目的 研究风毛菊 Saussurea japonica植物的化学成分,以及羟化和苷化位移效应规律。方法 利用普通硅胶柱层析和反相硅胶HPLC分离、纯化,并经超导核磁共振 (NMR)和质谱(MS)等波谱技术确定其结构;通过与已报道类似物碳谱数值比较,得到了双环氧木脂素类化合物C-1位被羟基取代的远程位移效应规律 ,以及双环氧木脂素和单环氧木脂素类 (落叶松脂素)酚羟基苷化位移效应规律。结果 从风毛菊全草的乙醇 (75 %)室温提取物中分得3个木脂素苷类化合物 ,其结构被确定为:(+)-1-hydroxypinoresinol-4″-β-D-glu-copyranoside,(+)-lariciresinol-4-β-D-glucopyranoside和(+)-1-lariciresinol-4-β-D-glucopyranoside;双环氧木脂素类的化合物C-1位被羟基取代的远程位移效应 [Δδ=δC1‘(未取代)-δC1′(羟基取代)=-4.2 ],双环氧木脂素和单环氧木脂素类酚羟基苷化位移效应规律为对位碳低场位移约 Δδ=3.0.结论 木脂素苷为首次从该属植物中获得;位移效应规律为以后两类天然木脂素结构的确定,尤其糖的连接位置的指定,提供了一定的判断依据。

Object To isolate and identify the chemical constituents of Saussurea japonica (Thunb.)DC. and to obtain some rules of chemical shift effects on hydroxy lation and O-glycosy lation. Methods The constituents were isolated by silica gelcolumn chroma tography and HPLC (RP-18) ,and their structures were elucidated through spectroscopic analysis (NMR and FABMS) . The rules were obtained by comparison with those of know nanalogous lignans.Results Three lignan glycosides were isolated andm identified as(+)-1-hydroxy pinoresinol-4″-β -D-glucopyrano side (Ⅵ),(+)-lariciresinol-4-β-D-gluco pyranoside(Ⅷ),and (+)-1-larici resinol-4′-β -D-glucopy rano side (Ⅸ),as well as the rules for effects of the hydroxy group at C-1(upshift about Δδ- 4.2)and O-glucosylation (downshift about Δδ+ 3.0) on ¹³ CNMR chemical shifts of (+)-pino resinol and (+) -larici resinol.Conclusion All these compounds were obtained from the plants of Saussurea DC. for the first time and the rules should be as some important evidences to assign the position of hydroxy lation and glycosylation.

中国科学院“百人计划”基金项目;中国科学院创新重大基础性研究基金项目