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1 中草药 Chinese Traditional and Herbal Drugs 第 45 卷第 10 期 2014 年 5 月 1373 鼠曲草的化学成分研究李胜华怀化学院生命科学系民族药用植物资源研究与利用湖南省重点实验室, 湖南怀化摘要 : 目的研究鼠曲草 Gnaphlium affine 全草化学成分方法运用多种色谱技术分离鼠曲草全草中黄酮苷类成分, 采用波谱技术和理化性质确定化合物的结构结果从鼠曲草全草 70% 乙醇提取物中分离得到 15 个化合物, 分别鉴定为 3-methoxyphenol1-O-α-L-rhamnopyranosyl-(1 6)-O-β-D-glucopyranoside(1) 3, 5-dihydroxy-2-(4-hydroxybenzyl)-3-methoxybibenzyl(2) 大黄素甲醚(3) 松柏醛(4) 木犀草素-4 -O-β-D- 葡萄糖苷 (5) 款冬二醇 3-O- 棕榈酸酯 (6) 白桦脂酸(7) 伞形香青酰胺 (8) 对羟基桂皮酸甲酯葡萄糖苷(9) valene-1(10)-ene-8, 11-diol(10) longumoside A(11) 大海米菊酰胺 K(12) 槲皮素-3-O- 芸香糖基 -7-O- 葡萄糖苷 (13) 木犀草素-7-O-β-D- 葡萄糖基 -(1 6)-[(6 -O- 咖啡酸 )-β-d- 葡萄糖苷 ](14) 毛蕊花苷 (15) 结论化合物 1 11 为首次从该属植物中得到, 化学物为首次从该植物中分离得到关键词 : 鼠曲草 ; 大黄素甲醚 ; 松柏醛 ; 款冬二醇 3-O- 棕榈酸酯 ; 伞形香青酰胺 ; 槲皮素 -3-O- 芸香糖基 -7-O- 葡萄糖苷中图分类号 :R284.1 文献标志码 :A 文章编号 : (2014) DOI: /j.issn Chemical constituents from Gnaphlium affine LI Sheng-hua Key Laboratory of Hunan Province for Study and Utilization of Ethnic Medicinal Plant Resources, Department of Life Science, Huaihua University, Huaihua , China Abstract: Objective To investigate the chemical constituents from the stems of Gnaphlium affine. Methods The constituents were isolated and purified by silica gel, Sephadex LH-20 column chromatography, and preparative TLC. The structures were identified on the basis of spectral data and physiochemical characteristics. Results Fifteen compounds were isolated from 70% ethanol extracts of G. affine and identified as 3-methoxyphenol1-O-α-L-rhamnopyranosyl-(1 6)-O-β-D-glucopyranoside (1), 3, 5-dihydroxy-2-(4- hydroxybenzyl)-3-methoxybibenzyl (2), physcion (3), aldehyde (4), luteolin-4 -O-β-D-glucoside (5), faradiol 3-O-palmitate (6), betulinic acid (7), anabellamide (8), 4-O-D-glucopyranosyl-p-coumaric acid methyl ester (9), valene-1 (10)-ene-8, 11-diol (10), longumoside A (11), grossamiade K (12), quercetin-3-o-rutin-7-o-glucoside (13), luteolin-7-o-β-d-glucopyranosyl-(1 6)-[(6 - O-caffeoylquinic)-β-D-glucopyranoside] (14), and isoverbascoside (15). Conclusion Compounds 2 and 11 are reported from the plants in Gnaphalium L. for the first time. Compounds 2, 3, 6, 8, 13, and 14 are isolated from this plant material for the first time. Key words: Gnaphlium affine D. Don; physcion; coniferyl aldehyde; faradiol 3-O-palmitate; anabellamide; quercetin-3-o-rutin-7-oglucoside 鼠曲草 Gnaphlium affine D. Don 又名佛耳草清明菜, 系菊科鼠曲草属植物, 具有调血脂降血糖降血压抗衰老抗炎抑菌增强免疫力等功效 [1] 每年清明节前后, 民间广泛利用鼠曲草嫩尖叶加工饵料, 故有清明菜之称有研究表明, 鼠曲草中含较多的黄酮类化合物黄酮类化合物具有抗氧化抗过敏抗炎抗菌抗突变抗肿瘤保肝作用, 具有保护心脑血管系统和抗病毒等广泛的生理活性 [2-5], 且毒性较低, 可以用作食品化妆品的天然添加剂目前有关鼠曲草的研究主要集中在黄酮类化合物的提取纯化工艺和药理研究, 但是相关化学成分报道甚少本实验以鼠曲草全草 75% 乙醇提取物为原料, 通过柱色谱等手段, 对其化学成分进行研究, 分离得到 15 个化合物, 分别鉴定为 3-methoxyphenol1-O-α-L-rhamnopyranosyl-(1 6)- O-β-D-glucopyranoside(1) 3, 5-dihydroxy-2-(4- 收稿日期 : 基金项目 : 湖南省重点建设学科经费资助 ( ); 湖南省科技计划资助项目 (2013FJ4324) 作者简介 : 李胜华 (1976 ), 男, 讲师, 主要从事植物化学成分研究 lishenghua110@126.com

2 1374 中草药 Chinese Traditional and Herbal Drugs 第 45 卷第 10 期 2014 年 5 月 hydroxybenzyl)-3-methoxybibenzyl(2) 大黄素甲醚 (physcion,3) 松柏醛(aldehyde,4) 木犀草素- 4 -O-β-D- 葡萄糖苷 (luteolin-4 -O-β-D-glucoside,5) 款冬二醇 3-O- 棕榈酸酯 (faradiol 3-O-palmitate,6) 白桦脂酸 (betulinic acid, 7 ) 伞形香青酰胺 (anabellamide,8) 对羟基桂皮酸甲酯葡萄糖苷(4- O-D-glucopyranosyl-p-coumaric acid methyl ester,9) valene-1(10)-ene-8, 11-diol(10) longumoside A (11) 大海米菊酰胺 K(grossamiade K,12) 槲皮素 -3-O- 芸香糖基 -7-O- 葡萄糖苷 (quercetin-3-o-rutin- 7-O-glucoside,13) 木犀草素-7-O-β-D- 葡萄糖基 - (1 6)-[(6 -O- 咖啡酸 )-β-d- 葡萄苷 ](luteolin-7-o-β- D-glucopyranosyl-(1 6)-[(6 -O-caffeoylquinic)-β-Dglucopyranoside],14) 毛蕊花苷(isoverbascoside, 15) 其中, 化合物 1 11 为首次从该属植物中得到 ; 化合物为首次从该植物中得到 1 仪器与材料 RDY 2A 显微熔点仪 ( 北京中仪友信科技有限公司 );Bruker AV 500/300 型核磁共振仪 ( 美国布鲁克公司 );Waters SynaptTM Q TOF 型质谱仪 ( 美国 Waters 公司 ); 柱色谱硅胶 (100~200 目 ) 薄层色谱硅胶 (GF 254 ) 均为青岛海洋化工厂产品 ; 所用试剂均为分析纯鼠曲草产自湖南省怀化市沅陵县, 经怀化学院刘光华讲师鉴定为菊科鼠曲草属植物鼠曲草 Gnaphlium affine D. Don 的干燥全草药材 (HHXY ) 存放于怀化学院生命科学系标本馆 2 提取与分离取鼠曲草全草 40 kg, 用 70% 乙醇分别加 10 倍量回流提取 2 次, 每次 2 h, 提取液合并后, 减压浓缩, 得浸膏 4.6 kg 将浸膏混悬于水中, 依次用石油醚氯仿醋酸乙酯正丁醇萃取减压回收溶剂后得石油醚部位 (253 g) 氯仿部位(659 g) 醋酸乙酯部位 (1 252 g) 正丁醇部位(1 230 g) 石油醚部位 (253 g) 进行硅胶柱色谱, 石油醚 - 醋酸乙酯 ( ) 梯度洗脱, 得化合物 1(12 mg) 2(15 mg) 3(23 mg) 4(24 mg) 氯仿部位(659 g) 进行硅胶柱色谱, 氯仿 - 甲醇 ( ) 梯度洗脱, 分为 5 个部分 Fr. 1~5;Fr. 2~4 分别经硅胶柱色谱反复分离, 以氯仿 - 甲烷 ( ) 石油醚- 丙酮 ( ) 梯度洗脱, 然后通过制备液相和重结晶等分离纯化手段得到化合物 5(23 mg) 6(18 mg) 7(65 mg) 8(32 mg) 醋酸乙酯部位 (50 g) 经硅胶柱色谱, 二氯甲烷 - 甲醇 ( ) 梯度洗脱, 得化合物 9(2 g) 10(86 mg) 11(114 mg) 12(26 mg) 正丁醇部位 (1 230 g) 经大孔吸附树脂柱分离, 乙醇 - 水梯度洗脱 (30% 50% 70%), 再经硅胶柱色谱分离, 醋酸乙酯 - 甲醇梯度 ( ) 洗脱, 得化合物 13(36 mg) 14(18 mg) 15(68 mg) 3 结构鉴定化合物 1: 无色粉末,ESI-MS m/z: 467 [M+ Cl], 分子式为 C 19 H 28 O 11 1 H-NMR (400 MHz, DMSO-d 6 ) δ: 7.03 (1H, d, J = 2.9 Hz, H-2), 7.03 (1H, m, H-4), 6.95 (1H, m, H-5), 7.16 (1H, d, J = 6.6 Hz, H-6), 4.86 (1H, d, J = 6.3 Hz, H-1 ), 3.50 (1H, t, J = 7.6 Hz, H-2 ), 3.48 (1H, t, J = 7.6 Hz, H-3 ), 3.40 (1H, t, J = 7.6 Hz, H-4 ), 3.54 (1H, dt, J = 6.8, 1.5 Hz, H-5 ), 4.02 (1H, dd, J = 9.0, 1.5 Hz, H-6 a), 3.62 (1H, dd, J = 9.0, 5.1 Hz, H-6 b) 4.72 (1H, d, J = 1.2 Hz, H-1 ), 3.83 (1H, dd, J = 2.8, 1.4 Hz, H-2 ), 3.70 (1H, dd, J = 8.0, 2.8 Hz, H-3 ), 3.37 (1H, t, J = 8.0 Hz, H-4 ), 3.66 (1H, m, H-5 ), 1.22 (1H, d, J = 5.2 Hz, H-6 ); 13 C-NMR (125 MHz, DMSO-d 6 ) δ: (C-1), (C-2), (C-3), (C-4), (C-5), (C-6);102.7 (C-1 ), 74.9 (C-2 ), 77.9 (C-3 ), 71.6 (C-4 ), 76.9 (C-5 ), 67.7 (C-6 ), (C-1 ), 72.2 (C-2 ), 74.0 (C-3 ), 72.4 (C-4 ), 69.8 (C-5 ), 18.0 (C-6 ) 以上数据与文献报道一致 [6], 故鉴定化合物 1 为 3-methoxyphenol1-O-α-L-rhamnopyranosyl-(1 6)-O-β-D-glucopyranoside 化合物 2: 无色针晶 ( 甲醇 ),ESI-MS m/z: 351 [M+H] +, 分子式为 C 22 H 22 O 4 1 H-NMR (400 MHz, CD 3 OD) δ: 7.03 (1H, t, J = 8.0 Hz, H-5 ), 6.87 (2H, d, J = 8.5 Hz, H-2, 6 ), 6.63 (2H, d, J = 8.5 Hz, H-3, 5 ), 6.57 (1H, dd, J = 9.1, 1.0 Hz, H-4 ), 6.54 (1H, d, J = 1.0 Hz, H-2 ), 6.53 (1H, d, J = 7.1 Hz, H-6 ), 6.33 (1H, d, J = 2.1 Hz, H-4), 6.28 (1H, d, J = 2.2 Hz, H-6), 3.84 (2H, s, 7 -CH 2 ), 3.74 (3H, s, 3-OCH 3 ), 2.71 (2H, m, α-ch 2 ), 2.55 (2H, m, α -CH 2 ); 13 C-NMR (125 MHz, CD 3 OD) δ: (C-3), (C-3 ), (C-5), (C-4 ), (C-1 ), (C-1), (C-1 ), (C-5 ), (C-2, 6 ), (C-2 ), (C-2), (C-6 ), (C-3, 5 ), (C-4 ), (C-6), 98.1 (C-4), 56.1 (3-OCH 3 ), 38.7 (C-α ), 36.6 (C-α), 30.7 (C-7 ) 以上数据与文献报道

3 中草药 Chinese Traditional and Herbal Drugs 第 45 卷第 10 期 2014 年 5 月 1375 基本一致 [7], 故鉴定化合物 2 为 3, 5-dihydroxy-2- (4-hydroxybenzyl)-3-methoxybibenzyl 化合物 3: 黄色块状结晶 ( 氯仿 ),ESI-MS m/z: 285 [M+H] + 1 H-NMR (400 MHz, CDCl 3 ) δ: (1H, s, 8-OH), (1H, s, 1-OH), 7.65 (1H, d, J = 1.0 Hz, H-4), 7.39 (1H, d, J = 2.5 Hz, H-5), 7.10 (1H, d, J = 1.0 Hz, H-2), 6.70 (1H, d, J = 2.5 Hz, H-7), 3.94 (3H, s, 6-OCH 3 ), 2.46 (3H, s, 3-CH 3 ); 13 C-NMR (75 MHz, CDCl 3 ) δ: (C-9), (C-10), (C-6), (C-8), (C-1), (C-3), (C-13), (C-12), (C-2), (C-4), (C-11), (C-14), (C-5), (C-7), 56.1 (6-OCH 3 ), 22.2 (3-CH 3 ) 以上数据与文献报道基本一致 [8], 故鉴定化合物 3 为大黄素甲醚化合物 4: 白色针晶 ( 丙酮 ),mp 82~85 1 H-NMR (400 MHz, CD 3 OD) δ: 9.95 (1H, d, J = 7.5 Hz, H-1), 7.40 (1H, d, J = 15.0 Hz, H-3), 7.12 (1H, dd, J = 8.0, 2.0 Hz, H-6 ), 7.07 (1H, d, J = 2.0 Hz, H-2 ), 6.96 (1H, d, J = 8.0 Hz, H-5 ), 6.59 (1H, dd, J = 15.0, 7.5 Hz, H-2), 3.95 (3H, s, 3-CH 3 ); 13 C-NMR (100 MHz, CD 3 OD) δ: (C-1), (C-4 ), (C-3), (C-3 ), (C-1 ), (C-6 ), (C-2), (C-5 ), (C-2 ), 56.7 (3-OCH 3 ) 以上数据与文献报道一致 [9], 故鉴定化合物 4 为松柏醛化合物 5: 黄色粉末 1 H-NMR (400 MHz, DMSO-d 6 ) δ: (1H, s, 5-OH), (1H, dd, J = 8.4, 2.1 Hz, H-6 ), 7.50 (1H, brs, H-2 ), 7.23 (1H, d, J = 8.4 Hz, H-5 ), 6.82 (1H, s, H-3), 6.48 (1H, d, J = 1.8 Hz, H-8), (1H, d, J = 1.8 Hz, H-6), 4.88 (1H, d, J = 7.4 Hz, H-1 ), 3.16~3.75 (6H, m, H-2, 6); 13 C-NMR (125 MHz, DMSO-d 6 ) δ: (C-2), (C-3), (C-4), (C-5), 99.0 (C-6), (C-7), 94.1 (C-8), (C-9), (C-10), (C-1 ), (C-2 ), (C-3 ), (C-4 ), (C-5 ), (C-6 ), (C-1 ), 73.3 (C-2 ), 75.9 (C-3 ), 70.0 (C-4 ), 77.3 (C-5 ), 60.7 (C-6 ) 以上数据与文献报道基本一致 [10], 故鉴定化合物 5 为木犀草素 -4 -O-β-D- 葡萄糖苷化合物 6: 浅黄色油状物 ;ESI-MS m/z: 703 [M+ Na] +, 679 [M-H] 1 H-NMR (400 MHz, CDCl 3 ) δ: 4.50 (1H, dd, J = 11.4, 5.4 Hz, H-3), 3.45 (1H, dd, J = 12.0, 4.8 Hz, H-16), 5.32 (1H, brd, J = 6.6 Hz, H-21), 0.73, 0.85, 0.86, 0.88, 1.00, 1.00, 1.06, 1.65 ( 各 3H, 8 -CH 3 );2.30 (2H, t, J = 7.2 Hz, 3 -CH 2 ), 0.89 (3H, t, J = 7.2 Hz, 16 -CH 3 ); 13 C-NMR (150 MHz, CDCl 3 ) δ: 38.4 (C-1), 27.2 (C-2), 80.5 (C-3), 37.8 (C-4), 55.4 (C-5), 18.2 (C-6), 34.1 (C-7), 41.1 (C-8), 49.9 (C-9), 37.0 (C-10), 21.6 (C-11), 27.2 (C-12), 38.7 (C-13), 37.5 (C-14), 36.5 (C-15), 76.3 (C-16), 39.9 (C-17), 47.6 (C-18), 35.9 (C-19), (C-20), (C-21), 34.9 (C-22), 28.0 (C-23), 16.3 (C-24), 16.6 (C-25), 16.6 (C-26), 16.3 (C-27), 16.0 (C-28), 22.4 (C-29), 21.5 (C-30), (C-1 ), 31.9 (C-2 ), 14.5 (C-16 ) 以上数据与文献报道基本一致 [11], 故鉴定化合物 6 为款冬二醇 3-O- 棕榈酸酯化合物 7: 白色无定形粉末,mp 272~274, Liebermann-Burchard 反应呈阳性,ESI-MS m/z: 455 [M-H], 分子式为 C 30 H 48 O 3 1 H-NMR (400 MHz, CD 3 COCD 3 ) δ: 1.69 (3H, brs, H-30), 0.75, 0.8 5, 0.9 5, 0.9 5, 1.01 ( 各 3H, brs, H-23, 24, 25, 26, 27), 4.71 (1H, brs, H-29α), 4.58 (1H, brs, H-29β); 13 C-NMR (150 MHz, CD 3 COCD 3 ) δ: 38.7 (C-1), 27.6 (C-2), 77.7 (C-3), 38.7 (C-4), 55.4 (C-5), 18.2 (C-6), 34.3 (C-7), 40.6 (C-8), 50.5 (C-9), 37.0 (C-10), 20.8 (C-11), 25.5 (C-12), 38.1 (C-13), 42.3 (C-14), 30.4 (C-15), 31.9 (C-16), (C-17), (C-18), 49.0 (C-19), (C-20), 28.6 (C-21), 36.6 (C-22), 15.6 (C-24), 27.3 (C-23), 15.1 (C-25), 15.7 (C-26), 14.1 (C-27), (C-28), (C-29), 20.8 (C-30) 以上数据与文献报道一致 [12], 故鉴定化合物 7 为白桦脂酸化合物 8: 白色粉末, 分子式 C 32 H 30 N 2 O 4 1 H-NMR (400 MHz, CDCl 3 ) δ: 7.70 (2H, m, H-2, 6), 7.68 (2H, m, H-17, 21), 7.50 (1H, m, H-4), 7.41 (1H, m, H-19), 7.40 (2H, m, H-18, 20), 7.30 (2H, m, H-3, 5), 7.29~7.21 (10H, m, H-3 ~7, 3 ~7 ), 6.64 (1H, d, J = 8.3 Hz, 14-NH), 6.56 (1H, d, J = 6.5 Hz, 8-NH), 4.92 (1H, q, J = 6.7 Hz, H-9), 4.62 (1H, m, H-13), 4.54 (1H, dd, J = 11.4, 3.3 Hz, H-12a), 4.04 (1H, dd, J = 11.3, 4.3 Hz, H-12b), 3.30 (1H, dd, J = 13.8, 6.4 Hz, H-1 a), 3.21 (1H, dd, J = 13.9, 7.0 Hz, H-1 b), 3.00 (1H, dd, J = 13.7, 6.5 Hz, H-1 a), 2.89 (1H, dd, J = 13.7, 8.3 Hz, H-1 b); 13 C-NMR (100 MHz, CDCl 3 ) δ: (C-10), (C-15), (C-7), (C-2 ), (C-2 ), (C-16), (C-1), (C-19), (C-4), (C-3, 7 ), (C-3, 7 ), (C-4, 6 ), (C-18, 20), (C-3, 5),

4 1376 中草药 Chinese Traditional and Herbal Drugs 第 45 卷第 10 期 2014 年 5 月 (C-4, 6 ), (C-5 ), (C-17, 21), (C-2, 6), (C-5 ), 65.6 (C-12), 54.6 (C-9), 50.4 (C-13), 37.7 (C-1 ), 37.4 (C-1 ) 以上数据与文献报道基本一致 [13], 故鉴定化合物 8 为伞形香青酰胺化合物 9: 类黄色无定形粉末,mp 187~189 EI-MS m/z: 341 [M] + 1 H-NMR (400 MHz, DMSO-d 6 ) δ: 7.59 (1H, d, J = 16.0 Hz, H-β), 7.50 (2H, d, J = 8.5 Hz, H-2, 6), 7.06 (2H, d, J = 8.5 Hz, H-3, 5), 6.35 (1H, d, J = 16.0 Hz, H-α), 4.91 (1H, d, J = 7.5 Hz, H-1 ), 3.84 (1H, d, J = 12.0 Hz, H-6 ), 3.71 (3H, s, -OCH 3 ), 3.64 (1H, d, J = 12.0 Hz, H-4 ); 13 C-NMR (125 MHz, DMSO-d 6 ) δ: (C=O), (C-4), (C-β), (C-2, 6), (C-1), (C-3, 5), (C-α), (C-1 ), 78.3 (C-5 ), 78.0 (C-3 ), 74.9 (C-2 ), 71.3 (C-4 ), 62.5 (C-6 ), 52.1 (-OCH 3 ) 以上数据与文献报道基本一致 [14], 故鉴定给化合物 9 为对羟基桂皮酸甲酯葡萄糖苷化合物 10: 针状结晶 ( 氯仿 ) 1 H-NMR (400 MHz, CDCl 3 ) δ: 5.38 (1H, t, J = 2.4 Hz, H-1), 3.66 (1H, ddd, J = 5.5, 10.4, 10.4 Hz, H-8), 2.36 (1H, ddd, J = 2.2, 13.0, 10.0 Hz, H-9α), 2.32 (1H, dd, J = 13.0, 5.5 Hz, H-9β), 1.96 (2H, m, H-3), 1.76 (1H, m, H-1), 1.74 (1H, m, H-7), 1.41 (2H, m, H-6), 1.34 (1H, t, J = 13.2 Hz, H-4), 1.24 (3H, s, H-12), 1.20 (3H, s, H-13), 0.96 (3H, s, H-15), 0.88 (3H, d, J = 6.6 Hz, H-14), 0.71 (1H, t, J = 13.2 Hz, H-2); 13 C-NMR (125 MHz, CDCl 3 ) δ: (C-10), (C-1), 75.1 (C-11), 74.0 (C-8), 49.0 (C-7), 41.9 (C-9), 40.6 (C-4), 40.0 (C-2), 37.4 (C-5), 30.2 (C-12), 27.1 (C-6), 25.8 (C-3), 23.6 (C-13), 18.4 (C-15), 15.9 (C-14) 以上数据与文献报道一致 [15], 故鉴定化合物 10 为 valene-1(10)-ene-8, 11-diol 化合物 11: 红棕色粉末 ; UV λ MeOH max (nm): 226.5; HR-ESI-MS m/z: [M+H] + 1 H-NMR (400 MHz, DMSO-d 6 ) δ: 7.41 (1H, d, J = 7.8 Hz, H-9), 7.34 (1H, d, J = 8.1 Hz, H-12), 7.17 (1H, d, J = 2.4 Hz, H-17), 7.08 (1H, td, J = 7.2, 1.8 Hz, H-11), 6.98 (1H, t, J = 7.2 Hz, H-10), 5.62 (1H, m, H-19), 5.59 (1H, m, H-5), 5.36 (1H, d, J = 2.0 Hz, H-21), 5.32 (1H, d, J = 17.0 Hz, H-18a), 5.16 (1H, dd, J = 11.0, 1.8 Hz, H-18b), 4.84 (1H, brs, H-3), 4.45 (1H, d, J = 8.1 Hz, H-1 ), 3.40 (1H, m, H-6a), 3.05 (1H, m, H-15), 2.63 (1H, d, J = 8.0 Hz, H-6b), 2.50~4.00 (6H, m, H-2 ~6, 23), 2.48 (1H, m, H-14b), 2.06 (1H, d, J = 12.4 Hz, H-14a); 13 C-NMR (150 MHz, DMSO-d 6 ) δ: (C-2), 54.2 (C-3), 58.0 (C-5), 21.9 (C-6), (C-7), (C-8), (C-9), (C-10), (C-11), (C-12), (C-13), 25.9 (C-14), 23.5 (C-15), (C-16), (C-17), (C-18), (C-19), 42.8 (C-20), 95.9 (C-21), (C-22), (C-23), 99.2 (C-1 ), 72.7 (C-2 ), 77.1 (C-3 ), 69.9 (C-4 ), 76.7 (C-5 ), 60.9 (C-6 ) 以上数据与文献报道一致 [16], 故鉴定化合物 11 为 longumoside A 化合物 12: 白色无定形粉末 ( 甲醇 ), 分子式为 C 28 H 29 NO 7,ESI-MS m/z: 492 [M+H] + 1 H-NMR (400 MHz, CD 3 OD) δ: 5.55 (1H, d, J = 6.4 Hz, H-2), 3.52 (1H, q, J = 6.4 Hz, H-3), 7.14 (1H, s, H-4), 7.07 (1H, d, J = 1.2 Hz, H-6), 6.94 (1H, d, J = 1.8 Hz, H-2 ), 6.76 (1H, d, J = 8.2 Hz, H-5 ), 6.82 (1H, dd, J = 1.8, 8.2 Hz, H-6 ), 3.82 (2H, m, H-1 ), 7.46 (1H, d, J = 15.7 Hz, H-1 ), 6.42 (1H, d, J = 15.7 Hz, H-2 ), 3.45 (2H, t, J = 8.7 Hz, H-1 ), 2.74 (2H, t, J = 7.3 Hz, H-2 ), 7.04 (2H, d, J = 8.5 Hz, H-2, 6 ), 6.71 (2H, d, J = 8.5 Hz, H-3, 5 ); 13 C-NMR (100 MHz, CD 3 OD) δ: 88.7 (C-2), 54.9 (C-3), (C-4), (C-5), (C-6), (C-7), (C-8), (C-9), (C-1 ), (C-2 ), (C-3 ), (C-4 ), (C-5 ), (C-6 ), 64.7 (C-1 ), (C-1 ), (C-2 ), 42.6 (C-1 ), 35.8 (C-2 ), (C-1 ), (C-2, 6 ), (C-3, 5 ), (C-4 ), 56.8 (7-OCH 3 ), 56.4 (3 -OCH 3 ), (-CONH-) 以上数据与文献报道基本一致 [17], 故鉴定化合物 12 为大海米菊酰胺 K 化合物 13: 黄色无定形粉末 ( 甲醇 ), 分子式为 C 33 H 38 O 25 1 H-NMR (400 MHz, DMSO-d 6 ) δ: 7.52 (1H, d, J = 2.4 Hz, H-2 ), 6.83 (1H, d, J = 8.4 Hz, H-5 ), 7.65 (1H, dd, J = 8.4, 2.4 Hz, H-6 ), 6.39 (1H, d, J = 2.0 Hz, H-8), 6.18 (1H, d, J = 2.0 Hz, H-6), 5.46 (1H, d, J = 7.6 Hz, Glc-H-1 ), 5.32 (1H, d, J = 7.6 Hz, Rha-H-1 ), 4.41 (1H, brs, Rha-H-1 ); 13 C-NMR (125 MHz, DMSO-d 6 ) δ: (C-2), (C-3), (C-4), (C-5), 98.9 (C-6), (C-7), 93.7 (C-8), (C-9), (C-10), (C-1 ), (C-2 ), (C-3 ), (C-4 ), (C-5 ), (C-6 ), (C-1 ), 74.1 (C-2 ), 76.6 (C-3 ), 70.8 (C-4 ), 76.0 (C-5 ), 65.2 (C-6 ), (C-1 ), 70.6 (C-2 ), 70.1 (C-3 ), 72.1 (C-4 ), 68.2 (C-5 ), 18.1

5 中草药 Chinese Traditional and Herbal Drugs 第 45 卷第 10 期 2014 年 5 月 1377 (C-6 ), (C-1 ), 73.2 (C-2 ), 76.6 (C-3 ), 70.1 (C-4 ), 77.7 (C-5 ), 61.1 (C-6 ) 以上数据与文献报道基本一致 [18], 故鉴定化合物 13 为槲皮素 - 3-O- 芸香糖基 -7-O- 葡萄糖苷化学物 14: 黄色针状晶体 ( 甲醇 ),ESI-MS m/z: 771 [M-H] 1 H-NMR (400 MHz, DMSO-d 6 ) δ: 7.44 (1H, dd, J = 8.4, 2.3 Hz, H-6 ), 7.41 (1H, d, J = 2.3 Hz, H-2 ), 6.97 (1H, d, J = 2.0 Hz, H-2 ), 6.94 (1H, dd, J = 8.4, 2.3 Hz, H-6 ), 6.75 (1H, d, J = 2.2 Hz, H-6), 6.71 (1H, d, J = 8.2 Hz, H-5 ), 6.68 (1H, s, H-3), 6.53 (1H, d, J = 2.2 Hz, H-8), 5.02 (1H, d, J = 7.2 Hz, H-1 ), 4.28 (1H, d, J = 7.8 Hz, H-1 ); 13 C-NMR (125 MHz, DMSO-d 6 ) δ: (C-2), (C-3), (C-4), (C-5), 99.6 (C-6), (C-7), 94.8 (C-8), (C-9), (C-10), (C-1 ), (C-2 ), (C-3 ), (C-4 ), (C-5 ), (C-6 ), (C-1 ), 73.1 (C-2 ), 76.3 (C-3 ), 69.8 (C-4 ), 75.4 (C-5 ), 69.4 (C-6 ), (C-1 ), 73.6 (C-2 ), 76.5 (C-3 ), 69.7 (C-4 ), 73.9 (C-5 ), 63.3 (C-6 ), (C-1 ), (C-2 ), (C-3 ), (C-4 ), (C-5 ), (C-6 ), (C-α), (C-β), (C=O), 以上数据与文献报道一致 [19], 故鉴定化合物 14 为木犀草素 -7-O-β-D- 葡萄糖基 -(1 6)-[(6 -O- 咖啡酸 )-β- D- 葡萄糖苷 ] 化合物 15: 淡黄色粉末, 分子式为 C 29 H 36 O 15, mp 132~133 EI-MS m/z: 624 [M] + 1 H-NMR (300 MHz, DMSO-d 6 ) δ: 6.63 (1H, d, J = 2.0 Hz, H-2), 6.75 (1H, d, J = 8.4 Hz, H-5), 6.48 (1H, dd, J = 8.4, 2.0 Hz, H-6), 2.7 (2H, m, H-7), 3.38 (2H, m, H-8), 4.34 (1H, d, J = 8.0 Hz, H-1 ), 5.02 (1H, brs, H-1 ), 1.08 (3H, d, J = 6.1 Hz, H-6 ), 6.19 (1H, d, J = 15.6 Hz, H-2 ), 7.45 (1H, d, J = 15.6 Hz, H-3 ), 7.02 (1H, d, J = 2.0 Hz, H-2 ), 6.60 (1H, d, J = 8.4 Hz, H-5 ), 6.96 (1H, dd, J = 8.4, 2.0 Hz, H-6 ); 13 C-NMR (75 MHz, DMSO-d 6 ) δ: (C-1), (C-2), (C-3), (C-4), (C-5), (C-6), 35.1 (C-7), 70.3 (C-8), (C-1 ), 74.6 (C-2 ), 79.2 (C-3 ), 70.5 (C-4 ), 73.5 (C-5 ), 60.8 (C-6 ), (C-1 ), 70.6 (C-2 ), 69.2 (C-3 ), 71.7 (C-4 ), 68.8 (C-5 ), 18.2 (C-6 ), (C-1 ), (C-2 ), (C-3 ), (C-1 ), (C-2 ), (C-3 ), (C-4 ), (C-5 ), (C-6 ) 以上数据与文献报道一致 [20], 故鉴定化合物 15 为毛蕊花苷参考文献 [1] 江苏新医学院. 中药大辞典 [M]. 上海 : 上海人民出版社, [2] 曹晖. 中药鼠曲草的本草考证 [J]. 江西中医学院学报, 1992, 4(2): [3] 潘明. 鼠曲草提取物抑菌作用初步研究 [J]. 四川食品与发酵, 2006, 42(6): [4] 王世宽, 潘明, 任路遥. 大有开发前景的野生蔬菜 : 鼠曲草 [J]. 食品研究与开发, 2005, 26(4): [5] 张鞍灵, 高锦明, 王妹清. 黄酮类化合物的分布及开发利用 [J]. 西北林学院学报, 2000, 15(1): [6] Zhang Y M, Xu J, Xiao L, et al. A New Phenolic Glycoside from Chamaecyparis obtusa var. breviramea f. crippsii [J]. Molucules, 2013, 18(12): [7] Matsuda H, Marikawa T, Xie H, et al. Antiallergic phenanthrenes and stilbenes from tubers of Gymnodenio conopsea [J]. Planta Med, 2004, 70(9): [8] Lu Y H, Wang Z T, Xu L S, et al. Three anthraquinones isolated from Aster tataricus L. F [J]. J Chin Pharm Sci, 2003, 12(2): [9] 谢洪刚, 张宏武, 张江, 等. 羊耳菊的化学成分 [J]. 中国天然药物, 2007, 5(5): [10] 李春梅, 王涛, 张祎, 等. 中药黄蜀葵花化学成分的分离与鉴定 (II) [J]. 沈阳药科大学学报, 2010, 27(10): [11] 林生, 张中晓, 沈云亨, 等. 菊叶千里光乙酸乙酯部位化学成分研究 [J]. 中国中药杂志, 2010, 35(9): [12] 李君丽, 黄豆豆, 原源, 等. 阔叶五层龙醋酸乙酯部位的化学成分研究 [J]. 现代药物与临床, 2013, 28(3): [13] 邵泰明, 宋小平, 陈光英, 等. 大果榕茎化学成分研究 [J]. 中草药, 2013, 44(16): [14] Luyengi L, Pezzuto J M, Waller D P, et al. Linusitamarin, a new phenylpropanoid glucoside from Linum usitatissimum [J]. J Nat Prod, 1993, 56(11): [15] Hakim E H, Achmad S A, Effend E L, et al. Structural studies of three sesquiterpenes from Litsea spp (Lauraceae) [J]. Aust J Chem, 1993, 46(9): [16] Lamidi M, Ollivier E, Mahiou V, et al. Glucoindolealkaloids from the bark of Nauclea diderrichii. 1 H and 13 C-NMR assignments of 3α-5β-tetrahydrodeoxycordifolinelactam and cadambine acid [J]. Magn Reson Chem, 2005, 43(5): [17] 杨炳友, 刘艳, 王欣, 等. 洋金花种子的化学成分研究 (I) [J]. 中草药, 2013, 44(14): [18] 王秋红, 刘玉婕, 苏阳, 线叶菊抗感染有效部位化学成分的研究 (I) [J]. 中草药, 2012, 43(1): [19] 阿呷尔布, 李会军, 陈君, 等. 藏药脉花党参的化学成分研究 [J]. 中国天然药物, 2012, 10(5): [20] 辛菲, 金艺淑, 沙沂. 马鞭草化学成分研究 [J]. 中国现代中药, 2008, 10(10):

Microsoft Word - 4期中文目次.doc

Microsoft Word - 4期中文目次.doc 中草药 Chinese Traditional and Herbal Drugs 第 45 卷第 4 期 2014 年 2 月 471 锦灯笼中哌嗪类化学成分研究舒尊鹏 1, 李新莉 2, 徐炳清 1, 王秋红 1, 杨炳友 1, 匡海学 1. 黑龙江中医药大学北药基础与应用研究省部共建教育部重点实验室, 黑龙江中药及天然药物药效物质基础研究重点实验室, 黑龙江哈尔滨 150040 2. 大连医科大学生物技术系,