多峰山竹干燥葉的化學(xué)成分研究

多峰山竹干燥葉的化學(xué)成分研究

多花竹子是科黃屬（gykoiza）的一種小型樹(shù)種，主要分布在中國(guó)南部，包括香港和臺(tái)灣等地區(qū)。該植物種子可榨油,供制皂和潤(rùn)滑油;果可食;根、果及樹(shù)皮入藥,具有消腫收斂、止痛之功效。至今為止,文獻(xiàn)對(duì)多花山竹子化學(xué)成分的研究報(bào)道較少,且主要集中于呫噸酮、雙黃酮等類型的化合物。為了進(jìn)一步對(duì)該植物枝葉進(jìn)行研究,以確定該植物枝葉是否也同樣具有藥理活性,本實(shí)驗(yàn)選取多花山竹子干燥枝葉為研究對(duì)象,從其75%乙醇提取物的石油醚萃取部位中分離得到了5個(gè)化合物,其結(jié)構(gòu)分別被鑒定為: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),1,6-二羥基-3,7-二甲氧基呫噸酮(1,6-dihydroxy-3,7-dimethoxyxanthone,Ⅳ),β-谷甾醇(β-sitosterol,Ⅴ)?；衔铫?Ⅴ均為首次從該種植物中分離得到,其中化合物Ⅲ和Ⅳ還為首次從該科植物中分離得到。1主體材料及反相材料XT-4雙目顯微熔點(diǎn)測(cè)定儀,溫度未校正;HP-5973型質(zhì)譜儀;INOVA-400核磁共振儀(TMS為內(nèi)標(biāo));柱層析硅膠和薄層層析硅膠均為青島海洋化工廠生產(chǎn);反相材料RP-18(40~63μm)為Merck公司生產(chǎn);SephadexLH-20(25~100μm)為AmershamBiosciences公司生產(chǎn)(Sweden);藥材于2009年9月份采于貴州省荔波縣,由貴陽(yáng)中醫(yī)學(xué)院的陳德媛教授鑒定為多花山竹子(Garciniamultiflora)的干燥枝葉。2樹(shù)體的薄層層析合成化合物多花山竹子干燥枝葉40kg,粉碎后,用75%乙醇回流提取4次(提取時(shí)間依次為4,3,3和2h),合并提取液,減壓濃縮至無(wú)醇味,所得浸膏用水混懸,使用石油醚進(jìn)行萃取,濃縮后,得到石油醚萃取物(約633g)。取石油醚萃取物(約633g),采用硅膠柱層析(200~300目)分離,用石油醚-乙酸乙酯混合溶劑系統(tǒng)梯度洗脫(石油醚-乙酸乙酯,1∶0→0∶1),采用薄層層析檢測(cè)合并,共分成8段。第3段通過(guò)反復(fù)經(jīng)硅膠柱層析,石油醚-氯仿混合溶劑系統(tǒng)梯度洗脫(石油醚-氯仿,10∶1→0∶1)得到化合物Ⅰ(61mg)和Ⅱ(19mg);第7段反復(fù)經(jīng)硅膠柱層析,石油醚-丙酮混合溶劑系統(tǒng)梯度洗脫(石油醚-丙酮,9∶1→0∶1)、SephadexLH-20凝膠柱層析(氯仿-甲醇,1∶1)和反相硅膠(RP-18)柱層析(甲醇-水,5∶5→1∶0)得到化合物Ⅲ(33mg)和Ⅳ(39mg),第6段反復(fù)經(jīng)硅膠柱層析,石油醚-丙酮混合溶劑系統(tǒng)梯度洗脫(石油醚-丙酮,15∶1→1∶0)和重結(jié)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:白色針晶(石油醚);mp277~281℃;分子式為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)。以上數(shù)據(jù)和文獻(xiàn)報(bào)道的木栓酮基本一致,故鑒定該化合物為木栓酮。化合物Ⅱ:無(wú)色片狀晶體(石油醚);mp263~266℃;分子式為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)。以上數(shù)據(jù)和文獻(xiàn)報(bào)道的表木栓醇基本一致,故鑒定該化合物為表木栓醇?；衔铫?白色粉末(氯仿);分子式為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)。以上數(shù)據(jù)和文獻(xiàn)報(bào)道的putricacid基本一致,故鑒定該化合物為putricacid?；衔铫?黃色針晶(丙酮);mp220~225℃;分子式為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