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Chemical constituents of Ainsliaea latifolia

宽叶兔儿风的化学成分研究



全 文 :中草药 Chinese Traditional and Herbal Drugs 第 45 卷 第 15 期 2014 年 8 月

·2148·
宽叶兔儿风的化学成分研究
董雪云,文 波,沈云亨*
福建中医药大学药学院,福建 福州 350108
摘 要:目的 对宽叶兔儿风 Ainsliaea latifolia 全草的化学成分进行研究。方法 采用硅胶柱色谱、凝胶柱色谱、中压制备
液相、高压制备液相等方法进行分离纯化,通过核磁共振、质谱等波谱手段对化合物进行结构鉴定。结果 从宽叶兔儿风
80%乙醇提取物中分离得到 13 个化合物,分别鉴定为木栓酮(1)、蒲公英萜醇乙酸酯(2)、3β-hydroxy-11α, 12α-epoxy-
friedoolean-14-ene(3)、careborin(4)、cis-careborin(5)、3α-E-feruloyltaraxerol(6)、3α-Z-feruloyltaraxerol(7)、3-oxo-11α-
methoxyolean-12-ene(8)、diaspanolide A(9)、diaspanolide B(10)、ainsliaolide A(11)、豆甾醇(12)、β-谷甾醇(13)。结
论 13 个化合物中包括 8 个三萜类化合物(1~8),3 个倍半萜类化合物(9~11),2 个甾体类化合物(12~13)。化合物 1~
13 均为首次从该植物中分离得到。
关键词:宽叶兔儿风;菊科;木栓酮;蒲公英萜醇乙酸酯;豆甾醇;β-谷甾醇
中图分类号:R284.1 文献标志码:A 文章编号:0253 - 2670(2014)15 - 2148 - 05
DOI: 10.7501/j.issn.0253-2670.2014.15.006
Chemical constituents of Ainsliaea latifolia
DONG Xue-yun, WEN Bo, SHEN Yun-heng
College of Pharmacy, Fujian University of Traditional Chinese Medicine, Fuzhou 350108, China
Abstract: Objective To isolate and identify the chemical constituents of Ainsliaea latifolia. Methods Compounds were isolated by
various kinds of column chromatographies on silica gel, Sephadex LH-20, MPLC, and HPLC, and their structures were elucidated by
the physicochemical properties and spectral analyses. Results Thirteen chemical constituents were obtained and identified as friedelin
(1), taraxeryl acetate (2), 3β-hydroxy-11α, 12α-epoxy-friedoolean-14-ene (3), careborin (4), cis-careborin (5), 3α-E-feruloyltaraxerol
(6), 3α-Z-feruloyltaraxerol (7), 3-oxo-11α-methoxyolean-12-ene (8), diaspanolide A (9), diaspanolide B (10), ainsliaolide A (11),
stigmasterol (12), and β-sitosterol (13). Conclusion Among the isolated 13 compounds, there are 8 triterpenoids (1—8), 3
sesquiterpenoids (9—11), and 2 steroidals (12—13). All the compounds are isolated from A. latifolia for the first time.
Key words: Ainsliaea latifolia (D. Don) Sch. -Bip.; Compositae; friedelin; taraxeryl acetate; stigmasterol; β-sitosterol

兔 儿 风 属 Ainsliaea DC. 隶 属 于 菊 科
(Compositae)帚菊木族(Mutisieae Cass.),全世界
约有 70 种,分布于亚洲东南部。我国有 44 种 4 个
变种,除 1 种产于东北外,其余均产于长江流域及
其以南各省[1]。到目前为止,从本属植物分到的化
合物主要有倍半萜内酯及其苷、三萜、甾体和黄酮
等[2]。宽叶兔儿风 Ainsliaea latifolia (D. Don) Sch. -Bip.
为菊科兔儿风属植物,分布于我国西藏、云南、四
川、贵州、广西及海南等地,民间主要用于治疗风
寒咳嗽、肠炎、痢疾、跌打损伤等[3]。目前尚未有
关于该植物化学成分及生物活性方面的研究报道。
为了从中寻找更多结构新颖的生物活性成分,本实
验对宽叶兔儿风的化学成分进行了研究,从其全草
80%乙醇提取物中得到了 13 个化合物,分别鉴定为
木栓酮(friedelin,1)、蒲公英萜醇乙酸酯(taraxeryl
acetate,2)、3β-hydroxy-11α, 12α-epoxy-friedoolean-
14-ene(3)、careborin(4)、cis-careborin(5)、
3α-E-feruloyltaraxerol(6)、3α-Z-feruloyltaraxerol(7)、
3-oxo-11α-methoxyolean-12-ene(8)、diaspanolide A
(9)、diaspanolide B(10)、ainsliaolide A(11)、豆
甾醇(stigmasterol,12)、β-谷甾醇(β-sitosterol,
13)。化合物 1~13 均为首次从该植物中分离得到,

收稿日期:2014-04-18
作者简介:董雪云,硕士在读,研究方向为天然药物化学。E-mail: 506622731@qq.com
*通信作者 沈云亨,男,博士,副教授,硕士生导师,主要从事结构新颖天然产物小分子的发现及功能研究,生物活性小分子结构修饰及构
效关系研究。E-mail: shenyunheng@hotmail.com
中草药 Chinese Traditional and Herbal Drugs 第 45 卷 第 15 期 2014 年 8 月

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其中包括 8 个三萜类(1~8),3 个倍半萜类(9~
11),2 个甾体类化合物(12~13)。部分结构见图 1。
1 仪器与材料
Bruker DRX—500 型核磁共振谱仪(德国 Bruker
公司);Agilent LC/MSD Trap XCT 质谱仪(美国
Agilent 公司);SK5200H 型超声发生器(上海科导
超声仪器有限公司);Sephadex LH-20(Pharmacia
公司);反相硅胶 C18(Merck 公司);薄层色谱硅胶
和 HSGF254硅胶预制板(烟台江友硅胶开发有限公
司);提取用乙醇为工业级,质谱用试剂为色谱级,
其余试剂均为分析纯。
宽叶兔儿风全草于 2013 年 9 月采自贵州贵阳,
经贵阳医学院生药教研室龙庆德教授鉴定为宽叶兔
儿风 Ainsliaea latifolia (D. Don) Sch. -Bip.,植物标
本(20130905)现保存在第二军医大学药学院天然
药化教研室。
O
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图 1 化合物 2~11 的结构
Fig. 1 Structures of compounds 2-11
2 提取与分离
宽叶兔儿风全草(15 kg)粉碎后用 80%乙醇浸
泡 4 次,每次 48 h,提取液回流蒸干后得 80%乙醇
提取物 2 kg。依次用石油醚、氯仿、醋酸乙酯、甲
醇进行固相萃取,取氯仿部位(105 g)进行硅胶柱
色谱,石油醚-醋酸乙酯(100∶1→50∶1→30∶1→
10∶1→5∶1→0∶1)梯度洗脱,得到 7 个流分(Fr.
1~7)。其中 Fr. 2(21 g)经硅胶柱分离,以石油醚-
丙酮(50∶1→0∶1)梯度洗脱,再经 Sephadex LH-20
柱色谱与制备薄层分离纯化得到化合物 1(1.6 g)、
2(24.5 mg)、12(75.6 mg)、13(43.8 mg)。Fr. 3
(17 g)用硅胶柱分离,以石油醚-醋酸乙酯(50∶1→
0∶1)进行梯度洗脱,再经 Sephadex LH-20 柱色谱
与制备薄层分离纯化得到化合物 9(43.6 mg)、10
(350 mg)、11(11.6 mg)。Fr. 5(13 g)用开放硅胶柱
分离,以石油醚-醋酸乙酯(50∶1→0∶1)进行梯度
洗脱,再经 Sephadex LH-20 柱色谱、制备薄层分
离纯化得到化合物 3(2.3 mg)、8(2.4 mg)。Fr. 6
(26 g)用 ODS 柱色谱分离,以甲醇-水进行梯度洗
脱,再经 Sephadex LH-20 柱色谱、制备薄层、高压
液相制备分离纯化得到化合物 4(6.6 mg)、5(6.0
mg)、6(15 mg)、7(44 mg)。
3 结构鉴定
化合物 1:白色固体,ESI-MS m/z: 449 [M+
Na]+, 425 [M-H]−,分子式为 C30H50O。1H-NMR
(500 MHz, CDCl3) δ: 2.39 (1H, m, H-2), 2.26 (2H, m,
H-2, 4), 1.95 (1H, m, H-1), 1.75 (1H, m, H-6), 1.66
(1H, m, H-1), 1.17 (3H, s, H-28), 1.04 (3H, s, H-27),
1.00 (3H, s, H-26), 0.99 (3H, s, H-27), 0.94 (3H, s,
H-29), 0.87 (3H, d, J = 6.6 Hz, H-23), 0.86 (3H, s,
中草药 Chinese Traditional and Herbal Drugs 第 45 卷 第 15 期 2014 年 8 月

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H-25), 0.71 (3H, s, H-24);13C-NMR (125 MHz,
CDCl3) δ: 22.2 (C-1), 41.5 (C-2), 213.1 (C-3), 58.2
(C-4), 42.1 (C-5), 41.3 (C-6), 18.2 (C-7), 53.1 (C-8),
37.4 (C-9), 59.4 (C-10), 35.6 (C-11), 30.5 (C-12), 39.7
(C-13), 38.3 (C-14), 32.4 (C-15), 36.0 (C-16), 30.0
(C-17), 42.8 (C-18), 35.3 (C-19), 28.1 (C-20), 32.7
(C-21), 39.2 (C-22), 6.8 (C-23), 14.6 (C-24), 17.9
(C-25), 20.2 (C-26), 18.6 (C-27), 32.1 (C-28), 35.0
(C-29), 31.8 (C-30)。以上数据与文献报道一致[4],
故鉴定化合物 1 为木栓酮。
化合物 2:白色固体,ESI-MS m/z: 491 [M+
Na]+, 467 [M-H]−,分子式为 C32H52O2。1H-NMR
(500 MHz, CDCl3) δ: 5.52 (1H, dd, J = 8.2, 3.2 Hz,
H-15), 4.45 (1H, dd, J = 10.6, 5.6 Hz, H-3), 2.04 (3H,
s, H-2′), 1.09 (3H, s, H-26), 0.95 (6H, s, H-24, 29),
0.91 (6H, s, H-30, 27), 0.87 (3H, s, H-23), 0.86 (3H, s,
H-25), 0.82 (3H, s, H-28);13C-NMR (125 MHz, CDCl3)
δ: 37.9 (C-1), 25.9 (C-2), 81.0 (C-3), 37.7 (C-4), 55.6
(C-5), 18.7 (C-6), 33.1 (C-7), 39.0 (C-8), 49.2 (C-9), 37.5
(C-10), 17.5 (C-11), 35.8 (C-12), 36.6 (C-13), 158.0
(C-14), 116.9 (C-15), 33.3 (C-16), 35.1 (C-17), 48.7
(C-18), 41.2 (C-19), 29.7 (C-20), 33.7 (C-21), 37.4
(C-22), 28.8 (C-23), 16.6 (C-24), 15.5 (C-25), 28.0
(C-26), 29.8 (C-27), 29.9 (C-28), 23.4 (C-29), 21.3
(C-30), 171.0 (C-1′), 21.3 (C-2′)。以上数据与文献报道
一致[5],故鉴定化合物 2 为蒲公英萜醇乙酸酯。
化合物 3:白色固体;ESI-MS m/z: 463 [M+
Na]+, 439 [M-H]−;分子式为 C30H48O2。1H-NMR
(500 MHz, CDCl3) δ: 5.55 (1H, dd, J = 8.1, 3.0 Hz,
H-15), 4.12 (1H, d, J = 7.1 Hz, H-3), 3.25 (1H, m,
H-11), 3.12 (1H, t, J = 5.1 Hz, H-12), 2.81 (1H, d, J =
4.6 Hz, H-9), 1.08 (6H, s, H-25, 26), 1.01 (3H, s,
H-24), 0.99 (3H, s, H-29), 0.97 (3H, s, H-27), 0.86
(3H, s, H-23), 0.82 (3H, s, H-28, 30);13C-NMR (125
MHz, CDCl3) δ: 38.2 (C-1), 26.8 (C-2), 79.0 (C-3),
38.6 (C-4), 54.6 (C-5), 18.9 (C-6), 33.1 (C-7), 38.9
(C-8), 52.0 (C-9), 37.5 (C-10), 53.6 (C-11), 58.3
(C-12), 36.6 (C-13), 157.1 (C-14), 118.9 (C-15), 35.2
(C-16), 35.4 (C-17), 48.1 (C-18), 40.3 (C-19), 28.7
(C-20), 36.5 (C-21), 38.2 (C-22), 27.9 (C-23), 16.9
(C-24), 15.4 (C-25), 27.0 (C-26), 30.2 (C-27), 29.9
(C-28), 33.6 (C-29), 19.5 (C-30)。以上数据与文献报
道一致[6],故鉴定化合物 3 为 3β-hydroxy-11α, 12α-
epoxy-friedoolean-14-ene。
化合物 4:白色固体,ESI-MS m/z: 595 [M+
Na]+, 571 [M-H]−,分子式为 C39H56O3。1H-NMR
(500 MHz, CDCl3) δ: 7.60 (1H, d, J = 15.9 Hz, H-3′),
7.43 (2H, d, J = 8.5 Hz, H-6′, 8′), 6.84 (2H, d, J = 8.5
Hz, H-5′, 9′), 6.30 (1H, d, J = 15.9 Hz, H-2′), 5.54
(1H, dd, J = 8.1, 3.1 Hz, H-15), 4.60 (1H, dd, J = 10.9,
5.4 Hz, H-3), 1.10 (3H, s, H-26), 0.98 (3H, s, H-25),
0.95 (6H, s, H-24, 29), 0.91 (6H, s, H-30, 27), 0.90
(3H, s, H-23), 0.82 (3H, s, H-28);13C-NMR (125
MHz, CDCl3) δ: 37.5 (C-1), 23.6 (C-2), 81.0 (C-3),
39.0 (C-4), 55.6 (C-5), 18.7 (C-6), 33.1 (C-7), 37.7
(C-8), 49.2 (C-9), 37.4 (C-10), 17.5 (C-11), 36.6
(C-12), 37.9 (C-13), 158.0 (C-14), 116.9 (C-15), 33.7
(C-16), 35.8 (C-17), 48.7 (C-18), 41.2 (C-19), 28.8
(C-20), 35.1 (C-21), 37.9 (C-22), 28.0 (C-23), 16.8
(C-24), 15.5 (C-25), 25.9 (C-26), 29.9 (C-27), 29.8
(C-28), 33.3 (C-29), 21.3 (C-30), 167.4 (C-1′), 116.2
(C-2′), 144.0 (C-3′), 127.3 (C-4′), 129.9 (C-5′, 9′),
115.8 (C-6′, 8′), 157.6 (C-7′)。以上数据与文献报道一
致[7],故鉴定化合物 4 为 careborin。
化合物 5:白色固体,ESI-MS m/z: 595 [M+
Na]+, 571 [M-H]−,分子式为 C39H56O3。1H-NMR
(500 MHz, CDCl3) δ: 7.61 (2H, d, J = 7.4 Hz, H-6′,
8′), 6.84 (1H, d, J = 12.7 Hz, H-3′), 6.77 (2H, d, J =
8.6 Hz, H-5′, 9′), 5.84 (1H, dd, J = 8.1, 12.6 Hz, H-2′),
5.54 (1H, dd, J = 8.1, 3.2 Hz, H-15), 4.52 (1H, dd, J =
11.0, 4.9 Hz, H-3), 1.09 (3H, s, H-26), 0.96 (6H, s,
H-24, 29), 0.91 (6H, s, H-30, 27), 0.87 (3H, s, H-25),
0.85 (3H, s, H-23), 0.82 (3H, s, H-28);13C-NMR (125
MHz, CDCl3) δ: 37.5 (C-1), 23.4 (C-2), 81.2 (C-3),
39.0 (C-4), 55.6 (C-5), 18.7 (C-6), 33.1 (C-7), 37.7
(C-8), 49.1 (C-9), 37.4 (C-10), 17.5 (C-11), 36.6
(C-12), 37.9 (C-13), 158.0 (C-14), 116.9 (C-15), 33.7
(C-16), 35.8 (C-17), 48.8 (C-18), 41.2 (C-19), 28.8
(C-20), 35.1 (C-21), 37.9 (C-22), 28.0 (C-23), 16.6
(C-24), 15.5 (C-25), 25.9 (C-26), 29.9 (C-27), 29.8
(C-28), 33.3 (C-29), 21.3 (C-30), 166.7 (C-1′), 116.9
(C-2′), 143.4 (C-3′), 127.4 (C-4′), 132.2 (C-5′, 9′),
115.1 (C-6′, 8′), 156.8 (C-7′)。以上数据与文献报道一
致[8],故鉴定化合物 5 为 cis-careborin。
化合物 6:白色固体,ESI-MS m/z: 625 [M+
Na]+, 601 [M-H]−,分子式为 C40H58O4。1H-NMR
中草药 Chinese Traditional and Herbal Drugs 第 45 卷 第 15 期 2014 年 8 月

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(500 MHz, CDCl3) δ: 7.59 (1H, d, J = 15.9 Hz, H-3′),
7.08 (1H, dd, J = 8.0, 1.5 Hz, H-9′), 7.06 (1H, d, J =
1.5 Hz, H-5′), 6.91 (1H, d, J = 8.1 Hz, H-8′), 6.29 (1H,
d, J = 15.9 Hz, H-2′), 5.57 (1H, dd, J = 8.1, 3.2 Hz,
H-15), 4.52 (1H, dd, J = 11.0, 4.9 Hz, H-3), 3.92 (3H,
s, H-10′), 1.10 (3H, s, H-26), 0.98 (3H, s, H-25), 0.95
(6H, s, H-24, 29), 0.91 (6H, s, H-30, 27), 0.90 (3H, s,
H-23), 0.82 (3H, s, H-28);13C-NMR (125 MHz,
CDCl3) δ: 37.5 (C-1), 23.5 (C-2), 80.7 (C-3), 39.0
(C-4), 55.7 (C-5), 18.7 (C-6), 33.1 (C-7), 37.7 (C-8),
49.1 (C-9), 37.4 (C-10), 17.5 (C-11), 36.6 (C-12), 37.9
(C-13), 158.0 (C-14), 116.9 (C-15), 33.7 (C-16), 35.8
(C-17), 48.8 (C-18), 41.2 (C-19), 28.8 (C-20), 35.1
(C-21), 37.9 (C-22), 28.0 (C-23), 16.6 (C-24), 15.5
(C-25), 25.9 (C-26), 29.9 (C-27), 29.8 (C-28), 33.3
(C-29), 21.3 (C-30), 167.1 (C-1′), 116.9 (C-2′), 143.3
(C-3′), 127.1 (C-4′), 109.2 (C-5′), 146.7 (C-6′), 147.8
(C-7′), 114.6 (C-8′), 123.0 (C-9′), 56.0 (C-10′)。以上
数据与文献报道一致[9],故鉴定化合物 6 为 3α-E-
feruloyltaraxerol。
化合物 7:白色固体,ESI-MS m/z: 625 [M+
Na]+, 601 [M-H]−,分子式为 C40H58O3。1H-NMR
(500 MHz, CDCl3) δ: 7.78 (1H, d, J = 1.8 Hz, H-5′),
7.10 (1H, dd, J = 8.2, 1.7 Hz, H-9′), 6.87 (1H, d, J =
8.2 Hz, H-8′), 6.77 (1H, d, J = 13 Hz, H-3′), 5.82 (1H,
d, J = 14.7 Hz, H-2′), 5.54 (1H, dd, J = 8.1, 3.2 Hz,
H-15), 4.52 (1H, dd, J = 11.0, 4.9 Hz, H-3), 3.92 (3H,
s, H-10′), 1.10 (3H, s, H-26), 0.98 (3H, s, H-25), 0.95
(6H, s, H-24, 29), 0.91 (6H, s, H-30, 27), 0.90 (3H, s,
H-23), 0.82 (3H, s, H-28);13C-NMR (125 MHz,
CDCl3) δ: 37.5 (C-1), 23.5 (C-2), 80.7 (C-3), 39.0
(C-4), 55.7 (C-5), 18.7 (C-6), 33.1 (C-7), 37.7 (C-8),
49.1 (C-9), 37.4 (C-10), 17.5 (C-11), 36.6 (C-12), 37.9
(C-13), 158.0 (C-14), 116.9 (C-15), 33.7 (C-16), 35.8
(C-17), 48.8 (C-18), 41.2 (C-19), 28.8 (C-20), 35.1
(C-21), 37.9 (C-22), 28.0 (C-23), 16.6 (C-24), 15.5
(C-25), 25.9 (C-26), 29.9 (C-27), 29.8 (C-28), 33.3
(C-29), 21.3 (C-30), 166.5 (C-1′), 116.9 (C-2′), 143.3
(C-3′), 127.3 (C-4′), 112.8 (C-5′), 145.9 (C-6′), 146.9
(C-7′), 113.8 (C-8′), 125.5 (C-9′), 56.0 (C-10′)。以上
数据与文献报道一致[9],故鉴定化合物 7 为 3α-Z-
feruloyltaraxerol。
化合物 8:无色油状物,ESI-MS m/z: 477 [M+
Na]+, 453 [M-H]−,分子式为 C31H50O2。1H-NMR
(500 MHz, CDCl3) δ: 5.36 (1H, d, J = 3.1 Hz, H-12),
3.93 (1H, dd, J = 9.4, 3.1 Hz, H-11), 3.24 (3H, s,
H-1′), 1.22 (3H, s, H-27), 1.15 (3H, s, H-25), 1.11
(3H, s, H-23), 1.07 (3H, s, H-24), 1.06 (3H, s, H-26),
0.90 (3H, s, H-30), 0.89 (3H, s, H-29), 0.84 (3H, s,
H-28);13C-NMR (125 MHz, CDCl3) δ: 40.3 (C-1),
34.4 (C-2), 218.1 (C-3), 47.7 (C-4), 55.5 (C-5), 19.7
(C-6), 32.9 (C-7), 42.9 (C-8), 50.3 (C-9), 37.7 (C-10),
76.3 (C-11), 121.6 (C-12), 149.3 (C-13), 42.0 (C-14),
26.2 (C-15), 26.8 (C-16), 32.4 (C-17), 47.2 (C-18),
46.4 (C-19), 31.1 (C-20), 34.7 (C-21), 36.9 (C-22),
26.7 (C-23), 21.5 (C-24), 16.4 (C-25), 18.1 (C-26),
25.1 (C-27), 28.5 (C-28), 33.2 (C-29), 23.6 (C-30),
53.7 (C-1′)。以上数据与文献报道一致[10],故鉴定化
合物 8 为 3-oxo-11α-methoxyolean-12-ene。
化合物 9:黄色油状物,ESI-MS m/z: 355 [M+
Na]+, 331 [M-H]−,分子式为 C20H28O4。1H-NMR
(500 MHz, CDCl3) δ: 5.54 (1H, m, H-3), 5.39 (1H, t,
J = 2.0 Hz, H-15), 5.25 (1H, t, J = 2.0 Hz, H-15), 4.89
(2H, d, J = 9.0 Hz, H-14), 4.08 (1H, t, J = 9.8 Hz,
H-6), 2.89 (1H, m, H-1), 2.83 (1H, m, H-5), 2.67 (1H,
m, H-7), 2.46 (3H, m, H-2, 9), 1.15 (3H, d, J = 7.8 Hz,
H-13), 0.96 (6H, d, J = 6.6 Hz, H-4′, 5′);13C-NMR
(125 MHz, CDCl3) δ: 43.7 (C-1), 36.2 (C-2), 74.4
(C-3), 148.9 (C-4), 50.1 (C-5), 83.7 (C-6), 45.7 (C-7),
28.7 (C-8), 36.2 (C-9), 148.4 (C-10), 39.2 (C-11),
179.6 (C-12), 11.4 (C-13), 113.4 (C-14), 113.2 (C-15),
172.8 (C-1′), 43.6 (C-2′), 25.7 (C-3′), 22.4 (C-4′), 22.4
(C-5′)。以上数据与文献报道一致[11],故鉴定化合物
9 为 diaspanolide A。
化合物 10:黄色油状物,ESI-MS m/z: 353 [M+
Na]+, 329 [M-H]−,分子式为 C20H26O4。1H-NMR
(500 MHz, CDCl3) δ: 6.21 (1H, d, J = 3.5 Hz, H-13),
5.56 (1H, m, H-3), 5.49 (1H, d, J = 3.1 Hz, H-13),
5.45 (1H, t, J = 2.0 Hz, H-15), 5.27 (1H, t, J = 2.1 Hz,
H-15), 4.97 (2H, d, J = 6.4 Hz, H-14), 4.06 (1H, dd,
J = 16.9, 7.6 Hz, H-6), 2.94 (1H, m, H-1), 2.85 (2H,
m, H-5, 7), 2.46 (2H, m, H-9), 1.78 (1H, m, H-2), 0.96
(6H, d, J = 6.6 Hz, H-4′, 5′);13C-NMR (125 MHz,
CDCl3) δ: 44.6 (C-1), 34.6 (C-2), 74.3 (C-3), 147.8
(C-4), 50.2 (C-5), 83.9 (C-6), 45.2 (C-7), 30.6 (C-8), 36.6
(C-9), 148.2 (C-10), 139.5 (C-11), 170.0 (C-12), 120.3
中草药 Chinese Traditional and Herbal Drugs 第 45 卷 第 15 期 2014 年 8 月

·2152·
(C-13), 114.3 (C-14), 113.4 (C-15), 172.8 (C-1′), 43.6
(C-2′), 25.8 (C-3′), 22.4 (C-4′), 22.4 (C-5′)。以上数据与
文献报道一致[12],故鉴定化合物 10 为 diaspanolide B。
化合物 11:黄色油状物,ESI-MS m/z: 351 [M+
Na]+, 327 [M-H]−,分子式为 C20H24O4。1H-NMR
(500 MHz, CDCl3) δ: 6.22 (1H, d, J = 3.5 Hz, H-13),
5.72 (1H, m, H-2′), 5.59 (1H, m, H-3), 5.49 (1H, d, J =
3.1 Hz, H-13), 5.47 (1H, t, J = 2.0 Hz, H-15), 5.30
(1H, t, J = 2.0 Hz, H-15), 4.97 (2H, d, J = 12.7 Hz,
H-14), 4.07 (1H, dd, J = 16.9, 7.6 Hz, H-6), 2.94 (1H,
m, H-1), 2.85 (2H, m, H-5, 7), 2.46 (2H, m, H-9), 2.19
(3H, d, J = 0.9 Hz, H-5′), 1.91 (3H, d, J = 1.0 Hz,
H-4′), 1.78 (1H, m, H-2), 0.96 (6H, d, J = 6.6 Hz,
H-4′, 5′);13C-NMR (125 MHz, CDCl3) δ: 44.7 (C-1),
34.6 (C-2), 73.7 (C-3), 147.9 (C-4), 50.3 (C-5), 84.0
(C-6), 45.2 (C-7), 30.7 (C-8), 36.8 (C-9), 148.4
(C-10), 139.6 (C-11), 170.0 (C-12), 120.3 (C-13), 114.4
(C-14), 113.2 (C-15), 166.3 (C-1′), 115.9 (C-2′), 157.4
(C-3′), 20.3 (C-4′), 27.4 (C-5′)。以上数据与文献报道
一致[13],故鉴定化合物 11 为 ainsliaolide A。
化合物 12:白色固体,ESI-MS m/z: 435 [M+
Na]+, 411 [M-H]−,分子式为 C29H48O。1H-NMR
(500 MHz, CDCl3) δ: 5.36 (1H, d, J = 5.2 Hz, H-6),
5.14 (1H, m, H-22), 5.01 (1H, m, H-23), 3.53 (1H, m,
H-3), 0.82 (3H, t, J = 7.2 Hz, H-29), 0.71 (3H, s,
H-18);13C-NMR (125 MHz, CDCl3) δ: 37.2 (C-1),
31.7 (C-2), 71.8 (C-3), 42.3 (C-4), 140.7 (C-5), 121.7
(C-6), 31.9 (C-7), 31.9 (C-8), 50.2 (C-9), 36.5 (C-10),
21.1 (C-11), 39.7 (C-12), 42.2 (C-13), 55.9 (C-14),
24.4 (C-15), 28.9 (C-16), 56.9 (C-17), 12.0 (C-18),
19.4 (C-19), 40.5 (C-20), 21.2 (C-21), 138.3 (C-22),
129.3 (C-23), 51.2 (C-24), 31.9 (C-25), 19.0 (C-26),
21.1 (C-27), 25.4 (C-28), 12.2 (C-29)。以上数据与文
献报道一致[14],故鉴定化合物 12 为豆甾醇。
化合物 13:白色固体,ESI-MS m/z: 437 [M+
Na]+, 413 [M-H]−,分子式为 C29H50O。1H-NMR
(500 MHz, CDCl3) δ: 5.36 (1H, m, H-6), 3.53 (1H, m,
H-3), 1.02 (3H, s, H-19), 0.92 (3H, d, J = 6.6 Hz,
H-21);13C-NMR (125 MHz, CDCl3) δ: 37.2 (C-1),
31.7 (C-2), 71.8 (C-3), 42.3 (C-4), 140.8 (C-5), 121.7
(C-6), 31.9 (C-7), 31.9 (C-8), 50.1 (C-9), 36.5 (C-10),
21.1 (C-11), 39.8 (C-12), 42.3 (C-13), 56.8 (C-14),
24.3 (C-15), 28.2 (C-16), 56.0 (C-17), 11.8 (C-18),
19.4 (C-19), 36.1 (C-20), 18.8 (C-21), 33.9 (C-22),
26.1 (C-23), 45.8 (C-24), 29.1 (C-25), 19.8 (C-26),
19.0 (C-27), 23.1 (C-28), 12.0 (C-29)。以上数据与文
献报道一致[15],故鉴定化合物 13 为 β-谷甾醇。
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