多峰山竹干燥叶的化学成分研究

多峰山竹干燥叶的化学成分研究

多花竹子是科黄属（gykoiza）的一种小型树种，主要分布在中国南部，包括香港和台湾等地区。该植物种子可榨油,供制皂和润滑油;果可食;根、果及树皮入药,具有消肿收敛、止痛之功效。至今为止,文献对多花山竹子化学成分的研究报道较少,且主要集中于呫吨酮、双黄酮等类型的化合物。为了进一步对该植物枝叶进行研究,以确定该植物枝叶是否也同样具有药理活性,本实验选取多花山竹子干燥枝叶为研究对象,从其75%乙醇提取物的石油醚萃取部位中分离得到了5个化合物,其结构分别被鉴定为:木栓酮(friedelan-3-one,Ⅰ),表木栓醇(friedelin-3β-ol,Ⅱ),putricacid(2-hydroxy-3,4-seco-friedelan-3-oicacid,Ⅲ),1,6-二羟基-3,7-二甲氧基呫吨酮(1,6-dihydroxy-3,7-dimethoxyxanthone,Ⅳ),β-谷甾醇(β-sitosterol,Ⅴ)。化合物Ⅰ-Ⅴ均为首次从该种植物中分离得到,其中化合物Ⅲ和Ⅳ还为首次从该科植物中分离得到。1主体材料及反相材料XT-4双目显微熔点测定仪,温度未校正;HP-5973型质谱仪;INOVA-400核磁共振仪(TMS为内标);柱层析硅胶和薄层层析硅胶均为青岛海洋化工厂生产;反相材料RP-18(40~63μm)为Merck公司生产;SephadexLH-20(25~100μm)为AmershamBiosciences公司生产(Sweden);药材于2009年9月份采于贵州省荔波县,由贵阳中医学院的陈德媛教授鉴定为多花山竹子(Garciniamultiflora)的干燥枝叶。2树体的薄层层析合成化合物多花山竹子干燥枝叶40kg,粉碎后,用75%乙醇回流提取4次(提取时间依次为4,3,3和2h),合并提取液,减压浓缩至无醇味,所得浸膏用水混悬,使用石油醚进行萃取,浓缩后,得到石油醚萃取物(约633g)。取石油醚萃取物(约633g),采用硅胶柱层析(200~300目)分离,用石油醚-乙酸乙酯混合溶剂系统梯度洗脱(石油醚-乙酸乙酯,1∶0→0∶1),采用薄层层析检测合并,共分成8段。第3段通过反复经硅胶柱层析,石油醚-氯仿混合溶剂系统梯度洗脱(石油醚-氯仿,10∶1→0∶1)得到化合物Ⅰ(61mg)和Ⅱ(19mg);第7段反复经硅胶柱层析,石油醚-丙酮混合溶剂系统梯度洗脱(石油醚-丙酮,9∶1→0∶1)、SephadexLH-20凝胶柱层析(氯仿-甲醇,1∶1)和反相硅胶(RP-18)柱层析(甲醇-水,5∶5→1∶0)得到化合物Ⅲ(33mg)和Ⅳ(39mg),第6段反复经硅胶柱层析,石油醚-丙酮混合溶剂系统梯度洗脱(石油醚-丙酮,15∶1→1∶0)和重结晶后得到化合物Ⅴ(21mg)。3木栓酮s,c-19,18.2,4.2%c-33e,13.2化合物Ⅰ:白色针晶(石油醚);mp277~281℃;分子式为C30H50O;EI-MSm/z426[M]+;1H-NMR(CDCl3,400MHz)δ:1.18(3H,s,H-28),1.05(3H,s,H-26),1.01(3H,s,H-27),1.00(3H,s,H-29),0.95(3H,s,H-30),0.89(3H,s,H-23),0.87(3H,s,H-25),0.73(3H,s,H-24);13C-NMR(CDCl3,100MHz)δ:213.3(s,C-3),59.4(d,C-10),58.1(d,C-4),53.0(d,C-8),42.7(d,C-18),42.1(s,C-5),41.5(t,C-2),41.2(t,C-6),39.6(s,C-14),39.2(t,C-22),38.2(s,C-13),37.4(s,C-9),35.9(t,C-16),35.5(t,C-11),35.3(t,C-19),35.00(q,C-29),32.7(t,C-21),32.3(t,C-15),32.0(q,C-28),31.7(q,C-30),30.4(t,C-12),29.9(s,C-17),28.1(s,C-20),22.2(t,C-1),20.2(q,C-26),18.6(q,C-27),18.2(t,C-7),17.9(q,C-25),14.6(q,C-24),6.8(q,C-23)。以上数据和文献报道的木栓酮基本一致,故鉴定该化合物为木栓酮。化合物Ⅱ:无色片状晶体(石油醚);mp263~266℃;分子式为C30H52O;EI-MSm/z428[M]+;1H-NMR(CDCl3,400MHz)δ:3.74(1H,m,H-3),1.17(3H,s,H-28),1.01(3H,s,H-26),1.00(3H,s,H-27),0.99(3H,s,H-29),0.91(3H,s,H-30),0.89(3H,s,H-25),0.88(3H,s,H-24),0.86(3H,s,H-23);13C-NMR(CDCl3,100MHz)δ:72.7(d,C-3),61.3(d,C-10),53.1(d,C-8),49.1(d,C-4),42.7(d,C-18),41.7(t,C-6),39.6(s,C-14),39.2(t,C-22),38.3(s,C-13),37.8(s,C-9),37.0(s,C-5),36.0(t,C-11),36.0(t,C-16),35.5(t,C-19),35.3(t,C-2),35.1(q,C-29),32.7(t,C-21),32.3(t,C-15),32.0(q,C-30),31.7(q,C-28),30.9(t,C-12),30.6(s,C-17),28.1(s,C-20),20.1(q,C-27),18.6(q,C-25),18.3(q,C-26),17.5(t,C-7),16.1(q,C-24),15.7(t,C-1),11.6(q,C-23)。以上数据和文献报道的表木栓醇基本一致,故鉴定该化合物为表木栓醇。化合物Ⅲ:白色粉末(氯仿);分子式为C+30H52O3;EI-MSm/z460[M];1H-NMR(CD3COCD3,400MHz)δ:8.02(1H,s,3-COOH),4.10(1H,dd,J=4.0,4.0Hz,H-2),1.19(3H,s,H-28),1.02(3H,s,H-26),1.00(3H,s,H-29),0.95(3H,s,H-30),0.93(3H,s,H-27),0.92(3H,s,H-25),0.82(3H,t,J=14.8Hz,H-23),0.76(3H,s,H-24);13C-NMR(CD3COCD3,100MHz)δ:179.5(s,C-3),72.2(d,C-2),55.3(d,C-10),53.7(d,C-8),43.6(d,C-18),40.2(s,C-5),39.8(s,C-14),39.6(t,C-22),39.2(t,C-6),39.0(s,C-13),38.7(s,C-9),36.6(t,C-4),36.6(t,C-16),35.9(t,C-11),35.8(t,C-19),35.2(q,C-29),33.5(t,C-21),32.9(t,C-15),32.4(q,C-30),32.2(q,C-28),32.0(t,C-1),31.0(t,C-12),30.6(s,C-17),28.7(s,C-20),20.5(q,C-26),20.1(q,C-24),19.2(q,C-27),18.9(q,C-25),18.8(t,C-7),7.8(q,C-23)。以上数据和文献报道的putricacid基本一致,故鉴定该化合物为putricacid。化合物Ⅳ:黄色针晶(丙酮);mp220~225℃;分子式为C115H12O6;EI-MSm/z208[M]+;H-NMR(DMSO-d6,400MHz)δ:13.09(1H,s,1-OH),9.87(1H,s,6-OH),7.39(1H,s,H-8),7.14(1H,s,H-5),6.55(1H,d,J=2.0Hz,H-4),6.37(1H,d,J=2.0Hz,H-2),3.95(3H,d,3-OCH3),3.88(3H,d,7-OCH3);13C-NMR(DMSO-d6,100MHz)δ:179.2(s,C-9),165.8(s,C-3),162.4(s,C-1),157.2(s,C-4a),155.3(s,C-4b),151.0(s,C-6),144.5(s,C-7),112.6(s,C-8a),102.6(d,C-5),102.4(d,C-8),100.1(s,C-8b),96.7(d,C-2),92.4(d,C-4),56.4(q,3-OCH3),56.1(q,7-OCH3)。以