中草药  2015, Vol. 46 Issue (18): 2683-2688
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引用本文doi: 10.7501/j.issn.0253-2670.2015.18.004
李淑敏, 杨俊玲, 刘艳萍, 付艳辉. 羊角棉中非生物碱类化学成分研究[J]. 中草药, 2015, 46(18): 2683-2688.
LI Shu-min, YANG Jun-ling, LIU Yan-ping, FU Yan-hui. Studies on non-alkaloid constituents from Alstonia mairei[J]. Chinese Traditional and Herbal Drugs, 2015, 46(18): 2683-2688.
羊角棉中非生物碱类化学成分研究
李淑敏1, 杨俊玲1, 刘艳萍1,2, 付艳辉2     
1. 山东药品食品职业学院, 山东 威海 264210;
2. 海南师范大学 热带药用植物化学教育部重点实验室, 海南 海口 571158
收稿日期: 2015-06-10;
基金项目: 国家自然科学基金资助项目(21302181);海南省应用技术研发与示范推广专项(ZDXM2015063);海南省自然科学基金(2014027)海南省高校科研项目(HNKY2014-41)
作者简介: 李淑敏,女,副教授,主要从事药物化学的研究与教学。E-mail:whlishumin@163.com
通讯作者: 付艳辉,副教授,硕士生导师。E-mail:fuyanhui80@163.com
摘要: 目的 研究夹竹桃科植物羊角棉Alstonia mairei枝叶中的非生物碱类化学成分。方法 采用硅胶柱色谱、反相硅胶柱色谱和Sephadex LH-20凝胶柱色谱以及制备型高效液相色谱等方法进行分离,采用理化分析以及NMR谱和MS谱等谱学方法鉴定化合物的结构。结果 从羊角棉枝叶90%乙醇提取物的石油醚萃取部位中分离得到了18个化合物,分别鉴定为羽扇豆醇(1)、30-醛基羽扇豆醇(2)、羽扇豆醇乙酸酯(3)、α-香树酯醇(4)、α-香树酯酮(5)、23-羟基熊果酸(6)、β-香树酯醇(7)、β-香树酯酮(8)、山楂酸(9)、木栓醇(10)、木栓酮(11)、杨芽黄素(12)、5,6-二羟基-7,4'-二甲氧基黄酮(13)、5,3'-二羟基-7,4'-二甲氧基黄酮(14)、7-羟基-5,3',4'-三甲氧基黄酮(15)、5,7,3',4'-四甲氧基黄酮(16)、5-羟基-6,7,8,4'-四甲氧基黄酮(17)和5-羟基-6,7,8,3',4'-五甲氧基黄酮(18)。结论 化合物1为首次从羊角棉中分离得到,其他化合物均为首次从鸡骨常山属植物中分离得到。
关键词: 夹竹桃科     羊角棉     23-羟基熊果酸     杨芽黄素     5,7,3',4'-四甲氧基黄酮    
Studies on non-alkaloid constituents from Alstonia mairei
LI Shu-min1, YANG Jun-ling1, LIU Yan-ping1,2, FU Yan-hui2    
1. Shandong Drug and Food Vocational College, Weihai 264210, China;
2. Key Laboratory of Tropical Medicinal Plant Chemistry, Ministry of Education, Hainan Normal University, Haikou 571158, China
Abstract: Objective To study the non-alkaloid constituents from the stems and leaves of Alstonia mairei. Methods The chemical constituents were separated and purified by silica gel, ODS, Sephadex LH-20 gel column chromatographies, and preparative HPLC. Their structures were determined by physicochemical properties, spectral data, as well as comparisons with the data in literature. Results Eighteen compounds were isolated from the petroleum ether fraction of 90% ethanol extract from the stems and leaves of A. mairei, and identified as lupeol (1), 30-oxo-lupeol (2), lupenyl acetate (3), α-amyrin (4), α-amyrenone (5), 23-hydroxyursolic acid (6), β-amyrin (7), β-amyrenone (8), maslinic acid (9), friedelinol (10), friedelin (11), tectochrysin (12), 5,6-dihydroxy-7,4'- dimethoxyflavone (13), 5,3'-dihydroxy-7,4'-dimethoxyflavone (14), 7-hydroxy-7,5,3',4'-trimethoxyflavone (15), 5,7,3',4'- tetramethoxyflavone (16), 5-hydroxy-6,7,8,4-tetramethoxyflavone (17), and 5-hydroxy-6,7,8,3',4'-pentamethoxyflavone (18). Conclusion All compounds are isolated from A. mairei for the first time. In addition to compound 1, the other compounds are isolated from the plants of Alstonia R. Br. for the first time.
Key words: Apocynaceae     Alstonia mairei Lévl.     23-hydroxyursolic acid     tectochrysin     5,7,3',4'-tetramethoxyflavone    

夹竹桃科（Apocynaceae）鸡骨常山属Alstonia R. Br. 植物全世界约有50种，分布于非洲和亚洲至波里尼西亚，我国有6种，产西南部和南部[1]。该属植物富含单萜吲哚生物碱，且大多具显著生物活性[2, 3, 4, 5, 6, 7]。羊角棉Alstonia mairei Lévl. 为夹竹桃科鸡骨常山属植物，为我国特有种，分布于云南、贵州和四川，以根和叶入药，具有清热、解毒、止痛、止血和排脓生肌等功效，可用于治疗外伤出血和疮毒等[1]。本课题组一直致力于富含生物碱的热带药用植物的化学成分及其药理活性研究，在前期研究中发现羊角棉枝叶的乙醇提取液具有显著的抗肿瘤活性，经系统查阅文献发现，对羊角棉的化学成分研究较罕见，且仅对其中生物碱类化学成分进行过研究[6, 7]，对其中非生物碱类化学成分的研究未见报道。为了进一步阐明羊角棉药效物质基础，本实验对羊角棉枝叶中的非生物碱类化学成分进行了系统研究，从其枝叶90%乙醇提取物的石油醚萃取部位中分离得到了18个化合物，分别鉴定为羽扇豆醇（lupeol，1）、30-醛基羽扇豆醇（30-oxo-lupeol，2）、羽扇豆醇乙酸酯（lupenyl acetate，3）、α-香树酯醇（α-amyrin，4）、α-香树酯酮（α-amyrenone，5）、23-羟基熊果酸（23-hydroxyursolic acid，6）、β-香树酯醇（β-amyrin，7）、β-香树酯酮（β-amyrenone，8）、山楂酸（maslinic acid，9）、木栓醇（friedelinol，10）、木栓酮（friedelin，11）、杨芽黄素（tectochrysin，12）、5,6-二羟基-7,4′-二甲氧基黄酮（5,6-dihydroxy- 7,4′-dimethoxyflavone，13）、5,3′-二羟基-7,4′-二甲氧基黄酮（5,3′-dihydroxy-7,4′-dimethoxyflavone，14）、7-羟基-5,3′,4′-三甲氧基黄酮（7-hydroxy- 5,3′,4′-trimethoxyflavone，15）、5,7,3′,4′-四甲氧基黄酮（5,7,3′,4′-tetramethoxyflavone，16）、5-羟基-6,7,8,4′-四甲氧基黄酮（5-hydroxy-6,7,8,4′-tetramethoxy- flavone，17）和5-羟基-6,7,8,3′,4′-五甲氧基黄酮（5-hydroxy-6,7,8,3′,4′-pentamethoxyflavone，18）。除化合物1为首次从羊角棉中分离得到以外，其他化合物均为首次从鸡骨常山属植物中分离得到。

1 仪器与材料

Bruker AV-400型超导核磁共振仪（德国Bruker公司）；Finnigan LCQ Advantage MAX型质谱仪（美国热电公司）；Agilent 1200分析型高效液相色谱仪（美国安捷伦科技有限公司）；Cosmosil C18分析型色谱柱（250 mm×4.6 mm，5 μm）；Dionex制备型高效液相色谱仪（美国戴安公司）；Cosmosil C18半制备型色谱柱（250 mm×10 mm，5 μm）；中低压制备色谱（瑞士Buchi公司）；薄层硅胶GF254和柱色谱硅胶（青岛海洋化工厂）；Sephadex LH-20（Amersham Blosclences公司）；ODS柱色谱材料（C18，10～40 μm，Merck公司）；所用试剂均为分析纯试剂。

羊角棉枝叶于2014年5月采集于云南省昭通市，经海南师范大学生命科学学院钟琼芯教授鉴定为夹竹桃科鸡骨常山属植物羊角棉Alstonia mairei Lévl. 的枝叶，凭证标本（20140501）保存于海南师范大学热带药用植物化学教育部重点实验室标本室。

2 提取与分离

羊角棉的干燥枝叶9.0 kg，粉碎，90%乙醇冷浸提取，每次冷浸1周，提取3次，提取液减压浓缩得浸膏1.6 kg。浸膏加水混悬，依次用石油醚和醋酸乙酯进行萃取，回收溶剂后得石油醚部位162.6 g和醋酸乙酯部位280.8 g。石油醚部位经硅胶（100～200目）柱色谱分离，石油醚-丙酮（100∶0→0∶100）为洗脱剂梯度洗脱得到6个流分（Fr. 1～8）。Fr. 2（10.6 g）经硅胶（200～300目）柱色谱分离，石油醚-醋酸乙酯（100∶0→0∶100）为洗脱剂梯度洗脱得5个亚流分Fr. 2A～2F。Fr. 2A经硅胶柱色谱分离，石油醚-醋酸乙酯（19∶1）等度洗脱得到化合物1（58.4 mg）、3（15.9 mg）和7（16.2 mg）；Fr. 2B经硅胶柱色谱分离，石油醚-丙酮（19∶1）等度洗脱得到化合物2（11.6 mg）、4（22.6 mg）和8（19.6 mg）；Fr. 2C经反复硅胶柱色谱，石油醚- 丙酮（9∶1）等度洗脱得到化合物5（15.8 mg）、9（9.6 mg）和11（44.2 mg）；Fr. 2D 经Sephadex LH-20（氯仿-甲醇）纯化得到化合物6（13.6 mg）和10（38.3 mg）。Fr. 3（25.8 g）经ODS反相柱色谱，甲醇-水（50∶50→100∶0）梯度洗脱，得到5个亚流分Fr. 3A～3E。Fr. 3A经制备型高效液相色谱，以甲醇-水（85∶15）为流动相，得到化合物12（9.6 mg）、15（32.6 mg）、17（16.2 mg）和18（36.6 mg）；Fr. 3B 经制备型高效液相色谱，以甲醇-水（75∶25）为流动相，得到化合物13（12.4 mg）、14（18.9 mg）和16（32.5 mg）。

3 结构鉴定

化合物1：白色无定形粉末，Liebermann- Burchard反应阳性；分子式为C30H50O，ESI-MS m/z: 427 [M＋H]+。1H-NMR (400 MHz,CDCl3) δ: 4.68 (1H,brs,H-29a),4.60 (1H,brs,H-29b),3.19 (1H,dd,J = 10.8,5.0 Hz,H-3),1.68 (3H,s,H-30),1.01 (3H,s,H-28),0.97 (3H,s,H-27),0.94 (3H,s,H-26),0.83 (3H,s,H-25),0.81 (3H,s,H-24),0.78 (3H,s,H-23)；13C-NMR (100 MHz,CDCl3) δ: 145.1 (C-20),110.2 (C-29),79.3 (C-3),55.6 (C-5),50.9 (C-9),49.0 (C-18),48.1 (C-19),42.9 (C-17),42.2 (C-14),40.8 (C-8),40.1 (C-22),38.9 (C-1),38.5 (C-4),38.0 (C-13),36.8 (C-10),35.6 (C-16),34.4 (C-7),30.3 (C-21),29.8 (C-2),28.0 (C-23),27.6 (C-15),25.4 (C-12),20.9 (C-11),19.3 (C-30),18.4 (C-6),18.1 (C-28),16.2 (C-25),15.5 (C-26),15.4 (C-24),14.2 (C-27)。以上数据与文献报道的数据基本一致[8]，故鉴定化合物1为羽扇豆醇。

化合物2：白色无定形粉末，Liebermann- Burchard反应阳性；分子式为C30H48O2，ESI-MS m/z: 441 [M＋H]+,463 [M＋Na]+。1H-NMR (400 MHz,CDCl3) δ: 9.49 (1H,brs,H-30),6.28 (1H,brs,H-29a),5.88 (1H,brs,H-29b),3.21 (1H,dd,J = 11.0,4.8 Hz,H-3),1.00 (3H,s,H-26),0.95 (3H,s,H-23),0.91 (3H,s,H-27),0.80 (3H,s,H-28),0.78 (3H,s,H-25),0.68 (3H,s,H-24)；13C-NMR (100 MHz,CDCl3) δ: 195.0 (C-30),156.9 (C-20),133.1 (C-29),78.9 (C-3),54.8 (C-5),51.2 (C-18),50.1 (C-9),42.8 (C-17),42.7 (C-14),40.9 (C-8),40.1 (C-22),39.2 (C-4),38.9 (C-1),37.9 (C-13),37.0 (C-10),36.6 (C-19),35.4 (C-16),34.3 (C-7),32.9 (C-21),28.1 (C-23),27.8 (C-12),27.6 (C-15),27.3 (C-2),21.0 (C-11),18.6 (C-6),17.9 (C-28),16.1 (C-25),15.8 (C-26),15.4 (C-24),14.3 (C-27)。以上数据与文献报道基本一致[9]，故鉴定化合物2为30-醛基羽扇豆醇。

化合物3：白色无定形粉末，Liebermann- Burchard反应阳性。分子式为C32H52O2，ESI-MS m/z: 469 [M＋H]+。1H-NMR (400 MHz,CDCl3) δ: 4.72 (1H,brs,H-29a),4.61 (1H,brs,H-29b),4.48 (1H,dd,J = 11.6,6.8 Hz,H-3),2.12 (3H,s,CH3CO),1.71 (3H,s,H-30),1.08 (3H,s,CH3),1.03 (3H,s,CH3),0.94 (3H,s,CH3),0.91 (3H,s,CH3),0.87 (3H,s,CH3),0.79 (3H,s,CH3)；13C-NMR (100 MHz,CDCl3) δ: 171.2 (CH3CO),150.8 (C-20),109.6 (C-29),80.9 (C-3),55.7 (C-5),50.8 (C-9),49.1 (C-18),48.6 (C-19),43.0 (C-17),42.7 (C-14),40.1 (C-22),39.8 (C-8),38.5 (C-1),38.2 (C-13),37.6 (C-4),36.9 (C-10),35.7 (C-16),34.8 (C-7),29.7 (C-21),27.9 (C-23),27.6 (C-15),25.7 (C-12),23.6 (C-2),22.0 (CH3CO),21.8 (C-11),19.8 (C-30),18.5 (C-6),18.1 (C-28),16.9 (C-25),16.4 (C-26),15.7 (C-24),14.9 (C-27)。以上数据与文献报道基本一致[10]，故鉴定化合物3为羽扇豆醇乙酸酯。

化合物4：白色无定形粉末，Liebermann- Burchard反应阳性；分子式为C30H50O，ESI-MS m/z: 427 [M＋H]+,449 [M＋Na]+。1H-NMR (400 MHz,CDCl3) δ: 5.21 (1H,t,J = 4.0 Hz,H-12),3.20 (1H,t,J = 7.0 Hz,H-3),1.12 (3H,s,H-27),1.06 (3H,s,H-23),1.03 (3H,s,H-25),1.00 (3H,s,H-24),0.93 (3H,d,J = 6.6 Hz,H-29),0.89 (3H,d,J = 6.6 Hz,H-30),0.85 (3H,s,H-28),0.79 (3H,s,H-26)；13C-NMR (100 MHz,CDCl3) δ: 139.2 (C-13),124.7 (C-12),79.0 (C-3),59.1 (C-18),55.4 (C-5),47.9 (C-9),41.8 (C-14),41.5 (C-22),40.3 (C-8),39.8 (C-20),39.2 (C-19),38.8 (C-4),38.4 (C-1),36.7 (C-10),33.6 (C-17),32.8 (C-7),32.6 (C-21),28.7 (C-15),28.5 (C-23),28.4 (C-28),27.8 (C-2),26.9 (C-16),24.3 (C-11),23.3 (C-27),22.1 (C-30),19.0 (C-6),18.7 (C-29),17.8 (C-26),17.3 (C-25),16.1 (C-24)。以上数据与文献报道基本一致[11]，故鉴定化合物4为α-香树酯醇。

化合物5：白色无定形粉末，Liebermann- Burchard反应阳性；分子式为C30H48O，ESI-MS m/z: 425 [M＋H]+,447 [M＋Na]+。1H-NMR (400 MHz,CDCl3) δ: 5.18 (1H,t,J = 4.0 Hz,H-12),1.10 (3H,s,H-27),1.06 (3H,s,H-23),1.03 (3H,s,H-25),1.00 (3H,s,H-24),0.96 (3H,d,J = 5.8 Hz,H-29),0.89 (3H,d,J = 5.8 Hz,H-30),0.86 (3H,s,H-28),0.82 (3H,s,H-26)；13C-NMR (100 MHz,CDCl3) δ: 217.8 (C-3),139.8 (C-13),124.3 (C-12),58.9 (C-18),55.4 (C-5),47.5 (C-4),47.2 (C-9),42.5 (C-14),41.6 (C-22),40.2 (C-8),39.8 (C-20),39.7 (C-19),39.6 (C-1),36.8 (C-10),34.3 (C-2),34.0 (C-17),32.6 (C-7),31.4 (C-21),29.0 (C-15),28.9 (C-28),28.3 (C-23),26.7 (C-16),23.6 (C-11),23.3 (C-27),21.8 (C-24),21.4 (C-30),20.1 (C-6),17.8 (C-29),17.2 (C-26),15.9 (C-25)。以上数据与文献报道的数据基本一致[12]，故鉴定化合物5为α-香树酯酮。

化合物6：白色无定形粉末，Liebermann- Burchard反应阳性；分子式为C30H48O4，ESI-MS m/z: 473 [M＋H]+。1H-NMR (400 MHz,CDCl3) δ: 5.47 (1H,t,J = 3.8 Hz,H-12),4.19 (1H,t,J = 6.8 Hz,H-3),4.16 (1H,d,J = 9.8 Hz,H-23a),3.71 (1H,d,J = 9.8 Hz,H-23b),2.58 (1H,d,J = 11.2 Hz,H-18),1.96 (3H,s,H-27),1.77 (3H,s,H-24),1.08 (3H,s,H-25),1.03 (3H,d,J = 6.6 Hz,H-29),0.99 (3H,s,H-26),0.96 (3H,d,J = 5.7 Hz,H-30)；13C-NMR (100 MHz,CDCl3) δ: 179.8 (C-28),139.2 (C-13),125.5 (C-12),79.2 (C-3),66.0 (C-23),53.4 (C-18),47.9 (C-5),48.6 (C-9),48.5 (C-17),42.9 (C-4),42.7 (C-14),39.9 (C-8),39.6 (C-19),39.3 (C-20),39.0 (C-1),38.6 (C-10),37.4 (C-22),33.3 (C-7),31.0 (C-21),28.5 (C-15),26.1 (C-2),24.9 (C-16),24.0 (C-11),23.6 (C-27),21.3 (C-30),18.4 (C-6),17.6 (C-26),17.6 (C-29),17.1 (C-25),15.8 (C-24)。以上数据与文献报道基本一致[13]，故鉴定化合物6为23-羟基熊果酸。

化合物7：白色无定形粉末，Liebermann- Burchard反应阳性；分子式为C30H50O，ESI-MS m/z: 427 [M＋H]+。1H-NMR (400 MHz,CDCl3) δ: 5.49 (1H,t,J = 4.0 Hz,H-12),3.51 (1H,m,H-3),1.19,1.13,1.10,1.05,1.03,0.99,0.83 (3H×7,s,7×-CH3)；13C-NMR (100 MHz,CDCl3) δ: 145.8 (C-13),122.1 (C-12),78.9 (C-3),55.7 (C-5),48.1 (C-9),47.6 (C-18),46.7 (C-19),41.8 (C-14),40.0 (C-8),38.9 (C-4),38.5 (C-1),37.3 (C-10),36.9 (C-22),34.5 (C-21),33.6 (C-29),33.1 (C-17),30.9 (C-20),28.8 (C-28),28.3 (C-23),27.5 (C-2),27.0 (C-16),26.6 (C-15),26.0 (C-27),23.9 (C-11),23.6 (C-30),19.1 (C-6),18.6 (C-6),17.2 (C-26),16.1 (C-24),15.8 (C-25)。以上数据与文献报道基本一致[14]，故鉴定化合物7为β-香树酯醇。

化合物8：白色无定形粉末，Liebermann- Burchard反应阳性；分子式为C30H48O，ESI-MS m/z: 425 [M＋H]+。1H-NMR (400 MHz,CDCl3) δ: 5.38 (1H,t,J = 4.2 Hz,H-12),1.18,1.12,1.09,1.03,0.99,0.95,0.86 (3H×7,s,7×-CH3)；13C-NMR (100 MHz,CDCl3) δ: 217.8 (C-3),145.6 (C-13),121.8 (C-12),55.8 (C-5),47.6 (C-4),47.3 (C-18),46.9 (C-9),46.8 (C-19),42.0 (C-14),39.8 (C-8),39.3 (C-1),37.4 (C-22),36.8 (C-10),34.8 (C-21),34.3 (C-2),33.6 (C-29),32.5 (C-17),32.3 (C-7),31.1 (C-20),28.8 (C-28),23.9 (C-11),26.9 (C-16 ),26.6 (C-23),26.3 (C-15),25.8 (C-27),23.8 (C-30),21.5 (C-24),20.3 (C-6),17.4 (C-26),15.8 (C-25)。以上数据与文献报道基本一致[15]，故鉴定化合物8为β-香树酯酮。

化合物9：白色无定形粉末，Liebermann- Burchard反应阳性；分子式为C30H48O4，ESI-MS m/z: 473 [M＋H]+。1H-NMR (400 MHz,C5D5N) δ: 5.52 (1H,t,J = 3.8,H-12),1.36,1.26,1.10,1.03,1.00,0.98,0.91 (3H×7,s,CH3×7)；13C-NMR (100 MHz,C5D5N) δ: 180.2 (C-28),144.9 (C-13),122.8 (C-12),83.8 (C-3),68.9 (C-2),56.3 (C-5),48.4 (C-9),47.8 (C-19),46.9 (C-17),46.4 (C-1),42.5 (C-14),42.1 (C-18),39.9 (C-8),39.6 (C-4),38.4 (C-10),34.2 (C-21),33.5 (C-29),33.5 (C-22),33.2 (C-7),31.1 (C-20),29.7 (C-23),28.6 (C-15),26.8 (C-27),23.9 (C-16),23.7 (C-30),23.4 (C-11),18.9 (C-6),18.1 (C-26),17.5 (C-24),16.9 (C-25)。以上数据与文献报道的数据基本一致[16]，故鉴定化合物9为山楂酸。

化合物10：白色无定形粉末，Liebermann- Burchard反应阳性；分子式为C30H52O，ESI-MS m/z: 429 [M＋H]+,451 [M＋Na]+。1H-NMR (400 MHz,CDCl3) δ: 1.21 (3H,s,H-28),1.06 (3H,s,H-27),1.02 (3H,s,H-29),0.99 (3H,s,H-26),0.95 (3H,s,H-30),0.89 (3H,d,J = 6.6 Hz,H-23),0.87 (3H,s,H-24),0.76 (3H,s,H-25)；13C-NMR (100 MHz,CDCl3) δ: 72.8 (C-3),61.6 (C-10),53.9 (C-8),49.1 (C-4),42.6 (C-18),42.0 (C-6),39.7 (C-5),39.6 (C-22),38.1 (C-14),37.6 (C-13),37.3 (C-9),36.3 (C-2),35.8 (C-11),35.2 (C-16),35.0 (C-19),34.8 (C-30),32.3 (C-21),32.1 (C-28),31.9 (C-15),31.6 (C-29),30.3 (C-12),29.8 (C-17),28.5 (C-20),20.1 (C-27),18.6 (C-25),18.2 (C-26),17.6 (C-7),16.8 (C-24),16.7 (C-1),11.1 (C-23)。以上数据与文献报道的数据基本一致[17]，故鉴定化合物10为木栓醇。

化合物11：白色无定形粉末，Liebermann- Burchard反应阳性；分子式为C30H50O，ESI-MS m/z: 427 [M＋H]+。1H-NMR (400 MHz,CDCl3) δ: 2.42 (1H,dd,J = 4.8,2.2 Hz,H-2a),2.39 (1H,dd,J = 4.8,2.2 Hz,H-2b),2.35 (1H,d,J = 4.0 Hz,H-4),1.18 (3H,s,H-28),1.08 (3H,s,H-27),1.00 (3H,s,H-30),0.96 (3H,s,H-26),0.94 (3H,s,H-29),0.89 (3H,d,J = 6.8 Hz,H-23),0.86 (3H,s,H-25),0.69 (3H,s,H-24)；13C-NMR (100 MHz,CDCl3) δ: 213.1 (C-3),59.6 (C-10),58.1 (C-4),52.9 (C-8),42.8 (C-18),42.5 (C-5),41.7 (C-2),41.5 (C-6),40.0 (C-13),39.6 (C-22),38.2 (C-14),37.7 (C-9),36.3 (C-16),36.0 (C-11),35.5 (C-19),35.2 (C-29),32.9 (C-21),32.5 (C-15),32.1 (C-28),31.9 (C-30),31.7 (C-17),30.7 (C-12),28.5 (C-20),22.8 (C-1),20.5 (C-26),19.0 (C-27),18.3 (C-7),17.9 (C-25),15.1 (C-24),7.2 (C-23)。以上数据与文献报道基本一致[18]，故鉴定化合物11为木栓酮。

化合物12：淡黄色无定形粉末，三氯化铁反应和盐酸-镁粉反应阳性；分子式为C16H12O4，ESI-MS m/z: 269 [M＋H]+。1H-NMR (400 MHz,DMSO-d6) δ: 12.78 (1H,s,5-OH),7.86 (2H,t,J = 8.0 Hz,H-3′,5′),7.59～7.66 (3H,m,H-3′,4′,5′),6.72 (1H,s,H-3),6.49 (1H,d,J = 2.2 Hz,H-8),6.32 (1H,d,J = 2.2 Hz,H-6),3.89 (3H,s,7-OCH3)；13C-NMR (100 MHz,DMSO-d6) δ: 181.9 (C-4),165.3 (C-7),163.9 (C-2),161.7 (C-5),157.8 (C-9),131.9 (C-4′),131.1 (C-1′),129.0 (C-3′,5′),126.5 (C-2′,6′),106.3 (C-10),105.8 (C-3),98.1 (C-6),92.8 (C-8),55.8 (7-OCH3)。以上数据与文献报道基本一致[19]，故鉴定化合物12为杨芽黄素。

化合物13：淡黄色无定形粉末，三氯化铁反应和盐酸-镁粉反应阳性；分子式为C17H14O6，ESI-MS m/z: 315 [M＋H]+。1H-NMR (400 MHz,DMSO-d6) δ: 12.56 (1H,s,5-OH),8.72 (1H,s,6-OH),8.08 (2H,d,J = 8.4 Hz,H-2′,6′),7.09 (2H,d,J = 8.4 Hz,H-3′,5′),6.96 (1H,s,H-3),6.88 (1H,s,H-8),3.90 (3H,s,4′-OCH3),3.86 (3H,s,7-OCH3)；13C-NMR (100 MHz,DMSO-d6) δ: 181.9 (C-4),163.2 (C-2),162.3 (C-4′),154.6 (C-7),150.0 (C-5),146.4 (C-9),129.8 (C-6),128.2 (C-2′,6′),122.9 (C-1′),114.6 (C-3′,5′),104.9 (C-10),103.2 (C-3),91.5 (C-8),56.6 (4′-OCH3),55.9 (7-OCH3)。以上数据与文献报道基本一致[20]，故鉴定化合物13为5,6-二羟基-7,4′-二甲氧基黄酮。

化合物14：淡黄色无定形粉末，三氯化铁反应和盐酸-镁粉反应阳性；分子式为C17H14O6，ESI-MS m/z: 315 [M＋H]+。1H-NMR (400 MHz,DMSO-d6) δ: 12.61 (1H,s,5-OH),8.92 (1H,s,3′-OH),7.49 (1H,dd,J = 8.6,2.0 Hz,H-6′),7.39 (1H,d,J = 2.0 Hz,H-2′),7.08 (1H,d,J = 8.6 Hz,H-5′),6.72 (1H,s,H-3),6.68 (1H,d,J = 2.2 Hz,H-8),6.28 (1H,d,J = 2.2 Hz,H-6),3.88 (3H,s,7-OCH3),3.81 (3H,s,4′-OCH3)；13C-NMR (100 MHz,DMSO-d6) δ: 182.1 (C-4),165.4 (C-7),163.9 (C-2),160.9 (C-5),157.6 (C-9),150.9 (C-4′),146.89 (C-3′),122.8 (C-1′),119.1 (C-6′),112.6 (C-2′),112.2 (C-5′),104.7 (C-10),103.9 (C-3),98.4 (C-6),93.1 (C-8),56.4 (4′-OCH3),55.8 (7-OCH3)。以上数据与文献报道基本一致[21]，故鉴定化合物14为5,3′-二羟基-7,4′-二甲氧基黄酮。

化合物15：淡黄色无定形粉末，三氯化铁反应和盐酸-镁粉反应阳性；分子式为C18H16O6，ESI-MS m/z: 329 [M＋H]+。1H-NMR (400 MHz,DMSO-d6) δ: 10.72 (1H,s,5-OH),7.58 (1H,dd,J = 8.2,1.8 Hz,H-6′),7.51 (1H,d,J = 1.8 Hz,H-2′),7.10 (1H,d,J = 8.2 Hz,H-5′),6.71 (1H,s,H-3),6.60 (1H,d,J = 2.0 Hz,H-8),6.38 (1H,d,J = 2.0 Hz,H-6),3.86 (3H,s,3′-OCH3),3.83 (3H,s,4′-OCH3),3.80 (3H,s,5-OCH3)；13C-NMR (100 MHz,DMSO-d6) δ: 176.3 (C-4),162.2 (C-7),160.6 (C-5),159.5 (C-2),158.9 (C-9),151.3 (C-4′),148.8 (C-3′),123.4 (C-1′),119.2 (C-6′),112.1 (C-5′),109.2 (C-2′),107.5 (C-10),106.8 (C-3),96.7 (C-6),95.5 (C-8),57.2 (3′-OCH3),56.9 (4′-OCH3),55.6 (5′-OCH3)。以上数据与文献报道的数据基本一致[21]，故鉴定化合物15为7-羟基-5,3′,4′-三甲氧基黄酮。

化合物16：淡黄色无定形粉末，盐酸-镁粉反应阳性；分子式为C19H18O6，ESI-MS m/z: 343 [M＋H]+。1H-NMR (400 MHz,DMSO-d6) δ: 7.51 (1H,dd,J = 8.8,1.8 Hz,H-6′),7.28 (1H,d,J = 1.8 Hz,H-2′),6.86 (1H,d,J = 8.8 Hz,H-5′),6.61 (1H,s,H-3),6.51 (1H,d,J = 2.0 Hz,H-8),6.32 (1H,d,J = 2.0 Hz,H-6),3.96 (3H,s,3′-OCH3),3.95 (3H,s,5-OCH3),3.93 (3H,s,4′-OCH3),3.87 (3H,s,7-OCH3)；13C-NMR (100 MHz,DMSO-d6) δ: 178.1 (C-4),164.0 (C-7),161.1 (C-2),160.9 (C-5),160.0 (C-9),151.9 (C-4′),149.4 (C-3′),123.9 (C-1′),119.8 (C-6′),110.9 (C-5′),109.5 (C-10),108.8 (C-2′),107.9 (C-3),96.5 (C-6),93.1 (C-8),56.6 (4′-OCH3),56.3 (5-OCH3),55.9 (3′-OCH3),55.6 (7-OCH3)。以上数据与文献报道基本一致[22]，故鉴定化合物16为5,7,3′,4′-四甲氧基黄酮。

化合物17：淡黄色无定形粉末，三氯化铁反应和盐酸-镁粉反应阳性；分子式为C19H18O7，ESI-MS m/z: 359 [M＋H]+。1H-NMR (400 MHz,DMSO-d6) δ: 11.96 (1H,s,5-OH),7.28 (2H,d,J = 8.4 Hz,H-2′,6′),6.36 (2H,d,J = 8.4 Hz,H-3′,5′),6.21 (1H,s,H-3),3.24 (3H,s,6-OCH3),3.18 (3H,s,7-OCH3),3.11 (3H,s,8-OCH3),3.08 (3H,s,4′-OCH3)；13C-NMR (100 MHz,DMSO-d6) δ: 182.6 (C-4),164.3 (C-2),162.7 (C-4′),153.1 (C-7),149.0 (C-5),145.8 (C-9),136.4 (C-6),132.8 (C-8),128.6 (C-2′,6′),123.1 (C-1′),115.3 (C-3′,5′),106.8 (C-10),104.1 (C-3),62.5 (6-OCH3),62.1 (7-OCH3),60.8 (8-OCH3),55.8 (4′-OCH3)。以上数据与文献报道基本一致[23]，故鉴定化合物17为5-羟基-6,7,8,4′-四甲氧基黄酮。

化合物18：淡黄色无定形粉末，三氯化铁反应和盐酸-镁粉反应阳性；分子式为C20H20O8，ESI-MS m/z: 389 [M＋H]+。1H-NMR (400 MHz,DMSO-d6) δ: 12.08 (1H,s,5-OH),7.56 (1H,dd,J = 8.0,2.2 Hz,H-6′),7.38 (1H,d,J = 2.2 Hz,H-2′),7.01 (1H,d,J = 8.0 Hz,H-5′),6.61 (1H,s,H-3),4.08 (3H,s,6-OCH3),3.98 (3H,s,7-OCH3),3.97 (3H,s,8-OCH3),3.95 (3H,s,3′-OCH3),3.93 (3H,s,4′-OCH3)；13C-NMR (100 MHz,DMSO-d6) δ: 182.8 (C-4),163.9 (C-2),152.8 (C-4′),152.4 (C-7),149.8 (C-3′),149.6 (C-9),145.8 (C-5),135.9 (C-6),132.8 (C-8),124.1 (C-1′),119.9 (C-6′),111.6 (C-5′),109.2 (C-2′),106.8 (C-10),103.9 (C-3),62.4 (6-OCH3),61.9 (7′-OCH3),60.9 (8-OCH3),56.4 (3′-OCH3),56.2 (4′-OCH3)。以上数据与文献报道基本一致[24]，故鉴定化合物18为5-羟基-6,7,8,3′,4′-五甲氧基黄酮。

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