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荷梗中的细胞毒活性生物碱(2)

时间:2014-01-03 14:26 文章来源:http://www.lunwenbuluo.com 作者:段绪红等 点击次数:

  化合物2白色颗粒状结晶(MeOH);改良碘化铋钾试剂显橘红色;1H-NMR(DMSO-d6,300MHz)δ:7.05(2H,d,J=8.5Hz,H-2′,6′),6.68(2H,d,J=8.5Hz,H-3′,5′),6.44(1H,s,H-5),6.65(1H,s,H-8),3.88(1H,dd,H-1),3.67(3H,s,-OMe),2.49~3.05(6H,m,H-3,4,9),1.80(1H,s,N-H);13C-NMR(DMSO-d6,75MHz)δ:56.5(C-1),41.4(C-3),28.8(C-4),127.3(C-4a),115.4(C-5),145.5(C-6),144.5(C-7),110.6(C-8),129.7(C-8a),39.9(C-9),129.8(C-1′),130.2(C-2′),114.9(C-3′),155.5(C-4′),114.9(C-5′),130.2(C-6′),55.6(7-OMe)。以上数据与文献[6]报道基本一致,鉴定为异乌药碱。

  化合物3无色针状结晶(CHCl3);改良碘化铋钾试剂显橘红色;1H-NMR(DMSO-d6,300MHz)δ:7.06(2H,d,J=8.5Hz,H-2′,6′),6.70(1H,s,H-8),6.68(2H,d,J=8.5Hz,H-3′,5′),6.61(1H,s,H-5),3.94(1H,dd,H-1),3.70(3H,s,-OMe),3.65(3H,s,-OMe),2.58~3.07(6H,m,H-3,4,9),1.89(3H,s,-Me);13C-NMR(DMSO-d6,75MHz)δ:56.1(C-1),40.4(C-3),27.3(C-4),125.5(C-4a),111.7(C-5),147.7(C-6),148.2(C-7),109.4(C-8),126.8(C-8a),39.4(C-9),126.9(C-1′),130.3(C-2′),116.1(C-3′),156.1(C-4′),116.1(C-5′),130.3(C-6′),56.0(6-OMe),55.9(7-OMe),22.6(-Me),177.3(CO)。以上数据与文献[7]报道基本一致,鉴定为N-乙酰基去甲杏黄罂粟碱。

  化合物4无色针刺状结晶(CHCl3);改良碘化铋钾试剂显橘红色;1H-NMR(CDCl3,300MHz)δ:8.34(1H,d,J=5.7Hz,H-3),7.43(1H,d,J=5.7Hz,H-4),7.32(1H,s,H-8),7.08(2H,d,J=8.5Hz,H-2′,6′),7.05(1H,s,H-5),6.67(2H,d,J=8.5Hz,H-3′,5′),4.00(3H,s,-OMe),3.89(3H,s,-OMe);13C-NMR(CDCl3,75MHz)δ:158.3(C-1),140.7(C-3),118.4(C-4),133.0(C-4a),105.7(C-5),152.3(C-6),149.7(C-7),104.5(C-8),122.2(C-8a),40.6(C-9),130.1(C-1′),129.7(C-2′),115.3(C-3′),155.7(C-4′),115.2(C-5′),129.6(C-6′),55.8(6-OMe),55.7(7-OMe)。以上数据与文献[8]报道基本一致,鉴定为厚壳桂素。

  化合物5桔红色细状结晶(CHCl3);改良碘化铋钾试剂显橘红色;ESI-MSm/z310[M-H]-;1H-NMR(CDCl3,300MHz)δ:7.96(2H,d,J=9.0Hz,H-2′,6′),6.91(2H,d,J=9.0Hz,H-3′,5′),6.88(1H,s,H-8),6.70(1H,s,H-5),3.91(3H,s,-OMe),3.89(2H,t,H-3),3.84(3H,s,-OMe),2.79(2H,t,H-4);13C-NMR(DMSO-d6,75MHz)δ:175.4(C-1),41.1(C-3),26.7(C-4),137.2(C-4a),103.6(C-5),158.1(C-6),164.7(C-7),109.9(C-8),120.3(C-8a),189.0(C-α),125.8(C-1′),132.5(C-2′),116.5(C-3′),151.8(C-4′),116.5(C-5′),132.5(C-6′),55.0(-OMe),52.5(-OMe)。以上数据与文献[9]报道基本一致,鉴定为velucryptine。

  化合物6黄色结晶(MeOH);紫外呈强蓝色荧光;改良碘化铋钾试剂显橘红色;ESI-MSm/z192[M+H]+;1H-NMR(CD3OD,300MHz)δ:8.38(1H,s,H-1),7.07(1H,s,H-8),6.95(1H,s,H-5),3.83(3H,s,-OMe),3.56(3H,s,N-CH3);13C-NMR(CD3OD,75MHz)δ:167.2(C-1),50.1(C-3),26.6(C-4),135.5(C-4a),113.6(C-5),162.5(C-6),150.7(C-7),118.1(C-8),115.6(C-8a),56.4(6-OMe),46.1(N-Me)。以上数据与文献[10]报道基本一致,鉴定为pycnarrhine。

  3结构鉴定

  化合物1无色块晶(CHCl3);改良碘化铋钾试剂显橘红色;1H-NMR(CD3COCD3,300MHz)δ:8.32(1H,d,J=7.9Hz,H-11),7.18~7.31(3H,m,H-8~10),6.63(1H,s,H-3),3.67(1H,dd,J=4.6,9.1Hz,H-6a),3.57(3H,s,-OMe),2.54~3.31(6H,m,H-4,5,7);13C-NMR(CD3COCD3,75MHz)δ:144.5(C-1),126.5(C-1a),129.6(C-1b),150.0(C-2),116.4(C-3),131.1(C-3a),30.4(C-4),44.1(C-5),54.8(C-6a),38.4(C-7),137.8(C-7a),128.8(C-8),128.4(C-9),128.1(C-10),127.7(C-11),133.5(C-11a),60.4(1-OMe)。以上数据与文献[5]报道基本一致,鉴定为阿西米洛宾。

  化合物2白色颗粒状结晶(MeOH);改良碘化铋钾试剂显橘红色;1H-NMR(DMSO-d6,300MHz)δ:7.05(2H,d,J=8.5Hz,H-2′,6′),6.68(2H,d,J=8.5Hz,H-3′,5′),6.44(1H,s,H-5),6.65(1H,s,H-8),3.88(1H,dd,H-1),3.67(3H,s,-OMe),2.49~3.05(6H,m,H-3,4,9),1.80(1H,s,N-H);13C-NMR(DMSO-d6,75MHz)δ:56.5(C-1),41.4(C-3),28.8(C-4),127.3(C-4a),115.4(C-5),145.5(C-6),144.5(C-7),110.6(C-8),129.7(C-8a),39.9(C-9),129.8(C-1′),130.2(C-2′),114.9(C-3′),155.5(C-4′),114.9(C-5′),130.2(C-6′),55.6(7-OMe)。以上数据与文献[6]报道基本一致,鉴定为异乌药碱。

  化合物3无色针状结晶(CHCl3);改良碘化铋钾试剂显橘红色;1H-NMR(DMSO-d6,300MHz)δ:7.06(2H,d,J=8.5Hz,H-2′,6′),6.70(1H,s,H-8),6.68(2H,d,J=8.5Hz,H-3′,5′),6.61(1H,s,H-5),3.94(1H,dd,H-1),3.70(3H,s,-OMe),3.65(3H,s,-OMe),2.58~3.07(6H,m,H-3,4,9),1.89(3H,s,-Me);13C-NMR(DMSO-d6,75MHz)δ:56.1(C-1),40.4(C-3),27.3(C-4),125.5(C-4a),111.7(C-5),147.7(C-6),148.2(C-7),109.4(C-8),126.8(C-8a),39.4(C-9),126.9(C-1′),130.3(C-2′),116.1(C-3′),156.1(C-4′),116.1(C-5′),130.3(C-6′),56.0(6-OMe),55.9(7-OMe),22.6(-Me),177.3(CO)。以上数据与文献[7]报道基本一致,鉴定为N-乙酰基去甲杏黄罂粟碱。

  化合物4无色针刺状结晶(CHCl3);改良碘化铋钾试剂显橘红色;1H-NMR(CDCl3,300MHz)δ:8.34(1H,d,J=5.7Hz,H-3),7.43(1H,d,J=5.7Hz,H-4),7.32(1H,s,H-8),7.08(2H,d,J=8.5Hz,H-2′,6′),7.05(1H,s,H-5),6.67(2H,d,J=8.5Hz,H-3′,5′),4.00(3H,s,-OMe),3.89(3H,s,-OMe);13C-NMR(CDCl3,75MHz)δ:158.3(C-1),140.7(C-3),118.4(C-4),133.0(C-4a),105.7(C-5),152.3(C-6),149.7(C-7),104.5(C-8),122.2(C-8a),40.6(C-9),130.1(C-1′),129.7(C-2′),115.3(C-3′),155.7(C-4′),115.2(C-5′),129.6(C-6′),55.8(6-OMe),55.7(7-OMe)。以上数据与文献[8]报道基本一致,鉴定为厚壳桂素。

  化合物5桔红色细状结晶(CHCl3);改良碘化铋钾试剂显橘红色;ESI-MSm/z310[M-H]-;1H-NMR(CDCl3,300MHz)δ:7.96(2H,d,J=9.0Hz,H-2′,6′),6.91(2H,d,J=9.0Hz,H-3′,5′),6.88(1H,s,H-8),6.70(1H,s,H-5),3.91(3H,s,-OMe),3.89(2H,t,H-3),3.84(3H,s,-OMe),2.79(2H,t,H-4);13C-NMR(DMSO-d6,75MHz)δ:175.4(C-1),41.1(C-3),26.7(C-4),137.2(C-4a),103.6(C-5),158.1(C-6),164.7(C-7),109.9(C-8),120.3(C-8a),189.0(C-α),125.8(C-1′),132.5(C-2′),116.5(C-3′),151.8(C-4′),116.5(C-5′),132.5(C-6′),55.0(-OMe),52.5(-OMe)。以上数据与文献[9]报道基本一致,鉴定为velucryptine。

  化合物6黄色结晶(MeOH);紫外呈强蓝色荧光;改良碘化铋钾试剂显橘红色;ESI-MSm/z192[M+H]+;1H-NMR(CD3OD,300MHz)δ:8.38(1H,s,H-1),7.07(1H,s,H-8),6.95(1H,s,H-5),3.83(3H,s,-OMe),3.56(3H,s,N-CH3);13C-NMR(CD3OD,75MHz)δ:167.2(C-1),50.1(C-3),26.6(C-4),135.5(C-4a),113.6(C-5),162.5(C-6),150.7(C-7),118.1(C-8),115.6(C-8a),56.4(6-OMe),46.1(N-Me)。以上数据与文献[10]报道基本一致,鉴定为pycnarrhine。

  化合物14无色针状结晶(CHCl3);改良碘化铋钾试剂显橘红色;ESI-MSm/z300[M+H]+。1H-NMR(DMSO-d6,300MHz)δ:6.92(2H,d,J=8.1Hz,H-2′,6′),6.63(2H,d,J=8.1Hz,H-3′,5′),6.42(1H,s,H-8),6.28(1H,s,H-5),3.55(3H,s,-OMe),3.53(1H,dd,H-1),2.37~3.05(6H,m,H-3,4,9),2.34(3H,s,N-Me);13C-NMR(DMSO-d6,75MHz)δ:63.5(C-1),47.1(C-3),23.9(C-4),125.8(C-4a),111.1(C-5),154.5(C-6),147.8(C-7),111.7(C-8),128.6(C-8a),40.5(Ar-CH2),131.5(C-1′),130.5(C-2′),116.3(C-3′),155.2(C-4′),116.3(C-5′),130.5(C-6′),55.5(-OMe),42.0(N-Me)。以上数据与文献[16]报道基本一致,鉴定为N-甲基乌药碱。

  化合物15淡黄色晶体(CHCl3);改良碘化铋钾试剂显橘红色;ESI-MSm/z292[M+H]+。1H-NMR(CDCl3,300MHz)δ:9.20(1H,d,J=8.4Hz,H-11),8.92(1H,d,J=5.3Hz,H-5),8.60(1H,dd,J=1.6,6.2Hz,H-8),7.82(1H,d,J=5.3Hz,H-4),7.78(1H,m,H-9),7.24(1H,s,H-3),4.11(3H,s,-OMe),4.03(3H,s,-OMe);13C-NMR(CDCl3,75MHz)δ:151.8(C-1),156.6(C-2),106.4(C-3),145.3(C-3a),122.0(C-3b),123.9(C-4),145.1(C-5),135.5(C-6a),182.8(C-7),132.1(C-7a,128.9(C-8),128.8(C-9),134.3(C-10),128.5(C-11),134.4(C-11a),120.0(C-11b),60.5(-OMe),56.3(-OMe)。以上数据与文献[12]报道基本一致,鉴定为观音莲明。


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