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黄苞大戟化学成分研究(2)

时间:2014-01-03 14:24 文章来源:http://www.lunwenbuluo.com 作者:杨大松 点击次数:

  化合物3黄色无定形粉末;1H-NMR(acetone-d6,400MHz)δ:7.82(1H,d,J=2.2Hz,H-2′),7.70(1H,dd,J=2.2,8.5Hz,H-6′),6.99(1H,d,J=8.5Hz,H-5′),6.52(1H,d,J=2.0Hz,H-8),6.26(1H,d,J=2.0Hz,H-6);13C-NMR(acetone-d6,150MHz)δ:147.0(C-2),136.8(C-3),176.6(C-4),162.3(C-5),99.1(C-6),165.0(C-7),94.5(C-8),157.8(C-9),104.1(C-10),123.8(C-1′),115.8(C-2′),145.9(C-3′),148.4(C-4′),116.3(C-5′),121.5(C-6′)。以上波谱数据与文献[6]报道的槲皮素数据基本一致。

  化合物4黄色无定形粉末;ESI-MSm/z417[M-H]-;1H-NMR(DMSO-d6,400MHz)δ:12.60(1H,brs,5-OH),8.07(2H,d,J=8.8Hz,H-2′,6′),6.87(2H,d,J=8.8Hz,H-3′,5′),6.43(1H,d,J=1.8Hz,H-8),6.19(1H,d,J=1.8Hz,H-6),5.33(1H,d,J=5.2Hz,H-1″),3.71(1H,t,J=5.2Hz,H-2″),3.67(1H,m,H-4″),3.64(1H,m,H-3″),3.56(1H,dd,J=5.1,11.6Hz,H-5″a),3.23(1H,d,J=11.6Hz,H-5″e);13C-NMR(DMSO-d6,100MHz)δ:156.4(C-2),133.5(C-3),177.6(C-4),161.2(C-5),98.7(C-6),164.3(C-7),93.7(C-8),156.3(C-9),104.0(C-10),120.7(C-1′),131.0(C-2′,6′),115.3(C-3′,5′),160.1(C-4′),101.2(C-1″),70.8(C-2″),71.6(C-3″),66.1(C-4″),64.3(C-5″)。以上波谱数据与文献[7]报道的kaempferol-3-O-α-L-arabinopyranoside数据基本一致。

  化合物5黄色无定型粉末;ESI-MSm/z433[M-H]-;1H-NMR(acetone-d6,400MHz)δ:12.37(1H,s,5-OH),9.78(1H,s,7-OH),8.58(1H,s,4′-OH),8.52(1H,s,3′-OH),7.74(1H,d,J=2.1Hz,H-2′),7.54(1H,dd,J=2.1,8.5Hz,H-6′),6.82(1H,d,J=8.5Hz,H-5′),6.39(1H,d,J=2.0Hz,H-8),6.14(1H,d,J=2.0Hz,H-6),5.15(1H,d,J=6.1Hz,H-1″),3.83(1H,t,J=6.1Hz,H-2″),3.74(1H,m,H-4″),3.67(1H,dd,J=4.2,12.1Hz,H-5″a),3.61(1H,m,H-3″),3.33(1H,dd,J=2.1,12.1Hz,H-5″e);13C-NMR(acetone-d6,100MHz)δ:157.9(C-2),135.3(C-3),179.0(C-4),162.9(C-5),99.6(C-6),165.1(C-7),94.5(C-8),157.8(C-9),105.4(C-10),122.7(C-1′),115.9(C-2′),145.5(C-3′),149.3(C-4′),117.2(C-5′),122.9(C-6′),104.0(C-1″),72.4(C-2″),73.6(C-3″),68.0(C-4″),66.0(C-5″)。以上波谱数据与文献[8]报道的quercetin-3-O-α-L-arabinopyranoside数据基本一致。

  化合物6黄色无定型粉末;ESI-MSm/z585[M-H]-;1H-NMR(DMSO-d6,500MHz)δ:12.53(1H,s,5-OH),7.71(1H,dd,J=1.6,8.5Hz,H-6′),7.49(1H,d,J=1.6Hz,H-2′),7.03(2H,s,H-2,6),6.85(1H,d,J=8.5Hz,H-5′),6.39(1H,d,J=1.6Hz,H-8),6.18(1H,d,J=1.6Hz,H-6),5.59(1H,d,J=6.5Hz,H-1″),5.33(1H,t,J=6.5Hz,H-2″),5.09~5.31(2H,m,H-3″,4″),5.09,4.90(各2H,brs,H-5″);13C-NMR(DMSO-d6,125MHz)δ:156.4(C-2,9),133.2(C-3),177.3(C-4),161.3(C-5),98.8(C-6,1″),165.2(C-7),93.6(C-8),104.0(C-10),120.9(C-1′),115.5(C-2′),145.2(C-3′),148.8(C-4′),115.7(C-5′),122.4(C-6′),72.4(C-2″),69.9(C-3″),67.1(C-4″),65.1(C-5″),119.6(C-1),109.1(C-2,6),145.6(C-3,5),138.6(C-4),165.2(C-7)。以上波谱数据与文献[9]报道的quercetin-3-O-(2″-galloyl)-α-L-arabinopyranoside数据基本一致。

  化合物7白色粉末;ESI-MSm/z451[M+Na]+;1H-NMR(CDCl3,500MHz)δ:6.50(1H,d,J=8.5Hz,H-7),6.24(1H,d,J=8.5Hz,H-6),5.22(1H,dd,J=8.3,15.3Hz,H-23),5.14(1H,dd,J=8.3,15.3Hz,H-22),3.97(1H,m,H-3),1.00(3H,s,H-19),0.99(3H,d,J=6.6Hz,H-21),0.90(3H,d,J=6.8Hz,H-28),0.88(3H,s,H-18),0.83(3H,d,J=7.0Hz,H-26),0.81(3H,d,J=7.0Hz,H-27);13C-NMR(CDCl3,100MHz)δ:30.1(C-1),34.6(C-2),66.4(C-3),39.3(C-4),82.1(C-5),135.2(C-6),130.7(C-7),79.4(C-8),51.6(C-9),36.9(C-10),20.6(C-11),36.9(C-12),44.5(C-13),51.0(C-14),23.4(C-15),28.6(C-16),56.1(C-17),12.8(C-18),18.1(C-19),39.7(C-20),20.8(C-21),135.4(C-22),132.2(C-23),42.7(C-24),33.0(C-25),19.6(C-26),19.9(C-27),17.5(C-28)。以上波谱数据与文献[10]报道的5α,8α-epidioxy-(22E,24R)-ergosta-6,22-dien-3β-ol数据基本一致。

  化合物8白色粉末;1H-NMR(CDCl3,400MHz)δ:5.81(1H,s,H-6),4.35(1H,m,H-3α),0.92(3H,d,J=6.4Hz,H-21),0.85(3H,t,J=7.6Hz,H-29),0.82(6H,d,J=2.2Hz,H-26,27),0.80(3H,s,H-19),0.74(3H,s,H-18);13C-NMR(CDCl3,125MHz)δ:37.1(C-1),34.2(C-2),73.3(C-3),39.6(C-4),168.4(C-5),126.3(C-6),200.3(C-7),45.9(C-8),53.7(C-9),38.1(C-10),21.0(C-11),38.6(C-12),42.6(C-13),55.9(C-14),23.1(C-15),28.1(C-16),56.1(C-17),12.0(C-18),18.7(C-19),36.1(C-20),19.0(C-21),33.9(C-22),24.1(C-23),29.7(C-24),29.5(C-25),19.8(C-26),19.5(C-27),26.3(C-28),12.0(C-29)。以上波谱数据与文献[11]报道的豆甾-5-烯-7-羰基-3β-甾醇数据基本一致。

  化合物9白色粉末;ESI-MSm/z463[M+Na]+;1H-NMR(CDCl3,500MHz)δ:4.71(1H,s,H-28a),4.66(1H,s,H-28b),3.14(1H,m,H-3α),1.21(3H,s,H-19),1.06(3H,d,J=3.2Hz,H-26),1.04(3H,d,J=3.2Hz,H-27),1.02(3H,d,J=6.3Hz,H-29),0.96(3H,d,J=6.3Hz,H-21),0.95(3H,s,H-30),0.70(3H,s,H-18);13C-NMR(CDCl3,150MHz)δ:34.4(C-1),30.9(C-2),75.5(C-3),39.3(C-4),46.9(C-5),39.1(C-6),198.4(C-7),139.7(C-8),165.0(C-9),39.4(C-10),24.7(C-11),30.3(C-12),45.1(C-13),48.0(C-14),32.2(C-15),29.0(C-16),49.1(C-17),15.8(C-18),17.8(C-19),36.6(C-20),18.8(C-21),35.1(C-22),31.5(C-23),157.0(C-24),34.0(C-25),22.1(C-26),22.1(C-27),106.2(C-28),14.5(C-29),25.3(C-30)。以上波谱数据与文献[12]报道的3β-hydroxy-4α,14α-dimethyl-5α-ergosta-8,24(28)-dien-7-one数据基本一致。

  化合物10白色针晶(丙酮),TLC上10%硫酸-乙醇溶液加热显紫红色,与β-谷甾醇对照品用不同展开系统共薄层色谱,二者Rf相同,故鉴定化合物10为β-谷甾醇。

  化合物11白色粉末;1H-NMR(CDCl3,400MHz)δ:5.64(1H,d,J=5.8Hz,H-6),5.09(1H,t,J=7.0Hz,H-24),3.47(1H,m,H-3),1.69(3H,s,H-27),1.61(3H,s,H-26),1.14(3H,s,H-28),1.06(3H,s,H-29),0.88(3H,s,H-19),0.86(3H,d,J=8.0Hz,H-21),0.84(3H,s,H-30),0.81(3H,s,H-18);13C-NMR(CDCl3,100MHz)δ:18.9(C-1),28.2(C-2),76.4(C-3),40.9(C-4),141.9(C-5),121.8(C-6),19.0(C-7),49.4(C-8),35.1(C-9),44.5(C-10),34.1(C-11),35.2(C-12),46.0(C-13),47.4(C-14),30.3(C-15),28.9(C-16),49.8(C-17),15.4(C-18),27.8(C-19),35.3(C-20),18.7(C-21),35.7(C-22),24.6(C-23),125.2(C-24),130.9(C-25),25.5(C-26),16.5(C-27),25.2(C-28),25.7(C-29),17.6(C-30)。以上波谱数据与文献[13]报道的10α-cucurbitadienol数据基本一致。

  化合物12微黄色无定形粉末;ESI-MSm/z215[M+Na]+;1H-NMR(acetone-d6,400MHz)δ:8.79(1H,s,-OH),7.84(1H,d,J=9.5Hz,H-4),7.19(1H,s,H-5),6.79(1H,s,H-8),6.17(1H,d,J=9.5Hz,H-3),3.90(3H,s,-OCH3);13C-NMR(acetone-d6,100MHz)δ:161.2(C-2),109.8(C-3),144.6(C-4),112.0(C-5),145.9(C-6),151.7(C-7),103.6(C-8),56.6(-OCH3)。以上波谱数据与文献[6]报道的莨菪亭数据基本一致。

  化合物13白色粉末;1H-NMR(acetone-d6,400MHz)δ:8.16(3H,s,OH-3,4,5),7.14(2H,s,H-2,6),4.23(2H,q,J=7.1Hz,-OCH2),1.28(3H,t,J=7.1Hz,-CH3);13C-NMR(acetone-d6,100MHz)δ:122.1(C-1),109.8(C-2,6),145.9(C-3,5),138.6(C-4),166.9(C-7),61.0(-CH2-),14.6(-CH3)。以上波谱数据与文献[14]报道的没食子酸乙酯数据基本一致。

  化合物14白色无定形粉末;1H-NMR(CDCl3,400MHz)δ:9.87(1H,s,H-7),7.81(2H,d,J=7.5Hz,H-2,6),6.96(2H,d,J=7.5Hz,H-3,5);13C-NMR(CDCl3,150MHz)δ:130.2(C-1),132.6(C-2,6),116.1(C-3,5),161.5(C-4),191.2(C-7)。以上波谱数据与文献[15]报道的对羟基苯甲醛数据基本一致。

  化合物15白色无定形粉末;ESI-MSm/z137[M-H]-;1H-NMR(CDCl3,500MHz)δ:7.11(1H,t,J=7.8Hz,H-5),6.72(1H,d,J=1.8Hz,H-2),6.68(1H,d,J=7.8Hz,H-6),6.68(1H,dd,J=1.8,7.8Hz,H-4),3.78(2H,t,J=6.6Hz,H-8),2.75(2H,t,J=6.6Hz,H-7);13C-NMR(CDCl3,125MHz)δ:140.2(C-1),115.9(C-2),156.5(C-3),113.4(C-4),129.6(C-5),120.5(C-6),38.9(C-7),63.3(C-8)。根据以上质谱和核磁数据鉴定化合物15为3-hydroxybenzeneethanol[16]。


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