-O-[O-吡喃阿拉伯糖基-(1→4)-O-吡
喃阿拉伯糖基-(1→3)-O-吡喃鼠李糖基-(1→2)-吡喃阿
拉伯糖基]-齐墩果酸-O-吡喃鼠李糖基-(1→4)-O-β-吡
喃葡萄糖基-(1→6)-β-吡喃葡萄糖基酯。
化合物 7:白色粉末。ESI-MS m/z: 965 [M+
Na]+, 941 [M-H]−。提示相对分子质量为 942。
1H-NMR (300 MHz, pyridine-d5) δ: 6.25 (1H, d, J =
7.8 Hz, 28-O-Glc-H-1), 6.0 (1H, s, Rha-H-1), 5.41
(1H, s, H-12), 4.98 (1H, d, J = 9.0 Hz, Glc-H-1), 1.68
(3H, d, J = 5.4 Hz, Rha-H-6), 0.99~1.33 (18H, s,
6×-CH3);13C-NMR (75 MHz, pyridine-d5) δ: 38.8
(C-1), 27.6 (C-2), 73.8 (C-3), 42.9 (C-4), 48.4 (C-5),
18.5 (C-6), 32.4 (C-7), 39.8 (C-8), 48.1 (C-9), 37.2
(C-10), 23.3 (C-11), 122.9 (C-12), 144.1 (C-13), 42.1
(C-14), 28.2 (C-15), 23.8 (C-16), 47.0 (C-17), 41.6
(C-18), 46.1 (C-19), 30.7 (C-20), 33.9 (C-21), 33.0
(C-22), 67.6 (C-23), 13.1 (C-24), 16.0 (C-25), 17.5
(C-26), 26.0 (C-27), 176.5 (C-28), 33.0 (C-29), 23.8
(C-30), 95.6 (28-O-Glc-C-1), 73.8 (28-O-Glc-C-2),
78.1 (28-O-Glc-C-3), 70.7 (28-O-Glc-C-4), 78.1
(28-O-Glc-C-5), 69.1 (28-O-Glc-C-6), 104.8 (Glc′-C-
1), 75.3 (Glc′-C-2), 76.4 (Glc′-C-3), 78.7 (Glc′-C-4),
77.1 (Glc′-C-5), 61.2 (Glc′-C-6), 102.7 (Ara-C-1),
72.5 (Ara-C-2), 72.7 (Ara-C-3), 74.0 (Ara-C-4), 70.3
(Ara-C-5), 18.5 (Ara-C-6)。以上数据与文献报道一
致[10],故鉴定化合物 7 为刺楸皂苷 G。
化合物 8:白色粉末。ESI-MS m/z: 1 037 [M+
Na]+, 1 013 [M-H]−。提示相对分子质量为 1 014。
1H-NMR (300 MHz, pyridine-d5) δ: 6.28 (1H, brs,
H-1″), 5.44 (1H, brs, H-12), 1.24~1.31 (9H, s,
3×-CH3), 1.1 (3H, s), 0.98 (3H, s), 0.90 (3H, s);13C-
NMR (75 MHz, pyridine-d5) δ: 38.9 (C-1), 26.3 (C-2),
81.0 (C-3), 43.5 (C-4), 47.5 (C-5), 18.0 (C-6), 32.7
(C-7), 39.6 (C-8), 48.1 (C-9), 36.8 (C-10), 23.5
(C-11), 122.5 (C-12), 144.7 (C-13), 42.0 (C-14), 28.2
(C-15), 23.7 (C-16), 46.5 (C-17), 41.8 (C-18), 46.3
(C-19), 30.8 (C-20) 34.1 (C-21), 33.2 (C-22), 63.8
(C-23), 14.0 (C-24), 16.0 (C-25), 17.3 (C-26), 26.1
(C-27), 180.2 (C-28), 33.2 (C-29), 23.7 (C-30), 104.6
(3-O-Ara-C-1), 75.1 (3-O-Ara-C-2), 75.1 (3-O-Ara-C-3),
69.3 (3-O-Ara-C-4), 66.3 (3-O-Ara-C-5), 101.3 (Rha-C-
1) 71.8 (Rha-C-2), 82.8 (Rha-C-3), 72.8 (Rha-C-4), 69.4
(Rha-C-5), 18.3 (Rha-C-6), 107.0 (Ara′-C-1), 75.4
(Ara′-C-2), 75.8 (Ara′-C-3), 76.0 (Ara′-C-4), 64.7
(Ara′-C-5), 103.5 (Ara″-C-1), 71.2 (Ara″-C-2), 74.2
(Ara″-C-3), 69.7 (Ara″-C-4), 67.2 (Ara″-C-5)。以上数据
与文献报道一致[9],故鉴定化合物 8 为 3-O-[O-吡喃阿
拉伯糖基-(1→4)-O-吡喃阿拉伯糖基-(1→3)-O-吡喃鼠
李糖基-(1→2)-吡喃阿拉伯糖基] 常春藤苷。
中草药 Chinese Traditional and Herbal Drugs 第 43 卷 第 11 期 2012 年 11 月
• 2145 •
化合物 9:白色粉末。ESI-MS m/z: 1 499 [M+
H]+。1H-NMR (300 MHz, pyridine-d5) δ: 6.21 (1H, d,
J = 7.8 Hz, 28-O-Glc-H-1), 0.83~1.15 (18H, s,
6×-CH3);13C-NMR (75 MHz, pyridine-d5) δ: 39.0
(C-1), 26.3 (C-2), 81.0 (C-3), 43.5 (C-4), 47.6 (C-5),
18.1 (C-6), 32.7 (C-7), 39.8 (C-8), 48.1 (C-9), 36.8
(C-10), 23.8 (C-11), 122.8 (C-12), 144.0 (C-13), 42.0
(C-14), 28.2 (C-15), 23.3 (C-16), 46.9 (C-17), 41.6
(C-18), 46.1 (C-19), 30.6 (C-20), 33.9 (C-21), 32.4
(C-22), 63.9 (C-23), 14.0 (C-24), 16.1 (C-25), 17.5
(C-26), 26.3 (C-27), 176.5 (C-28), 33.0 (C-29), 23.8
(C-30), 104.5 (3-O-Ara-C-1), 75.4 (3-O-Ara-C-2),
74.9 (3-O-Ara-C-3), 69.5 (3-O-Ara-C-4), 66.0 (3-O-
Ara-C-5), 101.2 (Rha-C-1), 71.8 (Rha-C-2), 82.8
(Rha-C-3), 72.8 (Rha-C-4), 69.5 (Rha-C-5), 18.4
(Rha-C-6), 107.0 (Xyl-C-1), 75.4 (Xyl-C-2), 76.0
(Xyl-C-3), 77.9 (Xyl-C-4), 64.7 (Xyl-C-5), 103.5
(Glc-C-1), 74.2 (Glc-C-2), 78.2 (Glc-C-3), 71.8
(Glc-C-4), 78.6 (Glc-C-5), 61.2 (Glc-C-6), 95.5 (28-O-
Glc-C-1), 73.8 (28-O-Glc-C-2), 78.6 (28-O-Glc-C-3),
70.7 (28-O-Glc-C-4), 77.9 (28-O-Glc-C-5), 69.1 (28-
O-Glc-C-6), 104.7 (Glc′-C-1), 75.2 (Glc′-C-2), 76.4
(Glc′-C-3), 78.6 (Glc′-C-4), 77.0 (Glc′-C-5), 61.2
(Glc′-C-6), 102.6 (Rha-C-1), 72.4 (Rha-C-2), 72.6
(Rha-C-3), 73.8 (Rha-C-4), 70.2 (Rha-C-5), 18.4
(Rha-C-6)。以上数据与文献报道一致[8],故鉴定化合
物 9 为 3-O-β-D-吡喃葡萄糖基-(1→4)-O-β-D-吡喃木
糖基 l-(1→3)-O-α-L-吡喃鼠李糖基-(1→2)-O-α-L-吡喃
阿拉伯糖-齐墩果酸-28-O-α-L-吡喃鼠李糖基-(1→4)-
β-D-吡喃葡萄糖基-(1→6)-O-β-D-吡喃葡萄糖酯苷。
化合物 10:白色粉末。ESI-MS m/z: 1 541 [M+
H]+。1H-NMR (300 MHz, pyridine-d5) δ: 6.20 (1H, d,
J = 7.8 Hz, 28-O-Glc-H-1), 0.86~1.28 (21H, s,
7×-CH3);13C-NMR (75 MHz, pyridine-d5) δ: 38.9
(C-1), 26.6 (C-2), 88.7 (C-3), 39.5 (C-4), 56.0 (C-5),
18.5 (C-6), 33.3 (C-7), 39.9 (C-8), 48.1 (C-9), 37.0
(C-10), 23.7 (C-11), 122.9 (C-12), 144.1 (C-13), 42.1
(C-14), 28.3 (C-15), 23.3 (C-16), 47.0 (C-17), 41.6
(C-18), 46.2 (C-19), 30.7 (C-20), 34.0 (C-21), 32.5
(C-22), 28.3 (C-23), 17.2 (C-24), 15.6 (C-25), 17.5
(C-26), 26.2 (C-27), 176.5 (C-28), 33.1 (C-29), 23.7
(C-30), 105.1 (3-O-Ara-C-1), 75.5 (3-O-Ara-C-2),
74.4 (3-O-Ara-C-3), 69.2 (3-O-Ara-C-4), 65.4 (3-O-
Ara-C-5), 101.4 (Rha-C-1), 71.9 (Rha-C-2), 83.0
(Rha-C-3), 72.9 (Rha-C-4), 69.6 (Rha-C-5), 18.5
(Rha-C-6), 107.1 (Xyl-C-1), 75.3 (Xyl-C-2), 76.2
(Xyl-C-3), 78.0 (Xyl-C-4), 64.9 (Xyl-C-5), 103.7
(Glc-C-1), 74.4 (Glc-C-2), 78.3 (Glc-C-3), 71.9
(Glc-C-4), 78.7 (Glc-C-5), 61.3 (Glc-C-6), 95.6
(28-O-Glc-C-1), 73.9 (28-O-Glc-C-2), 78.7 (28-O-
Glc-C-3), 70.8 (28-O-Glc-C-4), 78.0 (28-O-Glc-C-5),
69.3 (28-O-Glc-C-6), 104.8 (Glc′-C-1), 75.1 (Glc′-C-2),
76.5 (Glc′-C-3), 78.7 (Glc′-C-4), 73.9 (Glc′-C-5), 61.3
(Glc′-C-6), 20.7 (-OAc), 170.8 (-C=O), 102.7 (Rha-C-
1), 72.6 (Rha-C-2), 72.8 (Rha-C-3), 74.0 (Rha-C-4),
70.8 (Rha-C-5), 18.5 (Rha-C-6)。以上数据与文献报
道一致[8],故鉴定化合物 10 为 3-O-β-D-吡喃葡萄糖
基-(1→4)-O-β-D-吡喃木糖基 l-(1→3)-O-α-L-吡喃鼠
李糖基-(1→2)-O-α-L-吡喃阿拉伯糖-齐墩果酸-28-
O-α-L-吡喃鼠李糖基 -(1→4)-β-D-吡喃葡萄糖基 -
(1→6)-O-6-O-乙酰基-β-D-吡喃葡萄糖酯苷。
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