天然产物研究与开发 ›› 2016, Vol. 28 ›› Issue (7): 1045-1050.doi: 10.16333/j.1001-6880.2016.7.010

• 研究简报 • 上一篇    下一篇

蜘蛛香化学成分与双环氧木脂素类化合物的波谱特征

雍妍,黄青,王茹静,陈银,谭玉柱*,张海*   

  1. 成都中医药大学药学院;中药材标准化教育部重点实验四川省中药资源系统研究与开发利用重点实验室——省部共建国家实验室培育基地,成都 611137
  • 出版日期:2016-07-30 发布日期:2017-01-17

Chemical Constituents from Valeriana jatamansi Jones and Spectral Characteristics of Diepoxide Lignans

YONG Yan,HUANG Qing,WANG Ru-jing,CHEN Yin,TAN Yu-zhu*,ZHANG Hai*   

  1. Pharmacy College,Chengdu University of Traditional Chinese Medicine;Ministry of Education Key Laboratory of Standardization of Chinese Herbal Medicine;State Key Laboratory Breeding Base of Systematic Research,Development and Utilization of Chinese Medicine Resources,Chengdu 611137,China
  • Online:2016-07-30 Published:2017-01-17

摘要: 利用ODS反相柱、硅胶柱、Sephadex LH-20等各种色谱分离技术,从蜘蛛香根及根茎的乙醇提取物中分离得到10个化合物,根据波谱分析对化合物进行结构鉴定,分别为:双四氢呋喃木脂素-4-O-β-D-吡喃葡萄糖苷(1)、4-hydroxybenzyl-β-D-glucopyranoside(2)、甲基熊果苷(3)、4-[(E)-3-乙氧基丙烯-1-基]-2-甲氧基苯酚(4)、eugenyl-O-β-D-glunopyranoside(5)、ethylconiferin(6)、8-羟基松脂醇-4′-O-β-D-吡喃葡萄糖苷(7)、棕榈酸(8)、原儿茶酸(9)、3-(4-β-D-glucopyranosyloxy-3,5-dimethoxy)-phenyl-2E-propenol(10)。化合物5、6为从败酱科首次分离得到。通过与已报道环氧木脂素类化合物碳谱数值比较,得到了木脂素羟化和苷化位移效应规律。双环氧四氢呋喃木脂素苷化位移规律与羟化位移规律与羟基取代数目关系紧密,苷化效应中无羟基取代或单羟基取代时发生苷化位置的相应芳环对位C-1′和邻位C-3′均发生低场位移(△δ1.7),双羟基取代时仅在发生苷化位置的相应芳环对位C-1′发生低场位移(△δ2.4),邻位C-3′变化较小(△δ0.5)。羟化效应中C-8或C-8′位羟基取代除了叔碳信号低场位移至季碳(△δ34.5~37.5)外,由于远程位移效应,在C-1位高场位移(△δ3.9~5.9),其中单羟基取代的邻位C-8′低场位移(△δ6.0),而双羟基取代低场位移(△δ34.5)。其位移效应规律对于双环氧四氢呋喃木脂素的结构确定,尤其糖的连接位置和羟化位置的指定,提供了一定的判断依据。

关键词: 蜘蛛香, 化学成分, 波谱特征

Abstract: Ten compounds were isolated from the root of Valeriana jatamansi Jones by ODS column,silica gel column and Sephadex LH-20 chromatography, etc. Their structures were elucidated by NMR,and were identified as double-tetrahydrofuran lignans-4-O-β-D-Glucopyranoside(1),4-hydroxybenzyl-β-D-glucopyranoside(2),methylarbutin(3),4-[(E)-3-ethoxyprop-1-enyl]-2-methoxyphenol(4),eugenyl-O-D-glunopyranoside(5),ethylconiferin(6),8-hydroxypinoresinol-4′-O-β-D-glucopyranoside(7), palmitic acid(8),protocatechuic acid(9),3-(4-β-D-Glucopyranosyloxy-3,5-dimethoxy)-phenyl-2E-propenol(10).Compounds 5、6 were isolated from Valerianaceae for the first time.The rule of hydroxylation and glycosidation shift effects on bisepoxy lignans were obtained by comparing the information of 13C NMR with known analogous.Glycosidation and hydroxylation 13C NMR chemical shift effects on double-tetrahydrofuran lignans were closely related to the number of hydroxyl-substitution.The rules for effects of glycosidation at C-1′and ortho-C-3′ downshift about △δ1.7 in no hydroxy or mono-hydroxy substitution,C-1′downshift about △δ2.4 in double-hydroxy substitution,while ortho-C-3′ only changes a little(△δ0.5).In hydroxylation,tertiary carbon downshift to quaternary carbon(△δ34.5-37.5) when hydroxy substitution at C-8 or C-8′.Besides,the C-1 upshift about △δ3.9-5.9 because of the effect of distance effect.C-8′ on mono-hydroxy substituted aromatic ring moves to low field(△δ6.0),while downshifts △δ34.5 for double-hydroxy substitution.The rules of displacement provided suggestion for the confirmation of double-tetrahydrofuran lignans,especially the position of hydroxylation and glycosylation.

Key words: Valeriana jatamansi Jones, chemical constituent, spectral characteristics

中图分类号: 

R93