宽叶大戟化学成分及鉴定范文

1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.。Fisher??Johns型显微熔点仪(温度未校正)，Perkin??Elmer241旋光仪，Perkin??Elmer983G红外光谱仪，Autospec??UltimaETOF质谱仪，INOVA??500核磁共振仪。柱色谱硅胶、薄层色谱硅胶板(青岛海洋化工厂)，SephadexLH??20(Pharmacia公司),其余试剂均为分析纯。

2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SephadexLH??20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)。

3结构鉴定

化合物1：白色粉末，mp73～75℃。EI??MSm/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[5]对照，鉴定为三十二烷酸。

化合物2：无色针晶，mp190～193℃，Libermann??Burchard反应呈阳性。IRνmax(KBr):3400,2910,

2850,1630,1450,1380,1040,880。EI??MSm/z(%)：426(M+,70),408(15),357(10),249(20),218(90),207(100),204(20),189(90),121(25)。1H??NMR(CDCl3,500MHz)δ：4.43(1H,m,H??3),4.6l(2H,m,H??21),0.80-1.20之间有7个甲基信号。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[6]鉴定为蒲公英醇。

化合物3：无色针晶，mp154～156℃。EI??MSm/z(%):412(M+,66),397(M+??CH3,16),369(M+??CH3??CO,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)。1H??NMR(CDCl3,500MHz)δ:5.17(1H,m,H??7),5.15(1H,dd,J=15.0,9.0Hz,H??22),5.03(1H,dd,J=15.0,8.5Hz,H??23),3.58(1H,m,H??3),1.02(3H,d,J=9.5Hz,H??21),0.85(3H,d,J=6.5Hz,H??26),0.82??0.80(3H×3,H??19,27,29),0.55(3H,s,H??18);13C??NMR(CDCl3,125MHz)δ:37.2(C??1),31.5(C??2),71.2(C??3),38.1(C??4),40.3(C??5),29.7(C??6),117.5(C??7),139.6(C??8),49.5(C??9),34.3(C??10),21.6(C??11),39.5(C??12),43.3(C??13),55.2(C??14),23.0(C??15),28.5(C??16),56.0(C??17),12.1(C??18),13.0(C??19),40.8(C??20),21.4(C??21),138.2(C??22),129.5(C??23),51.3(C??24),31.9(C??25),21.1(C??26),19.0(C??27),25.4(C??28),12.2(C??29)。根据以上数据并与文献[7]比较，鉴定为α?膊ㄧ薮肌?

4：无色针晶，mp178～180℃。EI??MSm/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);1H??NMR(CDCl3,500MHz)δ:4.68(1H,d,J=3.0Hz,H??30a),4.56(1H,d,J=3.0Hz,H??30b),3.20(1H,dd,J=12.0,5.0Hz,H??3),1.68(3H,s,29??CH3),1.03,0.96,0.94,0.82,0.78,0.76(各3H,s,23,24,25,26,27,28??CH3);13C??NMR(CDCl3,125MHz)δ:38.7(C??1),27.4(C??2),79.0(C??3),38.8(C??4),55.3(C??5),18.3(C??6),34.3(C??7),40.8(C??8),50.4(C??9),37.1(C??10),20.9(C??11),25.1(C??12),38.0(C??13),42.8(C??14),27.4(C??15),35.6(C??16),43.0(C??17),48.0(C??18),48.3(C??19),150.9(C??20),29.8(C??21),40.0(C??22),27.9(C??23),15.4(C??24),16.1(C??25),15.9(C??26),14.5(C??27),18.0(C??28),19.3(C??29),109.3(C??30)。根据以上数据及文献[8]鉴定为羽扇豆醇。

化合物5：无色针晶，mp134～136℃。EI??MSm/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?补如薮肌?

化合物6：无色针晶，mp256～258℃。EI??MSm/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);1H??NMR(C5D5N,500MHz)δ:4.93(1H,brs,H??30a),4.76(1H,brs,H??30b),3.53(1H,m,H??3),3.44(1H,brt,J=7.0Hz,H??19),2.75(2H,m,H??2),2.23(2H,t,J=5.0Hz,H??16),0.81,1.00,1.05,1.06,1.21,1.78(各3H,s,6个角甲基);13C??NMR(C5D5N,125MHz)δ:39.5(C??1),28.3(C??2),78.1(C??3),39.3(C??4),55.9(C??5),18.8(C??6),34.8(C??7),41.1(C??8),50.9(C??9),37.5(C??10),21.2(C??11),26.1(C??12),38.6(C??13),42.8(C??14),31.2(C??15),32.8(C??16),56.6(C??17),49.7(C??18),47.7(C??19),151.3(C??20),30.2(C??21),37.6(C??22),28.6(C??23),16.3(C??24),16.4(C??25),16.4(C??26),14.9(C??27),178.8(C??28),19.4(C??29),109.9(C??30)。根据以上数据及文献[3]鉴定为白桦酸。

化合物7：白色粉末，mp178～180℃。EI??MSm/z(%):456(M+,9),248(28),297(31),203(100),189(17);1H??NMR(C5D5N,500MHz)δ:5.72(1H,brs,H??11),3.45(1H,m,H??3),0.89,0.94,1.00,1.02,1.05,1.22,1.24(各3H,s,7个角甲基);13C??NMR(C5D5N,125MHz)δ:38.5(C??1),27.7(C??2),77.7(C??3),38.7(C??4),55.4(C??5),18.4(C??6),32.5(C??7),39.1(C??8),47.7(C??9),36.9(C??10),23.4(C??11),122.6(C??12),144.4(C??13),41.6(C??14),27.7(C??15),23.2(C??16),46.3(C??17),40.7(C??18),46.1(C??19),30.7(C??20),33.8(C??21),32.5(C??22),27.9(C??23),15.3(C??24),15.1(C??25),17.1(C??26),25.8(C??27),179.8(C??28),32.9(C??29),23.4(C??30)。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[3]鉴定为齐墩果酸。新晨

化合物8：白色粉末，mp253～255℃。1H??NMR(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=11.0,5.1Hz,H??3),3.79(1H,d,J=10.9Hz,H??28a),3.34(1H,d,J=10.9Hz,H??28b),4.69(1H,d,J=2.1Hz,H??30a),4.59(1H,d,J=2.1Hz,H??30b);13C??NMR(CDCl3,125MHz)δ:38.7(C??1),27.4(C??2),79.0(C??3),38.9(C??4),55.3(C??5),18.3(C??6),34.2(C??7),41.0(C??8),50.4(C??9),37.2(C??10),20.8(C??11),25.2(C??12),37.3(C??13),42.7(C??14),29.2(C??15),25.2(C??16),40.9(C??17),48.8(C??18),47.8(C??19),150.5(C??20),29.8(C??21),34.2(C??22),28.0(C??23),15.3(C??24),16.0(C??25),16.1(C??26),14.8(C??27),60.6(C??28),19.1(C??29),110.0(C??30)。根据以上数据及文献[3]鉴定为桦木醇。

【参考文献】

[1]中国科学院中国植物志编辑委员会.中国植物志[M].第44卷,第3分册.北京:科学出版社,1997:121.

[2]张雷红,江永南,罗懿斌,等.宽叶大戟中黄酮类化学成分的研究[J].中草药,2009,40(3):366-368.

[3]张雷红,张现涛,叶文才,等.宽叶大戟化学成分的研究[J].天然产物研究与开发,2006,18(1):58-60.