五味子根的化学成分研究

Chemical constituents from roots of Schisandra chinensis

目的研究木兰科植物北五味子Schisandra chinensis(Turcz.)Baill.干燥根的化学成分及其苯丙素类化学成分的神经保护作用。方法综合运用硅胶、MCI、ODS、Sephadex LH-20及HPLC等色谱方法对五味子根中化学成分进行了系统的分离纯化,利用MS、NMR等手段对分离得到的化学成分进行结构鉴定。采用CCK8法评价分离得到化合物对H2O2诱导PC12细胞的神经保护作用。结果从五味子根70%乙醇提取物中分离并鉴定了37个化合物,包括22个苯丙素类:C-藜芦酰乙二醇(1)、baihuaqianhuaside(2)、methyl-4-O-comaroylquinate(3)、7R,8S-threo-4,7,9,9′-tetra-hydroxy-3,3′-dimethoxy-8-O-4′-neolignan(4)、二氢去氢双松柏醇(5)、开环异落叶松树脂酚(6)、(-)-secoisolariciresinol-9-O-β-Dxylopyranoside(7)、(+)-异落叶松树脂醇(8)、ent-isolariciresinol-9’-O-β-D-xylopyranoside(9)、schizandriside(10)、左旋马尾松树脂醇(11)、罗汉松脂素(12)、2-hydroxy-2-(3′,4′-dihydroxy-phenyl)methyl-3-(3′′,4′′-dimethoxy-phenyl)methyl-γ-butyrolactone(13)、去甲络石苷(14)、络石苷(15)、牛蒡子苷(16)、(+)-neo-olivil(17)、matairesinol4’-O-β-D-glucopyranoside(18)、3,7-dihydroxy-1,2,13,14-tetramethoxydibenzocyclooctadiene12-O-β-D-glucopyranoside(19)、五味子酯D(20)、leptolepisolD(21)、xanthiumnolicC(22);7个单萜类:反式-索布瑞醇(23)、magnoliaterpenoidC(24)、(1S,2S,4R)-2-hydroxy-1,8-cineole-β-D-glucopyranoside(25)、(1S,4R,6R)-6-hydroxy-bornan-2-one 6-O-β-D-glucopyranoside(26)、(1R,4R,5S)-5-endo-hydroxycam-phor5-O-β-D-glucopyrao-side(27)、鸡矢藤苷(28)、paediatrics acid methyl ester(29);5个芳香族类:3-ethoxy-4-hydroxy-benzoicacid(30)、没食子酸乙酯(31)、benzylβ-D-glucopyranoside(32)、3,4-dimethoxyphenyl-β-D-glucopyranoside(33)、草夹竹桃苷(34);2个黄酮类:表儿茶素(35)、taxifolin-3-O-β-D-xylopyranoside(36),以及1个二芳基庚烷类化合物:rhoiptelol C(37)。结论化合物1~3、6~7、13~17、21、25~31、37为首次从木兰科中分离出来,化合物4~5、9~12、22~23、32、34、36为首次从五味子属植物中分离得到,化合物8、18、33、35为首次从五味子中分离得到。体外神经保护活性研究表明,在6.25μmol/L时苯丙素类化合物3、10、17细胞存活率较高。

Objective To study the chemical constituents from the roots of Schisandra chinensis,and the neuroprotective effect of phenylpropanoid chemical constituents.Methods The chemical constituents from the roots of S.chinensis were isolated with silica gel,MCI,ODS,Sephadex LH-20 column chromatographies together with HPLC,and their structures were determined by entirely analyzing MS and NMR spectrums.The neuroprotective effect of the isolated compounds on PC12 cells induced by H2O2 was evaluated by the CCK8 method.Results A total of 37 compounds were isolated and identified from the roots of S.chinensis,including 22 phenylpropanoids:c-veratroylglycol(1),baihuaqianhuaside(2),methyl-4-O-comaroy-lquinate(3),7R,8S-threo-4,7,9,9′-tetrahydroxy-3,3′-dimethoxy-8-O-4′-neolignan(4),dihydrodehydro-diconiferyl alcohol(5),(−)-secoisolariciresinol(6),(−)-secoisolariciresinol-9-O-β-D-xylopyranoside(7),(+)-isolariciresinol(8),ent-isolariciresinol-9'-O-β-D-xylopyranoside(9),schizandriside(10),(−)-massoniresinol(11),(−)-matairesinol(12),2-hydroxy-2-(3′,4′-dihydroxyphenyl)methyl-3-(3″,4″-dimethoxyphenyl)methyl-γ-butyrolactone(13),nortra-cheloside(14),tracheloside(15),arctiin(16),(+)-neo-olivil(17),matairesinol4'-O-β-D-glucopyranoside(18),3,7-dihydroxy-1,2,13,14-tetramethoxydibenzo-cyclooctadiene12-O-β-D-glucopyranoside(19),schisantherin D(20),leptolepisol D(21),xanthiumnolic C(22),seven monoterpenoids:trans-sobrerol(23),magnoliaterpenoid C(24),(1S,2S,4R)-2-hydroxy-1,8-cineole-β-D-glucopyranoside(25),(1S,4R,6R)-6-hydroxy-bornan-2-one-6-O-β-D-glucopyranoside(26),(1R,4R,5S)-5-endo-hydroxycamphor5-O-β-D-glucopyraoside(27),paederoside(28),paediatrics acid methyl ester(29),five aromatics:3-ethoxy-4-hydroxy-benzoic acid(30),ethyl gallate(31),benzylβ-D-glucopyranoside(32),3,4-dimethoxyphenyl-β-D-glucopyranoside(33),androsin(34),two flavonoids:epicatechin(35),taxifolin-3-O-β-D-xylopyranoside(36),and one diarylheptane-type compound:rhoiptelol C(37).Conclusion Compounds 1-3,6-7,13-17,21,25-31 and 37 are isolated from Magnoliaceae for the first time.Compounds 4-5,9-12,22-23,32,34 and 36 are isolated from Schisandra for the first time,and compounds 8,18,33 and 35 are isolated from S.chinensis for the first time.In vitro cellular neuroprotective activity studies showed that the phenylpropanoids 3,10 and 17 exhibited significant in vitro cytoprotective activity at 6.25μmol/L.