大戟的化学成分测定

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[摘 要]目的研究宽叶大戟的化学成分.方法采用硅胶柱层析法、SephadexLH20凝胶柱层析法,对宽叶大戟全草体积分数95%乙醇提取物的氯仿萃取部分进行分离,根据理化性质和波谱数据确定各化合物的结构.结果分离并鉴定了8个化合物,分别为:三十二烷酸(1)、蒲公英醇(2)、α波甾醇(3)、羽扇豆醇(4)、β谷甾醇(5)、白桦酸(6)、齐墩果酸(7)和桦木醇(8).结论化合物1-4为首次从宽叶大戟中分离得到.

[关 键 词]宽叶大戟;化学成分;提取;分离;结构鉴定

中图分类号:R284.1文献标识码:A文章编号:

宽叶大戟(EuphorbialatifoliaMeyerexLedeb.)为大戟科大戟属多年生草本植物.产于新疆伊犁、塔城至哈巴河,生于海拔1000~1500m的河谷、草甸、林缘及灌丛,主要分布于中亚和西伯利亚.张雷红等从宽叶大戟中分离得到了三萜、黄酮等成分.本研究从宽叶大戟体积分数95%乙醇提取物的氯仿萃取部分分离得到了8个化合物,分别鉴定为三十二烷酸(1)、蒲公英醇(2)、α波甾醇(3)、羽扇豆醇(4)、β谷甾醇(5)、白桦酸(6)、齐墩果酸(7)和桦木醇(8).其中化合物1-4为首次从宽叶大戟中分离得到.

一、仪器、试剂与药材

宽叶大戟药材于2007年7月采自新疆阿尔泰地区,经中国医学科学院药用植物研究所李国强副研究员鉴定为EuphorbialatifoliaMeyerexLedeb..FisherJohns型显微熔点仪(温度未校正),PerkinElmer241旋光仪,PerkinElmer983G红外光谱仪,AutospecUltimaETOF质谱仪,INOVA500核磁共振仪.柱色谱硅胶、薄层色谱硅胶板(青岛海洋化工厂),SephadexLH20(Pharmacia公司),其余试剂均为分析纯.

二、提取与分离

取宽叶大戟全草8.2kg,粉碎,以体积分数95%乙醇提取3次,每次2h,过滤,合并滤液,浓缩得乙醇浸膏.浸膏加适量水成混悬液,依次用石油醚、三氯甲烷、乙酸乙酯及正丁醇萃取,浓缩得5个不同极性部分.三氯甲烷萃取物经反复硅胶柱层析和SephadexLH20凝胶柱层析得化合物1(15mg)、2(8mg)、3(9mg)、4(14mg)、5(25mg)、6(12mg)、7(20mg)、8(10mg).

三、结构鉴定

化合物1:白色粉末,mp73~75℃.EIMSm/z(%):480(M+),一系列失去14amu的碎片离子峰,129(51),111(20),97(38),85(42),73(66),60(40),57(89),44(100).经与文献对照,鉴定为三十二烷酸.

化合物2:无色针晶,mp190~193℃,LibermannBurchard反应呈阳性.IRνmax(KBr):3400,2910,

2850,1630,1450,1380,1040,880.EIMSm/z(%):426(M+,70),408(15),357(10),249(20),218(90),207(100),204(20),189(90),121(25).1HNMR(CDCl3,500MHz)δ:4.43(1H,m,H3),4.6l(2H,m,H21),0.80-1.20之间有7个信号.与对照品比较,混合熔点不下降,TLC检测Rf值一致.根据以上数据及文献鉴定为蒲公英醇.

化合物3:无色针晶,mp154~156℃.EIMSm/z(%):412(M+,66),397(M+CH3,16),369(M+CH3CO,21),351(5),300(19),271(失去侧链,100),255(36),246(21),231(13),229(21),213(14),81(76),69(40).1HNMR(CDCl3,500MHz)δ:5.17(1H,m,H7),5.15(1H,dd,J等于15.0,9.0Hz,H22),5.03(1H,dd,J等于15.0,8.5Hz,H23),3.58(1H,m,H3),1.02(3H,d,J等于9.5Hz,H21),0.85(3H,d,J等于6.5Hz,H26),0.820.80(3H×3,H19,27,29),0.55(3H,s,H18);13CNMR(CDCl3,125MHz)δ:37.2(C1),31.5(C2),71.2(C3),38.1(),40.3(C5),29.7(C6),117.5(C7),139.6(C8),49.5(C9),34.3(C10),21.6(C11),39.5(C12),43.3(C13),55.2(C14),23.0(C15),28.5(C16),56.0(C17),12.1(C18),13.0(C19),40.8(C20),21.4(C21),138.2(C22),129.5(C23),51.3(C24),31.9(C25),21.1(C26),19.0(C27),25.4(C28),12.2(C29).根据以上数据并与文献比较,鉴定为α波甾醇.

4:无色针晶,mp178~180℃.EIMSm/z(%):426[M]+,426(65),411(16),408(21),393(8),383(3),218(45),207(47),203(35),189(57),175(23),147(25),135(50);1HNMR(CDCl3,500MHz)δ:4.68(1H,d,J等于3.0Hz,H30a),4.56(1H,d,J等于3.0Hz,H30b),3.20(1H,dd,J等于12.0,5.0Hz,H3),1.68(3H,s,29CH3),1.03,0.96,0.94,0.82,0.78,0.76(各3H,s,23,24,25,26,27,28CH3);13CNMR(CDCl3,125MHz)δ:38.7(C1),27.4(C2),79.0(C3),38.8(),55.3(C5),18.3(C6),34.3(C7),40.8(C8),50.4(C9),37.1(C10),20.9(C11),25.1(C12),38.0(C13),42.8(C14),27.4(C15),35.6(C16),43.0(C17),48.0(C18),48.3(C19),150.9(C20),29.8(C21),40.0(C22),27.9(C23),15.4(C24),16.1(C25),15.9(C26),14.5(C27),18.0(C28),19.3(C29),109.3(C30).根据以上数据及文献鉴定为羽扇豆醇.化合物5:无色针晶,mp134~136℃.EIMSm/z:414[M]+,396,330,329,273,255.经与对照品比较,混合熔点不下降,TLC检测Rf值一致,证明两者为同一化合物,鉴定为β谷甾醇.

化合物6:无色针晶,mp256~258℃.EIMSm/z(%):456(M+,31),438(12),410(8),395(5),248(33),220(21),207(32),189(40),175(55),161(52),145(44),133(100),123(71),109(79),94(60),77(73),57(76);1HNMR(C5D5N,500MHz)δ:4.93(1H,brs,H30a),4.76(1H,brs,H30b),3.53(1H,m,H3),3.44(1H,brt,J等于7.0Hz,H19),2.75(2H,m,H2),2.23(2H,t,J等于5.0Hz,H16),0.81,1.00,1.05,1.06,1.21,1.78(各3H,s,6个角);13CNMR(C5D5N,125MHz)δ:39.5(C1),28.3(C2),78.1(C3),39.3(),55.9(C5),18.8(C6),34.8(C7),41.1(C8),50.9(C9),37.5(C10),21.2(C11),26.1(C12),38.6(C13),42.8(C14),31.2(C15),32.8(C16),56.6(C17),49.7(C18),47.7(C19),151.3(C20),30.2(C21),37.6(C22),28.6(C23),16.3(C24),16.4(C25),16.4(C26),14.9(C27),178.8(C28),19.4(C29),109.9(C30).根据以上数据及文献鉴定为白桦酸.


化合物7:白色粉末,mp178~180℃.EIMSm/z(%):456(M+,9),248(28),297(31),203(100),189(17);1HNMR(C5D5N,500MHz)δ:5.72(1H,brs,H11),3.45(1H,m,H3),0.89,0.94,1.00,1.02,1.05,1.22,1.24(各3H,s,7个角);13CNMR(C5D5N,125MHz)δ:38.5(C1),27.7(C2),77.7(C3),38.7(),55.4(C5),18.4(C6),32.5(C7),39.1(C8),47.7(C9),36.9(C10),23.4(C11),122.6(C12),144.4(C13),41.6(C14),27.7(C15),23.2(C16),46.3(C17),40.7(C18),46.1(C19),30.7(C20),33.8(C21),32.5(C22),27.9(C23),15.3(C24),15.1(C25),17.1(C26),25.8(C27),179.8(C28),32.9(C29),23.4(C30).与对照品比较,混合熔点不下降,TLC检测Rf值一致,再根据文献鉴定为齐墩果酸.

化合物8:白色粉末,mp253~255℃.1HNMR(CDCl3,500MHz)δ:0.77(3H,s),0.84(3H,s),0.99(3H,s),1.27(3H,s),1.69(3H,s),3.18(1H,dd,J等于11.0,5.1Hz,H3),3.79(1H,d,J等于10.9Hz,H28a),3.34(1H,d,J等于10.9Hz,H28b),4.69(1H,d,J等于2.1Hz,H30a),4.59(1H,d,J等于2.1Hz,H30b);13CNMR(CDCl3,125MHz)δ:38.7(C1),27.4(C2),79.0(C3),38.9(),55.3(C5),18.3(C6),34.2(C7),41.0(C8),50.4(C9),37.2(C10),20.8(C11),25.2(C12),37.3(C13),42.7(C14),29.2(C15),25.2(C16),40.9(C17),48.8(C18),47.8(C19),150.5(C20),29.8(C21),34.2(C22),28.0(C23),15.3(C24),16.0(C25),16.1(C26),14.8(C27),60.6(C28),19.1(C29),110.0(C30).根据以上数据及文献鉴定为桦木醇.