中草药  2016, Vol. 47 Issue (13): 2236-2240
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引用本文doi: 10.7501/j.issn.0253-2670.2016.13.006
毛瑞华, 钟志宏, 吴文明, 刘叶, 阮汉利 . 鄂西大蓟茎叶化学成分研究[J]. 中草药, 2016, 47(13): 2236-2240.
MAO Rui-hua, ZHONG Zhi-hong, WU Wen-ming, LIU Ye, RUAN Han-li . Chemical constituents from stems and leaves of Cirsium henryi[J]. Chinese Traditional and Herbal Drugs, 2016, 47(13): 2236-2240 .
鄂西大蓟茎叶化学成分研究
毛瑞华, 钟志宏, 吴文明, 刘叶, 阮汉利     
华中科技大学同济医学院药学院, 湖北 武汉 430030
收稿日期: 2016-02-25
基金项目: 国家自然科学基金资助项目(21572073,31270394)
作者简介: 毛瑞华,男,在读硕士,研究方向为天然药物化学。Tel:18078388232 E-mail:505595086@qq.com
通信作者: 阮汉利,女,博士生导师,教授,研究方向为天然药物化学。Tel:18907105601 E-mail:ruanhl@hust.edu.cn
摘要: 目的 研究鄂西大蓟Cirsium henryi茎叶的化学成分。 方法 使用多种柱色谱技术对鄂西大蓟茎叶95%乙醇提取物的石油醚、醋酸乙酯和正丁醇部位进行分离纯化,根据波谱数据和理化性质确定各化合物的结构。 结果 从鄂西大蓟茎叶石油醚部位分离得到7个化合物,分别鉴定为硬脂酸(1)、二羟丙基软脂酸酯(2)、软脂酸(3)、蒲公英甾醇(4)、伪蒲公英甾醇(5)、蒲公英甾醇乙酸酯(6)、β-谷甾醇(7);从醋酸乙酯部位分离得到6个化合物,分别鉴定为胡萝卜苷(8)、原儿茶酸(9)、蒙花苷(11)、芹菜素(12)、槲皮苷(13)、金合欢素(14);从正丁醇部位分离得到3个化合物,分别鉴定为尿嘧啶(10)、金合欢素-7-O-β-D-葡萄糖苷(15)、4-羟基-3,5-二甲氧基苯甲酸(16)。 结论 化合物3、10~16为首次从该植物中分离得到,化合物10、13、16为首次从蓟属植物中分离得到。
关键词: 鄂西大蓟     黄酮     三萜     尿嘧啶     槲皮苷     4-羟基-3,5-二甲氧基苯甲酸    
Chemical constituents from stems and leaves of Cirsium henryi
MAO Rui-hua, ZHONG Zhi-hong, WU Wen-ming, LIU Ye, RUAN Han-li     
Faculty of Pharmaceutical Sciences, Tongji Medical College of Huazhong University of Science and Technology, Wuhan 430030, China
Abstract: Objective To study the chemical constituents from the stems and leaves of Cirsium henryi. Methods The chemical constituents were isolated by various chromatography techniques and their structures were elucidated on the basis of spectroscopic analysis. Results Sixteen compounds were isolated and identified to be stearic acid (1), 2,3-dihydroxypropyl hexadecanoate (2), palmitic acid (3), taraxasterol (4), pseudo taraxasterol (5), taraxa-sterol acetate (6), β-sitosterol (7), daucosterol (8), protocatechuic acid (9), uracil (10), linarin (11), apigenin (12), quercitrin (13), acacetin (14), acacetin-7-O-β-D-glucoside (15), and 4-hydroxy- 3,5-dimethoxy benzoic acid (16), respectively. Conclusion Compounds 3 and 10-16 are isolated from the plant for the first time, and compounds 10, 13, and 16 are isolated from the plants of Cirsium Mill. Emend. Scop. for the first time.
Key words: Cirsium henryi (Franch.) Diels     flavones     triterpenoids     uracil     quercitrin     4-hydroxy-3,5-dimethoxy benzoic acid    

鄂西大蓟Cirsium henryi (Franch.) Diels系菊科（Compositae）蓟属Cirsium Mill. Emend. Scop. 多年生草本植物，又名刺包蓟，以根和茎叶入药。该植物广泛分布于鄂西山区，具有凉血止血、祛瘀消肿之功效，民间用于治疗咯血、便血、尿血、崩漏下血、瘀肿疮毒等症[1-2]。已有研究报道该属植物中含有三萜、甾醇、黄酮、黄酮苷、长链炔烯醇和挥发油[3]等化学成分。本课题组前期从鄂西大蓟根中分离鉴定了10个化合物，其中乙酰丁香酸（p-hydroxycinnamic acid）和香草酸（vanilIic acid）对小鼠肿瘤细胞S180增殖具有显著的抑制作用[4-5]。为了更加深入地研究鄂西大蓟的化学成分，阐明其药效学物质基础，本实验对鄂西大蓟茎叶的化学成分进行了系统研究，从中分离鉴定了16个化合物，分别为硬脂酸（stearic acid，1）、二羟丙基软脂酸酯（2,3-dihydroxypropyl hexadecanoate，2）、软脂酸（palmitic acid，3）、蒲公英甾醇（taraxasterol，4）、伪蒲公英甾醇（pseudo taraxasterol，5）、蒲公英甾醇乙酸酯（taraxasterol acetate，6）、β-谷甾醇（β-sitosterol，7）、胡萝卜苷（daucosterol，8）、原儿茶酸（protocatechuic acid，9）、尿嘧啶（uracil，10）、蒙花苷（linarin，11）、芹菜素（apigenin，12）、槲皮苷（quercitrin，13）、金合欢素（acacetin，14）、金合欢素-7-O-β-D-葡萄糖苷（acacetin-7-O-β-D-glucoside，15）、4-羟基-3,5-二甲氧基苯甲酸（4-hydroxy-3,5-dimethoxy benzoic acid，16）。化合物1～16的结构见图 1。其中化合物3、10～16为首次从该植物中分离得到，化合物10、13、16为首次从蓟属植物中分离得到。

图 1 化合物1～16的结构 Fig.1 Structures of compounds 1—16

1 仪器与材料

Bruker AM-400 MHz核磁共振仪（Bruker公司）；HR-ESI-MS质谱仪（赛默飞公司）；X4型显微熔点仪（北京泰克仪器有限公司）；旋转蒸发仪（上海亚荣生化仪器厂）；柱色谱硅胶（200～300目）和薄层色谱硅胶GF254（青岛海洋化工）；所用试剂均为分析纯。

鄂西大蓟于2004年11月采集于湖北神农架地区，经神农架药检所石世贵主任药师鉴定为菊科管状花亚科菜蓟族蓟属植物鄂西大蓟Cirsium henryi (Franch.) Diels，植物标本现保存于华中科技大学同济医学院天然药物化学教研室，标本号为20041101。

2 提取与分离

鄂西大蓟茎叶20 kg，阴干后粉碎，用95%乙醇渗漉提取4次，合并提取液，滤液减压浓缩，得到乙醇浸膏376 g，将浸膏混悬于温水后，依次用石油醚、醋酸乙酯、正丁醇萃取，回收溶剂后得到石油醚部分120 g，醋酸乙酯部分86 g，正丁醇部分40 g。石油醚部分经硅胶柱色谱分离，石油醚-醋酸乙酯（100∶0→0∶50）和醋酸乙酯-甲醇（50∶0→0∶100）为洗脱剂梯度洗脱得到4个流分Fr. 1.1～Fr. 1.4。Fr. 1.1（3.5 g）经硅胶柱色谱分离，石油醚-醋酸乙酯（100∶0→10∶90）得到化合物1（17.5 mg）、2（19 mg）；Fr. 1.2（6.8 g）经硅胶柱色谱分离，石油醚-醋酸乙酯（100∶0→10∶90）洗脱得到化合物3（1.2 g）；Fr. 1.3（5.4 g）经硅胶柱色谱分离，石油醚-醋酸乙酯（100∶0→5∶95）洗脱得到化合物4（200 mg）、5（32 mg）、6（25 mg）；Fr. 1.4（7.6 g）经重结晶得到化合物7（367 mg）。醋酸乙酯部分经硅胶色谱分离，石油醚-醋酸乙酯（100∶0→10∶90）梯度洗脱，合并相同流分，再经硅胶柱色谱反复分离纯化得到化合物8（120 mg）、9（13 mg）、11（22 mg）、13（65 mg）、14（32 mg）。正丁醇部分经硅胶色谱分离，石油醚-醋酸乙酯（100∶0→10∶90）以及醋酸乙酯-甲醇（100∶0→10∶90）梯度洗脱，合并相同流分，再经硅胶柱色谱反复分离及纯化得到化合物10（21 mg）、12（17 mg）、15（27 mg）、16（22 mg）。

3 结构鉴定

化合物1：白色粉末，mp 67～69 ℃。1H-NMR (400 MHz,CDCl3) δ: 2.31 (2H,t,J = 7.8 Hz,H-2),1.63 (2H,m,H-3),1.28 (28H,m,H-4～17),0.88 (3H,t,J = 7.2 Hz,H-18)；13C-NMR (100 MHz,CDCl3) δ: 180.1 (C-1),34.0 (C-2),31.9 (C-16),29.7,29.6,29.4,29.4,29.2,29.1 (多个亚甲基C信号，C-4～15),24.7 (C-3),22.7 (C-17),14.51 (C-18)。以上数据与文献报道基本一致[6]，故鉴定化合物1为硬脂酸。

化合物2：白色颗粒。1H-NMR (400 MHz,CDCl3) δ: 4.20 (1H,m,H-1a),4.10 (1H,m,H-1b),3.96 (1H,m,H-2),3.72 (1H,m,H-3a),3.65 (1H,dd,J = 11.0,4.0 Hz,H-3b),2.40 (2H,t,J = 7.0 Hz,H-2′),1.64 (2H,m,H-3′),1.21～1.27 (24H,m,H-4′～H-15′),0.90 (3H,t,J = 7.0 Hz,H-16′)；13C-NMR (100 MHz,CDCl3) δ: 174.4 (C-1′),70.3 (C-2),65.2 (C-1),63.4 (C-3),34.2 (C-2′),32.0 (C-3′),29.7,29.6,29.5,29.4,29.3,29.2 (多个亚甲基C信号，C-4′～13′),25.0 (C-14′),22.7 (C-15′),14.1 (C-16′)。以上数据与文献报道基本一致[7]，故鉴定化合物2为二羟丙基软脂酸酯。

化合物3：白色粉末。1H-NMR (400 MHz,CDCl3) δ: 2.25 (2H,t,J = 7.8 Hz,H-2),1.61 (2H,m,H-3),1.31 (24H,m,H-4～15),0.92 (3H,t,J = 7.2 Hz,H-16)；13C-NMR (100 MHz,CDCl3) δ: 179.5 (C-1),36.4 (C-2),24.9 (C-3),29.9,29.8,29.6,29.5 (多个亚甲基C信号，C-4～13),31.9 (C-14),23.6 (C-15),14.5 (C-16)。以上数据与文献报道基本一致[8]，故鉴定化合物3为软脂酸。

化合物4：无色粉末。1H-NMR (400 MHz,CDCl3) δ: 4.61 (2H,m,H-30),3.20 (1H,dd,J = 10.2,2.4 Hz,H-3),0.96 (3H,d,J = 7.0 Hz,H-29),1.04 (3H,s,H-26),0.90 (3H,s,H-27),1.02 (3H,s,H-23),0.93 (3H,s,H-28),0.83 (3H,s,H-25),0.77 (3H,s,H-24)；13C-NMR (100 MHz,CDCl3) δ: 38.8 (C-1),26.9 (C-2),79.2 (C-3),38.9 (C-4),55.3 (C-5),18.0 (C-6),33.8 (C-7),40.0 (C-8),50.1 (C-9),37.2 (C-10),21.4 (C-11),26.8 (C-12),38.8 (C-13),42.3 (C-14),26.9 (C-15),38.3 (C-16),33.2 (C-17),48.7 (C-18),39.4 (C-19),154.7 (C-20),35.4 (C-21),38.8 (C-22),28.0 (C-23),15.9 (C-24),16.8(C-25),16.3 (C-26),14.8 (C-27),19.5 (C-28),25.6 (C-29),107.1 (C-30)。以上数据与文献报道基本一致[9]，故鉴定化合物4为蒲公英甾醇。

化合物5：无色粉末，mp 196～198 ℃。1H-NMR (400 MHz,CDCl3) δ: 4.61 (2H,m,H-30),3.20 (1H,dd,J = 10.2,2.4 Hz,H-3),1.63 (3H,s,H-29),1.04 (3H,s,H-26),1.02 (3H,s,H-23),0.93 (3H,s,H-28),0.90 (3H,s,H-27),0.83 (3H,s,H-25),0.76 (3H,s,H-24)；13C-NMR (100 MHz,CDCl3) δ: 38.8 (C-1),27.4 (C-2),79.0 (C-3),40.1 (C-4),55.2 (C-5),21.4 (C-6),34.4 (C-7),41.1 (C-8),50.4 (C-9),38.8 (C-10),21.6 (C-11),28.0 (C-12),39.4 (C-13),42.2 (C-14),27.0 (C-15),38.3 (C-16),36.3 (C-17),48.6 (C-18),37.1 (C-19),139.9 (C-20),118.0 (C-21),41.1 (C-22),34.1 (C-23),15.4 (C-24),18.3 (C-25),16.0 (C-26),14.7 (C-27),18.3 (C-28),26.2 (C-29),25.5 (C-30)。以上数据与文献报道基本一致[9]，故鉴定化合物5为伪蒲公英甾醇。

化合物6：无色粉末，mp 213～215 ℃。1H-NMR (400 MHz,CDCl3) δ: 4.70 (2H,s,H-30),4.55 (1H,brs,H-3),2.04 (3H,s,3-CH3CO),0.92～2.48 (20H,m,H-1,2,6,7,11,12,15,16,21,22),1.08 (3H,d,J = 5.0 Hz,H-29),0.99 (3H,s,H-26),0.96 (3H,s,H-27),0.94 (3H,s,H-28),0.91 (3H,s,H-23),0.91 (3H,s,H-24),0.86 (3H,s,H-25)；13C-NMR (100 MHz,CDCl3) δ: 38.6 (C-1),26.5 (C-2),81.3 (C-3),37.8 (C-4),55.3 (C-5),18.5 (C-6),34.3 (C-7),41.2 (C-8),50.7 (C-9),37.4 (C-10),21.7 (C-11),26.0 (C-12),39.5 (C-13),42.3 (C-14),26.7 (C-15),38.1 (C-16),34.8 (C-17),48.9 (C-18),39.4 (C-19),154.9 (C-20),25.7 (C-21),39.1 (C-22),28.2 (C-23),15.6 (C-24),16.8 (C-25),16.4 (C-26),15.0 (C-27),19.7 (C-28),25.2 (C-29),107.3 (C-30),171.3 (3-C = O),21.6 (3-CH3CO)。以上数据与文献报道基本一致[10]，故鉴定化合物6为蒲公英甾醇乙酸酯。

化合物7：无色针状结晶（甲醇）。1H-NMR (400 MHz,CDCl3) δ: 5.34 (1H,d,J = 5.2 Hz,H-6),3.50 (1H,m,H-3),1.00 (3H,s,H-19),0.92 (3H,d,J = 8.0 Hz,H-21),0.86 (3H,t,J = 8.0 Hz,H-29),0.82 (3H,d,J = 7.6 Hz,H-26),0.80 (3H,d,J = 7.6 Hz,H-27),0.66 (3H,s,H-18)；13C-NMR (100 MHz,CDCl3) δ: 141.2 (C-5),120.0 (C-6),69.5 (C-3),56.0 (C-17),55.4 (C-14),49.8 (C-9),45.1 (C-24),42.0 (C-13),42.0 (C-4),39.5 (C-12),37.2 (C-1),36.5 (C-20),36.7 (C-10),33.4 (C-22),31.7 (C-2),31.2 (C-7),31.6 (C-8),28.9 (C-25),28.5 (C-16),25.7 (C-23),24.2 (C-15),23.6 (C-28),21.7 (C-11),20.4 (C-26),19.3 (C-27),19.3 (C-19),19.0 (C-21),11.4 (C-18),11.3 (C-29)。以上数据与文献报道基本一致[11]，故鉴定化合物7为β-谷甾醇。

化合物8：白色粉末。1H-NMR (400 MHz,Pyr-d5) δ: 3.94 (1H,m,H-3),5.36 (1H,d,J = 2.6 Hz,H-6),0.69 (3H,s,H-18),0.96 (3H,s,H-19),1.00 (3H,d,J = 6.1 Hz,H-21),0.88 (3H,d,J = 7.1 Hz,H-26),0.90 (3H,d,J = 7.1 Hz,H-27),0.91 (3H,t,J = 7.4 Hz,H-29),5.07 (1H,d,J = 7.7 Hz,H-1′),4.01 (1H,t,J = 7.8 Hz,H-2′),4.23 (1H,m,H-3′),4.23 (1H,m,H-4′),3.94 (1H,m,H-5′),4.42 (1H,d,J = 11.7 Hz,H-6′a),4.37 (1H,dd,J = 11.7,4.7 Hz,H-6′b)；13C-NMR (100 MHz,Pyr-d5) δ: 141.4 (C-5),122.4 (C-6),103.1 (C-1′),79.1 (C-3′),79.0 (C-3),78.6 (C-5′),75.9 (C-2′),72.2 (C-4′),63.4 (C-6′),57.3 (C-14),56.8 (C-17),50.9 (C-9),46.6 (C-24),43.0 (C-13),40.5 (C-12),40.0 (C-4),38.0 (C-1),37.4 (C-10),36.9 (C-20),34.7 (C-22),32.7 (C-7),32.6 (C-8),30.8 (C-2),30.0 (C-25),29.3 (C-16),27.0 (C-23),25.0 (C-15),23.9 (C-28),21.8 (C-11),20.5 (C-27),19.9 (C-26),19.7 (C-19),19.5 (C-21),12.7 (C-29),12.5 (C-18)。以上数据与文献报道基本一致[12]，故鉴定化合物8为β-胡萝卜苷。

化合物9：无色片状结晶（甲醇），mp 199～201 ℃。1H-NMR (400 MHz,DMSO-d6) δ: 7.33 (1H,d,J = 2.0 Hz,H-2),7.27 (1H,dd,J = 8.2,2.0 Hz,H-6),6.76 (1H,d,J = 8.2 Hz,H-5)。以上数据与文献报道基本一致[13]，故鉴定化合物9为原儿茶酸。

化合物10：灰白色粉末。1H-NMR (400 MHz,DMSO-d6) δ: 11.02 (1H,s,NH-3),10.83 (1H,brs,1-NH),7.41 (1H,d,J = 5.7 Hz,H-6),5.45 (1H,d,J = 5.7 Hz,H-5)；13C-NMR (100 MHz,DMSO-d6) δ: 164.0 (C-4),151.2 (C-2),141.9 (C-6),99.9 (C-5)。以上数据与文献报道基本一致[14]，故鉴定化合物10为尿嘧啶。

化合物11：淡黄色无定形粉末，mp 255～257 ℃，FeCl3、Mg-HCl及Molish反应阳性，EI-MS m/z: 593 [M＋H]+。1H-NMR (400 MHz,DMSO-d6) δ: 3.84 (3H,s,4′-OCH3),6.45 (1H,d,J = 2.2 Hz,H-6),6.79 (1H,d,J = 2.2 Hz,H-8),6.94 (1H,s,H-3),7.14 (2H,d,J = 9.0 Hz,H-3′,5′),8.05 (2H,d,J = 7.0 Hz,H-2′,6′),12.9 (1H,s,5-OH),1.07 (3H,d,J = 6.4 Hz,Rha-H-6),4.54 (1H,s,Rha-H-1),5.06 (1H,d,J = 7.3 Hz,Glc-H-1)；13C-NMR (100 MHz,DMSO-d6) δ: 55.3 (4′-OCH3),94.5 (C-8),99.6 (C-6),104.3 (C-3),105.5 (C-10),114.4 (C-3′),114.4 (C-5′),122.8 (C-1′),128.2 (C-2′),128.2 (C-6′),156.6 (C-9),161.5 (C-5),162.2 (C-4′),162.6 (C-7),164.1 (C-2),182.3 (C-4),65.8 (Glc-C-6),69.3 (Glc-C-4),73.3 (Glc-C-2),75.4 (Glc-C-5),76.0 (Glc-C-3),99.8 (Glc-C-1),17.5 (Rha-C-6),68.5 (Rha-C-5),70.5 (Rha-C-2),71.2 (Rha-C-3),72.3 (Rha-C-4),100.4 (Rha-C-1)。以上数据与文献报道基本一致[15]，故鉴定化合物11为蒙花苷。

化合物12：淡黄色粉末（甲醇），mp＞300 ℃。1H-NMR (400 MHz,DMSO-d6) δ: 12.95 (1H,s,5-OH),10.57 (1H,brs,7-OH),10.57 (1H,brs,4′-OH),7.90 (1H,d,J = 8.8 Hz,H-2′),7.90 (1H,d,J = 8.8 Hz,H-6′),6.91 (1H,d,J = 8.8 Hz,H-3′),6.91 (1H,d,J = 8.8 Hz,H-5′),6.75 (1H,s,H-3),6.46 (1H,d,J = 2.0 Hz,H-8),6.17 (1H,d,J = 2.0 Hz,H-6)；13C-NMR (100 MHz,DMSO-d6) δ: 164.3 (C-7),102.6 (C-3),181.5 (C-4),161.7 (C-5),98.8 (C-6),163.8 (C-2),94.2 (C-8),157.3 (C-9),103.5 (C-10),120.9 (C-1),128.2 (C-2′),128.2 (C-6′),116.2 (C-3′),116.2 (C-5′),160.8 (C-4′)。以上数据与文献报道基本一致[16]，故鉴定化合物12为芹菜素。

化合物13：黄色细针晶（甲醇），mp 251～253 ℃。1H-NMR (400 MHz,DMSO-d6) δ: 0.81 (3H,d,J = 6.0 Hz,Rha-5-CH3),3.08～3.30 (1H,m,Rha-H-4),3.08～3.30 (1H,m,Rha-H-5),3.46～3.52 (1H,m,Rha-H-3),3.94～3.99 (1H,m,Rha-H-2),5.24 (1H,d,J = 1.7 Hz,Rha-H-1),6.20 (1H,d,J = 2.2 Hz,H-6),6.38 (1H,d,J = 2.2 Hz,H-8),6.87 (1H,d,J = 8.4 Hz,H-5′),7.26 (1H,dd,J = 8.7,2.0 Hz,H-6′),7.29 (1H,d,J = 2.0 Hz,H-2′),9.36,9.73,10.89 (各1H,brs,7,3′,4′-OH),12.66 (1H,s,5-OH)；13C-NMR (100 MHz,DMSO-d6) δ: 17.8 (Rha-C-6),70.3 (Rha-C-5),70.6 (Rha-C-3),70.8 (Rha-C-2),71.5 (Rha-C-4),93.9 (C-8),99.0 (C-6),102.2 (Rha-C-1),104.4 (C-10),115.7 (C-2′),115.9 (C-5′),120.9 (C-6′),121.0 (C-1′),134.7 (C-3),145.7 (C-3′),148.9 (C-4′),156.9 (C-9),157.8 (C-2),161.8 (C-5),164.8 (C-7),178.3 (C-4)。以上数据与文献报道基本一致[17]，故鉴定化合物13为槲皮苷。

化合物14：黄色针晶（甲醇），mp 259～262 ℃，盐酸-镁粉反应阳性，EI-MS m/z: 284 [M]+。H-NMR (400 MHz,DMSO-d6) δ: 12.96 (1H,s,5-OH),10.81 (1H,s,8-OH),7.94 (2H,d,J = 8.7 Hz,H-2′,6′),6.93 (2H,d,J = 8.8 Hz,H-3′,5′),6.90 (1H,d,J = 2.5 Hz,H-6),6.87 (1H,s,H-3),6.43 (1H,d,J = 2.1 Hz,H-8),3.88 (3H,s,4′-OCH3)；13C-NMR (100 MHz,DMSO-d6) δ: 182.2 (C-4),164.6 (C-7),162.8 (C-2),161.9 (C-5),157.8 (C-9),128.9 (C-2′,6′),122.0 (C-1′),115.4 (C-3′,5′),105.3 (C-10),103.3 (C-3),99.3 (C-6),94.3 (C-8),55.4 (4′-OCH3)。以上数据与文献报道基本一致[16]，故鉴定化合物14为金合欢素。

化合物15：淡黄色结晶（甲醇），mp 260～262 ℃，盐酸-镁粉和Molish反应均为阳性，酸水解检出葡萄糖。1H-NMR (400 MHz,DMSO-d6) δ: 12.92 (1H,s,5-OH),8.05 (2H,d,J = 8.9 Hz,H-2′,6′),7.14 (2H,d,J = 8.9 Hz,H-3′,5′),6.95 (1H,s,H-3),6.86 (1H,d,J = 1.8 Hz,H-8),6.46 (1H,d,J = 1.8 Hz,H-6),5.08 (1H,d,J = 7.4 Hz,Glc-H-1),3.87 (3H,s,4′-OCH3)；13C-NMR (100 MHz,DMSO-d6) δ: 163.9 (C-2),103.9 (C-3),182.2 (C-4),161.6 (C-5),99.7 (C-6),163.2 (C-7),95.1 (C-8),157.1 (C-9),105.6 (C-10),55.73 (C-4′-OCH3),122.8 (C-1′),128.6 (C-2′),114.8 (C-3′),162.3 (C-4′),114.7 (C-5′),128.6 (C-6′),100.1 (Glc-C-1),73.3 (Glc-C-2),76.6 (Glc-C-3),69.7 (Glc-C-4),76.3 (Glc-C-5),60.8 (Glc-C-6)。以上数据与文献报道基本一致[18]，故鉴定化合物15为金合欢素-7-O-β-D-葡萄糖苷。

化合物16：淡黄色针状结晶（甲醇），mp 194 ℃。1H-NMR (400 MHz,CD3OD) δ: 7.32 (2H,s,H-2,6),3.87 (6H,s,3,5-OCH3)；13C-NMR (100 MHz,CD3OD) δ: 170.0 (C-7),149.0 (C-3,5),142.0 (C-4),122.1 (C-1),108.7 (C-2,6),59.9 (3,5-OCH3)。以上数据与文献报道基本一致[19]，故鉴定化合物16为4-羟基-3,5-二甲氧基苯甲酸。

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