分析研究乙酸乙酯化学成分

　　两头毛在云南作为一种彝族常用草药,得到广泛的临床运用,并具有较好抗炎疗效,因此称其为“肝炎草”,由于其在对抗炎症方面效果显着,而炎症是通向肿瘤的一种渠道,考虑到炎症和肿瘤的关系密切,本实验拟对两头毛的化学成分进行系统研究,试图寻找其有对抗肿瘤细胞靶点的活性化合物。本实验分离的化合物,对两头毛化学成分有进一步认识,对寻找具有抗肿瘤活性成分,提供一定的理论依据,同时对两头毛的利用和开发具有重要的指导作用。

　　用三氯甲烷-甲醇(7∶3)洗脱,最后过硅胶柱,石油醚-乙酸乙酯(8∶1)洗脱,分别得到化合物3(25mg),化合物4(30mg)。Fr.4部分过MCI柱,用85%丙酮洗脱后,经硅胶柱色谱,三氯甲烷-甲醇(20∶1,15∶1,10∶1,8∶1,6∶1)进行梯度洗脱,得到Fr.4.1~Fr.4.4,共4个部分,Fr.4.3经SephadexLH-20凝胶柱,以三氯甲烷-甲醇(5∶5)洗脱,得到化合物5(18mg)。3结构鉴定化合物1白色粉末,mp222~224℃,ESI-MSm/z221[M+H]+。1H-NMR(500MHz,CDCl3)δH:5.05(1H,d,J=2.5Hz,H-6b),4.77(1H,d,J=2.5Hz,H-6a),4.28(1H,m,H-4),2.14(1H,dt,J=11.0,6.5Hz,H-3α),2.02(1H,m,H-9β),1.99(1H,m,H-8),1.95(1H,dt,J=11.0,7.0Hz,H-2),1.83(1H,m,H-3β),1.82(1H,d,J=14.0Hz,H-12β),1.78(1H,m,H-11),1.79(1H,d,J=14.0Hz,H-12α),1.61(1H,brd,H-10β),1.46(1H,dt,J=11.0,2.5Hz,H-10α),1.25(1H,m,H-9α),1.11(3H,s,H-14),1.19(3H,s,H-15),0.88(3H,d,J=7.0Hz);13C-NMR(125MHz,CDCl3)δC:162.7(C-5),104.3(C-6),77.3(C-4),58.5(C-1),55.6(C-12),49.3(C-11),46.1(C-2),39.1(C-13),39.0(C-3),38.3(C-8),35.1(C-15),28.2(C-10),26.9(C-14),26.3(C-9),17.6(C-7)。

　　上述NMR数据与文献[4]报道一致,确证该化合物为suberosenolA。化合物2白色粉末,mp142~144℃,ESI-MSm/z221[M+H]+。1H-NMR(500MHz,CDCl3)δH:5.17(1H,s,H-6a),4.79(1H,s,H-6b),4.56(1H,d,5.5,H-4),2.39(1H,dd,J=11.5,7.5Hz,H-2),1.78(1H,ddd,J=13.5,7.5,4.0Hz,H-3α),2.08(1H,ddd,J=13.5Hz,7.0Hz,4.5Hz,H-3β),2.01(2H,m,H-8,9β),1.77(1H,m,H-11),1.66(1H,d,J=14.0Hz,H-12α),1.60(1H,m,H-10β),1.57(1H,d,J=14.0Hz,H-12β),1.48(1H,m,H-10α),1.28(1H,m,H-9α),1.15(3H,s,H-15),1.10(3H,s,H-14),0.96(3H,d,J=7.0Hz,H-7);13C-NMR(125MHz,CDCl3)δC:162.2(C-5),107.6(C-6),76.7(C-4),59.0(C-1),55.0(C-12),49.7(C-11),49.0(C-2),39.7(C-13),37.8(C-3),36.9(C-8),34.9(C-15),27.9(C-10),26.9(C-14),26.7(C-9),17.8(C-7)。

　　上述NMR数据与文献[4]报道一致,确证该化合物为suberosenolB。化合物3无色油状物,mp252~254℃,ESI-MSm/z219[M+H]+。1H-NMR(500MHz,CDCl3)δH:5.97(1H,d,J=0.75Hz,H-6a),4.98(1H,d,J=0.75Hz,H-6b),2.67(1H,dd,J=19.0,11.5Hz,H-3β),2.45(1H,dd,J=19.0,9.5Hz,H-3α),2.33(1H,t,J=11.5Hz,H-2),2.15(2H,m,H-8),2.08(1H,m,H-9β),1.88(1H,brs,H-11),1.80(1H,d,J=14.5Hz,H-12a),1.70(1H,d,J=14.5Hz,H-12b),1.71(1H,m,H-10β),1.60(1H,m,H-10α),1.35(1H,ddd,J=13.0,5.5,1.0Hz,H-9α),1.20(3H,s,H-15),1.17(3H,s,H-14),0.90(3H,d,J=7.0Hz,H-7);13C-NMR(125MHz,CDCl3)δC:208.5(C-4),151.8(C-5),115.3(C-6),57.8(C-1),54.3(C-12),49.8(C-11),45.2(C-2),41.8(C-3),40.2(C-13),36.5(C-8),35.0(C-15),27.8(C-10),27.0(C-14),26.5(C-9),17.4(C-7)。上述NMR数据与文献[5]报道一致,确证该化合物为suberosenone。化合物4黄色针晶,mp237~239℃,ESI-MSm/z433[M+H]+.1H-NMR(500MHz,DMSO-d6)δH:1.14(3H,d,J=6.5Hz,CH3-5″),3.3~3.5(2H,m,H-3″,4″),3.66(1H,d,J=8.5Hz,H-2″),3.85(1H,brs,H-5″),5.56(1H,d,J=1.1Hz,H-1″),6.41(1H,d,J=2.0Hz,H-6),6.82(1H,d,J=2.0Hz,H-8),6.93(2H,d,J=8.5Hz,H-3',5'),8.09(2H,d,J=8.5,H-2',6');13C-NMR(125MHz,DMSO-d6)δC:17.7(C-6″),69.7(C-5″),69.9(C-2″),69.9(C-3″),71.5(C-4″),94.4(C-8),98.3(C-1″),98.7(C-6),115.5(C-3',5'),121.5(C-1'),129.6(C-2',6'),155.5(C-9),159.2(C-4'),160.4(C-5),161.3(C-7),176.1(C-4)。上述NMR数据与文献[6]报道一致,确证该化合物为山奈酚-7-O-α-L-鼠李糖苷。化合物5淡黄色针状结晶(甲醇),mp171~172℃。1H-NMR(500MHz,MeOD)δH:7.58(1H,d,J=2.0Hz,H-2),7.15(1H,d,J=8.0Hz,H-5),7.04(1H,dd,J=8.0,2.0Hz,H-6),6.78(1H,d,J=15.8Hz,H-7),6.30(1H,d,J=15.8Hz,H-8),3.88(3H,s,-OCH3);13C-NMR(125MHz,MeOD)δC:128.0(C-1),112.0(C-2),150.8(C-3),149.6(C-4),116.2(C-5),116.8(C-6),147.2(C-7),124.4(C-8),171.3(C-9),56.7(-OCH3)。以上数据与文献[7]报道的阿魏酸的基本一致。

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