中草药  2016, Vol. 47 Issue (10): 1670-1675
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引用本文doi: 10.7501/j.issn.0253-2670.2016.10.008
王同为, 黄丽刚, 陈光英, 韩长日, 宋小平, 付艳辉, 赵成爱 . 毛叶鹰爪花中化学成分研究[J]. 中草药, 2016, 47(10): 1670-1675.
WANG Tong-wei, HUANG Li-gang, CHEN Guang-ying, HAN Chang-ri, SONG Xiao-ping, FU Yan-hui, ZHAO Cheng-ai . Studies on chemical constituents from Artabotrys pilosus[J]. Chinese Traditional and Herbal Drugs, 2016, 47(10): 1670-1675 .
毛叶鹰爪花中化学成分研究
王同为1,2, 黄丽刚2, 陈光英2, 韩长日2, 宋小平2, 付艳辉2, 赵成爱1     
1. 吉林农业大学资源与环境学院, 吉林 长春 130118 ;
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: 2016-01-05
基金项目: 国际科技合作与交流专项项目(2014DFA40850);国家自然科学基金资助课题(31360069,21302181);海南省应用技术研发与示范推广专项(ZDXM2015063);海南省高校科研项目(HNKY2014-41)
作者简介: 王同为,男,硕士研究生,主要从事活性天然产物的发现。E-mail:wtwei@126.com
通信作者: 赵成爱,教授,硕士生导师,主要从事活性天然产物的发现与与应用。E-mail:zca136@163.com
付艳辉,副教授,硕士生导师,主要从事活性天然产物的发现与与应用。E-mail:fuyanhui80@163.com
摘要: 目的 研究番荔枝科鹰爪花属植物毛叶鹰爪花Artabotrys pilosus枝叶中的化学成分。 方法 采用硅胶柱色谱、反相硅胶柱色谱、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、NMR谱和MS谱等谱学方法鉴定化合物的结构。 结果 从毛叶鹰爪花枝叶90%乙醇提取物的醋酸乙酯部位中分离得到了16个化合物,分别鉴定为达玛二烯醇乙酸酯(1)、羽扇豆醇(2)、羽扇豆醇乙酸酯(3)、白桦酸(4)、熊果醇(5)、熊果酸(6)、β-香树脂醇(7)、古柯二醇(8)、木栓醇(9)、木栓酮(10)、α-波菜甾酮(11)、豆甾-7-烯-3β-醇(12)、豆甾-5-烯-3β-醇-7-酮(13)、豆甾-3,6-二酮(14)、豆甾醇(15)和β-谷甾醇(16)。 结论 化合物15和16为首次从毛叶鹰爪花中分离得到,其他化合物为首次从鹰爪花属植物中分离得到。
关键词: 毛叶鹰爪花     三萜类化合物     甾体类化合物     达玛二烯醇乙酸酯     羽扇豆醇     熊果酸    
Studies on chemical constituents from Artabotrys pilosus
WANG Tong-wei1,2, HUANG Li-gang2, CHEN Guang-ying2, HAN Chang-ri2, SONG Xiao-ping2, FU Yan-hui2, ZHAO Cheng-ai1     
1. College of Resources and Environment, Jilin Agricultural University, Changchun 130118, China ;
2. Key Laboratory of Tropical Medicinal Plant Chemistry, Ministry of Education, Hainan Normal University, Haikou 571158, China
Abstract: Objective To study the chemical constituents from twigs and leaves of Artabotrys pilosus. Methods The chemical constituents of A. pilosus 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 Sixteen compounds were isolated from the acetic ether fraction of 90% ethanol extract from the twigs and leaves of A. pilosus, and identified as dammaradienylacetate (1), lupeol (2), lupenyl acetate (3), betulinic acid (4), uvaol (5), ursolic acid (6), β-amyrin (7), erythrodiol (8), friedelinol (9), friedelin (10), α-spinasterone (11), stigmast-7-ene-3β-ol (12), stigmast-5-ene-3β-ol-7-one (13), stigmastan-3,6-diketone (14), stigmasterol (15), and β-sitosterol (16). Conclusion All compounds are isolated from A. pilosus for the first time. Except for compounds 15 and 16, other compounds are isolated from the plants of Artabotrys R. Br. for the first time.
Key words: Artabotrys pilosus Merr. et Chun     triterpenoids     steroids     dammaradienylacetate     lupeol     ursolic acid    

番荔枝科(Annonaceae)鹰爪花属Artabotrys R. Br. 植物全世界约100种，分布于热带、亚热带地区，我国有4种，产自西南部至东南部[1]。在民间，鹰爪花属植物作为药用植物已有很长历史，具有清热解毒、消炎止痛的作用，常用作治疗疟疾和头颈部淋巴结核。现代药理学研究表明，该属植物具有广泛的生物活性，如抗肿瘤、抗菌、抗疟以及杀虫等[2-6]。毛叶鹰爪花Artabotrys pilosus Merr. et Chun为海南特有植物，常生于低海拔至中海拔的山地林中[1]。本课题组在前期研究中发现毛叶鹰爪花乙醇提取物的醋酸乙酯萃取部位对A549(人肺癌细胞)、LOVO(人肠癌细胞)、6T-CEM(人T细胞白血病细胞)、

及QGY-7703(人肝癌细胞)等4种癌细胞均有较强的体外增殖抑制作用。尤其是对LOVO和QGY-7703，其IC50分别达到1.6、3.8 μg/mL。关于毛叶鹰爪花中化学成分及其生物活性的研究，仅见本课题组报道其中具有显著细胞毒活性的裂环多氧取代环己烯类化合物[7]。为了进一步阐明毛叶鹰爪花的药效物质基础，本实验对毛叶鹰爪花枝叶抗肿瘤活性部位中的化学成分进行了系统研究，从其枝叶90%乙醇提取物的醋酸乙酯萃取部位中分离得到了16个化合物，分别鉴定为达玛二烯醇乙酸酯(dammaradienylacetate，1)、羽扇豆醇(lupeol，2)、羽扇豆醇乙酸酯(lupenyl acetate，3)、白桦酸(betulinic acid，4)、熊果醇(uvaol，5)、熊果酸(ursolic acid，6)、β-香树脂醇(β-amyrin，7)、古柯二醇(erythrodiol，8)、木栓醇(friedelinol，9)、木栓酮(friedelin，10)、α-波菜甾酮(α-spinasterone，11)、豆甾-7-烯-3β-醇(stigmast-7-ene-3β-ol，12)、豆甾-5-烯-3β-醇-7-酮(stigmast-5-ene-3β-ol-7-one，13)、豆甾-3,6-二酮(stigmastan-3,6-diketone，14)、豆甾醇(stigmasterol，15)和β-谷甾醇(β-sitosterol，16)。化合物15和16为首次从毛叶鹰爪花中分离得到，其他化合物为首次从鹰爪花属植物中分离得到。

1 仪器与材料

WRX-4显微熔点仪(上海易测仪器设备有限公司)；Bruker AV-400型超导核磁共振仪(德国Bruker公司)；Finnigan LCQ Advantage MAX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制备型色谱柱(250 mm×10 mm，5 μm)；中低压制备色谱(瑞士Buchi公司)；旋转蒸发仪(日本EYELA公司N-1001型)；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。

毛叶鹰爪花枝叶于2014年4月采集于海南省昌江县霸王岭自然保护区，经海南师范大学生命科学学院钟琼芯教授鉴定为番荔枝科鹰爪花属植物毛叶鹰爪花Artabotrys pilosus Merr. et Chun的枝叶，凭证标本(20140408)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 提取分离

毛叶鹰爪花的干燥枝叶40.0 kg，粉碎后用90%乙醇冷浸提取4次，每次冷浸1周，提取液减压浓缩得浸膏2.8 kg。浸膏加水混悬，依次用石油醚和醋酸乙酯萃取，回收溶剂后得石油醚萃取部位260.2 g和醋酸乙酯萃取部位780.3 g。醋酸乙酯萃取部位(780.0 g)经硅胶柱色谱分离，石油醚-丙酮(100：0→0：100)为洗脱剂梯度洗脱得到6个流分(Fr. 1～6)。Fr. 2(21.5 g)经硅胶柱色谱分离，石油醚-醋酸乙酯(100：0→0：100)为洗脱机梯度洗脱5个亚流分(Fr. 2A～2F)。Fr. 2A经重结晶得到化合物15(423.6 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11(28.5 mg)、13(8.9 mg)和16(54.6 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4(19.2 mg)、12(32.7 mg)和14(42.8 mg)；Fr. 2D经反复硅胶柱色谱，石油醚-丙酮(9：1)等度洗脱得到化合物3(16.7 mg)和10(24.6 mg)；Fr. 2F经Sephadex LH-20(氯仿-甲醇)纯化得到化合物2(13.9 mg)和7(88.3 mg)。Fr. 3(13.4 g)经ODS反相柱层析，甲醇-水(60：40→100：0)梯度洗脱，得到5个亚流分(Fr. 3A～3F)。Fr. 3B经硅胶柱色谱，石油醚-丙酮(9：1)等度洗脱得到化合物5(45.2 mg)和8(99.6 mg)；Fr. 3C经经制备型高效液相以乙腈-水(75：25)为流动相，得到化合物1(22.8 mg)、6(14.3 mg)和9(28.3 mg)。

3 结构鉴定

化合物1：白色无定形粉末，Liebermann-Burchard反应呈阳性；C32H52O2，ESI-MS m/z: 469 [M＋H]+, 491 [M＋Na]+；1H-NMR (400 MHz, CDCl3) δ: 5.16 (1H, t, J = 8.8 Hz, H-24), 4.68 (1H, d, J = 8.8 Hz, H-21), 4.51 (1H, m, H-3), 2.06, 1.74, 1.63, 0.98, 0.90, 0.88, 0.86, 0.85 (3H×8, s, CH3×8)；13C-NMR (100 MHz, CDCl3) δ: 170.8 (CH3CO), 152.6 (C-20), 131.2 (C-25), 124.5 (C-24), 107.2 (C-21), 81.2 (C-3), 56.1 (C-5), 51.3 (C-9), 49.3 (C-14), 47.8 (C-13), 45.3 (C-17), 40.5 (C-8), 38.6 (C-10), 38.1 (C-1), 36.9 (C-4), 35.2 (C-7), 33.9 (C-22), 31.2 (C-15), 29.0 (C-16), 28.1 (C-28), 26.9 (C-12), 25.8 (C-26), 25.1 (C-23), 23.6 (C-2), 21.5 (C-11), 21.2 (CH3CO), 17.9 (C-6), 17.5 (C-27), 16.6 (C-19), 16.3 (C-18), 16.0 (C-30), 15.8 (C-29)。以上数据与文献报道基本一致[8]，故鉴定化合物1为达玛二烯醇乙酸酯。

化合物2：白色无定形粉末，Liebermann-Burchard反应呈阳性；C30H50O，ESI-MS m/z: 427 [M＋H]+, 449 [M＋Na]+；1H-NMR (400 MHz, CDCl3) δ: 4.69 (1H, d, J = 2.0 Hz, H-29a), 4.61 (1H, d, J = 2.0 Hz, H-29b), 3.21 (1H, dd, J = 10.8, 4.8 Hz, H-3), 1.68, 1.10, 1.01, 0.97, 0.83, 0.79, 0.76 (3H×7, s, CH3×7)；13C-NMR (100 MHz, CDCl3) δ: 151.2 (C-20), 110.0 (C-29), 79.3 (C-3), 55.6 (C-5), 50.57 (C-9), 48.6 (C-18), 478.1 (C-19), 43.0 (C-17), 42.2 (C-14), 41.1 (C-8), 40.2 (C-22), 38.5 (C-4), 38.8 (C-1), 38.1 (C-13), 36.9 (C-10), 35.6 (C-16), 34.4 (C-7), 29.9 (C-21), 29.6 (C-2), 28.2 (C-23), 27.6 (C-15), 25.4 (C-12), 21.2 (C-11), 19.4 (C-30), 18.5 (C-6), 18.1 (C-28), 15.9 (C-25), 15.7 (C-26), 15.4 (C-24), 14.2 (C-27)。以上数据与文献报道基本一致[9]，故鉴定化合物2为羽扇豆醇。

化合物3：白色无定形粉末，Liebermann-Burchard反应呈阳性；C32H52O2，ESI-MS m/z: 469 [M＋H]+, 491 [M＋Na]+；1H-NMR (400 MHz, CDCl3) δ: 4.68 (1H, J = 2.0 Hz, H-29a), 4.62 (1H, J = 2.0 Hz, H-29b), 4.52 (1H, dd, J = 12.8, 6.6 Hz, H-3), 2.12, 1.66, 1.06, 0.98, 0.89, 0.87, 0.86, 0.79 (3H×8, s, CH3×8)；13C-NMR (100 MHz, CDCl3) δ: 171.1 (CH3CO), 150.5 (C-20), 109.4 (C-29), 80.7 (C-3), 55.5 (C-5), 50.5 (C-9), 48.4 (C-18), 48.3 (C-19), 43.1 (C-17), 42.7 (C-14), 40.2 (C-22), 40.1 (C-8), 38.6 (C-1), 38.2 (C-13), 37.6 (C-4), 37.3 (C-10), 35.6 (C-16), 34.6 (C-7), 29.5 (C-21), 27.6 (C-23), 27.5 (C-15), 25.4 (C-12), 23.4 (C-2), 21.7 (CH3CO), 21.5 (C-11), 19.5 (C-30), 18.3 (C-6), 18.1 (C-28), 16.7 (C-25), 16.4 (C-26), 16.2 (C-24), 14.8 (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反应呈阳性；C30H48O3，ESI-MS m/z: 457 [M＋H]+，479 [M＋Na]+；1H-NMR (400 MHz, CDCl3) δ: 4.68 (1H, brs, H-29a), 4.61 (1H, brs, H-29b), 3.18 (1H, dd, J = 10.8, 4.8 Hz, H-3α), 3.01 (1H, m, H-19), 1.71, 0.97, 0.95, 0.93, 0.80, 0.76 (3H×6, s, CH3×6)；13C-NMR (100 MHz, CDCl3) δ: 180.1 (C-28), 149.8 (C-20), 110.2 (C-29), 79.2 (C-3), 55.9 (C-17), 55.7 (C-5), 50.8 (C-9), 49.6 (C-19), 46.8 (C-18), 42.8 (C-14), 41.0 (C-8), 39.1 (C-4), 38.7 (C-1), 38.3 (C-13), 36.9 (C-10), 36.6 (C-22), 34.5 (C-7), 32.4 (C-16), 31.2 (C-15), 29.9 (C-21), 28.1 (C-23), 27.8 (C-2), 25.7 (C-12), 20.8 (C-11), 19.8 (C-30), 18.5 (C-6), 16.4 (C-26), 15.9 (C-25), 15.5 (C-24), 14.8 (C-27)。以上数据与文献报道基本一致[11]，故鉴定化合物4为白桦酸。

化合物5：白色无定形粉末，Liebermann-Burchard反应呈阳性；C30H50O2，ESI-MS m/z: 443 [M＋H]+；1H-NMR (400 MHz, CDCl3) δ: 5.11 (1H, t, J = 3.8 Hz, H-12), 3.48 (1H, d, J = 10.8 Hz, H-28a), 3.21 (1H, dd, J = 10.8, 5.0 Hz, H-3), 3.19 (1H, d, J = 10.8 Hz, H-28b), 1.09, 0.99, 0.98, 0.93, 0.78 (3H×5, s, CH3×5), 1.01 (3H, d, J = 5.8 Hz, H-30), 0.76 (3H, d, J = 5.8 Hz, H-29)；13C-NMR (100 MHz, CDCl3) δ: 139.1 (C-13), 124.9 (C-12), 78.8 (C-3), 69.7 (C-28), 54.8 (C-5), 53.9 (C-18), 48.1 (C-9), 41.8 (C-14), 39.7 (C-8), 39.3 (C-19), 39.2 (C-20), 39.0 (C-1), 37.9 (C-4), 37.1 (C-10), 34.9 (C-17), 33.0 (C-7), 30.7 (C-21), 30.5 (C-22), 25.8 (C-2), 27.9 (C-15), 27.2 (C-23), 23.5 (C-27), 23.2 (C-16), 23.1 (C-11), 20.9 (C-30), 18.2 (C-6), 17.3 (C-26), 17.0 (C-29), 15.8 (C-25), 15.4 (C-24)。以上数据与文献报道基本一致[12]，故鉴定化合物5为熊果醇。

化合物6：白色无定形粉末，Liebermann-Burchard反应呈阳性；C30H48O3，ESI-MS m/z: 457 [M＋H]+；1H-NMR (400 MHz, pyridine-d5) δ: 5.01 (1H, brs, H-12), 3.51 (1H, m, H-3), 2.69 (1H, d, J = 10.8 Hz, H-18), 1.31, 1.27, 1.10, 1.05, 0.90 (3H×5, s, CH3×5), 1.02 (3H, J = 6.0 Hz, H-30), 0.97 (3H, d, J = 6.0 Hz, H-29)；13C-NMR (100 MHz, pyridine-d5) δ: 180.1 (C-28), 139.8 (C-13), 126.0 (C-12), 78.5 (C-3), 56.2 (C-5), 53.8 (C-18), 48.5 (C-9), 48.3 (C-17), 42.7 (C-14), 40.1 (C-8), 39.8 (C-19), 39.6 (C-20), 39.4 (C-4), 39.3 (C-1), 37.8 (C-22), 37.4 (C-10), 34.1 (C-7), 31.5 (C-21), 29.2 (C-23), 28.6 (C-15), 28.1 (C-2), 25.0 (C-16), 23.9 (C-27), 23.6 (C-11), 20.9 (C-30), 18.8 (C-6), 18.1 (C-26), 17.5 (C-29), 17.1 (C-25), 16.2 (C-24)。以上数据与文献报道基本一致[13]，故鉴定化合物6为熊果酸。

化合物7：白色无定形粉末，Liebermann-Burchard反应呈阳性；C30H50O，ESI-MS m/z: 427 [M＋H]+；1H-NMR (400 MHz, CDCl3) δ: 5.51 (1H, d, J = 4.2 Hz, H-12), 3.56 (1H, m, H-3), 1.18, 1.13, 1.10, 1.02, 0.99, 0.96, 0.79 (3H×7, s, CH3×7)；13C-NMR (100 MHz, CDCl3) δ: 145.8 (C-13), 122.1 (C-12), 79.0 (C-3), 55.8 (C-5), 48.2 (C-9), 47.8 (C-18), 46.9 (C-19), 41.7 (C-14), 40.1 (C-8), 39.2 (C-4), 38.8 (C-1), 37.4 (C-10), 37.0 (C-22), 34.5 (C-21), 33.6 (C-29), 33.0 (C-17), 31.2 (C-20), 28.9 (C-28), 27.9 (C-23), 27.4 (C-2), 27.0 (C-16), 26.85 (C-15), 26.0 (C-27), 24.1 (C-11), 23.7 (C-30), 19.1 (C-6), 18.7 (C-6), 17.1 (C-26), 16.2 (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-香树脂醇。

化合物8：白色无定形粉末，Liebermann-Burchard反应呈阳性；C30H50O2，ESI-MS m/z: 443 [M＋H]+；1H-NMR (400 MHz, CDCl3) δ: 5.18 (1H, t, J = 3.8 Hz, H-12), 3.52 (1H, d, J = 10.8 Hz, H-18a), 3.19 (1H, m, H-3), 3.16 (1H, d, J = 10.8 Hz, H-18b), 1.18, 0.98, 0.96, 0.93, 0.88, 0.86, 0.78 (3H×7, s, CH3×7)；13C-NMR (100 MHz, CDCl3) δ: 143.9 (C-13), 122.1 (C-12), 78.8 (C-3), 70.1 (C-28), 54.9 (C-5), 47.4 (C-17), 47.3 (C-9), 46.3 (C-19), 42.3 (C-18), 41.6 (C-14), 40.2 (C-8), 39.2 (C-4), 38.5 (C-1), 37.1 (C-10), 33.8 (C-21), 32.9 (C-29), 32.4 (C-7), 30.7 (C-22), 31.0 (C-20), 27.9 (C-23), 26.9 (C-2), 25.8 (C-27), 25.4 (C-15), 23.5 (C-30), 23.6 (C-11), 21.8 (C-16), 18.2 (C-6), 16.8 (C-26), 15.8 (C-24), 15.6 (C-25)。以上数据与文献报道基本一致[15]，故鉴定化合物8为古柯二醇。

化合物9：白色无定形粉末，Liebermann-Burchard反应呈阳性；C30H52O，ESI-MS m/z: 429 [M＋H]+, 451 [M＋Na]+；1H-NMR (400 MHz, CDCl3) δ: 1.18 (3H, s, H-28), 1.04 (3H, s, H-27), 0.99 (3H, s, H-29), 0.98 (3H, s, H-26), 0.94 (3H, s, H-30), 0.90 (3H, d, J = 6.6 Hz, H-23), 0.86 (3H, s, H-24), 0.73 (3H, s, H-25)；13C-NMR (100 MHz, CDCl3) δ: 72.6 (C-3), 61.5 (C-10), 53.8 (C-8), 48.9 (C-4), 42.5 (C-18), 41.8 (C-6), 39.6 (C-5), 39.7 (C-22), 37.9 (C-14), 37.4 (C-13), 37.2 (C-9), 36.2 (C-2), 35.8 (C-11), 35.3 (C-16), 34.9 (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), 19.9 (C-27), 18.5 (C-25), 18.3 (C-26), 17.5 (C-7), 16.6 (C-24), 16.5 (C-1), 10.8 (C-23)。以上数据与文献报道基本一致[16]，故鉴定化合物9为木栓醇。

化合物10：白色无定形粉末，Liebermann- Burchard反应呈阳性；C30H50O，ESI-MS m/z: 427 [M＋H]+, 449 [M＋Na]+；1H-NMR (400 MHz, CDCl3) δ: 2.45 (1H, dd, J = 4.8, 2.0 Hz, H-2a), 2.42 (1H, dd, J = 4.8, 2.0 Hz, H-2b), 2.39 (1H, d, J = 4.2 Hz, H-4), 1.20 (3H, s, H-28), 1.05 (3H, s, H-27), 1.00 (3H, s, H-30), 0.96 (3H, s, H-26), 0.93 (3H, s, H-29), 0.89 (3H, d, J = 7.0 Hz, H-23), 0.87 (3H, s, H-25), 0.69 (3H, s, H-24)；13C-NMR (100 MHz, CDCl3) δ: 213.1 (C-3), 59.6 (C-10), 57.9 (C-4), 52.8 (C-8), 43.0 (C-18), 42.5 (C-5), 41.4 (C-2), 41.3 (C-6), 40.0 (C-13), 39.7 (C-22), 38.2 (C-14), 37.5 (C-9), 36.3 (C-16), 36.0 (C-11), 35.6 (C-19), 35.2 (C-29), 33.1 (C-21), 32.8 (C-15), 32.4 (C-28), 31.9 (C-30), 31.7 (C-17), 31.0 (C-12), 28.3 (C-20), 22.7 (C-1), 20.5 (C-26), 19.1 (C-27), 18.4 (C-7), 18.0 (C-25), 15.2 (C-24), 6.9 (C-23)。以上数据与文献报道基本一致[17]，故鉴定化合物10为木栓酮。

化合物11：白色无定形粉末，Liebermann- Burchard反应呈阳性；C29H46O，ESI-MS m/z: 411 [M＋H]+, 433 [M＋Na]+；1H-NMR (400 MHz, CDCl3) δ: 5.21 (1H, brs, H-7), 5.15 (1H, dd, J = 14.8, 8.6 Hz, H-22), 4.99 (1H, dd, J = 14.8, 8.6 Hz, H-23), 1.05 (3H, d, J = 6.8 Hz, H-21), 0.99 (3H, s, H-19), 0.88 (3H, d, J = 6.8 Hz, H-27), 0.84 (3H, d, J = 6.8 Hz, H-26), 0.79 (3H, t, J = 6.8 Hz, H-29), 0.56 (3H, s, H-18)；13C-NMR (100 MHz, CDCl3) δ: 212.0 (C-3), 140.2 (C-8), 138.2 (C-22), 130.2 (C-23), 116.9 (C-7), 55.8 (C-17), 54.9 (C-14), 51.2 (C-24), 48.8 (C-9), 44.3 (C-4), 43.2 (C-13), 42.8 (C-5), 40.7 (C-20), 40.1 (C-12), 38.9 (C-1), 38.1 (C-2), 34.5 (C-10), 31.9 (C-25), 29.8 (C-6), 29.0 (C-16), 25.4 (C-28), 23.1 (C-15), 22.0 (C-11), 21.8 (C-27), 21.5 (C-21), 13.1 (C-19), 12.5 (C-29) 12.2 (C-18), 20.1 (C-26)。以上数据与文献报道基本一致[18]，故鉴定化合物11为α-波菜甾酮。

化合物12：白色无定形粉末，Liebermann-

Burchard反应呈阳性；C29H50O，ESI-MS m/z: 415 [M＋H]+, 437 [M＋Na]+；1H-NMR (400 MHz, CDCl3) δ: 5.19 (1H, m, H-7), 3.62 (1H, m, H-3), 0.97 (3H, d, J = 6.8 Hz, H-21), 0.90 (3H, t, J = 7.2 Hz, H-29), 0.86 (3H, d, J = 6.8 Hz, H-26), 0.84 (3H, d, J = 6.8 Hz, H-27), 0.79 (3H, s, H-19), 0.62 (3H, s, H-18)；13C-NMR (100 MHz, CDCl3) δ: 140.2 (C-8), 117.8 (C-7), 71.1 (C-3), 56.0 (C-17), 54.9 (C-14), 49.8 (C-9), 45.8 (C-24), 43.4 (C-13), 40.6 (C-5), 39.8 (C-12), 38.1 (C-4), 37.2 (C-1), 36.7 (C-20), 34.9 (C-10), 33.8 (C-22), 31.5 (C-2), 30.2 (C-6), 29.1 (C-25), 27.9 (C-16), 26.0 (C-23), 22.9 (C-15), 22.7 (C-28), 21.5 (C-11), 19.8 (C-27), 19.0 (C-26), 18.4 (C-21), 12.3 (C-19), 12.2 (C-29), 11.8 (C-18)。以上数据与文献报道基本一致[19]，故鉴定化合物12为豆甾-7-烯-3β-醇。

化合物13：白色无定形粉末，Liebermann- Burchard反应呈阳性；C29H48O2，ESI-MS m/z: 429 [M＋H]+, 451 [M＋Na]+；1H-NMR (400 MHz, CDCl3) δ: 5.71 (1H, s, H-6), 3.68 (1H, m, H-3), 1.19 (3H, s, H-19), 0.89 (3H, d, J = 6.8 Hz, H-21), 0.86 (3H, d, J = 6.8 Hz, H-26), 0.85 (3H, t, J = 6.8 Hz, H-29), 0.79 (3H, d, J = 6.8 Hz, H-27), 0.71 (3H, s, H-18)；13C-NMR (100 MHz, CDCl3) δ: 201.9 (C-7), 1654.8 (C-5), 125.8 (C-6), 69.9 (C-3), 54.5 (C-17), 50.2 (C-9), 50.0 (C-14), 46.1 (C-24), 45.3 (C-8), 42.1 (C-4), 42.0 (C-13), 39.2 (C-12), 38.4 (C-10), 36.5 (C-1), 35.8 (C-20), 34.0 (C-22), 30.8 (C-2), 28.7 (C-25), 28.4 (C-16), 26.2 (C-15), 25.9 (C-23), 22.8 (C-28), 20.9 (C-11), 20.0 (C-26), 18.9 (C-27), 18.8 (C-21), 16.9 (C-19), 12.3 (C-18), 11.9 (C-29)。以上数据与文献报道基本一致[20]，故鉴定化合物13为豆甾-5-烯-3β-醇-7-酮。

化合物14：白色无定形粉末，Liebermann- Burchard反应呈阳性；C29H48O2，ESI-MS m/z: 429 [M＋H]+, 451 [M＋Na]+；1H-NMR (400 MHz, CDCl3) δ: 0.98 (3H, s, H-19), 0.92 (3H, d, J = 6.6 Hz, H-21), 0.78～0.85 (3H×3, m, H-26, 27, 29), 0.70 (3H, s, H-18)；13C-NMR (100 MHz, CDCl3) δ: 211.0 (C-3), 209.0 (C-6), 56.9 (C-5), 56.2 (C-17), 55.8 (C-14), 53.3 (C-9), 38.8 (C-2), 38.0 (C-1), 37.1 (C-4), 45.9 (C-7), 45.3 (C-24), 43.1 (C-13), 41.2 (C-10), 38.1 (C-12), 36.9 (C-8), 35.8 (C-20), 33.4 (C-22), 29.2 (C-25), 28.1 (C-16), 26.2 (C-23), 24.1 (C-15), 23.2 (C-28), 21.6 (C-11), 20.1 (C-26), 19.1 (C-27), 18.6 (C-21), 12.5 (C-18), 12.1 (C-19), 11.8 (C-29)。以上数据与文献报道基本一致[21]，故鉴定化合物14为豆甾-3,6-二酮。

化合物15：无色针状结晶(丙酮)，mp 149～151 ℃；Liebermann-Burchard反应呈阳性；C29H48O，ESI-MS m/z: 413 [M＋H]+, 435 [M＋Na]+；1H-NMR (400 MHz, CDCl3) δ: 5.28 (1H, d, J = 4.8 Hz, H-6), 5.09 (1H, dd, J = 14.8, 7.6 Hz, H-22), 4.98 (1H, dd, J = 14.8, 7.6 Hz, H-23), 3.48 (1H, t, J = 5.4 Hz, H-3), 0.96 (3H, d, J = 7.2 Hz, H-21), 0.90 (3H, t, J = 7.2 Hz, H-29), 0.87 (3H, d, J = 7.2 Hz, H-26), 0.82 (3H, d, J = 7.2 Hz, H-27), 0.79 (3H, s, H-19), 0.70 (3H, s, H-18)；13C-NMR (100 MHz, CDCl3) δ: 139.8 (C-5), 138.3 (C-22), 128.9 (C-23), 120.8 (C-6), 71.5 (C-3), 57.0 (C-17), 56.1 (C-14), 51.2 (C-24), 51.0 (C-9), 42.6 (C-13), 39.9 (C-20), 39.7 (C-12), 39.2 (C-4), 37.1 (C-10), 32.2 (C-8), 32.0 (C-25), 31.8 (C-2), 31.4 (C-7), 30.9 (C-1), 28.8 (C-16), 25.6 (C-28), 24.3 (C-15), 21.6 (C-11), 21.2 (C-21), 20.9 (C-27), 20.0 (C-19), 18.8 (C-26), 12.3 (C-29), 11.9 (C-18)。以上数据与文献报道基本一致[22]，故鉴定化合物15为豆甾醇。

化合物16：无色针状结晶(氯仿)，mp 139～140 ℃；Liebermann-Burchard反应呈阳性。与β-谷甾醇对照品在3种展开系统中共TLC，它们的Rf值及显色均一致，且混合熔点不下降，故鉴定化合物16为β-谷甾醇。

参考文献
[1] 中国科学院中国植物志编辑委员会. 中国植物志(第30卷)[M]. 北京: 科学出版社, 1978 .
[2] 顾关云, 蒋昱. 番荔枝科植物细胞毒成分的研究概况Ⅲ[J]. 国外医药:植物药分册, 1995,10 (4) :153–156.
[3] Tattersfield F, Potter C. The insecticidal properties of certain species of Annona and of an Indian strain of Mundulea sericea[J]. Ann Appl Biol, 1940, 27 (2) :262–273 .
[4] Radloff P D, Philipps J, Nkeyi M, et al. Arteflene compared with mefloquine for treating Plasmodium falciparum malaria in children[J]. Am J Trop Med Hyg, 1996, 55 (3) :259–262 .
[5] Singh D K, Basha S A, Sarma B K, et al. Antifungal activity of a phytoterpenoid (AOS-A) isolated from Artabotrytis odoratissimus on spore germination of some fungi[J]. Mycobiology, 2006, 34 (3) :120–123 .
[6] Srivastava B, Singh P, Srivastava A K, et al. Efficacy of Artabotrys odoratissimus oil as a plant based antimicrobial against storage fungi and a flatoxin B1 secretion[J]. Int J Food Sci Technol, 2009, 44 (10) :1909–1915 .
[7] 刘艳萍, 黄丽刚, 汪晓翠, 等. 毛叶鹰爪花中一个新颖的裂环多氧取代环己烯类化合物[J]. 有机化学, 2015,35 (9) :1981–1984.
[8] 徐菁, 高鸿悦, 马淑丽, 等. 马兰化学成分及生物活性研究[J]. 中草药, 2014,45 (22) :3246–3250.
[9] 周思祥, 姚志容, 李军, 等. 枸骨叶的化学成分研究[J]. 中草药, 2012,43 (3) :444–447.
[10] 袁珂, 贾安, 张爱莲. 少花斑鸠菊化学成分的研究(I)[J]. 中国药学杂志, 2006,41 (19) :1458–1460.
[11] Yang D S, Li Z L, Yang Y P, et al. Chemical constituents from Hypericum beanii[J]. Chin Herb Med, 2015, 7 (4) :375–379 .
[12] 张峰, 张俊清, 孔令义, 等. 薜荔化学成分研究[J]. 中草药, 2009,40 (10) :1554–1555.
[13] 焦威, 鲁改丽, 邵华武, 等. 暖地大叶藓化学成分的研究[J]. 天然产物研究与开发, 2010,22 (2) :235–237.
[14] 邓可众, 熊英, 高文远. 半边莲的化学成分研究[J]. 中草药, 2009,40 (8) :1198–1201.
[15] 高慧媛, 吴立军, 黑柳正典. 光皮木瓜的化学成分[J]. 中国天然药物, 2003,1 (2) :82–84.
[16] 林理根, 柯昌强, 叶阳. 黑面神根部化学成分的研究[J]. 中草药, 2013,44 (22) :3119–3122.
[17] 黄帅, 张敬文, 张银勇, 等. 小娃娃皮的化学成分研究[J]. 中草药, 2014,45 (15) :2153–2156.
[18] 张淏, 李行诺, 孙博航, 等. 苦楝皮的化学成分[J]. 沈阳药科大学学报, 2008,25 (7) :534–536.
[19] 傅旭阳, 田均勉. 瞿麦的化学成分研究[J]. 中草药, 2015,46 (5) :645–648.
[20] Jin Y P, Shi Y P. Terpenoids and steroids from Lappula anocarpa[J]. Pharmazie, 2004, 59 (11) :885–888 .
[21] Marina D G, Pietro M, Lucio P. Stigmasterols from Typha Latifolia[J]. J Nat Prod, 1990, 53 (6) :1430–1435 .
[22] 董雪云, 文波, 沈云亨, 等. 宽叶兔儿风的化学成分研究[J]. 中草药, 2014,45 (15) :2148–2152.