中草药  2016, Vol. 47 Issue (11): 1856-1860
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平卧菊三七的化学成分研究(Ⅰ)
巩升帅1,2,3, 刘艳丽2, 李艳1,3, 李笑然2, 冯育林1,3, 许琼明1,2, 杨世林1,2,3     
1. 江西中医药大学, 江西 南昌 330006 ;
2. 苏州大学药学院, 江苏 苏州 215123 ;
3. 创新药物与高效节能降耗制药设备国家重点实验室, 江西 南昌 330006
摘要: 目的 研究平卧菊三七Gynura procumbens全草的化学成分。 方法 利用反复硅胶柱色谱、Sephadex LH-20凝胶柱色谱、中压柱色谱及半制备高效液相色谱等方法分离纯化,通过NMR、MS等鉴定化合物结构。 结果 从平卧菊三七全草的70%乙醇提取物中分离得到16个化合物,分别鉴定为槲皮素(1)、芹菜素(2)、木犀草素(3)、山柰酚(4)、黄芪苷(5)、山柰酚-5-O-(6"-O-乙酰基)-β-D-吡喃葡萄糖苷(6)、7-甲醚黄芩素(7)、4-甲氧基肉桂酸(8)、苄基葡萄糖苷(9)、2-苯乙基-O-β-D-吡喃葡萄糖苷(10)、3,5-二咖啡酰基奎宁酸甲酯(11)、3,5-二咖啡酰基奎宁酸乙酯(12)、3,4-二咖啡酰基奎宁酸甲酯(13)、4,5-二咖啡酰基奎宁酸甲酯(14)、原儿茶酸(15)和丁香酚苷(16)。 结论 化合物7、8、12、14和16为首次从菊三七属植物中分离得到,化合物3、6、9~11和13为首次从该植物中分离得到。
关键词: 平卧菊三七     黄酮     7-甲醚黄芩素     4-甲氧基肉桂酸     3,5-二咖啡酰基奎宁酸乙酯     4,5-二咖啡酰基奎宁酸甲酯    
Chemical constituents from whole plant of Gynura procumbens (Ⅰ)
GONG Sheng-shuai1,2,3, LIU Yan-li2, LI Yan1,3, LI Xiao-ran2, FENG Yu-lin1,3, XU Qiong-ming1,2, YANG Shi-lin1,2,3     
1. Jiangxi University of Traditional Chinese Medicine, Nanchang 330006, China ;
2. College of Pharmaceutical Science, Soochow University, Suzhou 215123, China ;
3. State Key Laboratory of Innovative Drug and Efficient Energy-Saving Pharmaceutical Equipment, Nanchang 330006, China
Abstract: Objective To investigate the chemical constituents from the whole plants of Gynura procumbens. Methods The chemical constituents were isolated and purified by repeated silica gel column chromatography, Sephadex LH-20 gel column chromatography, medium pressure column chromatography, and semi-preparative HPLC, and their structures were elucidated by chemical properties and spectroscopic analyses. Results Sixteen compounds were identified to be quercetin (1), apigenin (2), luteolin (3), kaempferol (4), astragaline (5), kaempferol-5-O-(6"-O-acetyl)-β-D-glucopyranoside (6), negletein (7), 4-methoxycinnamic acid (8), benzyl-O-β-D-glucopyranoside (9), 2-phenylethyl-O-β-D-glucopyranoside (10), 3,5-dicaffeoylquinic acid methyl ester (11), 3,5-dicaffeoylquinic acid ethyl ester (12), 3,4-dicaffeoylquinic acid methyl ester (13), 4,5-dicaffeoylquinic acid methyl ester (14), protocatechuic acid (15), and eugenol glucoside (16). Conclusion Compounds 7, 8, 12, 14, and 16 are obtained from the plants in Gynura Cass. for the first time, and compounds 3, 6, 9-11 and 13 are obtained from this plant for the first time.
Key words: Gynura procumbens (Lour.) Merr     flavonoids     negletein     4-methoxycinnamic acid     3,5-dicaffeoylquinic acid ethyl ester     4,5-dicaffeoylquinic acid methyl ester    

平卧菊三七Gynura procumbens (Lour.) Merr为菊科(Compositae)千里光族(Senecioneae Cass.)菊三七属Gynura Cass. 植物,又名蛇接骨、续命草、神仙草,味辛、微苦,性凉,为多年生草本药食两用植物,生于林间溪旁的坡地砂质土上,分布于东南亚及我国南部及西南部地区[1]。平卧菊三七具有良好的止血、镇痛、抗炎、抗疟、抗肿瘤、降血糖等药理活性,主要用于治疗跌打损伤、风湿关节痛和痛风[2-3]。文献报道其主要含有黄酮、脂肪酸、多酚和类固醇等成分[4]。为进一步研究其活性成分,本实验对平卧菊三七的化学成分进行研究,分离得到16个化合物,分别鉴定为槲皮素(quercetin,1)、芹菜素(apigenin,2)、木犀草素(luteolin,3)、山柰酚(kaempferol,4)、黄芪苷(astragaline,5)、山柰酚-5-O-(6″-O-乙酰基)-β-D-吡喃葡萄糖苷[kaempferol-5-O-(6″-O-acetyl)-β-D-glucopyranoside,6]、7-甲醚黄芩素(negletein,7)、4-甲氧基肉桂酸(4-methoxycinnamic acid,8)、苄基葡萄糖苷(benzyl- O-β-D-glucopyranoside,9)、2-苯乙基-O-β-D-吡喃葡萄糖苷(2-phenylethyl-O-β-D-glucopyranoside,10)、3,5-二咖啡酰基奎宁酸甲酯(3,5-dicaffeoyl- quinic acid methyl ester,11)、3,5-二咖啡酰基奎宁酸乙酯(3,5-dicaffeoylquinic acid ethyl ester,12)、3,4-二咖啡酰基奎宁酸甲酯(3,4-dicaffeoylquinic acid methyl ester,13)、4,5-二咖啡酰基奎宁酸甲酯(4,5-dicaffeoylquinic acid methyl ester,14)、原儿茶酸(protocatechuic acid,15)、丁香酚苷(eugenol glucoside,16)。其中,化合物7、8、12、14和16为首次从菊三七属植物中分离得到,化合物3、6、9~11和13为首次从该植物中分离得到。

1 仪器与材料

Bruker AVANCE III 600核磁共振仪(德国布鲁克公司);QTrap 4500+型质谱仪(加拿大AB SCIEX);半制备高效液相色谱仪(LC-20AT,SPD-20A,日本岛津公司);C18半制备色谱柱(250 mm×10 mm,5 μm,美国Kromsil公司);Sephadex LH-20凝胶(美国GE公司);电子天平(EL204,梅特勒-托利多仪器有限公司);旋转蒸发仪(东京理化器械独资工厂);化学试剂(分析纯,国药集团化学试剂有限公司);氘代试剂(德国Merck公司);薄层色谱硅胶板(HSGF254,烟台江友硅胶开发有限公司);各种柱色谱用硅胶均为青岛海洋化工有限公司出品。

平卧菊三七采自江西省靖安县,由南昌市食品药品检验所吴蓓副主任药师鉴定为平卧菊三七Gynura procumbens (Lour.) Merr全草。

2 提取与分离

平卧菊三七药材15 kg粉碎,加8倍量70%乙醇加热提取1.5 h,滤过,滤渣再用8倍量70%乙醇加热提取1.5 h,滤过。合并滤液,浓缩,蒸干,得药材乙醇提取液浸膏。用适量蒸馏水将浸膏分散,分别依次用石油醚、二氯甲烷、醋酸乙酯多次萃取,各部分萃取液经减压回收溶剂,得石油醚萃取物310 g,二氯甲烷萃取物370 g,醋酸乙酯萃取物110 g,水部位900 g。将醋酸乙酯萃取物经硅胶柱色谱,依次用二氯甲烷-甲醇(100∶0、95∶5、85∶15、70∶30、50∶50、100∶0)洗脱,得到6个部位Fr. 1~6。Fr. 2经硅胶柱色谱,依次用石油醚-醋酸乙酯(70∶30、60∶40、50∶50、40∶60、30∶70、0∶100)洗脱,得到6个部分Fr. 2-1~2-6。Fr. 2-2通过Sephadex LH-20柱色谱及半制备高效液相色谱分离得到化合物1(29 mg)、2(6 mg)、3(8 mg)、4(38 mg)、7(45 mg)和15(330 mg),Fr. 2-4通过Sephadex LH-20柱色谱及半制备高效液相色谱分离得到化合物11(15 mg)和12(11 mg),Fr. 2-5通过Sephadex LH-20柱色谱及半制备高效液相色谱分离得到化合物9(9 mg)、10(10 mg)、16(16 mg)和5(17 mg);Fr. 2-6通过Sephadex LH-20柱色谱及半制备高效液相色谱分离得到化合物6(8 mg)、8(2 mg)、13(15 mg)和14(12 mg)。

3 结构鉴定

化合物1:黄色粉末(甲醇);ESI-MS m/z: 301 [M-H],分子式为C15H10O71H-NMR (600 MHz,C5D5N) δ: 8.62 (1H,d,J = 2.0 Hz,H-2′),8.13 (1H,dd,J = 8.3,2.0 Hz,H-6′),7.40 (1H,d,J = 8.4 Hz,H-5′),6.78 (1H,d,J = 2.0 Hz,H-6),6.74 (1H,d,J = 2.0 Hz,H-8);13C-NMR (150 MHz,C5D5N) δ: 94.6 (C-6′),99.6 (C-8),104.8 (C-10),117.0 (C-5′),121.4 (C-6′),138.2 (C-3),147.4 (C-2),148.1 (C-4′),157.8 (C-5),162.8 (C-9),165.9 (C-7),177.6 (C-4)。以上数据与文献报道基本一致[5],故鉴定化合物1为槲皮素。

化合物2:黄色粉末(甲醇);ESI-MS m/z: 269 [M-H],分子式为C15H10O51H-NMR (600 MHz,C5D5N) δ: 13.08,10.80,10.40 (3H,s,3×OH),7.94 (2H,d,J = 8.6 Hz,H-2′,6′),6.95 (2H,d,J = 8.6 Hz,H-3′,5′),6.50 (1H,d,J = 1.6 Hz,H-8),6.81 (1H,s,H-3),6.17 (1H,d,J = 1.6 Hz,H-6);13C-NMR (150 MHz,C5D5N) δ: 166.5 (C-2),104.6 (C-3),183.4 (C-4),159.2 (C-5),100.7 (C-6),165.2 (C-7),95.5 (C-8),163.8 (C-9),105.6 (C-10),123.0 (C-1′),129.5 (C-2′,6′),117.5 (C-3′,5′),163.3 (C-4′)。以上数据与文献报道基本一致[6],故鉴定化合物2为芹菜素。

化合物3:黄色粉末(甲醇);ESI-MS m/z: 285 [M-H],分子式为C15H10O61H-NMR (600 MHz,C5D5N) δ: 7.92 (1H,d,J = 1.8 Hz,H-2′),7.56 (1H,dd,J = 8.4,1.7 Hz,H-6′),7.30 (1H,d,J = 8.3 Hz,H-5′),6.94 (1H,s,H-3),6.78 (1H,d,J = 1.8 Hz,H-8),6.71 (1H,d,J = 1.8 Hz,H-6);13C-NMR (150 MHz,C5D5N) δ: 165.5 (C-2),104.7 (C-3),183.4 (C-4),159.2 (C-5),100.6 (C-6),166.4 (C-7),95.4 (C-8),163.8 (C-9),105.7 (C-10),123.5 (C-1′),115.3 (C-2′),148.4 (C-3′),152.3 (C-4′),117.5 (C-5′),120.2 (C-6′)。以上数据与文献报道基本一致[7],故鉴定化合物3为木犀草素。

化合物4:黄色粉末(甲醇);ESI-MS m/z: 285 [M-H],分子式为C15H10O61H-NMR (600 MHz,C5D5N) δ: 8.12 (2H,d,J = 8.6 Hz,H-2′,6′),6.95 (2H,d,J = 8.6 Hz,H-3′,5′),6.43 (1H,d,J = 1.2 Hz,H-8),6.23 (1H,d,J = 1.2 Hz,H-6);13C-NMR (150 MHz,C5D5N) δ: 177.9 (C-4),166.1 (C-7),163.0 (C-5),161.3 (C-9),158.0 (C-4′),148.1 (C-2),138.4 (C-3),131.1 (C-2′,6′),124.0 (C-1′),116.9 (C-3′,5′),105.0 (C-10),99.8 (C-6),94.9 (C-8)。以上数据与文献报道基本一致[8],故鉴定化合物4为山柰酚。

化合物5:黄色粉末(甲醇);ESI-MS m/z: 447 [M-H],分子式为C21H20O111H-NMR (600 MHz,C5D5N) δ: 8.46 (2H,d,J = 8.6 Hz,H-2′,6′),7.21 (1H,d,J = 5.9 Hz,H-8),6.73 (2H,dd,J = 1.2,5.9 Hz,H-3′,5′),6.32 (1H,d,J = 5.9 Hz,H-6),4.44~4.02 (6H,m,sugar-H);13C-NMR (150 MHz,C5D5N) δ: 158.2 (C-2),135.2 (C-3),179.4 (C-4),157.5 (C-5),100.5 (C-6),166.6 (C-7),95.3 (C-8),163.5 (C-9),105.9 (C-10),122.6 (C-1′),132.5 (C-2′,6′),116.7 (C-3′,5′),162.3 (C-4′),104.7 (C-1″),79.7 (C-5″),79.2 (C-3″),76.7 (C-2″),72.1 (C-4″),63.3 (C-6″)。以上数据与文献报道基本一致[9],故鉴定化合物5为黄芪苷。

化合物6:黄色结晶(甲醇);ESI-MS m/z: 473 [M-H],分子式为C23H22O111H-NMR (600 MHz,C5D5N) δ: 8.05 (2H,q,J = 10.4 Hz,H-2′,6′),69.0 (2H,q,J = 10.4 Hz,H-3′,5′),6.45 (1H,d,J = 2.0 Hz,H-8),6.25 (1H,d,J = 2.0 Hz,H-6),5.18 (1H,d,J = 10.4 Hz,H-1″),3.18~4.17 (6H,m,sugar-H),4.50 (3H,s,-COCH3);13C-NMR (150 MHz,C5D5N) δ: 158.0 (C-2),135.3 (C-3),179.0 (C-4),163.1 (C-5),100.2 (C-6),166.4 (C-7),95.0 (C-8),158.1 (C-9),105.5 (C-10),122.1 (C-1′),132.2 (C-2′,6′),116.3 (C-3′,5′),162.0 (C-4′),104.4 (C-1″),76.0 (C-2″),78.6 (C-3″),71.4 (C-4″),76.3 (C-5″),64.5 (C-6″),171.0 (COCH3),20.8 (COCH3)。以上数据与文献报道基本一致[10],故鉴定化合物6为山柰酚-5-O-(6″-O-乙酰基)-β-D-吡喃葡萄糖苷。

化合物7:黄色针晶(醋酸乙酯);ESI-MS m/z: 283 [M-H],分子式为C16H12O51H-NMR (600 MHz,C5D5N) δ: 13.21 (1H,s,OH),7.90 (2H,m,Ar-2H),7.60 (3H,m,Ar-3H),7.12 (1H,s,H-8),6.66 (1H,s,H-3),3.90 (3H,s,OCH3);13C-NMR (150 MHz,C5D5N) δ: 156.2 (C-2),106.4 (C-3),184.0 (C-4),150.5 (C-5),132.8 (C-6),164.6 (C-7),92.3 (C-8),148.4 (C-9),107.5 (C-10),132.6 (C-1′),127.4 (C-2′),130.1 (C-3′),133.1 (C-4′),130.1 (C-5′),127.4 (C-6′),57.2 (OCH3)。以上数据与文献报道基本一致[11],故鉴定化合物7为7-甲醚黄芩素。

化合物8:褐色结晶(甲醇);ESI-MS m/z: 177 [M-H],分子式为C10H10O31H-NMR (600 MHz,MeOD) δ: 7.61 (1H,d,J = 16.0 Hz,H-7),7.45 (2H,d,J = 8.6 Hz,H-2,6),6.80 (2H,d,J = 8.7 Hz,H-3,5),6.32 (1H,d,J = 15.9 Hz,H-8),3.75 (3H,s,OCH3);13C-NMR (150 MHz,MeOD) δ: 169.8 (C-9),161.3 (C-4),146.6 (C-7),131.1 (C-2,6),127.1 (C-1),116.8 (C-3,5),114.9 (C-8),52.0 (OCH3)。以上数据与文献报道基本一致[12],故鉴定化合物8为4-甲氧基肉桂酸。

化合物9:无色油状物(甲醇);ESI-MS m/z: 269 [M-H],分子式为C13H18O61H-NMR (600 MHz,C5D5N) δ: 7.53 (2H,d,J = 7.1 Hz,H-2,6),7.35 ( 2H,t,J = 7.1 Hz,H-3,5),7.27 (1H,t,J = 7.1 Hz,H-4),4.67,4.93 (2H,d,J = 11.9 Hz,H-7),4.45 (1H,d,J = 7.7 Hz,H-1′),3.66 (1H,dd,J = 11.9,4.0 Hz,H-6′a),3.90 (1H,dd,J = 11.9,2.0 Hz,H-6′b),3.24~3.64 (4H,m,H-2′~5′);13C-NMR (150 MHz,C5D5N) δ: 139.3 (C-1),128.6 (C-2,6),129.0 (C-3,5),128.1 (C-4),72.0 (C-7),104.4 (C-1′),75.6 (C-2′),79.0 (C-3′),71.2 (C-4′),79.0 (C-5′),63.2 (C-6′)。以上数据与文献报道基本一致[13],故鉴定化合物9为苄基葡萄糖苷。

化合物10:无色油状物(甲醇);ESI-MS m/z: 283 [M-H],分子式为C14H20O61H-NMR (600 MHz,MeOD) δ: 7.33~7.18 (5H,m,H-2,3,4,5,6),4.13 (1H,m,H-8a),3.70 (1H,m,H-8b),2.98 (2H,m,H-7);13C-NMR (150 MHz,MeOD) δ: 140.1 (C-1),130.0 (C-2,6),129.3 (C-3,5),127.2 (C-4),71.7 (C-8),37.2 (C-7),104.4 (C-1′),78.0 (C-3′),78.1 (C-5′),75.1 (C-2′),71.7 (C-4′),62.8 (C-6′)。以上数据与文献报道基本一致[14],故鉴定化合物10为2-苯乙基-O-β-D-吡喃葡萄糖苷。

化合物11:白色粉末(甲醇);ESI-MS m/z: 529 [M-H],分子式为C26H26O121H-NMR (600 MHz,MeOD) δ: 7.67 (1H,d,J = 15.9 Hz,H-7″),7.59 (1H,d,J = 15.9 Hz,H-7′),7.11 (2H,d,J = 1.8 Hz,H-2′,2″),7.01 (2H,d,J = 8.1 Hz,H-5′,5″),6.83 (2H,dd,J = 8.1,3.7 Hz,H-6′,6″),6.38 (1H,d,J = 15.9 Hz,H-8′),6.29 (1H,d,J = 15.9 Hz,H-8″),5.42 (1H,dd,J = 8.1,3.7 Hz,H-5),5.36 (1H,m,H-3),4.03 (1H,dd,J = 8.1,3.7 Hz,H-4),3.74 (3H,s,COOCH3),2.42~2.31 (2H,m,H-6ax,2eq),2.26 (1H,dd,J = 14.1,3.7 Hz,H-6eq),2.16 (1H,dd,J = 13.8,8.1 Hz,H-2ax);13C-NMR (150 MHz,MeOD) δ: 74.7 (C-1),35.7 (C-2),72.0 (C-3),69.7 (C-4),72.2 (C-5),36.7 (C-6),127.6,127.9 (C-1′,1″),115.2 (C-2′,2″),146.8,146.9 (C-3′,3″),149.5,149.7 (C-4′,4″),116.5,116.6 (C-5′,5″),123.0,123.1 (C-6′,6″),147.1,147.4 (C-7′,7″),114.9,115.5 (C-8′,8″),168.0,168.7 (C-9′,9″),175.6 (COOCH3),53.0 (COOCH3)。以上数据与文献报道基本一致[15],故鉴定化合物11为3,5-二咖啡酰基奎宁酸甲酯。

化合物12:白色粉末(甲醇);ESI-MS m/z: 543 [M-H],分子式为C27H28O121H-NMR (600 MHz,MeOD) δ: 7.64 (1H,d,J = 15.9 Hz,H-8″),7.60 (1H,d,J = 15.9 Hz,H-8′),7.14 (1H,d,J = 1.9 Hz,H-2″),7.09 (1H,d,J = 1.9 Hz,H-2′),7.04 (1H,dd,J = 8.1,1.9 Hz,H-5″),7.02 (1H,dd,J = 8.1,1.9 Hz,H-5′),6.89 (1H,d,J = 8.1 Hz,H-6″),6.84 (1H,d,J = 8.1 Hz,H-6′),6.39 (1H,d,J = 15.9 Hz,H-7′),6.27 (1H,d,J = 15.9 Hz,H-7″),5.49~5.43 (1H,m,H-3),5.36 (1H,m,H-5),4.20 (2H,q,J = 7.1 Hz,H-8),4.03 (1H,dd,J = 6.3,2.9 Hz,H-4),2.38 (2H,m,H-2),2.27~2.16 (2H,m,H-6),1.29 (3H,t,J = 7.1 Hz,H-9);13C-NMR (150 MHz,MeOD) δ: 74.6 (C-1),36.7 (C-2),72.0 (C-3),69.8 (C-4),72.3 (C-5),35.6 (C-6),127.6,127.9 (C-1′,1″),116.6,116.8 (C-2′,2″),115.5,116.5 (C-3′,3″),149.5,149.7 (C-4′,4″),147.1,147.4 (C-5′,5″),114.9,115.2 (C-6′,6″),123.0 (C-7′,7″),146.8,146.9 (C-8′,8″),168.0,168.7 (C-9′,9″),175.2 (COOR),62.6 (OCH2),14.3 (OCH2CH3)。以上数据与文献报道基本一致[16],故鉴定化合物12为3,5-二咖啡酰基奎宁酸乙酯。

化合物13:白色粉末(甲醇);ESI-MS m/z: 529 [M-H],分子式为C26H26O121H-NMR (600 MHz,C5D5N) δ: 7.60 (1H,d,J = 8.1 Hz,H-7′),7.54 (1H,d,J = 8.1 Hz,H-7″),7.15 (1H,d,J = 1.7 Hz,H-2′),7.06 (1H,d,J = 1.7 Hz,H-2″),6.65 (1H,dd,J = 8.1,2.5 Hz,H-6′),6.61 (1H,dd,J = 8.1,2.5 Hz,H-6″),6.58 (2H,d,J = 2.5 Hz,H-5′,5″),6.15 (1H,d,J = 8.1 Hz,H-8′),6.06 (1H,d,J = 8.1 Hz,H-8″),5.41 (1H,m,H-3),4.97 (1H,dd,J = 8.1,1.7 Hz,H-4),4.22 (1H,m,H-5),3.73 (3H,s,OCH3),2.23 (2H,m,H-2),2.14 (2H,m,H-6);13C-NMR (150 MHz,C5D5N) δ: 75.5 (C-1),38.9 (C-2),68.9 (C-3),74.9 (C-4),68.2 (C-5),38.9 (C-6),126.9 (C-1′,1″),116.0,116.1 (C-2′,2″),146.8,146.9 (C-3′,3″),150.8,150.9 (C-4′,4″),116.9,117.0 (C-5′,5″),122.5 (C-6′,6″),147.8,147.9 (C-7′,7″),114.7,114.9 (C-8′,8″),167.0,167.5 (C-9′,9″),174.9 (COOCH3),52.6 (-OCH3)。以上数据与文献报道基本一致[17],故鉴定化合物13为3,4-二咖啡酰基奎宁酸甲酯。

化合物14:白色粉末(甲醇);ESI-MS m/z: 529 [M-H],分子式为C26H26O121H-NMR (600 MHz,MeOD) δ: 7.55 (1H,d,J = 6.6 Hz,H-7′),7.53 (1H,d,J = 6.5 Hz,H-7″),7.02 (2H,m,H-2′,2″),6.90 (1H,dd,J = 8.1,1.7 Hz,H-6′),6.87 (1H,dd,J = 8.2,1.5 Hz,H-6″),6.75 (1H,d,J = 8.2 Hz,H-5′),6.73 (1H,d,J = 8.1 Hz,H-5″),6.27 (1H,d,J = 3.3 Hz,H-8′),6.24 (1H,d,J = 3.3 Hz,H-8″),5.61 (1H,m,H-5),5.02 (1H,dd,J = 8.2,3.1 Hz,H-4),4.35 (1H,m,H-3),3.74 (3H,s,OCH3);13C-NMR (150 MHz,MeOD) δ: 75.2 (C-1),41.3 (C-2),69.8 (C-3),75.2 (C-4),66.0 (C-5),36.8 (C-6),127.7 (C-1′,1″),115.1 (C-2′,2″),146.8 (C-3′,3″),149.6 (C-4′,4″),116.5 (C-5′,5″),123.1,123.3 (C-6′,6″),147.4 (C-7′,7″),114.8,115.0 (C-8′,8″),168.5,168.6 (C-9′,9″),176.2 (COOCH3),53.0 (-OCH3)。以上数据与文献报道基本一致[18],故鉴定化合物14为4,5-二咖啡酰基奎宁酸甲酯。

化合物15:无色针晶(甲醇);ESI-MS m/z: 153[M-H],分子式为C7H6O41H-NMR (600 MHz,MeOD) δ: 7.48 (1H,s,H-2),7.44 (1H,d,J = 6.1 Hz,H-6),6.83 (1H,d,J = 6.1 Hz,H-5);13C-NMR (150 MHz,MeOD) δ: 170.4 (C=O),151.4 (C-4),145.9 (C-3),124.0 (C-6),123.0 (C-1),117.7 (C-5),115.8 (C-2)。以上数据与文献报道基本一致[19],故鉴定化合物15为原儿茶酸。

化合物16:白色粉末(甲醇);ESI-MS m/z: 325 [M-H],分子式为C16H22O71H-NMR (600 MHz,MeOD) δ: 7.13 (1H,d,J = 8.2 Hz,H-6),6.87 (1H,s,H-3),6.77 (1H,d,J = 8.2 Hz,H-5),6.00 (1H,m,H-8),5.12 (1H,d,J = 19.4 Hz,H-9b),5.08 (1H,d,J = 19.4 Hz,H-9a),4.91 (1H,d,J = 8.0 Hz,H-1′),3.91 (1H,dd,J = 12.0,1.8 Hz,H-6b′),3.88 (3H,s,H-10),3.74 (1H,dd,J = 11.3,3.5 Hz,H-6a′),3.45~3.35 (6H,m,H-2′,3′,4′,5′,7);13C-NMR (150 MHz,MeOD) δ: 150.8 (C-2),146.3 (C-1),139.0 (C-8),136.5 (C-4),122.1 (C-5),118.3 (C-6),115.9 (C-9),114.2 (C-3),103.1 (C-1′),78.2 (C-3′),77.83 (C-5′),74.9 (C-2′),71.4 (C-4′),62.5 (C-6′),56.7 (C-10),40.7 (C-7)。以上数据与文献报道基本一致[20],故鉴定化合物16为丁香酚苷。

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