王 勇
(江苏省食品药品监督检验研究院,南京210019)
南方红豆杉[Taxus wallichiana var.mairei(Lemée et H.Lév.)L.K.Fu et Nan Li]系红豆杉属(Taxus)植物。主要分布于安徽、浙江、台湾、福建、江西等地区。20世纪70年代,美国植物化学家Wani 等从T.brevifalia Nutt.树皮中提取分离得到二萜类生物碱紫杉醇,现广泛用于肺癌、肝癌、乳腺癌及妇科肿瘤的治疗。迄今为止,红豆杉植物的树皮、叶、树枝、树根、种子、心材不同药用部位已报道分离鉴定400 多个紫杉烷类二萜化合物。为了进一步探索国产红豆杉属植物药效活性成分及拓展紫杉烷类成分的新资源,本课题组进一步开展南方红豆杉枝叶化学成分的研究。从其枝叶的乙醇提取物中分离得到了12个紫杉烷类二萜化合物。采用波谱解析等方法确定其结构分别为:2-deacetoxytaxinine E(1),2-deacetoxytaxinine J(2),7-deacetoxytaxinine J(3),taxinine J(4),7,2′-didesacetoxyaustrospicatine(5),N-methyltaxol C(6),2-deacetoxydecinnamoyl taxinine J(7),taxol(8),7-epi-taxol(9),7-epi-10-deacetoxytaxol(10),cephalomannine(11),7-epi-cephalomannine(12)。其中,化合物1,3为首次从该植物枝叶中分离得到。
熔点用X-5型显微熔点测定仪测定(温度计未校正);NMR 用Bruker AV-400 型核磁共振仪测定;ESI-MS 用Finnigan LCQ Advantage MAX 质 谱 仪 测定;制备型液相型号为岛津20A 色谱仪配备DAD检测器。柱色谱用硅胶为青岛海洋化工厂产品;制备液相所用乙腈为Merck公司产品,其余所用试剂均为化学纯或分析纯。
实验药材由江苏红豆杉生物科技有限公司提供,经江苏省中国科学院植物研究所彭峰研究员鉴定为红豆杉属植物南方红豆杉(变种)Taxus wallichiana.var.mairei.(Lemée et H.Lév.)L.K.Fu et Nan Li,凭证标本(标本编号No.20110306)保存在江苏省食品药品监督检验研究院。
干燥南方红豆杉枝叶10 kg,粉碎,95% 乙醇60 ℃回流5 h,提取3 次,回收溶剂得浸膏2 kg。浸膏加水混悬,依次用正己烷、氯仿萃取。取氯仿层减压回收至干,得氯仿萃取物200 g。取氯仿萃取物约90 g,采用硅胶(100~200 目)柱色谱,以氯仿-甲醇(100∶0→50∶50)梯度洗脱,所得流分再分别经硅胶柱色谱、制备型HPLC 和重结晶进行纯化,得到化合物1(100 mg)、2(80 mg)、3(90 mg)、4(100 mg)、5(100 mg)、6(10 mg)、7(50 mg)、8(20 mg)、9(100 mg)、10(50 mg)、11(30 mg)和12(50 mg)。
化合物1 无色方晶(CH3OH),mp:176 ~178 ℃;ESI-MS:m/z 615[M+Na]+;IR(KBr)νmax:1 713,1 635,1 451 cm-1。1H NMR(400 MHz,CDCl3)δ:7.75(1H,d,J = 16.0 Hz,H-3),7.39 ~7.48(5H,m,phenyl),6.56(1H,d,J = 16.0 Hz,H-2′),6.12(1H,d,J = 10.7 Hz,H-10),5.88(1H,d,J = 10.7 Hz,H-9),5.77(1H,t,J = 2.0 Hz,H-13),5.53(1H,m,H-5),5.30(1H,s,H-20β),4.90(1H,s,H-20α),3.10(1H,d,J = 5.3 Hz,H-3),2.75(1H,m,H-14β),1.01(1H,dd,J = 14.6,7.6 Hz,H-14α),2.24,1.62,1.08,0.78(each 3H,s,H-18,16,17,19),2.05,2.01,1.73(each 3H,s,3×COCH3)。13C NMR(100 MHz,CDCl3)δ:169.9(10-CH3CO-),170.6(13-CH3CO-),170.4(9-CH3CO-),166.1(C-1′),148.5(C-4),145.1(C-3′),136.8(C-12),135.2(C-11),134.2(C-4′),130.0(C-7′),129.0(C-6′),129.0(C-8′),127.9(C-5′),127.9(C-9′),118.7(C-2′),114.2(C-20),77.4(C-9),76.2(C-5),72.5(C-10),70.6(C-13),43.0(C-8),40.1(C-1),39.1(C-15),37.9(C-3),32.3(C-14),31.2(C-17),28.2(C-6),27.7(C-2),27.3(C-7),26.9(C-16),21.0(10-CH3CO-),20.9(9-CH3CO-),20.8(13-CH3CO-),17.7(C-19),15.2(C-18)。以上数据与文献报道的2-deacetoxytaxinine E[1]一致。
化合物2 无色方晶(CH3OH),mp:171 ~172 ℃;ESI-MS:m/z 673[M+Na]+;IR(KBr)νmax:1 715,1 635,1 436 cm-1。1H NMR(400 MHz,CDCl3)δ:7.76(1H,d,J = 16.0 Hz,H-3′),7.38~7.49(5H,m,phenyl),6.56(1H,d,J = 16.0 Hz,H-2′),6.28(1H,d,J = 10.7 Hz,H-10),5.92(1H,d,J = 10.7 Hz,H-9),5.80(1H,t,J = 7.2 Hz,H-13),5.68(1H,m,H-5),5.56(1H,m,H-7),5.38(1H,s,H-20β),5.01(1H,s,H-20α)],δH3.02(1H,d,J =5.3 Hz,H-3),2.72(1H,m,H-14β),0.97(1H,dd,J = 14.6,7.6 Hz,H-14α),2.32,1.62,1.09,0.87(each 3H,s,H-18,16,17,19),2.06,2.03,1.98,1.74(each 3H,s,4×COCH3)。13C NMR(100 MHz,CDCl3)δ:170.6(13-CH3CO-),170.2(9-CH3CO-),169.8(10-CH3CO-),169.1(7-CH3CO-),166.1(C-1′),146.3(C-4),145.7(C-3′),137.2(C-12),135.0(C-11),134.1(C-4′),130.5(C-7′),129.0(C-6′),129.0(C-8′),128.0(C-5′),128.0(C-9′),118.4(C-2′),115.9(C-20),76.6(C-9),74.8(C-5),71.7(C-10),70.6(C-13),70.0(C-7),46.3(C-8),40.1(C-1),39.4(C-15),37.4(C-3),31.8(C-14),31.1(C-17),34.5(C-6),27.2(C-2),27.1(C-16),21.4(7-CH3CO-),21.0(10-CH3CO-),20.9(9-CH3CO-),20.8(13-CH3CO-),15.2(C-19),13.2(C-18)。以上数据与文献报道的2-deacetoxytaxinine J[2]一致。
化 合物3 无 色 结 晶(CH3OH),mp:222~224 ℃。ESI-MS:m/z 673[M+Na]+;IR(KBr)νmax:1 716,1 636,1 435 cm-1。1H NMR(400 MHz,CDCl3)δ:7.80(1H,d,J = 16.0 Hz,H-3′),7.41 ~7.52(5H,m,phenyl),6.68(1H,d,J = 16.0 Hz,H-2′),6.08(1H,d,J = 10.6 Hz,H-10),5.96(1H,d,J = 10.6 Hz,H-9),5.80(1H,t,J = 7.2 Hz,H-13),5.48(1H,m,H-5),5.50(1H,m,H-2),5.43(1H,s,H-20β),4.97(1H,s,H-20α)],3.38(1H,d,J = 6.4 Hz,H-3),2.67(1H,m,H-14β),1.46(1H,dd,J =14.6,7.6 Hz,H-14α),2.33,1.78,1.13,0.94(each 3H,s,H-18,16,17,19),2.04,2.03,1.94,1.81(each 3H,s,4×COCH3)。13C NMR(100 MHz,CDCl3)δ:170.7(13-CH3CO-),170.0(9-CH3CO-),169.9(10-CH3CO-),169.4(2-CH3CO-),166.2(C-1′),145.5(C-3′),142.2(C-4),137.1(C-12),134.2(C-4′),133.8(C-11),130.6(C-7′),129.0(C-6′),129.0(C-8′),128.0(C-5′),128.0(C-9′),118.7(C-2′),118.3(C-20),78.6(C-5),76.6(C-9),72.9(C-2),72.3(C-10),70.4(C-13),48.2(C-1),44.3(C-8),43.7(C-3),37.5(C-15),31.5(C-17),28.8(C-14),28.6(C-6),27.3(C-7),26.7(C-16),21.4(2-CH3CO-),21.0(10-CH3CO-),20.8(13-CH3CO-),20.8(9-CH3CO-),17.8(C-19),15.5(C-18)。以上数据与文献报道的7-deacetoxytaxinine J[3]一致。
化 合物4 无 色 结 晶(CH3OH),mp:248~250 ℃。ESI-MS:m/z 731[M+Na]+;IR(KBr)νmax:1 715,1 634,1 436 cm-1。1H NMR(400 MHz,CDCl3)δ:7.82(1H,d,J = 16.0 Hz,H-3′),6.64(1H,d,J = 16.0 Hz,H-2′),7.42 ~7.53(5H,m,phenyl),6.24(1H,d,J = 10.7 Hz,H-10),5.90(1H,d,J = 10.7 Hz,H-9),5.82(1H,t,J = 7.2 Hz,H-13),5.53(1H,m,H-5),5.50(1H,m,H-2),5.47(1H,s,H-20β),5.00(1H,s,H-20α),3.35(1H,d,J =5.3 Hz,H-3),2.65(1H,m,H-14β),1.46(1H,dd,J = 14.6,7.6 Hz,H-14α),2.35,1.78,1.13,1.09(each 3H,s,H-18,16,17,19),2.08,2.04,2.03,1.94,1.81(each 3H,s,5×COCH3)。13C NMR(100 MHz,CDCl3)δ:170.7(13-CH3CO-),169.8(9-CH3CO-),169.8(10-CH3CO-),169.4(7-CH3CO-),169.2(2-CH3CO-),166.2(C-1′),146.0(C-3′),140.3(C-4),137.1(C-12),134.2(C-4′),133.6(C-11),130.7(C-7′),129.0(C-6′),129.0(C-8′),128.2(C-5′),128.2(C-9′),119.0(C-2′),118.4(C-20),76.7(C-10),76.0(C-5),71.7(C-9),70.9(C-2),70.5(C-7),69.8(C-13),48.7(C-1),47.1(C-8),42.8(C-3),37.6(C-15),31.6(C-17),28.6(C-6),28.3(C-14),27.1(C-16),21.5(2-CH3CO-),21.3(7-CH3CO-),21.0(9-CH3CO-),21.0(10-CH3CO-),20.8(13-CH3CO-),15.9(C-19),13.7(C-18)。以上数据与文献报道的taxinine J[4]一致。
化 合物5 无 色方 晶(CH3OH),mp:200~203 ℃。 ESI-MS:m/z 638[M+H]+;IR(KBr)νmax:1 716,1 642,1 450 cm-1。1H NMR(400 MHz,CDCl3)δ:7.26 ~7.35(5H,m,phenyl),6.04(1H,d,J = 10.7 Hz,H-10),5.82(1H,br.s,H-9),5.84(1H,br.s,H-13),5.30(1H,br.s,H-5),5.16(1H,s,H-20β),4.82(1H,s,H-20α),2.82(1H,d,J =5.3 Hz,H-3),2.68(1H,ddd,J = 14.6,7.6,4.6 Hz,H-14β),1.06(1H,dd,J = 14.6,7.6 Hz,H-14α),2.20[(6H,s,2×-N(CH3)2)],2.13,1.60,1.13,0.67(each 3H,s,H-18,16,17,19),2.07,2.05,2.03(each 3H,s,3×COCH3)。13C NMR(100 MHz,CDCl3) δ:170.5(13-CH3CO-),170.4(10-CH3CO-),160.0(9-CH3CO-),170.8(C-1′),148.5(C-4),139.0(C-12),137.0(C-11),134.8(C-4′),128.4(C-7′),128.2(C-6′),128.2(C-8′),127.7(C-5′),127.7(C-9′),114.3(C-20),77.3(C-9),75.7(C-5),72.5(C-10),70.5(C-13),67.8(C-3′),42.8(C-8),42.8[3′-N(CH3)2],40.3(C-1),40.3(C-2′),39.1(C-15),38.1(C-3),31.9(C-14),31.1(C-16),28.1(C-2),27.2(C-7),27.1(C-6),27.1(C-17),21.3(10-CH3CO-),21.1(9-CH3CO-),20.8(13-CH3CO-),17.7(C-19),15.3(C-18)。以上数据与文献报道的7,2′-didesacetoxyaustrospicatine[5]一致。
化合物6 无色粉末(CHCl3),浓硫酸-香草醛显紫色。ESI-MS:m/z 862[M+H]+;IR(KBr)νmax:1 716,1 647,1 450 cm-1。1H NMR(400 MHz,CDCl3)δ:8.10(1H,d,J = 3.8 Hz),7.61(1H,m),7.42(1H,m),7.40(5H,m,phenyl),6.30(1H,s,H-10),6.17(1H,t,H-13),5.68(1H,d,J = 7.0 Hz,H-2),4.33(1H,m,H-7),4.28(1H,d,J = 8.4 Hz,H-20α),4.16(1H,s,d,J = 8.4 Hz,H-20β),3.79(1H,d,J = 7.0 Hz,H-3),2.51(1H,m,H-6α)和1.84(1H,m,H-6β),2.34(1H,m,H-14α)和2.32(1H,m,H-14β),2.23 和2.21(each 3H,s,2×COCH3),1.87,1.67,1.27,1.14(each 3H,s,H-18,19,17,16)。13C NMR(100 MHz,CDCl3)δ:203.9(C-9),175.1(C-1′),173.6(C-4′),171.2(4-CH3CO-),170.2(10-CH3CO-),166.9,133.6,133.6,130.2,129.2,129.2,128.9(2-OBz),142.7(C-12),136.6(C-11),132.8,128.9,128.6,128.6,128.1,128.1(3′-phenyl),84.4(C-5),80.91(C-4),79.1(C-1),76.5(C-20),75.7(C-10),75.1(C-2),72.8(C-13),72.1(C-7),72.1(C-2′),61.4(C-3′),58.6(C-8),45.6(C-3),43.2(C-15),36.7(C-14),35.6(C-6),35.3[N(CH3)2],34.0(C-5′),31.5(C-7′),26.8(C-17),24.7(C-6′),22.4(4-CH3CO-),22.2(C-8′),21.9(C-16),20.9(10-CH3CO-),14.8(C-18),13.9(C-9′),9.5(C-19)。以上数据与文献报道的Nmethyltaxol C[6]一致。
化合物7 无色方晶(CH3OH),mp:171 ~172 ℃。ESI-MS:m/z 543[M+Na]+;IR(KBr)νmax:1 716,1 647,1 445 cm-1。1H NMR(400 MHz,CDCl3)δ:6.24(1H,d,J = 11.0 Hz,H-10),5.80(1H,d,J = 11.0 Hz,H-9),5.71(1H,dd,J = 10.4,4.0 Hz,H-13),5.66(1H,dd,J = 12.2,5.1 Hz,H-7),4.28(1H,brs,H-5),5.16(1H,br.s,H-20β),4.82(1H,br.s,H-20α),3.20(1H,d,J = 5.0 Hz,H-3),2.76(1H,J = 15.2,10.7 8.5 Hz,H-14β),1.05(1H,dd,J = 15.2,4.6 Hz,H-14α),2.18,1.55,0.98,0.79(each 3H,s,H-18,16,17,19),2.04,2.03,2.01,1.93(each 3H,s,4×COCH3)。13C NMR(100 MHz,CDCl3)δ:170.3(13-CH3CO-),170.1(9-CH3CO-),169.7(10-CH3CO-),169.2(7-CH3CO-),166.1(C-1′),151.4(C-4),145.7(C-3′),137.8(C-12),136.0(C-11),134.1(C-4′),130.5(C-7′),129.0(C-6′),129.0(C-8′),128.0(C-5′),128.0(C-9′),112.6(C-2′),112.6(C-20),76.7(C-9),73.3(C-5),72.1(C-10),70.0(C-13),69.8(C-7),46.8(C-8),39.7(C-1),38.9(C-15),36.0(C-6),35.5(C-3),32.4(C-14),32.1(C-17),26.9(C-2),26.3(C-16),21.4(7-CH3CO-),21.0(10-CH3CO-),20.9(9-CH3CO-),20.8(13-CH3CO-),15.9(C-19),12.6(C-18)。 以 上 数 据 与 文 献 报 道 的2-deacetoxydecinnamoyl taxinine J[7]一致。
化合物8 无色结晶(CH3OH),mp:213 ~215 ℃。 ESI-MS:m/z 854[M+H]+;IR(KBr)νmax:1 710,1 651,1 456 cm-1。1H NMR(400 MHz,CDCl3)δ:6.27(1H,s,H-10),6.22(1H,t,H-13),5.68(1H,d,J = 7.0 Hz,H-2),4.30(1H,m,H-7),4.31(1H,d,J = 8.4 Hz,H-20α),4.21(1H,s,d,J =8.4 Hz,H-20β),3.79(1H,d,J = 7.0 Hz,H-3),2.51(1H,m,H-6α),1.90(1H,m,H-6β),2.35(1H,m,H-14α),2.32(1H,m,H-14β),2.38,2.23(each 3H,s,2×COCH3),1.79,1.68,1.23,1.13(each 3H,s,H-18,19,17,16)。13C NMR(100 MHz,CDCl3)δ:203.6(C-9),172.7(C-1′),171.2(10-CH3CO-),170.4(4-CH3CO-),167.1(C-4′),167.1,138.0,138.0,130.2,129.2,129.2,128.4(2-OBz),142.0(C-12),133.7,132.0,128.7,128.7,127.0,127.0(3′-phenyl),133.7,130.2,129.0,129.0,128.7,128.7(4′-phenyl),133.2(C-11),84.4(C-5),81.2(C-4),79.0(C-1),76.5(C-20),75.6(C-10),75.0(C-2),73.2(C-2′),72.4(C-13),72.2(C-7),58.6(C-8),55.1(C-3′),45.7(C-3),43.2(C-15),35.7(C-14),35.6(C-6),26.9(C-17),22.6(4-CH3CO-),21.8(C-16),20.9(10-CH3CO-),14.8(C-19),9.6(C-18)。以上数据与文献报道的taxol[8]一致。
化 合物9 无 色 结 晶(CH3OH),mp:213~215 ℃。ESI-MS:m/z 854[M+Na]+;IR(KBr)νmax:1 711,1 655,1 456 cm-1。1H NMR(400 MHz,CDCl3)δ:6.78(1H,s,H-10),6.22(1H,t,H-13),5.76(1H,d,J = 7.0 Hz,H-2),3.69(1H,m,H-7),3.92(1H,d,J = 7.0 Hz,H-3),2.42(1H,m,H-14α),2.25(1H,m,H-14β),2.34(1H,m,H-6α),2.27(1H,m,H-6β),2.49,2.18(each 3H,s,2×COCH3),1.78,1.66,1.18,1.14(each 3H,s,H-18,19,17,16)。与Taxol 的1H NMR 对比,发现两者主要区别在于:在δH4.0未发现四元氧环(H-20,20′)的特征四重峰信号,δH4.5 也未发现C4-C20位环外双键上的特征氢信号;在δH3.69 处有一宽单峰为H-7 信号,而taxol 的H-7 在δH4.30 处表现为多重峰;在δH4.38 处出现一个双氢宽单峰信号为H-20 位上的两个氢信号,而Taxol 的H-20 信号在δH4.21 和δH4.31 表现为一组AB 四重峰,化合物9的H-10(δH6.78)相比Taxol H-10(δH6.27)出现在的相对低场,提示化合物9 是7 位异构化的紫杉烷类化合物。13C NMR(100 MHz,CDCl3)δ:207.2(C-9),172.7(C-1′),172.6(10-CH3CO-),172.3(4-CH3CO-),169.4(C-4′),167.1,138.0,138.0,130.2,129.4,129.4,128.3(2-OBz),142.0(C-12),133.4,132.0,128.8,128.8,127.1,127.1(3′-phenyl),133.7,130.3,129.4,129.4,128.7,128.7(4′-phenyl),133.4(C-11),82.8(C-5),82.1(C-4),79.1(C-1),76.7(C-20),75.8(C-10),75.4(C-2),73.2(C-2′),72.4(C-13),72.2(C-7),57.6(C-8),54.9(C-3′),42.7(C-15),40.4(C-3),35.3(C-14),35.3(C-6),26.0(C-17),22.6(4-CH3CO-),21.3(C-16),20.9(10-CH3CO-),14.7(C-19),9.6(C-18)。以上数据与文献报道的7-epi-taxol[8]一致。
化合物10 无色结晶(CH3OH),mp:207 ~210 ℃。 ESI-MS:m/z 812[M+H]+;IR(KBr)νmax:1 716,1 650,1 458 cm-1。1H NMR(400 MHz,CDCl3)δ:6.23(1H,t,H-13),5.73(1H,d,J = 7.4 Hz,H-2),5.42(1H,s,H-10)和3.67(1H,br.d,H-7),3.92(1H,d,J = 7.4 Hz,H-3),2.39(1H,m,H-14α),2.22(1H,m,H-14β),2.35(1H,m,H-6α),2.28(1H,m,H-6β),1.75,1.72,1.19,1.08(each 3H,s,H-18,19,17,16)。13C NMR(100 MHz,CDCl3)δ:215.0(C-9),172.7(C-1′),172.5(4-CH3CO-),167.2(C-4′),167.1,138.0,138.0,130.2,129.4,129.4,128.3(2-OBz),137.8(C-12),133.7,132.0,128.8,128.8,127.1,127.1(3′-phenyl),133.7,130.3,129.4,129.4,128.7,128.7(4′-phenyl),135.7(C-11),82.7(C-5),82.1(C-4),79.2(C-1),77.8(C-10),76.7(C-20),75.9(C-7),75.5(C-2),73.2(C-2′),72.5(C-13),57.3(C-8),55.0(C-3′),42.6(C-15),40.4(C-3),36.4(C-14),35.4(C-6),26.0(C-16),20.6(C-17),22.6(4-CH3CO-),16.7(C-19),14.4(C-18)。以上数据与文献报道的7-epi-10-deacetoxytaxol[9]一致。
化合物11 无色针状晶体(CH3OH),mp :184~186 ℃。 ESI-MS:m/z 832[M+H]+;IR(KBr)νmax:1 711,1 651,1 470 cm-1。1H NMR(400 MHz,CDCl3)δ:6.27(1H,s,H-10),δH6.20(1H,t,H-13),5.67(1H,d,J = 7.0 Hz,H-2),4.38(1H,m,H-7),4.30(1H,d,J = 8.4 Hz,H-20α),4.20(1H,s,d,J =8.4 Hz,H-20β),3.79(1H,d,J = 7.0 Hz,H-3),2.26(1H,m,H-14α),2.23(1H,m,H-14β),2.53(1H,m,H-6α),2.35,2.24(each 3H,s,2×COCH3),1.87(1H,m,H-6b),1.80,1.68,1.25,1.15(each 3H,s,H-18,19,17,16)。13C NMR(100 MHz,CDCl3)δ:203.7(C-9),172.8(C-1′),171.2(4-CH3CO-),170.3(10-CH3CO-),169.1(C-4′),167.0,138.2,138.2,130.2,129.2,129.2,129.0(2-OBz),142.0(C-12),133.7,131.4,128.7,128.7,127.0,127.0(3′-phenyl),138.2(C-5′),133.2(C-11),131.9(C-6′),84.4(C-5),81.1(C-4),79.0(C-1),76.7(C-20),75.6(C-10),75.0(C-2),73.3(C-2′),72.3(C-13),72.1(C-7),58.6(C-8),54.9(C-3′),45.6(C-3),43.2(C-15),35.6(C-6),35.6(C-14),26.9(C-17),21.9(C-16),22.6(4-CH3CO-),14.8(C-18),14.0(C-7′),14.0(5′-CH3),9.6(C-19)。 以 上 数 据 与 文 献 报 道 的cephalomannine[8]一致。
化合物12 无色针状晶体(CH3OH),mp:184~186 ℃。 ESI-MS:m/z 832[M+H]+;IR(KBr)νmax:1 721,1 656,1 465 cm-1。1H NMR(400 MHz,CDCl3)δ:6.82(1H,s,H-10),δH6.22(1H,t,H-13),5.67(1H,d,J = 7.0 Hz,H-2),3.67(1H,br d,H-7),4.39(2H,br d,H-20),3.84(1H,d,J = 7.0 Hz,H-3),2.35(1H,m,H-14α),2.26(1H,m,H-14β),2.51(1H,m,H-6α),1.87(1H,m,H-6β),2.35,2.25(each 3H,s,2×COCH3),1.81,1.69,1.24,1.14(each 3H,s,H-18,19,17,16)。 与cephalomannine 的1H NMR 对比发现:化合物12 在δH3.67处有一宽单峰为H-7 信号,而cephalomannine 的H-7 在δH4.39 处表现为多重峰;化合物12 在δH4.39处出现一个双氢宽单峰信号为H-20位上的两个氢信号,cephalomannine 的H-20 信号在δH4.20 和δH4.30 表现为一组AB 四重峰;化合物12 的H-10(δH6.82)相比cephalomannine 的H-10(δH6.27)出现在的相对低场,提示化合物12 可能为7 位异构化的 三 尖 杉 宁 碱。13C NMR(100 MHz,CDCl3)δ:207.3(C-9),172.8(C-1′),172.3(10-CH3CO-),169.3(4-CH3CO-),169.0(C-4′),167.2,138.1,138.1,130.2,129.3,129.3,129.0(2-OBz),139.8(C-12),133.7,131.4,128.9,128.9,128.2,128.2(3′-phenyl),138.1(C-5′),133.3(C-11),131.8(C-6′),82.8(C-5),82.0(C-4),79.2(C-1),76.7(C-20),75.7(C-10),75.3(C-2),73.4(C-2′),72.4(C-13),72.1(C-7),57.6(C-8),54.7(C-3′),43.7(C-15),42.6(C-3),35.3(C-6),35.3(C-14),26.0(C-17),21.4(C-16),22.5(4-CH3CO-),20.9(10-CH3CO-),14.8(C-18),14.8(C-7′),12.5(5′-CH3),9.5(C-19)。以上数据与文献报道的7-epicephalomannine[6]一致。
本研究对南方红豆杉枝叶氯仿萃取部位的化学成分进行了研究。分离鉴定了12个紫杉烷类二萜化合物,其中2 个为首次从该植物枝叶中分离得到。