菊苣根化学成分研究_何轶

菊苣根化学成分研究

何　轶1,郭亚健2,高云艳2

(1.中国药品生物制品检定所中药室,北京　100050;

2.北京中医药大学中药学院北京　100029)

[摘要]　目的:分离鉴定菊苣根中的化学成分。方法:硅胶、大孔树脂、ODS等柱色谱分离纯化,核磁、质谱、紫外、红外光谱及物理常数鉴定结构。结果:分离鉴定了12个化学成分。结论:2,3,4,92四氢21H2吡啶并2(3,42b)吲哚232羧酸为首次从菊科中分离得到,壬二酸、胡萝卜苷为首次从该植物中分离得到。

[关键词]　菊苣,化学成分;分离;鉴定

[中图分类号]R284.1　[文献标识码]B　[文章编号]100125302(2002)0320209202

菊苣为菊科植物菊苣的根,是我国内蒙古地区习用药材,具有清热利湿、健胃等功效[1]。菊苣根主要含有三萜、倍半萜、有机酸等类成分[2～6],但国内研究较少。我们从菊苣根中分离得到12个化学成分,鉴定为乙酸降香萜烯醇酯(bauerenyl acetate,Ⅰ),蒲公英萜酮(taraxerone,Ⅱ),伪蒲公英甾醇(ψ2 taraxasterol,Ⅲ),β2谷甾醇(β2sitosterol,Ⅳ),胡萝卜苷(daucosterol,Ⅴ),52羟甲基222糠醛(52hydrox2 ymethyl222furfural,Ⅵ),山莴苣苦素(lactucopicrin,Ⅶ),山莴苣素(lactucin,Ⅷ),壬二酸(azelaic acid,Ⅸ),2,3,4,92四氢21H2吡啶并2(3,42b)吲哚232羧酸[2,3,4,92tetrahydro21H2pyrido2(3,42b)indole232 carboxylic acid,Ⅹ],菊苣萜苷C(cichorioside C,Ⅺ),菊苣萜苷B(cichorioside B,Ⅻ)。

1　仪器,试剂及材料

Boetius PHM K05型显微熔点测定仪(未校正), Autospec2Ultima ETOF和ZAB22F型质谱仪,J EOL J NM2AL300和Bruker DRX2500型核磁共振仪, Nicolet20SX B型脉冲傅立叶变换红外光谱仪。硅胶为青岛海洋化工厂生产,Sephadex L H220为Phar2 macia公司产品,大孔树脂(AB28型)为天津南开大学化工厂生产,柱色谱用ODS(43～63μm)为Phar2 macia公司产品。药材由山东奇可力保健品公司提供,经北京中医药大学中药学院沈连生教授鉴定为菊苣Cichori um i ntybus L.的根。

[收稿日期]　2001206220

[通讯作者]　电话:(010)670177552314　传真:(010)67023650　E2mail:ejsheyi@ 2　提取与分离

菊苣根10kg,粉碎成粗粉,95%乙醇连续回流提取,提取物适量水分散,正己烷、氯仿、乙酸乙酯和正丁醇萃取。萃取液经硅胶、Sephadex L H220柱分离,正己烷部分得化合物Ⅰ～Ⅴ;氯仿部分得化合物Ⅵ～Ⅷ;乙酸乙酯部分得化合物Ⅸ;正丁醇部分经大孔树脂柱水洗除糖,30%乙醇冲洗,再经硅胶, Sephadex L H220及ODS柱分离得化合物Ⅹ～Ⅻ。3　鉴定

化合物Ⅰ,Ⅱ,Ⅳ,Ⅵ,Ⅶ,Ⅷ,Ⅺ,Ⅻ经物理常数以及波谱测定并与文献对照,分别鉴定为乙酸降香萜烯醇酯(Ⅰ),蒲公英萜酮(Ⅱ),β2谷甾醇(Ⅳ),52羟甲基222糠醛(Ⅵ),山莴苣苦素(Ⅶ),山莴苣素(Ⅷ),菊苣萜苷C(Ⅺ),菊苣萜苷B(Ⅻ)。

化合物Ⅲ　白色小针晶,mp146～148℃,易溶于氯仿、甲醇,难溶于水。Liebermann2Burchard反应阳性。IR,1H NMR,13C NMR数据与文献报道基本一致[7],确定为伪蒲公英甾醇(ψ2taraxasterol)。可能由蒲公英甾醇转变[9]。

化合物Ⅴ　白色粉末,mp287～289℃,Molish, Liebermann2Burchard反应阳性,薄层水解苷元为β2谷甾醇,糖为葡萄糖。与胡萝卜苷对照品薄层Rf值及IR数据一致确定为胡萝卜苷。

化合物Ⅸ　白色片晶,mp101～105℃。IR (K Br)cm-1:2936,2872,2699,1696(C O), 1436,1315,1253,1196,922,727[(CH2)7]。ESI2MS m/z:399(2M+Na),377(2M+1),211(M+Na), 189(M+1),125,98。EI2MS m/z:152,124,111,98,

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84,83,73,69,60,55(100),41。IR,EI2MS谱图与标准谱图一致[10,11],确定为壬二酸。

化合物Ⅹ　淡黄色小针晶,mp>300℃。UV λH2O

max

nm:271.0,218.0。IR(K Br)cm-1:3287(N-H),3018,1643(C O),1601,1410,1222,740。EI2MS m/z:216,199,171,144,143(100),115,95, 85,72。高分辨质谱显示分子式为C12H12N2O2(测定值216.089909,计算值216.089878)。1H NMR (DMSO2d6)δ:10.89(1H,s,H29),7.43(1H,d,J= 8.0Hz,H25),7.32(1H,d,J=8.0Hz,H28),7.06 (1H,t,J=8.0Hz,H27),6.98(1H,t,J=8.0Hz,H2 6),4.20,4.16(each1H,d,J=15.0Hz,H21ab), 3.62(1H,dd,J=5.0,11.5Hz,H23),3.12(1H,dd,J= 5.0,16.5Hz,H24a),2.82(1H,dd,J=11.5,16.5 Hz,H24b)。13C NMR(DMSO2d6)δ:169.6(COOH), 136.1(C28a),128.1(C29a),126.3(C25a),121.2(C2 7),118.7(C26),117.7(C25),111.1(C28),106.6(C2 4a),56.5(C23),40.5(C21),23.0(C24)。与文献数据一致[12,13],确定为2,3,4,92四氢21H2吡啶并(3, 42b)吲哚232羧酸。

[致谢]　MS由中国医学科学院药物研究所再帕尔代测,NMR由北京大学医学部乔梁、倪雪梅及北京微量化学研究所涂光忠代测,IR由北京中医药大学胡沛然代测。

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Studies on Chemical Constituents of Root of Cichorium intybus

HE Y i1,GUO Y a2jian2,G AO Yun2yan2

(1.National Institute for the Control of Pharmaceutical and Biological Products,Beijing　100050,China

2.Beijing University of Chinese Medicine,Beijing　100029,China)

[Abstract]　Objective:To study the chemical constituents in the root of Cichorium intybus.Method:The compounds were iso2 lated and identified by column chromatography and NMR,IR,MS data.R esult:Twelve compounds were isolated and identified.Con2 clusion:2,3,4,92tetrahydro21H2pyrido2(3,42b)indole232carboxylic acid was isolated from the Cichorium genus for the first time,aze2 laic acid and daucosterol were isolated from the the plant for the first time.

[K ey w ords]　Cichorium intybus;chemical constituents;isolation;identification

[责任编辑　徐美珍]・

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