篱蓼地下部分的化学成分研究

Chemical constituents from underground parts of Fallopia dumetorum

目的 研究篱蓼Fallopia dumetorum地下部分的化学成分。方法 利用硅胶、Sephadex LH-20、C18-ODS等柱色谱,以及半制备高效液相色谱(HPLC)技术进行系统分离纯化,结合质谱(MS)、核磁共振谱(NMR)等波谱数据和文献对照等手段鉴定化合物结构;对部分化合物进行体外抗氧化活性测试。结果 从篱蓼地下部分醋酸乙酯提取物中分离得到27个化合物,分别鉴定为对羟基肉桂酸甲酯(1)、反式-4-甲氧基肉桂酸(2)、methyl gallate 3-O-β-D-glucopyranoside(3)、smilaside J(4)、lapathoside A(5)、vanicoside B(6)、hedyotisol A(7)、表儿茶酚(8)、红花素(9)、木犀草素(10)、槲皮素(11)、异槲皮苷(quercetin 3-O-β-D-glucopyranoside,12)、槲皮素-3-O-β-D-木糖苷(quercetin 3-O-β-D-xylopyranoside,13)、2,3,5,4’-tetrahydroxystilbene-2-O-β-D-glucopyranoside(14)、1,3,6-trihydroxy-8-methylxanthone(15)、大黄素(16)、大黄素-8-β-D-葡萄糖苷(17)、polygonumnolide B2(18)、决明酮8-O-β-D-葡萄糖苷(19)、altenuene(20)、isoaltenuene(21)、(2R,4a R,8a R)-3,4,4a,8a-tetrahydro-4a-hydroxy-2,6,7,8a-tetramethyl-2-(4,8,12-trimethyltridecyl)-2H-chromene-5,8-dione(22)、豆甾-4-烯-3-酮(23)、stigmast-4-ene-3,6-dione(24)、β-谷甾醇(25)、schleicheol 2(26)和α-amyrenol(27)。其中化合物1、8、9、11、13、14、18和27在100μmol/L浓度下对ABTS自由基有显著的抑制活性,同时化合物8和11在100μmol/L浓度下对DPPH自由基也具有明显的抑制活性。结论 化合物2~4、7、9、13、15、20~22、24和26为首次从蓼科植物中分离得到,化合物1、5、8和27为首次从该属植物中报道,化合物6、14、16~19和23为首次从篱蓼中分离得分到。化合物1、8、9、11、13、14、18和27具有体外抗氧化活性。

Objective To study the chemical basis of the underground parts of Liliao(Fallopia dumetorum). Methods The purification of the ethyl acetate extract of the underground parts of F. dumetorum was carried out using silica gel, Sephadex LH-20,C18-ODS column chromatography, and semi-preparative high performance liquid chromatography(HPLC), and the structures of all isolates were identified by a combination of NMR, MS spectroscopic analyses and comparison with the spectral data reported in the literatures. Results A total of 27 compounds were isolated from the ethyl acetate extract of underground parts of F. dumetorum and their structures were determined as trans-p-hydroxycinnamic acid methyl ester(1),(E)-4-methoxycinnamic acid(2), methyl gallate 3-O-β-D-glucopyranoside(3), smilaside J(4), lapathoside A(5), vanicoside B(6),hedyotisol A(7), epicatechin(8), carthamidin(9),luteolin(10), quercetin(11), quercetin 3-O-β-D-glucopyranoside(12), quercetin 3-O-β-D-xylopyranoside(13), 2,3,5,4’-tetrahydroxystilbene-2-O-β-D-glucopyranoside(14), 1,3,6-trihydroxy-8-methylxanthone(15), emodin(16), emodin 8-β-Dglucopyranoside(17), polygonumnolide B2(18), torachrysone 8-O-β-D-glucoside(19), altenuene(20), isoaltenuene(21),(2R,4a R,8a R)-3,4,4a,8a-tetrahydro-4a-hydroxy-2,6,7,8a-tetramethyl-2-(4,8,12-trimethyltridecyl)-2H-chromene-5,8-dione(22), β-sitostenone(23), stigmast-4-ene-3,6-dione(24), β-sitosterol(25), schleicheol 2(26), α-amyrenol(27). The selected compounds with large amounts were tested for in vitro antioxidant activities, the results showed that compounds 1, 8, 9, 11, 13, 14, 18 and 27 reveal significant inhibitory activities against ABTS(2,2’-azinobis-(3-ethylbenzthiazoline-6-sulphonate)) free radicals at the concentration of 100 μmol/L, while compounds 8 and 11 have obvious inhibitory activity against DPPH(2,2-diphenyl-1-picrylhydrazyl) free radicals at the concentration of 100 μmol/L. Conclusion Compounds 2—4, 7, 9, 13, 15, 20—22, 24, and 26 are first isolated from the plants of family Polygonaceae. Compounds 1, 5, 8 and 27 are first reported from the genus Fallopia. In addition, this is the first report of compounds 6, 14, 16—19 and 23 from the plant species F. dumetorum. Compounds 1, 8, 9, 11, 13, 14, 18 and 27 shows antioxidative activity.