蒙古苍耳全草化学成分研究

引用本文	doi: 10.7501/j.issn.0253-2670.2015.03.004

张树军, 刘焕, 李军, 王金兰, 张文治. 蒙古苍耳全草化学成分研究[J]. 中草药, 2015, 46(3): 329-333. 复制到剪切板

ZHANG Shu-jun, LIU Huan, LI Jun, WANG Jin-lan, ZHANG Wen-zhi. Study on chemical constituents from whole herbs of Xanthium mongolicum[J]. Chinese Traditional and Herbal Drugs, 2015, 46(3): 329-333. 复制到剪切板

蒙古苍耳全草化学成分研究

张树军, 刘焕, 李军, 王金兰, 张文治

齐齐哈尔大学化学与化学工程学院, 黑龙江齐齐哈尔 161006

收稿日期: 2014-11-24;

基金项目：黑龙江省自然科学基金项目(B201205);黑龙江省海外学人项目(1254HQ009)

作者简介：张树军,男,辽宁凌源人,博士,教授,硕士生导师,主要从事天然产物相关研究.E-mail:shjzhang2005@126.com

摘要：目的研究蒙古苍耳Xanthium mongolicum全草的化学成分.方法采用硅胶柱色谱和高效液相色谱等方法分离纯化,根据理化性质及波谱数据鉴定化合物结构.结果从蒙古苍耳全草甲醇提取物中分离得到17个化合物,分别鉴定为lasidiol p-methoxybenzoat(1)、β-芹子烯(2)、苍耳亭(3)、苍耳皂素(4)、羽扇豆酮(5)、胡萝卜苷(6)、4β,5β-epoxy xanthatin-1α, 4α-endoperoxide(7)、(6S,9R)-vomifoliol(8)、dehydrovomifoliol(9)、顺-3-己烯醇-β-D-葡萄糖苷(10)、4-oxo-bedfordia acid(11)、11α,13-dihydro-8-epi-xanfbut(12)、东莨菪内酯(13)、松脂素(14)、β-谷甾醇(15)、槲皮素(16)、对羟基苯甲酸甲酯(17).结论化合物2、8～10、17为首次从该属植物中分离得到;1、5、7、11、13为首次从该植物中分离得到.

关键词：蒙古苍耳 β-芹子烯 (6S,9R)-vomifoliol 顺-3-己烯醇-β-D-葡萄糖苷东莨菪内酯对羟基苯甲酸甲酯

Study on chemical constituents from whole herbs of Xanthium mongolicum

ZHANG Shu-jun, LIU Huan, LI Jun, WANG Jin-lan, ZHANG Wen-zhi

Institute of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, China

Abstract: Objective To study the chemical constituents in the whole herbs of Xanthium mongolicum. Methods The chemical constituents were isolated and purified by chromatography on silica gel column and HPLC, and their structures were elucidated by spectral analysis. Results Seventeen compounds were isolated and identified as lasidiol p-methoxybenzoat (1), β-selinene (2), xanthatin (3), xanthinosin (4), luteone (5), daucosterol (6), 4β,5β-epoxy xanthatin-1α,4α-endoperoxide (7), (6S,9R)-vomifoliol (8), dehydrovomifoliol (9), 3(Z)-hexenyl-β-D-glycoside (10), 4-oxo-bedfordia acid (11), 11α,13-dihydro-8-epi-xanfbut (12), scopolin (13), pinoresinol (14), β-sitosterol (15), quercetin (16), and methyl p-hydroxybenzonate (17). Conclusion The compounds 2, 8, 9, 10, and 17 are isolated from the plants of Xanthium L. for the first time and the compounds 1, 5, 7, 11 and 13 are isolated from the whole herbs of X. mongolicum for the first time.

Key words: Xanthium mongolicum Kitag. β-selinene (6S,9R)-vomifoliol 3(Z)-hexenol-β-D-glycoside scopolin methyl p-hydroxyl- benzonate

蒙古苍耳Xanthium mongolicum Kitag. 为菊科（Compositae）一年生草本植物，主要分布于美洲的北部和中部、欧洲、亚洲及非洲北部，我国有3种及1变种，广泛分布于全国各地，具有抗菌、抗病毒、抗肿瘤、抗氧化、抗炎、镇痛等作用，主治鼻塞流涕、风寒湿痹、皮肤湿疹、麻风、疮疥搔痒等症，是一种资源丰富、药用活性广泛的野生药用植物。本课题组前期从蒙古苍耳茎叶醋酸乙酯萃取物中分离鉴定了8个化合物，并对苍耳亭、苍耳皂素和二氢苍耳亭3个化合物的抗炎活性进行了初步研究^[1]，为了进一步研究其药理活性，开发利用植物资源，本实验对蒙古苍耳全草甲醇提取物化学成分进一步研究，从中分离得到17个化合物，分别鉴定为lasidiol p-methoxy-benzoat（1）、β-芹子烯（β-selinene，2）、苍耳亭（xanthatin，3）、苍耳皂素（xanthinosin，4）、羽扇豆酮（luteone，5）、胡萝卜苷（daucosterol，6）、4β,5β-epoxy xanthatin-1α,4α- endoperoxide（7）、(6S,9R)-vomifoliol（8）、dehydrovomifoliol（9）、3(Z)-己烯醇-β-D-葡萄糖苷 [3(Z)-hexenol-β-D-glycoside，10]、4-oxo-bedfordia acid（11）、11α,13-dihydro-8-epi-xanfbut（12）、东莨菪内酯（scopolin，13）、松脂素（pinoresinol，14）、β-谷甾醇（β-sitosterol，15）、槲皮素（quercetin，16）、对羟基苯甲酸甲酯（methyl p-hydroxybenzonate，17）。其中化合物2、8～10、17为首次从该属植物中分离得到；化合物1、5、7、11、13为首次从该植物中分离得到。

1 仪器与材料

X-6显微熔点测定仪（北京泰克仪器有限公司）；Bruker AM-400和Bruker AM-600型核磁共振波谱仪；美国鲁道夫公司AUTOPOL V型旋光仪；高效液相色谱仪：HITACHI L-7100泵，HITACHI L-3350示差折光检测器，GL SCIRNCES Inc. Inertsil PREP- ODS（250 mm×10 mm）和PREP-Sil（250 mm×10 mm）不锈钢柱；柱色谱用硅胶为青岛海洋化工厂产品（200～300目）；薄层色谱硅胶板为烟台化工厂生产，有机溶剂为国药集团上海试剂厂产品，其他试剂为分析纯。

苍耳全草2012年6月12日于齐齐哈尔市内采集，室内阴干，经齐齐哈尔大学植物学教授沙伟鉴定为Xanthium mongolicum Kitag.，标本（XM- 20120612）收藏于齐齐哈尔大学天然产物研究室。

2 提取与分离

干燥的蒙古苍耳全草10.1 kg剪碎，每次用甲醇10.0 L室温浸泡5 d后滤过，重复3次，合并浸出液，减压浓缩至1.0 L左右，加水2.5 L混悬，依次用正己烷、醋酸乙酯和正丁醇萃取3次，合并相同溶剂萃取液减压浓缩至恒定质量，得到正己烷萃取物102.4 g、醋酸乙酯萃取物18.8 g、正丁醇萃取物65.9 g。

取正己烷萃取物19.6 g，经硅胶柱色谱、正相半制备HPLC以及重结晶等方法分离纯化得化合物1（163.3 mg）、2（100.6 mg）、5（38.7 mg）、6（70.3 mg）、11（15.2 mg）、15（131.6 mg）；苍耳醋酸乙酯萃取物18.8 g经硅胶柱色谱、正相半制备HPLC以及重结晶等方法分离纯化得化合物3（205.8 mg）、4（203.5 mg）、7（3.3 mg）、8（2.1 mg）、9（2.7 mg）、12（1.5 mg）、13（41.4 mg）、14（20.3 mg）、16（10.6 mg）、17（22.0 mg）；取苍耳正丁醇萃取物30.2 g经硅胶柱色谱及反相半制备HPLC分离纯化得化合物10（110.6 mg）。

3 结构鉴定

化合物1：微黄色蜡状物，mp 43.3～49.5 ℃。¹H-NMR (600 MHz,CDCl₃) δ: 8.01 (2H,d,J = 9.0 Hz,H-2′,6′),6.95 (2H,d,J = 9.0 Hz,H-3′,5′),5.51 (1H,brd,J = 4.2 Hz,H-2),5.31 (1H,d,J = 4.2 Hz,H-1),3.86 (3H,s,-OCH₃),2.41 (1H,m,H-4),2.31 (1H,m,H-4),2.08 (1H,m,H-10),2.06 (1H,d,J = 10.7 Hz,H-11),1.87 (1H,m,H-5),1.75 (1H,m,H-9),1.71 (1H,m,H-8),1.70 (3H,brs,H-15),1.64 (1H,m,H-5),1.54 (1H,m,H-9),1.43 (1H,m,H-8),1.08 (3H,s,H-14),1.06 (3H,d,J = 6.8 Hz,H-13),0.96 (3H,d,J = 6.8 Hz,H-12)；¹³C-NMR (150 MHz,CDCl₃) δ: 165.9 (-CO),163.3 (C-4′),143.3 (C-3),131.6 (C-2′,6′),123.1 (C-1′),121.8 (C-2),113.7 (C-3′,5′),83.3 (C-6),77.9 (C-1),56.8 (C-10),55.5 (-OCH₃),53.6 (C-7),36.1 (C-9),35.6 (C-5),30.3 (C-4),26.7 (C-11),25.8 (C-15),24.8 (C-8),24.6 (C-13),22.9 (C-14),21.3 (C-12)。以上数据与文献报道一致^[2]，故鉴定化合物1为lasidiol p-methoxybenzoate。

化合物2：淡黄色脂状物，[α]_25D+41.9°(c 0.09,CHCl₃)。¹H-NMR (600 MHz,CDCl₃) δ: 4.72 (1H,s,H-14),4.71 (1H,s,H-14),4.70 (1H,d,J = 1.8 Hz,H-12),4.44 (1H,d,J = 1.8 Hz,H-12),2.31 (1H,brt,J = 13.9 Hz,H-3),1.99 (2H,m,H-3,7),1.82 (1H,brd,J = 11.5 Hz,H-5),1.75 (3H,s,H-13),1.65～1.40 (6H,m,H-2,6,8),1.28 (2H,m,H-1a,9a),0.85 (2H,m,H-1b,9b),0.72 (3H,s,H-15)；¹³C-NMR (150 MHz,CDCl₃) δ: 151.1 (C-4),150.9 (C-11),108.1 (C-12),105.4 (C-14),49.9 (C-5),45.9 (C-7),42.0 (C-1),41.2 (C-3),36.9 (C-10),29.7 (C-6),29.5 (C-8),26.8 (C-2),23.5 (C-9),21.0 (C-15),16.4 (C-13)。以上数据与文献报道基本一致^[3]，故鉴定化合物2为β-芹子烯。

化合物3：块状透明晶体（醋酸乙酯），mp 114.5～115 ℃。¹H-NMR (400 MHz,CDCl₃) δ: 7.07 (1H,d,J = 16.0 Hz,H-2),6.30 (1H,dd,J = 9.1,3.4 Hz,H-5),6.21 (1H,d,J = 3.3 Hz,H-13a),6.20 (1H,d,J = 16.0 Hz,H-3),5.50 (1H,d,J = 3.3 Hz,H-13b),4.30 (1H,dt,J = 12.2,2.6 Hz,H-8),3.09 (1H,m,H-10),2.80 (1H,ddd,J = 14.2,9.1,2.6 Hz,H-6a),2.56 (1H,m,H-7),2.39 (1H,dt,J = 13.0,3.0 Hz,H-9b),2.31 (3H,s,H-15),2.23 (1H,ddd,J = 14.2,12.5,3.4 Hz,H-6b),1.87 (1H,dt,J = 12.2,3.8 Hz,H-9a),1.16 (3H,d,J = 7.6 Hz,H-14)；¹³C-NMR (100 MHz,CDCl₃) δ: 198.3 (C-4),169.6 (C-12),150.2 (C-2),144.6 (C-1),140.3 (C-11),137.9 (C-5),124.6 (C-3),118.6 (C-13),81.5 (C-8),48.9 (C-7),36.6 (C-9),30.3 (C-10),27.6 (C-15),26.8 (C-6),18.5 (C-14)。以上数据与文献报道一致^[4]，故鉴定化合物3为苍耳亭。

化合物4：无色脂状物。¹H-NMR (400 MHz,CDCl₃) δ: 6.16 (1H,d,J = 3.4 Hz,H-13b),5.53 (1H,dd,J = 8.9,2.9 Hz,H-5),5.44 (1H,d,J = 3.4 Hz,H-13a),4.24 (1H,dt,J = 12.6,2.9 Hz,H-8),2.52 (1H,m,H-6a),2.20 (1H,m,H-9b),2.12 (3H,s,H-15),2.04 (1H,m,H-6b),1.77 (1H,m,H-9a),1.15 (3H,d,J = 7.3 Hz,H-14)；¹³C-NMR (100 MHz,CDCl₃) δ: 208.4 (C-4),170.2 (C-12),147.1 (C-1),138.9 (C-11),122.2 (C-5),118.5 (C-13),82.0 (C-8),48.1 (C-7),42.8 (C-3),37.0 (C-9),34.5 (C-2),33.8 (C-10),30.2 (C- 15),25.8 (C-6),18.6 (C-14)。以上数据与文献报道一致^[4]，故鉴定化合物4为苍耳皂素。

化合物5：针状透明结晶（醋酸乙酯），mp 180.1～182.8 ℃。¹H-NMR (600 MHz,CDCl₃) δ: 4.67 (1H,d,J = 3.1 Hz,H-29a),4.55 (1H,d,J = 3.1 Hz,H-29b),1.66 (3H,brs,H-30),1.06 (6H,s,H-23,26),1.03 (3H,s,H-24),0.92 (3H,s,H-27),0.87 (3H,s,H-25),0.78 (3H,s,H-28)；¹³C-NMR (150 MHz,CDCl₃) δ: 218.3 (C-3),150.9 (C-20),109.4 (C-29),54.9 (C-5),49.8 (C-9),48.3 (C-18),47.9 (C-19),47.4 (C-4),42.9 (C-14),42.9 (C-17),40.8 (C-8),39.9 (C-22),39.6 (C-1),38.2 (C-13),36.9 (C-10),35.5 (C-16),34.2 (C-2),33.6 (C-7),29.7 (C-21),27.4 (C-15),26.7 (C-23),25.2 (C-12),21.4 (C-11),21.0 (C-24),19.6 (C-6),19.3 (C-30),18.0 (C-28),15.9 (C-25),15.8 (C-26),14.5 (C-27)。以上数据与文献报道一致^[5]，故鉴定化合物5为羽扇豆酮。

化合物6：白色颗粒状结晶（甲醇），mp 277～280 ℃。¹H-NMR (400 MHz,DMSO-d₆) 和¹³C-NMR (100 MHz,DMSO-d₆) 与文献报道一致^[6]，故鉴定化合物6为胡萝卜苷。

化合物7：无色结晶（醋酸乙酯），[α]_25D+59° (c 0.10,CHCl₃)。¹H-NMR (600 MHz,CDCl₃) δ: 6.54 (1H,d,J = 8.4 Hz,H-3),6.42 (1H,d,J = 8.4 Hz,H-2),6.26 (1H,d,J = 3.6 Hz,H-13a),5.52 (1H,d,J = 3.0 Hz,H-13b),4.21 (1H,dd,J = 11.4,6.0 Hz,H-5),3.98 (1H,ddd,J = 12.0,10.2,3.0 Hz,H-8),2.74 (1H,m,H-7),2.34 (1H,m,H-10),2.29 (1H,m,H-6α),2.25 (1H,m,H-6β),2.23 (1H,m,H-9α),1.54 (3H,s,H-15),1.23 (3H,d,J = 6.7 Hz,H-14),1.03 (1H,m,H-9β)；¹³C-NMR (150 MHz,CDCl₃) δ: 169.6 (C-12),138.0 (C-11),135.3 (C-3),124.6 (C-2),121.2 (C-13),95.2 (C-4),81.6 (C-8),79.4 (C-1),77.5 (C-5),38.8 (C-7),36.5 (C-9),35.0 (C-6),30.8 (C-10),20.1 (C-15),14.3 (C-14)。以上数据与文献报道一致^[7]，故鉴定化合物7为4β,5β-epoxy-xanthatin-1α,4α- endoperoxide。

化合物8：无色晶体（醋酸乙酯），mp 112～114 ℃；[α]18D +215.2° (c 1.0,MeOH)。¹H-NMR (600 MHz,CDCl₃) δ: 5.90 (1H,brs,H-4),5.87 (1H,dd,J = 15.7,5.4 Hz,H-8),5.79 (1H,d,J = 15.7 Hz,H-7),4.41 (1H,dt,J = 6.4,5.4 Hz,H-9),2.44 (1H,d,J = 17.1 Hz,H-2b),2.24 (1H,d,J = 17.1 Hz,H-2a),1.89 (3H,d,J = 1.1 Hz,H-13),1.30 (3H,d,J = 6.4 Hz,H-10),1.08 (3H,s,H-11),1.01 (3H,s,H-12)；¹³C-NMR (150 MHz,CDCl₃) δ: 197.8 (C-3),162.6 (C-5),135.6 (C-8),128.9 (C-7),126.8 (C-4),78.9 (C-6),67.9 (C-9),49.6 (C-2),41.1 (C-1),24.0 (C-12),23.6 (C-11),22.8 (C-10),18.8 (C-13)。以上数据与文献报道一致^[8]，故鉴定化合物8为(6S,9R)-vomifoliol。

化合物9：无色无定形体。¹H-NMR (600 MHz,CDCl₃) δ: 6.83 (1H,J = 15.6 Hz,H-8),6.46 (1H,d,J = 15.6 Hz,H-7),5.96 (1H,s,H-3),2.50 (1H,J = 17.3 Hz,H-2),2.34 (1H,d,J = 17.3 Hz,H-4),2.30 (3H,s,H-10),1.88 (3H,d,J = 1.4 Hz,H-11),1.11 (3H,s,H-12),1.02 (3H,s,H-13)；¹³C-NMR (150 MHz,CDCl₃) δ: 196.9 (C-9),197.3 (C-3),160.4 (C- 5),144.9 (C-7),130.4 (C-8),127.9 (C-4),79.3 (C-6),49.6 (C-2),41.4 (C-1),28.4 (C-10),24.3 (C-12),22.9 (C-13),18.7 (C-11)。以上数据与文献报道一致^[9]，故鉴定化合物9为dehydrovomifoliol。

化合物10：无色晶体（甲醇），mp 165～168 ℃；[α]_25D-107.5° (c 1.0,H₂O)。¹H-NMR (600 MHz,DMSO-d₆) δ: 5.44 (1H,m,H-3),5.34 (1H,m,H-4),5.00～4.81 (3H,m,3×-OH),4.46 (1H,brs,-OH),4.12 (1H,d,J = 7.8 Hz,H-1′),3.72 (1H,q,J = 7.4 Hz,H-1a),3.64 (1H,brd,J = 11.5 Hz,H-6′),3.42 (2H,m,H-1,6′),3.20～2.80 (4H,m,H-2′～5′),2.28 (2H,q,J = 7.0 Hz,H-2),2.02 (2H,m,H-5),0.92 (3H,t,J = 7.5 Hz,H-6)；¹³C-NMR (150 MHz,DMSO-d₆) δ: 133.4 (C-3),125.5 (C-4),103.2 (C-1′),77.3 (C-5′),77.2 (C-3′),73.9 (C-2′),70.5 (C-4′),68.6 (C-1),61.5 (C-6′),27.9 (C-2),20.6 (C-5),14.6 (C-6)。以上数据与文献报道一致^[10]，故鉴定化合物10为顺-3-己烯醇-β-D-葡萄糖苷。

化合物11：白色晶体（醋酸乙酯）。¹H-NMR (600 MHz,CDCl₃) δ: 6.27 (1H,s,H-13a),5.64 (1H,s,H-13b),5.42 (1H,dd,J = 9.1,3.5 Hz,H-5),2.52 (2H,m,H-3),2.51 (1H,m,H-10),2.25 (4H,m,H-2,6α,7),2.18 (3H,s,H-15),2.06 (1H,dd,J = 14.8,9.3 Hz,H-6β),1.79 (2H,m,H-8,9),1.68 (1H,m,H-8),1.62 (1H,m,H-9),1.10 (3H,d,J = 7.2 Hz,H-14)；¹³C- NMR (150 MHz,CDCl₃) δ: 208.4 (C-4),170.6 (C-12),146.8 (C-2),142.9 (C-11),139.8 (C-1),122.5 (C-5),118.9 (C-13),48.2 (C-7),42.5 (C-3),37.0 (C-10),34.5 (C-8),33.8 (C-2),30.2 (C-6),25.8 (C-15),18.6 (C-14)。以上数据与文献报道基本一致^[11]，故鉴定化合物11为4-oxo-bedfordia acid。

化合物12：白色固体（醋酸乙酯），mp 77.5～78.6 ℃。¹H-NMR (600 MHz,CDCl₃) δ: 7.05 (1H,d,J = 16.2 Hz,H-2),6.26 (1H,dd,J = 9.6,3.6 Hz,H-5),6.18 (1H,d,J = 16.2 Hz,H-3),4.54 (1H,dt,J = 12.6,3.0 Hz,H-8),3.02 (1H,m,H-11),2.72 (1H,m,H-10),2.42 (1H,m,H-6),2.32 (1H,m,H-6),2.30 (3H,s,H-15),2.20 (1H,m,H-7),2.10 (1H,m,H-9),1.69 (1H,m,H-9),1.23 (3H,d,J = 7.8 Hz,H-13),1.16 (3H,d,J = 7.8 Hz,H-14)；¹³C-NMR (150 MHz,CDCl₃) δ: 198.8 (C-4),179.0 (C-12),146.5 (C-2),143.4 (C-1),136.5 (C-5),125.8 (C-3),79.9 (C-8),40.3 (C-11),38.2 (C-7),36.4 (C-9),31.2 (C-10),27.5 (C-15),22.8 (C-6),21.6 (C-14),12.3 (C-13)。以上数据与文献报道一致^[2]，故鉴定化合物12为11α,13- dihydro-8-epi-xanfbut。

化合物13：淡黄色针晶（醋酸乙酯），mp 203～205 ℃；在紫外灯（254 nm）下呈亮蓝色荧光。¹H-NMR (400 MHz,CDCl₃) δ: 7.60 (1H,d,J = 9.6 Hz,H-4),6.27 (1H,d,J = 9.6 Hz,H-3),6.92 (1H,s,H-5),6.85 (1H,s,H-8),6.27 (1H,d,J = 9.2 Hz,H-3),6.15 (1H,s,-OH),3.95 (3H,s,-OCH₃)；¹³C-NMR (100 MHz,CDCl₃) δ: 161.4 (C-2),152.0 (C-9),149.6 (C-7),143.9 (C-6),143.3 (C-4),113.4 (C-3),111.4 (C-10),107.4 (C-5),103.1 (C-8),56.4 (C-OCH₃)。以上数据与文献报道一致^[12]，故鉴定化合物13为东莨菪内酯。

化合物14：白色针状结晶（甲醇），mp 122.0～123.5 ℃。¹H-NMR (400 MHz,DMSO-d₆) δ: 6.90 (2H,d,J = 2.4 Hz,H-2,2′),6.89 (2H,d,J = 8.0 Hz,H-5,5′),6.82 (2H,dd,J = 8.0,2.4 Hz,H-6,6′),5.58 (2H,s,Ar-OH),4.74 (2H,d,J = 4.4 Hz,H-7,7′),4.24 (2H,m,H-9,9′),3.91 (6H,s,2×-OCH₃),3.86 (2H,dd,J = 9.2,3.2 Hz,H-9,9′),3.10 (2H,m,H-8,8′)；¹³C- NMR (100 MHz,CDCl₃) δ: 146.7 (C-3,3′),145.2 (C-4,4′),132.9 (C-1,1′),119.3 (C-6,6′),114.2 (C-5,5′),108.6 (C-2,2′),85.8 (C-7,7′),71.6 (C-9,9′),55.9 (3,3′-OCH₃),54.1 (C-8,8′)。以上数据与文献报道一致^[13]，故鉴定化合物14为松脂素。

化合物15：无色针状结晶（醋酸乙酯），mp 128～130 ℃。¹H-NMR (400 MHz,CDCl₃) δ: 5.35 (1H,brd,J = 4.8 Hz,H-6),3.54 (1H,tt,J = 9.6,4.8 Hz,H-3),1.01 (3H,s,H-18),0.92 (3H,d,J = 6.7 Hz,H-21),0.86 (3H,t,J = 8.0 Hz,H-26),0.84 (3H,d,J = 7.2 Hz,H-28),0.81 (3H,d,J = 7.2 Hz,H-29),0.68 (3H,s,H-19)。以上数据与文献报道一致^[4]，故鉴定化合物15为β-谷甾醇。

化合物16：黄色粉末（甲醇），mp 312～315 ℃；¹H-NMR (600 MHz,DMSO-d₆) δ: 12.50 (1H,brs,5-OH),10.74 (1H,brs,7-OH),9.34 (3H,brs,3,3′,4′-OH),7.66 (1H,d,J = 2.0 Hz,H-2′),7.53 (1H,dd,J = 8.4,2.0 Hz,H-6′),6.87 (1H,d,J = 8.4 Hz,H-5′),6.39 (1H,d,J = 2.0 Hz,H-8),6.1 (1H,d,J = 2.0 Hz,H-6)；¹³C-NMR (150 MHz,DMSO-d₆) δ: 176.0 (C-4),163.1 (C-7),160.8 (C-9),156.1 (C-2),147.6 (C-5),146.1 (C-3′),135.7 (C-3),121.9 (C-1′),119.9 (C-6′),115.4 (C-5′),115.0 (C-2′),102.8 (C-10),98.1 (C-6),93.3 (C-8)。以上数据与文献报道一致^[4]，故鉴定化合物16为槲皮素。

化合物17：无色针状结晶（醋酸乙酯），mp 122～124 ℃。¹H-NMR (600 MHz,CDCl₃) δ: 8.03 (2H,d,J = 9.0 Hz,H-2,6),6.93 (2H,d,J = 9.0 Hz,H-3,5),3.88 (3H,s,-OCH₃)；¹³C-NMR (150 MHz,CDCl₃) δ: 167.2 (-CO-),160.1 (C-4),131.8 (C-2,6),127.9 (C-3,5),122.4 (C-1),51.9 (-OCH₃)。以上数据与文献报道一致^[14]，故鉴定化合物17为对羟基苯甲酸甲酯。

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中草药 2015, Vol. 46 Issue (3): 329-333	0	PDF