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Chemical constituents of Aganosma marginata

香花藤化学成分的研究



全 文 :中草药 Chinese Traditional and Herbal Drugs 第 46卷 第 12期 2015年 6月

·1742·
香花藤化学成分的研究
汪 琼,徐永艳*
西南林业大学园林学院,云南 昆明 650224
摘 要:目的 对香花藤 Aganosma marginata 全株化学成分进行研究。方法 采用硅胶色谱柱、Sephadex LH-20 色谱柱、
MCI 色谱柱等方法进行分离纯化,根据化合物的理化性质和波谱数据鉴定其结构。结果 从香花藤 70%乙醇提取物中分离
得到 23 个化合物,分别鉴定为 periseoside C(1)、3-O-β-D-吡喃葡萄糖-3β,15α-二羟基孕甾-5-烯-20-酮(2)、3β,20α-二羟基-5-
烯-孕甾(3)、24-methylstigmast-5-en-3-ol(4)、29-norcycloart-23-ene-3,25-diol(5)、29-norcycloartan-3-ol(6)、京尼平苷酸
(7)、丁香树脂醇(8)、丁香脂素-4,4′-O-双-β-D-吡喃葡萄糖苷(9)、丁香酸-4-O-β-D-葡萄糖苷(10)、水杨酸(11)、东莨菪
内酯(12)、壬二酸(13)、3-O-[β-D-xylopyranosyl]-(1→4)-β-D-allopyranoside-14-hydroxycard-20(22)-enolide(14)、bis (2-ethylhexyl)
phthalate(15)、山柰酚 3-O-α-L-吡喃鼠李糖-(1→4)-α-L-吡喃葡萄糖苷(16)、山柰酚 3-O-α-L-吡喃葡萄糖-(1→2)-β-D-吡喃葡
萄糖苷(17)、山柰酚 3-O-α-L-吡喃鼠李糖-(1→4)-[α-L-吡喃鼠李糖-(1→4)]-β-D-吡喃葡萄糖苷(18)、山柰酚 3-O-α-L-吡喃鼠
李糖-(1→4)-[β-D-吡喃葡萄糖-(1→4)]-β-D-吡喃葡萄糖苷(19)、二十六碳酸-1-甘油酯(20)、5,8,12-trihydroxy-9-octadecenoic
acid(21)、(2S,3S,4R)-phytosphingosine(22)、水粉覃素(23)。结论 所有化合物均为首次从该属植物中分离得到。
关键词:香花藤;京尼平苷酸;丁香树脂醇;丁香脂素-4,4′-O-双-β-D-吡喃葡萄糖苷;东莨菪内酯;山柰酚 3-O-α-L-吡喃鼠
李糖-(1→4)-α-L-吡喃葡萄糖苷
中图分类号:R284.1 文献标志码:A 文章编号:0253 - 2670(2015)12 - 1742 - 07
DOI: 10.7501/j.issn.0253-2670.2015.12.006
Chemical constituents of Aganosma marginata
WANG Qiong, XU Yong-yan
Landscape Architecture College of Southwest Forestry University, Kunming 650224, China
Abstract: Objective To investigate the chemical constituents from Aganosma marginata and to provide the material basis for the
quality control. Methods The chemical constituents were separated and purified by silica gel Sephadex LH-20, MCI. Their structures
were determined by physicochemical properties and spectral data analyses. Results Twenty three compounds were isolated from A.
marginata and identified as: periseoside C (1), 3-O-β-D-glucopyranosyl-3β,15α-dihydroxypregn-5-en-20-one (2), 3β,20α-dihydroxy-
5-en-pregane (3), 28-methylstigmast-5-en-3-ol (4), 29-norcycloart-23-ene-3,25-diol (5), 29-norcycloartan-3-ol (6), geniposidic acid
(7), syringaresinol (8), syringaresinol-4,4′-O-bis-β-D-glucopyranoside (9), syringic acid 4-O-β-D-glucopyranoside (10), salicylic acid
(11), scopoletin (12), azelaic acid (13), 3-O-[β-D-xylopyranosyl]-(1→4)-β-D-allopyranoside-14-hydroxycard-20 (22)-enolide (14), bis
(2-ethylhexyl) phthalate (15), kaempferol-3-O-α-L-rhamnopyranosyl-(l→4)-α-L-glucopyranoside (16), kaempferol-3-O-α-L-
glucopyranoside-(1→2)-β-D-glucopyranoside (17), kaempferol-3-O-α-L-rhamnopyranosyl-(1→4)-[α-L-rhamnopyranosyl (1→4)]-β-
D-glucopyranoside (18), kaempferol-3-O-α-L-rhamnopyranosyl-(1→4)-[β-D-glucopyranosyl-(1→4)]-β-D-glucopyranoside (19),
hexacosanoicacid 1-carbonate (20), 5,8,12-trihydroxy-9-octadecenoic acid (21), (2S,3S,4R)-phytosphingosine (22), and nebularine
(23). Conclusion All the compounds are obtained from plants of Aganosma G. Don for the first time.
Key words: Aganosma marginata (Roxb.) G. Don; geniposidic acid; syringaresinol; syringaresinol-4,4′-O-bis-β-D-glucopyranoside;
scopoletin; 3-O-α-L-rhamnopyranosyl-(l→4)-α-L-glucopyranoside

夹竹桃科(Apocynaceae)香花藤属 Aganosma G.
Don 有 15 种,分布于亚洲热带地区,该属植物我国
有 5 个种和 3 个变种,产于南部和西南部。香花藤
Aganosma marginata (Roxb.) G. Don 的根、叶味淡、

收稿日期:2014-12-26
基金项目:西南林业大学园林植物与观赏园艺重点实验室资助项目
作者简介:汪 琼(1974—),女,博士,副教授,研究方向为天然药物化学。Tel: (0871)63863023
*通信作者 徐永艳,女,副教授,硕士生导师,主要从事园林植物研究。Tel: (0871)63863023 E-mail: millmeng@sohu.com
中草药 Chinese Traditional and Herbal Drugs 第 46卷 第 12期 2015年 6月

·1743·
平,能利水消肿,用于治疗水肿[1]。根据细谷孝博
对植物提取物(KKP)的筛选,发现香花藤的提取
物能干扰 Gli-1 蛋白表达,抑制其转录活性[2]。根据
Prayong 等[3]对香花藤细胞活性筛选,发现 50%乙醇
香花藤茎提取物对恶性肝癌具有中度细胞毒性和较
小的选择性。根据查阅文献,本属植物的研究资料
缺乏,仅就其植物分类方面进行一定的研究,而对
其化学成分的研究从未见报道,香花藤化学成分的
研究可为今后该属植物的研究提供一定的借鉴作
用。本实验从香花藤全株 70%乙醇提取物中分离得
到 23 个化合物,分别鉴定为 periseoside C(1)、
3-O-β-D-吡喃葡萄糖-3β,15α-二羟基孕甾-5-烯-20-
酮(3-O-β-D-glucopyranosyl-3β,15α-dihydroxypregn-
5-en-20-one,2)、3β,20α-二羟基-5-烯-孕甾(3β,20α-
dihydroxy-5-en-pregane,3)、24-methyl-stigmast-5-
en-3-ol(4)、29-norcycloart-23-ene-3,25-diol(5)、29-nor-
cycloartan-3-ol(6)、京尼平苷酸(geniposidic acid,
7)、丁香树脂醇(syringaresinol,8)、丁香脂素-4,4′-O-
双 -β-D-吡喃葡萄糖苷( syringaresinol-4,4′-O-bis-
β-D-glucopyranoside,9)、丁香酸-4-O-β-D-葡萄糖
苷(syringic acid 4-O-β-D-glucopyranoside,10)、水
杨酸(salicylic acid,11)、东莨菪内酯(scopoletin,
12)、壬二酸(azelaic acid,13)、3-O-[β-D-xylopyra-
nosyl]-(1→4)-β-D-allopyranoside-14-hydroxycard-
20(22)-enolide(14)、bis (2-ethylhexyl) phthalate
(15)、山柰酚 3-O-α-L-吡喃鼠李糖-(1→4)-α-L-吡喃
葡萄糖苷 [kaempferol-3-O-α-L-rhamnopyranosyl-(l→
4)-α-L-glucopyranoside,16]、山柰酚 3-O-α-L-吡喃
葡萄糖-(1→2)-β-D-吡喃葡萄糖苷(kaempferol-3-O-
α-L-glucopyranoside-(1 → 2)-β-D-glucopyranoside ,
17)、山柰酚 3-O-α-L-吡喃鼠李糖-(1→4)-[α-L-吡喃
鼠李糖-(1→4)]-β-D-吡喃葡萄糖苷(kaempferol-3-
O-α-L-rhamnopyranosyl-(1→ 4)-[α-L-rhamnopyranosyl-
(1→4)]-β-D-glucopyranoside,18)、山柰酚 3-O-α-L-
吡喃鼠李糖-(1→4)-[β-D-吡喃葡萄糖 (1→4)]-β-D-
吡喃葡萄糖苷(kaempferol-3-O-α-L-rhamnopyranosyl-
(1 → 4)-[β-D-glucopyranosyl (1 → 4)]-β-D-
glucopyranoside , 19)、二十六碳酸 -1- 甘油酯
(hexacosanoicacid 1-carbonate,20)、5,8,12-trihydroxy-
9-octadecenoic acid(21)、 (2S,3S,4R)-phytosphin-
gosine(22)、水粉覃素(nebularine,23)。所有
化合物均为首次从香花藤属植物中分离得到并进
行结构鉴定。
1 仪器与试剂
XRC-1 微量熔点仪(四川大学科学仪器厂),
BrukerAM-400/500 核磁共振光谱仪, BIO-Rad
FTS-135 型红外光谱仪,Auto Spec-3000 质谱仪(英
国 VG 公司)。柱色谱硅胶(200~300 目)、GF254
和硅胶 G 为青岛海洋化工厂产品,Sephadex LH-20
凝胶(Pharmacia 公司),RP18 gel(Merck 公司),
MCI gel CHP-20P(粒径 70~150 μm,日本三菱化
学公司)。
香花藤采自云南西双版纳,由中国科学院版纳
植物所张顺成鉴定为香花藤 Aganosma marginata
(Roxb.) G. Don 的全株,标本(200601523)保存在中
国科学院昆明植物研究所植物化学实验室罗士德研
究组。
2 提取与分离
干香花藤全株 5.1 kg,用 70%乙醇热提取 3 次
(4、4、3 h),然后分别用石油醚、醋酸乙酯、正丁
醇各萃取 3 次(每次 3 L)。醋酸乙酯和正丁醇部分
合并后(113 g)经硅胶柱色谱,氯仿-甲醇(1∶0~
0∶1)梯度洗脱,收集到 5 个组分 1~5。组分 2(14
g)过 MCI 柱(甲醇-水 8∶2)脱叶绿素后,经正相
硅胶柱色谱,氯仿-丙酮(1∶0→0∶1)洗脱,再经
Sephadex LH-20、RP18、反复硅胶柱色谱处理后得
到化合物 11(32 mg)、12(46 mg)、20(21 mg)。
组分 3(17 g)过 MCI 柱(甲醇-水 8∶2)脱叶绿素
后,再分别经正相硅胶柱色谱,氯仿-丙酮(1∶0→0∶
1)洗脱,用 Sephadex LH-20、RP18 反相柱色谱后,
再反复用正相硅胶柱色谱处理后得到化合物 2(13
mg)、3(45 mg)、4(68 mg)、5(17 mg)、6(28 mg)、
8(5 mg)、21(378 mg)。组分 4(19 g)过 MCI
(甲醇-水 8∶2)脱色素后,再经正相硅胶(20 g)
柱色谱,氯仿-丙酮(1∶0→0∶1)进行洗脱,然后
再用 Sephadex LH-20,反相柱色谱后,再反复用硅
胶柱色谱处理后得到化合物 9(9 mg)、10(10 mg)、
13(9 mg)、15(7 mg)、22(21 mg),组分 5(22 g)
过 MCI(甲醇-水 0∶0→1∶0)脱色素和糖后,然
后再用 Sephadex LH-20,反相柱色谱后,再反复用
硅胶柱色谱处理后得到化合物 7(24 mg)、14(13
mg)、16(39 mg)、17(19 mg)、18(33 mg)、19
(27 mg)、23(17 mg)。
3 结构鉴定
化合物 1:白色粉末,分子式为 C33H54O12,
FAB-MS m/z: 641 [M-H]- (100), 479 (11), 391 (6),
中草药 Chinese Traditional and Herbal Drugs 第 46卷 第 12期 2015年 6月

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101 (47)。1H-NMR (400 MHz, CD3OD) δ: 1.99 (1H,
m, H-1a), 1.35 (1H, m, H-1b), 1.59 (1H, m, H-2a),
1.22 (1H, m, H-2b), 4.26 (1H, m, H-3), 2.61 (1H, d,
J = 7.8 Hz, H-4a), 1.34 (1H, m, H-4b), 5.11 (1H, brs,
H-6), 2.00 (1H, m, H-7a), 1.65 (1H, m, H-7b), 1.22
(1H, m, H-8), 1.55 (1H, m, H-9), 1.37 (2H, t, J = 11.1
Hz, H-11), 1.61 (1H, m, H-12a), 1.62 (1H, m, H-17),
0.86 (1H, m, H-12b), 1.78 (1H, m, H-14), 1.62 (1H,
m, H-15a), 1.09 (1H, m, H-15b), 1.55 (1H, m, H-16a),
1.40 (1H, m, H-16b), 0.85 (3H, s, H-18), 0.63 (3H, s,
H-19), 4.27 (2H, overlap, H-5″, 20), 5.01 (1H, d, J =
7.7 Hz, H-1′), 4.29 (1H, m, H-2′), 4.55 (1H, brs,
H″-6a), 4.27 (1H, m, H″-6b), 1.17 (3H, d, J = 5.8 Hz,
H-21);13C-NMR (100 MHz, CD3OD) δ: 34.8 (t, C-1),
30.1 (t, C-2), 77.2 (t, C-3), 39.4 (t, C-4), 139.9 (s,
C-5), 117.6 (d, C-6), 30.1 (t, C-7), 40.3 (t, C-8), 49.9
(d, C-9), 34.6 (s, C-10), 21.9 (t, C-11), 37.4 (t, C-12),
43.9 (s, C-13), 55.0 (d, C-14), 25.7 (t, C-15), 23.5 (t,
C-16), 56.7 (d, C-17), 12.0 (q, C-18), 13.1 (q, C-19),
75.1 (d, C-20), 19.0 (t, C-21), 102.4 (d, C-1′), 75.4 (d,
C-2′), 78.8 (d, C-3′), 72.4 (d, C-4′), 78.6 (d, C-5′), 63.5
(t, C-6′), 101.1 (d, C-1″), 75.3 (s, C-2″), 78.7 (d,
C-3″), 71.8 (d, C-4″), 78.3 (d, C-5″), 62.9 (t, C-6″)。以
上数据与文献报道基本一致[4],故鉴定化合物 1 为
periseoside C。
化合物 2:无色晶体,分子式为 C27H42O8,
FAB-MS m/z: 493 [M-H]- (100), 471 (3), 431 (5),
381 (3), 80 (4)。1H-NMR (400 MHz, CD3OD) δ: 5.27
(1H, d, J = 2.2 Hz, H-6), 4.38 (1H, d, J = 7.8 Hz,
H-1′), 3.63 (2H, m, H-3, 15), 3.63 (4H, m, H-2′, 3′, 4′,
6′), 3.14 (1H, m, H-5′), 2.81 (1H, m, H-17), 0.82 (3H,
s, H-19), 0.54 (3H, s, H-18);13C-NMR (100 MHz,
CD3OD) δ: 216.2 (s, C-20), 138.1 (s, C-5), 120.6 (d,
C-6), 102.4 (d, C-1′), 79.0 (d, C-3), 78.9 (d, C-3′),
77.9 (d, C-5′), 75.2 (d, C-4′), 71.7 (d, C-2′), 63.7 (d,
C-15), 62.9 (t, C-6′), 54.0 (d, C-17), 50.9 (d, C-14),
49.8 (d, C-9), 44.3 (s, C-13), 41.5 (d, C-8), 38.3 (t,
C-4), 35.4 (t, C-12), 35.2 (s, C-10), 31.5 (q, C-19),
31.5 (t, C-1), 30.8 (t, C-7), 30.4 (t, C-2), 25.9 (t,
C-16), 23.9 (t, C-11), 13.3 (q, C-21), 8.1 (q, C-18)。以
上数据与文献报道基本一致[5],故鉴定化合物 2 为
3-O-β-D-吡喃葡萄糖-3β,15α-二羟基孕甾-5-烯-20-酮。
化合物 3:白色粉末,分子式为 C21H34O2,EI-MS
m/z: 318 [M]+ (100), 300 (31), 282 (36), 267 (53), 246
(28)。1H-NMR (400 MHz, C5D5N) δ: 5.06 (1H, d, J =
3.9 Hz, H-6), 3.84 (1H, m, H-3), 1.30 (3H, d, J = 6.0
Hz, 21-CH3), 0.78 (3H, s, 18-CH3), 0.97 (3H, s,
19-CH3);13C-NMR (100 MHz, C5D5N) δ: 138.5 (s,
C-5), 115.6 (d, C-6), 75.5 (d, C-3), 69.9 (d, C-20),
58.8 (d, C-17), 54.9 (d, C-14), 44.3 (s, C-13), 40.3 (t,
C-4), 36.3 (d, C-9), 36.3 (d, C-8), 34.0 (s, C-10), 33.2
(t, C-12), 30.8 (t, C-1), 28.5 (t, C-7), 27.1 (t, C-2),
25.9 (t, C-16), 25.2 (q, C-19), 24.4 (q, C-21), 23.7 (t,
C-15), 22.0 (t, C-11), 12.6 (q, C-18)。以上数据与文
献报道基本一致[6],故鉴定化合物 3 为 3β,20α-二
羟基-5-烯-孕甾。
化合物 4:白色粉末,分子式为 C30H52O,
FAB-MS m/z: 427 [M-H]- (100), 381 (7), 393 (22)。
1H-NMR (400 MHz, C5D5N) δ: 3.46 (1H, m, H-3),
1.08 (3H, s, H-18), 1.06 (3H, s, H-19), 0.68 (3H, s,
H-29), 0.98 (3H, d, J = 6.4 Hz, H-21), 0.88 (3H, d, J =
5.3 Hz, H-27), 0.87 (3H, d, J = 5.3 Hz, H-28);
13C-NMR (100 MHz, C5D5N) δ: 142.1 (s, C-5), 121.3
(d, C-6), 71.4 (d, C-3), 57.0 (d, C-17), 56.4 (d, C-14),
50.6 (d, C-9), 49.7 (s, C-4), 46.2 (d, C-13), 43.5 (t,
C-12), 37.9 (t, C-22), 36.5 (s, C-10), 36.5 (d, C-20),
34.3 (t, C-29), 32.7 (d, C-25), 32.3 (t, C-2), 30.1 (t,
C-7), 29.6 (d, C-25), 28.6 (t, C-16), 26.5 (t, C-2), 25.6
(s, C-24), 24.6 (t, C-15), 21.4 (t, C-11), 20.0 (q, C-18),
20.0 (q, C-19), 19.7 (q, C-21), 19.7 (q, C-27), 19.3 (q,
C-29), 19.1 (q, C-30), 12.1 (q, C-25)。以上数据与文
献报道基本一致 [7],故鉴定化合物 4 为 24-
methylstigmast-5-en-3-ol。
化合物 5:白色粉末,分子式为 C29H48O2,
FAB-MS m/z: 427 [M-H]- (15), 411 (100), 393
(22)。1H-NMR (400 MHz, C5D5N) δ: 5.98 (1H, d, J =
15.6 Hz, H-24), 5.92 (1H, d, J = 15.6 Hz, H-25), 3.46
(1H, m, H-3), 1.54 (3H, s, H-26), 1.03 (3H, s, H-27),
0.99 (3H, s, H-18), 0.88 (3H, s, H-29), 1.25 (3H, d, J =
6.5 Hz, H-21), 0.95 (3H, d, J = 6.2 Hz, H-28);
13C-NMR (100 MHz, C5D5N) δ: 141.7 (d, C-24),
124.6 (d, C-23), 75.8 (d, C-3), 69.8 (s, C-25), 52.2 (d,
C-17), 49.2 (s, C-14), 47.0 (d, C-8), 45.6 (s, C-14),
45.3 (s, C-13), 45.4 (d, C-6), 43.8 (d, C-4), 39.5 (t,
C-22), 36.9 (d, C-20), 35.9 (t, C-12), 35.6 (t, C-1),
33.1 (t, C-11), 31.3 (t, C-15), 30.9 (q, C-26), 30.9 (q,
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C-27), 30.0 (s, C-10), 28.3 (t, C-2), 27.2 (t, C-7), 25.5
(t, C-6), 25.1 (t, C-16), 23.6 (s, C-9), 19.3 (q, C-21),
18.6 (q, C-29), 18.1 (q, C-28), 15.2 (q, C-18)。以上数
据与文献报道基本一致 [8],故鉴定化合物 5 为
29-norcycloart-23-ene-3,25-diol。
化合物 6:白色粉末,分子式为 C29H50O,
FAB-MS m/z: 413 [M-H]- (100), 381 (7), 393 (22)。
1H-NMR (400 MHz, C5D5N) δ: 3.46 (1H, m, H-3),
1.54 (3H, s, H-26), 1.52 (1H, s, H-19a), 1.28 (1H, s,
H-19b), 1.00 (3H, s, H-27), 0.89 (3H, s, H-29), 1.25
(1H, d, J = 6.4 Hz, H-28);13C-NMR (100 MHz,
C5D5N) δ: 75.9 (d, C-3), 52.9 (d, C-17), 49.7 (s, C-13),
47.1 (d, C-8), 45.7 (s, C-14), 45.4 (d, C-6), 43.8 (d,
C-4), 36.4 (d, C-20), 35.9 (t, C-12), 35.6 (t, C-1), 33.3
(t, C-11), 31.4 (t, C-15), 30.1 (s, C-10), 28.5 (t, C-2),
27.4 (t, C-7), 26.2 (q, C-26), 26.1 (q, C-27), 25.9 (t,
C-6), 25.5 (t, C-16), 23.7 (s, C-9), 19.4 (q, C-21), 18.9
(q, C-29), 18.1 (q, C-28), 15.2 (q, C-18)。以上数据与
文献报道基本一致 [9],故鉴定化合物 6 为 29-
norcycloartan-3-ol。
化合物 7:白色粉末,分子式为 C16H22O10,
FAB-MS m/z: 527 (77), 373 [M-H]- (100), 311 (7)。
1H-NMR (500 MHz, C5D5N) δ: 7.95 (1H, s, H-3), 5.98
(1H, s, H-6), 5.72 (1H, d, J = 7.0 Hz, H-1′), 5.43 (1H,
d, J = 7.8 Hz, H-1″), 4.80 (1H, d, J = 14.6 Hz, H-6′a),
4.53 (1H, d, J = 14.7 Hz, H-6′b), 4.47 (1H, d, J = 11.8
Hz, H-10);13C-NMR (125 MHz, C5D5N) δ: 169.7 (s,
C-11), 151.9 (d, C-3), 145.6 (s, C-7), 126.8 (d, C-6),
113.0 (s, C-4), 101.2 (d, C-1), 97.9 (d, C-1′), 78.8 (d,
C-5′), 78.5 (d, C-3′), 74.8 (d, C-2′), 71.5 (d, C-4′), 62.6
(t, C-6′), 60.9 (t, C-10), 47.2 (d, C-9), 39.3 (t, C-8),
36.1 (d, C-5)。以上数据与文献报道基本一致[10],故
鉴定化合物 7为京尼平苷酸。
化合物 8:白色晶体(水),分子式为 C22H26O8,
EI-MS m/z: 419 [M]+ (100), 203 (42), 236 (45), 221
(29), 210 (42), 193 (44), 154 (59); KBrmaxIR ν (cm−1):
3 441, 3 005, 2 943, 1 612, 1 520, 1 456, 1 426, 1 379,
1 247, 1 204, 1 156, 1 063, 986, 962, 912, 851, 728。
1H-NMR (400 MHz, C5D5N) δ: 6.99 (4H, s, H-2, 6, 2′,
6′), 4.67 (2H, d, J = 4.3 Hz, H-7, 7′), 4.21 (2H, dd, J =
8.9, 6.8 Hz, H-9a, 9′a), 3.83 (2H, dd, J = 9.0, 3.5 Hz,
H-9b, 9′b), 3.78 (12H, s, 4×-OCH3), 3.05 (2H, m,
H-8, 8′);13C-NMR (100 MHz, C5D5N) δ: 153. 9 (s,
C-3, 5), 137.4 (s, C-4, 4′), 132.1 (s, C-1, 1′), 104.0 (d,
C-2, 2′, 6, 6′), 86.1 (d, C-7, 7′), 72.2 (t, C-9, 9′), 56.4
(s, 4×-OCH3), 54.8 (d, C-8, 8′)。以上数据与文献报
道基本一致[11],故鉴定化合物 8为丁香树脂醇。
化合物 9 白色粉末,分子式为 C34H46O18,
FAB-MS m/z: 741 [M-H]- (60), 637 (17), 185 (43),
137 (55)。1H-NMR (500 MHz, C5D5N) δ: 7.03 (4H, s,
H-2, 2′, 6, 6′), 5.82 (2H, m, H-1′′′, 1′′′′), 4.94 (2H, d,
J = 3.2 Hz, H-7, 7′), 3.78 (6H, s, 2×-OCH3), 3.59
(6H, s, 2×-OCH3);13C-NMR (125 MHz, C5D5N) δ:
154.0 (s, C-3, 5), 138.3 (s, C-4, 4′), 123.1 (s, C-1, 1′),
105.0 (d, C-2, 2′, 6, 6′), 104.9 (d, C-1′′′, 1′′′′), 86.2 (d,
C-7, 7′), 78.7 (d, C-3′′′, 3′′′′), 78.4 (d, C-5′′′, 5′′′′), 76.1
(d, C-2′′′, 2′′′′), 72.3 (t, C-9, 9′), 71.7 (d, C-4′′′, 4′′′′),
62.7 (t, C-6′′′, 6′′′′), 56.7 (q, 4×-OCH3), 54.8 (d, C-8,
8′)。以上数据与文献报道基本一致[12],故鉴定化合
物 9为丁香脂素-4,4′-O-双-β-D-葡萄糖苷。
化合物 10:白色粉末,分子式为 C15H20O10,
FAB-MS m/z: 359 [M-H]- (100), 325 (6), 255 (7)。
1H-NMR (500 MHz, D2O) δ: 7.76 (2H, s, H-2, 6), 5.99
(1H, d, J = 7.5 Hz, H-1′), 4.41 (1H, m, H-2′), 4.38
(1H, m, H-6′a), 4.35 (1H, m, H-6′b), 4.33 (1H, m,
H-5′), 4.31 (1H, m, H-4′), 4.28 (1H, m, H-3′), 3.76
(3H, s, -OCH3), 3.58 (3H, s, -OCH3);13C-NMR (125
MHz, D2O) δ: 167.5 (s, C=O), 153.7 (s, C-3, 5), 137.5
(s, C-4), 128.2 (s, C-1), 109.2 (d, C-2, 6), 104.1 (d,
C-1′), 77.8 (d, C-3′), 77.1 (d, C-5′), 75.1 (d, C-2′), 70.8
(d, C-4′), 62.0 (t, C-6′), 57.9 (q, -OCH3)。以上数据与
文献报道基本一致[13],故鉴定化合物 10为丁香酸-
4β-D-吡喃葡萄糖苷。
化合物 11:白色晶体(水),分子式为 C7H6O3,
FAB-MS m/z: 137 [M-H]- (100), 119 (5), 82 (10)。
1H-NMR (500 MHz, C5D5N) δ: 8.27 (1H, d, J = 7.8
Hz, H-6), 7.46 (1H, t, J = 7.9, 7.4 Hz, H-4), 7.18 (1H,
J = 8.3 Hz, H-3), 6.94 (1H, t, J = 7.5 Hz, H-5);
13C-NMR (125 MHz, C5D5N) δ: 174.8 (s, C-1), 163.0
(s, C-2), 135.3 (d, C-4), 131.5 (d, C-6), 119.2 (d, C-5),
117.7 (d, C-3), 115.9 (s, C-1)。以上数据与文献报道
基本一致[14],故鉴定化合物 11为水杨酸。
化合物 12:白色晶体(水),分子式为 C10H8O4,
FAB-MS m/z: 176 (4), 191 [M-H]- (100), 283 (34),
307 (39)。1H-NMR (500 MHz, C5D5N) δ: 7.67 (1H, d,
J = 9.4 Hz, H-4), 7.12 (1H, s, H-5), 7.03 (1H, s, H-8),
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6.29 (1H, d, J = 9.4 Hz, H-3), 3.75 (3H, s, -OCH3);
13C-NMR (125 MHz, C5D5N) δ: 161.5 (s, C-2), 109.5
(d, C-3), 144.1 (d, C-4), 112.4 (d, C-5), 153.1 (s, C-6),
151.2 (s, C-7), 104.2 (d, C-8), 146.3 (s, C-9), 111.1 (s,
C-10), 56.3 (q, -OCH3)。以上数据与文献报道基本一
致[15],故鉴定化合物 12为东莨菪内酯。
化合物 13:白色粉末,分子式为 C9H16O4,
FAB-MS m/z: 187 [M-H]- (100), 169 (5), 127 (9)。
1H-NMR (400 MHz, C5D5N) δ: 2.46 (4H, m, H-2, 8),
1.74 (4H,m, H-3, 7), 1.28 (6H, m, H-4, 5, 6);
13C-NMR (100 MHz, C5D5N) δ: 176.1 (s, C-1, 9), 34.9
(t, C-2, 8), 29.5 (t, C-4, 5, 6), 25.7 (t, C-3, 7)。以上数
据与文献报道基本一致[16],故鉴定化合物 13 为壬
二酸。
化合物 14:白色粉末,分子式为 C35H54O12,
FAB-MS m/z: 665 [M-H]- (21), 635 (5), 391 (39),
339 (4), 277 (100)。1H-NMR (400 MHz, C5D5N) δ:
6.12 (1H, s, H-21), 5.13 (1H, d, J = 7.5 Hz, H-1′), 4.95
(1H, d, J = 7.5 Hz, H-1″), 4.50 (1H, m, H-3′), 4.27
(1H, d, J = 6.1 Hz, H-3), 4.24 (2H, overlap, H-23),
4.10 (2H, overlap, H-4′, 3′′), 4.00 (4H, overlap, H-2′,
5′, 2′′, 5′′), 3.59 (3H, s, -OCH3), 0.99 (3H, d, J = 3.4
Hz, H-6′), 0.72 (3H, s, H-19);13C-NMR (100 MHz,
C5D5N) δ: 176.0 (s, C-23), 174.7 (s, C-20), 117.8 (d,
C-22), 105.4 (d, C-1′), 105.2 (d, C-1″), 84.7 (s, C-14),
83.0 (d, C-4′), 82.9 (d, C-3), 79.5 (d, C-3″), 78.3 (d,
C-3′), 75.4 (d, C-5″), 75.2 (t, C-21), 73.9 (d, C-2′),
71.8 (d, C-2″), 63.1 (t, C-5′), 57.5 (q, -OCH3), 51.5 (d,
C-17), 50.1 (s, C-13), 50.1 (d, C-5), 44.5 (d, C-9), 41.8
(d, C-8), 39.8 (t, C-4), 36.2 (t, C-1), 33.2 (t, C-2), 30.1 (t,
C-12), 29.3 (t, C-7), 28.1 (t, C-15), 27.4 (t, C-16), 21.7
(t, C-11), 19.0 (q, C-19), 16.3 (q, C-6′), 12.4 (q,
C-18)。以上数据与文献报道基本一致[17],故鉴定化
合 物 14 为 3-O-[β-D-xylopyranosyl]-(1→4)-β-D-
allopyranoside-14-hydroxycard-20(22)-enolide。
化合物 15:白色粉末,分子式为 C24H38O4,
FAB-MS m/z: 389 [M-H]- (100), 375 (5), 277 (44)。
1H-NMR (400 MHz, C5D5N) δ: 7.90 (2H, d, J = 6.4
Hz, H-3, 6), 7.55 (2H, d, J = 6.4 Hz, H-4, 5), 4.38 (4H,
m, overlap, H-1′,1′′), 0.89 (3H, d, J = 7.5 Hz, H-6′),
0.84 (3H, d, J = 6.8 Hz,H-5′′);13C-NMR (100 MHz,
C5D5N) δ: 168.1 (s, C-1, 8), 131.7 (d, C-3, 6), 129.5
(d, C-4, 5), 68.3 (t, C-1′, 1′′), 39.2 (t, C-3′), 30.8 (t,
C-4′), 30.1 (t, C-5′), 29.7 (t, C-3′′), 24.2 (t, C-4′′), 14.4
(q, C-6′), 11.3 (q, C-5′′)。以上数据与文献报道基本一
致 [18],故鉴定化合物 15 为 bis (2-ethylhexyl)
phthalate。
化合物 16:黄色粉末,分子式为 C27H30O15,
FAB-MS m/z: 593 [M-H]- (80), 478 (2), 80 (3)。
1H-NMR (500 MHz, C5D5N) δ: 8.42 (2H, d, J = 8.7
Hz, H-2′, 6′), 7.23 (2H, d, J = 8.7 Hz, H-3′, 5′), 6.92
(1H, brs, H-8), 6.75 (1H, brs, H-6), 4.65 (1H, d, J =
2.9 Hz, H-1″), 4.63 (1H, d, J = 2.9 Hz, H-1′′′), 1.63
(3H, d, J = 5.6 Hz, H-6′′′);13C-NMR (125 MHz,
C5D5N) δ: 178.9 (s, C-4), 162.8 (s, C-7), 162.3 (s,
C-5), 161.9 (s, C-4′), 157.8 (s, C-2), 156.9 (s, C-9),
132.0 (s, C-3), 121.9 (s, C-1′), 123.8 (d, C-3′, 5′),
116.2 (d, C-2′, 6′), 106.9 (s, C-10), 103.7 (d, C-6),
100.4 (d, C-1″), 100.0 (d, C-1′′′), 94.9 (d, C-8), 79.2
(d, C-3″), 78.5 (d, C-5″), 76.1 (d, C-2″), 73.6 (d,
C-4″), 72.4 (d, C-2′′′), 71.6 (d, C-3′′′), 71.5 (d, C-5′′′),
62.6 (t, C-6″), 18.7 (q, C-6′′′)。以上数据与文献报道
基本一致[19],故鉴定化合物 16 为山柰酚 3-O-α-吡
喃鼠李糖-(1→4)-α-L-吡喃葡萄糖苷。
化合物 17:黄色粉末,分子式为 C27H30O16,
FAB-MS m/z: 609 [M-H]- (100)。1H-NMR (400
MHz, C5D5N) δ: 8.42 (2H, d, J = 8.7 Hz, H-2′, 6′),
7.35 (2H, d, J = 8.7 Hz, H-3′, 5′), 6.69 (1H, d, J = 2.0
Hz, H-8), 6.63 (1H, d, J = 2.0 Hz, H-6), 5.61 (1H, d,
J = 7.7 Hz, H-1″), 5.47 (1H, brs, H-1′′′), 4.39~4.17
(9H, m, overlap, H-2″~6″a, 2′′′~6′′′), 3.97 (1H, d,
J = 2.7 Hz, H-6′′b);13C-NMR (100 MHz, C5D5N) δ:
178.9 (s, C-4), 165.7 (s, C-7), 163.0 (s, C-5), 161.7 (s,
C-4′), 157.4 (s, C-2), 156.5 (s, C-9), 134.5 (s, C-3),
132.0 (d, C-2′, 6′), 122.2 (s, C-1′), 116.3 (d, C-3′, 5′),
106.2 (d, C-1″), 105.3 (s, C-10), 100.0 (d, C-1′′′), 99.8
(d, C-6), 94.5 (d, C-8), 84.2 (d, C-2″), 79.0 (d, C-3′′′),
78.8 (d, C-3″), 78.5 (d, C-5′′′), 78.5 (d, C-5″), 76.2 (d,
C-2′′′), 71.4 (d, C-4″), 71.2 (d, C-4′′′), 62.6 (t, C-6″),
62.3 (t, C-6′′′)。以上数据与文献报道基本一致[20],
故鉴定化合物 17 为山柰酚 3-O-α-L-吡喃葡萄糖-
(1→2)-β-D-吡喃葡萄糖苷。
化合物 18:黄色粉末,分子式为 C33H40O19,
FAB-MS m/z: 739 [M-H]- (100)。1H-NMR (400
MHz, C5D5N) δ: 8.46 (2H, d, J = 8.7 Hz, H-2′, 6′),
7.32 (2H, d, J = 8.7 Hz, H-3′, 5′), 6.84 (1H, brs, H-8),
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6.72 (1H, brs, H-6), 5.62 (1H, d, J = 7.5 Hz, H-1″),
5.05 (1H, d, J = 1.7 Hz, H-1′′′), 5.03 (1H, d, J = 1.9
Hz, H-1′′′), 1.64 (1H, d, J = 5.6 Hz, H-5″), 1.63 (1H,
d, J = 5.6 Hz, H-5′′′);13C-NMR (100 MHz, C5D5N) δ:
178.9 (s, C-4), 165.6 (s, C-7), 162.2 (s, C-5), 161.5 (s,
C-4′), 156.8 (s, C-2), 156.5 (s, C-9), 134.4 (s, C-3),
132.1 (d, C-2′, 6′), 121.2 (s, C-1′), 116.5 (d, C-3′, 5′),
104.3 (s, C-1″), 104.2 (d, C-1′′′), 103.8 (d, C-1′′′′),
99.8 (d, C-8), 94.8 (d, C-6), 78.5 (d, C-3″), 75.8 (d,
C-5″), 73.6 (d, C-4″), 72.3 (d, C-4′′′), 71.9 (d, C-4′′′′),
71.7 (d, C-2″), 70.9 (d, C-3′′′), 70.8 (d, C-3′′′′), 70.5
(d, C-2′′′), 70.1 (d, C-5′′′), 69.5 (d, C-5′′′), 69.3 (d,
C-5′′′′), 62.6 (t, C-6″), 17.9 (q, C-6′′′), 17.5 (q, C-6′′′′)。
以上数据与文献报道基本一致[21],故鉴定化合物 18
为山柰酚 3-O-α-L-吡喃鼠李糖-(1→4)-[α-L-吡喃鼠
李糖-(1→4)]-β-D-吡喃葡萄糖苷。
化合物 19:黄色粉末,分子式为 C33H40O20,
FAB-MS m/z: 755 [M-H]- (5), 701 (3), 609 (100),
447 (7), 285 (54), 127 (7)。1H-NMR (400 MHz,
C5D5N) δ: 8.47 (2H, d, J = 8.7 Hz, H-2′, 6′), 7.39 (2H,
d, J = 8.7 Hz, H-3′, 5′), 6.84 (1H, brs, H-8), 6.72 (1H,
brs, H-6), 5.62 (1H, d, J = 7.5 Hz, H-1″), 4.70 (1H,
brs, H-1′′′), 4.64 (1H, d, J = 7.5 Hz, H-1′′′′), 1.63 (3H,
d, J = 5.6 Hz, H-6′′′′);13C-NMR (100 MHz, C5D5N) δ:
179.0 (s, C-4), 162.6 (s, C-7), 162.4 (s, C-5), 161.9 (s,
C-4′), 156.8 (s, C-2), 156.7 (s, C-9), 134.6 (s, C-3),
132.2 (d, C-2′, 6′), 121.9 (s, C-1′), 116.4 (d, C-3′, 5′),
106.9 (s, C-10), 106.3 (d, C-1″), 100.4 (d, C-1′′′),
100.0 (d, C-1′′′′), 99.8 (d, C-6), 94.7 (d, C-8), 84.3 (d,
C-2″), 79.23 (d, C-3″), 78.8 (d, C-3′′′), 78.6 (d, C-5″),
78.5 (d, C-5′′′), 76.2 (d, C-2′′′′), 73.6 (d, C-4″), 72.4
(d, C-4′′′), 71.7 (d, C-4′′′′), 71.5 (d, C-2′′′), 71.3 (d,
C-3′′′′), 71.1 (d, C-5′′′′), 62.5 (t, C-6″), 62.2 (t, C-6′′′),
18.7 (q, C-6′′′′)。以上数据与文献报道基本一致[22],
故鉴定化合物 19 为山柰酚 3-O-α-L-吡喃鼠李糖-
(1→4)-[β-D-吡喃葡萄糖 (1→4)]-β-D-吡喃葡萄糖苷。
化合物 20:无色蜡状物,分子式为 C29H58O4,
EI-MS m/z: 470 [M]+ (1)。 1H-NMR (400 MHz,
C5D5N) δ: 4.71 (1H, m, H-1a), 4.64 (1H, m, H-1b),
4.44 (1H, t, J = 5.4, 5.2 Hz, H-2), 4.12 (2H, d, J = 5.4
Hz, H-3), 2.34 (2H, t, J = 7.5, 7.4 Hz, H-2′), 0.86 (3H,
m, H-25′);13C-NMR (100 MHz, C5D5N) δ: 174.3 (s,
C-1′), 69.6 (d, C-2), 66.7 (t, C-1), 63.4 (t, C-3), 33.8 (t,
C-2′), 29.4~28.8 (t, C-4′~22′), 24.5 (t, C-3′), 22.3 (t,
C-24′), 31.6 (t, C-25′), 13.6 (q, C-26′)。以上数据与文
献报道基本一致[23],故鉴定化合物 20为二十六碳
酸-1-甘油酯。
化合物 21:白色粉末,分子式为 C18H34O5,
FAB-MS m/z: 329 [M-H]- (100), 315 (12), 301 (4)。
1H-NMR (500 MHz, C5D5N) δ: 5.57 (1H, m, H-9),
5.56 (1H, m, H-10), 3.33 (1H, m, H-5), 0.88 (3H, s,
H-18);13C-NMR (125 MHz, C5D5N) δ: 176.9 (s, C-1),
135.6 (d, C-9), 129.5 (d, C-10), 75.2 (d, C-8), 74.6 (d,
C-12), 71.7 (d, C-5), 36.7 (t, C-2), 34.0 (t, C-11), 31.8
(t, C-7), 29.2 (t, C-6), 28.9 (t, C-3), 28.8 (t, C-4), 25.3
(t, C-13), 25.1 (t, C-14), 24.7 (t, C-15), 24.7 (t, C-16),
22.5 (t, C-17), 13.9 (q, C-18),以上数据与文献报道
基本一致[24],故鉴定化合物 21为 5,8,12-trihydroxy-
9-octadecenoic acid。
化合物 22:白色粉末,分子式为 C44H83NO9,
KBr
maxIR ν (cm−1): 3 375, 2 923, 1 629, 1 538, 1 465,
1 076, 721;FAB-MS m/z: 787 [M-H-H2O]- (100),
625 (30), 653 (20)。1H-NMR (400 MHz, C5D5N) δ:
8.37 (1H, d, J = 8.8 Hz, NH), 5.97 (2H, m, H-4, 5),
5.48 (2H, m, H-8, 9), 4.91 (1H, d, J = 4.6 Hz, H-1′′),
0.85 (3H, m, H-18), 0.87 (3H, m, H-20′);13C-NMR
(100 MHz, C5D5N) δ: 175.7 (s, C-1′), 132.1 (d, C-4),
132.1 (d, C-5), 131.1 (d, C-8), 130.0 (d, C-9), 105.7
(d, C-1′′), 78.6 (d, C-3), 78.5 (d, C-2′), 75.2 (d, C-3′′),
72.5 (d, C-5′′), 72.3 (d, C-2′′), 71.5 (d, C-4′′), 70.2 (t,
C-1), 62.7 (t, C-6′′), 54.6 (d, C-2), 35.7 (t, C-6), 33.0
(t, C-7), 32.9 (t, C-10), 32.1 (t, C-3′), 30.1 (t, C-4′),
30.0 (t, C-11), 29.9 (t, C-12), 29.7 (t, C-13), 29.6 (t,
C-14), 26.0 (t, C-16), 23.0 (t, C-17), 14.3 (q, C-18)。以
上数据与文献报道基本一致[25],故鉴定化合物 22
为 (2S,3S,4R)-phytosphingosine。
化合物 23:白色粉末,分子式为 C10H12N4O4,
mp 182~183 ℃;[α]35D −46.8° (c 2.0,H2O);FAB-MS
m/z: 251 [M-H]- (81), 235 (5), 190 (19), 98 (17)。
1H-NMR (400 MHz, C5D5N) δ: 8.73 (1H, brs, H-8),
8.71 (1H, brs, H-6), 8.60 (1H, brs, H-2), 6.72 (1H, d,
J = 5.8 Hz, H-1′), 5.47 (1H, m, H-2′), 5.06 (1H, m,
H-3′), 4.76 (1H, m, H-4′), 4.29 (1H, dd, J = 12.4, 2.5
Hz, H-5′a), 4.23 (1H, dd, J = 12.4, 2.5 Hz, H-5′b);
13C-NMR (100 MHz, C5D5N) δ: 157.7 (s, C-4), 153.3
(d, C-2), 149.9 (d, C-8), 140.6 (d, C-6), 121.5 (s, C-5),
中草药 Chinese Traditional and Herbal Drugs 第 46卷 第 12期 2015年 6月

·1748·
90.8 (d, C-1′), 87.8 (d, C-4′), 75.6 (d, C-2′), 72.4 (d,
C-3′), 63.1 (t, C-5′)。以上数据与文献报道基本一致[26],
故鉴定化合物 23为水粉覃素。
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