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1、云南红豆杉心木的化学成分研究中草焉ChineseTraditionalandHerbalDrugs第38卷第7期2007年7月?979?的抗HBV活性.从化合物单体水平证明药用植物空心莲子草具有抗HBV活性,同时,为了进一步阐明该药用植物的药效作用物质基础,还需对其进行系统的化学成分研究和体内作用机制的深入探讨.致谢:武汉大学生命科学院病毒学教育部重点实验室测试化合物的抗HBV活性.References:1E2E3E4E5678JiangsuNewMedicalCollege.DictionaryofChineseMateriaMedica(中药大辞典)M.Shanghai:ShanghaiP
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9、A,ChenML,AesG,ela1.ProductionofhepatitisBvirusparticlesinHepG2caIlstransectedwithclonedhepatitisBvirusDNAJ_.ProcNatlAcadSciUSA,1987,84(4):10051006.云南红豆杉心木的化学成分研究陈雪英,梁敬钰卜(1.中国药科大学天然药物化学教研室,江苏南京210009;2.杭州民生药业集团有限公司,浙江杭州31001i)摘要:目的进一步了解云南红豆杉心木部位的化学成分.方法云南红豆杉心木的乙醇提取物,经用萃取,硅胶柱色谱,凝胶柱色谱等方法分离,从其氯仿萃取部位分离鉴定
10、得18个化合物,采用波谱解析(uV,IR,ESIMS,HNMR,”CNMR)等方法确定其结构.结果这18个化合物分别为12个紫杉烷:2a,5a,7B,9a,lOft,13a一六乙酰氧基一4(20),11-紫杉二烯(I),紫杉素(),紫杉一4(20),11-二烯一2a,5a,1O三乙酰氧基一143,2一甲基丁基(),1O羟基一2a,5a,14三乙酰氧基一4(2O),11-紫杉二烯(N),1-去羟基巴卡亭N(V),巴卡亭N(),巴卡亭(VI),7,9一去乙酰基巴卡亭(VE),10一去乙酰基云南红豆杉素(IX),19一乙酰氧一5一去乙酰基巴卡亭I(x),巴卡亭I(XI),taxuchinA(x);4
11、个木脂素:开环异落叶松树脂素(x),aconidendrin(XN),异紫杉脂素(XV),落叶松脂醇(XVI);2个其它化合物:肌醇甲醚(XVI),谷甾醇(x).其中化合物I,V,VI,x,XVI为心木部位首次分得的成分.结论云南红豆杉心木部位的化学成分同云南红豆杉其他部位有一定的差异,但就红豆杉属而言没有什么差异.关键词:云南红豆杉;心木;二萜;木脂素中图分类号:R284.1文献标识码:A文章编号:02532670(2007)070979一O4收稿日期:200610-15作者简介:陈雪英(1974一),女,福建福州人,博士,主要从事天然活性成分研究和新药开发.Email:xueyingc20
12、01yahoo.eom.en*通讯作者梁敬钰Tel:(025)85391289Fax:(025)83353855Email:jyliangplublie1.ptt.js.en980中草菊ChineseTraditionalandHerbalDrugs第38卷第7期2007年7,ElChemicalconstituentsinheartwoodofTaxusyunnanensisCHENXueying.LIANGJingyu(1.DepartmentofPhytochemistry,ChinaPharmaceuticalUniversity,Nanjing210009,China;2.Hangz
13、houMinshengPharmaceuticalGroupCo.,Ltd.,Hangzhou310011,China)Abstract:ObjectiveTointensivelyinvestigatethechemicalconstituentsintheheartwoodofTaxusyunnanensisChengetL.K.Fu.MethodsTheheartwoodwasextractedwithethanol.theethanolextractwassubjectedtotheextractionwithmethylenetrichloride,whichwassubmitted
14、tochromatographyonsilicagelandSephadexLH一20columntoisolatesomecompounds.Andtheirstructureswereelucidatedonthebasisofspectralanalysis(UV,IR,ESIMS,HNMR,C-NMR).ResultsThecompoundswereidentifiedas2a,5a,7p,9a,10p,13ahexaacetoxy一4(2O),11-taxadiene(I),taxusin(),taxa一4(2O),11-diene一2a,5a,10triacetoxy一14,2一m
15、ethybutyrate(m),10hydroxy一2a,5a,14triacetoxy一4(20),11-taxadiene(il/),1-dehydroxybaccatinil/(V),baccatin(VI),baccatinVI(),7,9-deacetylbaccatinVI(),1Odeacetyltaxuyannine(IX),1accetoxy一5一deacetylbaccatinI(X),baccatinI(X1),taxuchinA(X),secoisolariciresinol(xm),aconidendrin(XN),isotaxiresinol(XV),laricir
16、esinol(XVI),sequoitol(XVI),口一sitosterol(x).AmongthemcompoundsI,V,VI,Xl,X,XV1wereobtainedfromtheheartwoodofT.yunnanensisforthefirsttime.ConclusionThechemicalconstituentsintheheartwooddifferfromtheotherpartsofT.yunnanensis,butthereislittledifferencewithinthespeciesofTaxu$L.Keywords:TaxusyunnanensisChe
17、ngetL.K.Fu;heartwood;diterpenes;lignan云南红豆杉TaxusyunnanensisChengetL.K.Fu产于云南西北部及西部,四川西南部与西藏东南部,生于2o0O3500m高山地带,安徽黄山地区海拔10002000m的丘陵,不丹,缅甸北部也有分布.自1990年张宗平等口报道其化学成分以来,各国学者对其进行了广泛的研究,到目前为止已从云南红豆杉的各个部位分离得到紫杉烷二萜1o0多个.红豆杉是珍稀保护植物,红豆杉植物中,心木所占的重量比最大.为了进一步了解云南红豆杉心木部位的化学成分,本实验对研究很少的云南红豆杉心木进行化学成分研究,从中分得18个化合物,并
18、应用波谱解析和理化鉴定方法鉴定了它们的结构.1仪器,试剂及材料双目镜显微镜熔点测定仪;PerkinElemer983型红外光谱仪(KBr压片);PE一241MC型旋光仪;BrukerACF一300(HNMR,300MHz)及BrukerACF一500(13CNMR,125MHz),TMS为内标;VG型质谱仪.所用薄层色谱硅胶,柱色谱硅胶和高效GF薄层板为青岛海洋化工厂生产;所有试剂均为分析纯.实验药材为云南红豆杉的干燥心木,原植物由云南省保山林业局庞士高工程师采集并鉴定.2提取与分离云南红豆杉的心木10kg,粉碎后用75乙醇提取,浓缩所得浸膏用石油醚和氯仿依次萃取,其氯仿部位再通过硅胶柱色谱,
19、凝胶柱色谱,重结晶等方法共分得18个化合物:I(15mg),(30mg),(20mg),(20mg),V(20mg),VI(15mg),(20mg),(150mg),(60mg),X(20mg),(2Omg),X(20mg),xm(1g),XN(0.2g),XV(O.5g),XVI(50mg),XVI(O.1g),X(10mg).3结构鉴定化合物I:无色结晶,mp207209.IRv(cm_1):2977,2940,1747,1441,1375,1026,942.HNMR(CDCl3,500MHz):1.98(m,overlap,H一1),5.55(1H,dd,J一6.9,2.2Hz,H一2)
20、,3.24(1H,d,J一6.9Hz,H一3),5.32(1H,dd,J一6.9,2.2Hz,H一5),1.99(1H,m,overlap,H一613),1.78(1H,m,H一6a),5.45(1H,dd,J一11.5,5.3Hz,H一7),5.93(1H,d,J一10.6Hz,H一9),6.19(1H,d,J一1O.6Hz,H一10),5.98(1H,t,J一8.5Hz,H13),2.57(1H,ddd,J一15.O,9.5,9.5Hz,H一1413),1.51(1H,dd,J一14.9,8.4Hz,H一14a),1.79(3H,s,H一16),1.19(3H,s,H一17),2.22(3
21、H,s,H一18),1.04(3H,s,H一19),5.41(1H,s,H一20a),4.85(1H,s,H一20b),2.26,2.12,2.O7,2.O5,2.04,2.01(63H,s,6OAcCH3).CNMR(CDCl3,125MHz):48.77(C一1),70.18(C一2),42.79(C一3),169.86(C一中草菊ChineseTraditionalandHerbalDrugs第38卷第7期2007年7月?981?4),75.70(C一5),34.64(C一6),69.68(C一7),46.89(C一8),75.70(C一9),71.24(C一10),132.82(C一1
22、1),137.09(C一12),70.43(C一13),27.70(C一14),37.38(C一15),27.70(C一16),31.36(C一17),15.03(C一18),13.57(C一19),118.78(C一20),21.50,21.15,21.15,21.03,20.68,20.49(6OAcCH),170.15,169.94,169.54,169.54,169.49,169.11(6OAcCO).以上数据与文献报道_2对照基本一致,故该化合物鉴定为2a,5a,7口,9a,10口,13a一六乙酰氧基一4(20),11一紫杉二烯.化合物:无色结晶,mp129130.IR,HNMR和C
23、NMR数据与文献报道l3对照基本一致,故该化合物鉴定为紫杉素.化合物:无色结晶,mp105107;ESIMsm/z:564EM+NH4;IRvKBr(cm):2964,2934,1736,1645,1456,1373,1236,1014;HNMR(DMSO,300MHz):1.75(1H,brs,H一1),5.25(1H,dd,J一2.1,7.4Hz,H一2),2.85(1H,d,J一6.4Hz,H一3),5.20(1H,brs,H一5),1.75(2H,rn,overlap,2H一6),1.22(1H,brd,J一12.7Hz,H一7a),1.85(1H,rn,H一7b),2.422.23(
24、3H,overlap,H一9a,2,13b),1.64(1H,overlap,H一9b),5.96(1H,dd,J一5.5,12.0Hz,H一10),2.75(1H,dd,J一9.2,19.1Hz,H一13a),4.84(1H,dd,J一4.8,9.1Hz,H一14),1.59(3H,s,16一CH3),1.20(3H,s,17一CH3),2.04(3H,s,18一CH3),0.78(3H,s,19一CH3),5.26(1H,s,H一20a),4.80(1H,s,H一20b),1.51,1.40(2H,m,H一3),0.82(3H,t,J一7.4Hz,H一4),1.05(3H,d,J一6.9H
25、z,H一5),2.12,2.01,1.95(33H,s,3OAcCH);CNMR(DMSO,75MHz):58.85(C一1),69.75(C一2),40.13(C一3),142.09(C一4),77.47(C一5),28.41(C一6),33.06(C一7),39.02(C一8),43.32(C一9),69.42(C一10),134.68(C一11),134.41(C一12),39.24(C一13),69.25(C一14),36.80(C一15),25.09(C一16),31.43(C一17),20.42(C一18),21.95(C一19),116.67(C一20),174.69(C一1),
26、41.51(C一2),26.21(C一3),11.18(C一4),16.26(C一5),21.40,21.01,20.96(3OAcCH),169.43,169.09,169.02(3OAcCO).以上数据与文献报道_4对照基本一致,故该化合物鉴定为紫杉一4(20),11一二烯一2a,5a,10口一三乙酰氧基一14口,2一甲基丁基.化合物:无色结晶,mp184186.IR,ESIMS,HNMR和CNMR数据与文献报道_5对照基本一致,故该化合物鉴定为10B一羟基一2a,5a,1413一三乙酰氧基一4(20),11一紫杉二烯.化合物V:无色结晶,mp234236.IRvKBr(cm):1742,
27、1373,1240,1229,1016.HNMR(CDCl,300MHz):5.56(1H,d,J一6.2Hz,H一2),2.87(1H,d,J一5.8Hz,H一3),4.99(1H,d,J一8.9Hz,H一5),5.52(1H,t,J一9.6Hz,H一7),5.92(1H,d,J一11.2Hz,H一9),6.14(1H,d,J一10.2Hz,H10),5.92(1H,overlap,H一13),1.79(3H,s,H一16),1.13(3H,s,H一17),1.96(3H,s,H一18),1.54(3H,s,H一19),4.50(1H,d,J一7.9Hz,H一20a),4.20(1H,d,J
28、一7.8Hz,H一20b),2.16,2.16,2.09,2.07,2.02,2.02(63H,s,6OAcCH.).以上数据与文献报道l3对照基本一致,故该化合物鉴定为1一去羟基巴卡亭.化合物:无色结晶,mp234236C.ESIMS,IR,HNMR和CNMR数据与文献报道l6对照基本一致,故该化合物鉴定为巴卡亭.化合物:无色结晶,mp229231C.ESIMS,IR,HNMR和”CNMR数据与文献报道_7对照基本一致,故该化合物鉴定为巴卡亭.化合物:无色结晶,mp216218;IR,HNMR和”CNMR数据与文献报道_8对照基本一致,故该化合物鉴定为7,9一去乙酰基巴卡亭.化合物:无色结晶
29、,mp127130.ESIMSm/z:828.3M+Na,844.2M+K,804.3EM+H一,840.3M+C1,840.3M+CH3COO一.IRv(cm):3447,1735,1707,1647,1543,1516,1454,1379,1269,1068,707.HNMR:5.68(1H,d,J一7.0Hz,H一2),3.90(1H,d,J一7.1Hz,H一3),4.92(1H,brd,J一7.8Hz,H一5),2.56(1H,ddd,J一14.5,9.4,6.5Hz,H一6B),1.84(1H,rn,overlap,H一6a),4.21(1H,d,J一8.6Hz,H一7),5.19(
30、1H,s,H一10),6.19(1H,t,J一8.6Hz,H一13),2.28(2H,dd,J一8.8,3.6Hz,H一14),1.13(3H,s,16一CH3),1.24(3H,s,17一CH3),1.75(3H,s,18一CH),1.81(3H,s,19一CH),4.30(1H,d,J一8.4Hz,H一20a),4.20(1H,d,J一8.6Hz,H一20b),4.67(1H,brs,H一2),5.57(1H,brd,J一7.7Hz,H一3),2.20(2H,t,J一7.6Hz,H一5),1.58(2H,rn,H一6),1.25(4H,rn,overlap,H一7,8),0.84(3H,t
31、,J一6.7Hz,H一9),6.29(1H,d,J一8.2Hz,3-NH),7.407.32(5H,rn,3一PhH),8.11(2H,dd,J一7.82,1.4Hz,2一.一Bz),7.61(1H,t,J一?982?中草蒋ChineseTraditionalandHerbalDrugs第38卷第7期2007年7月7.3Hz,2-pBz),7.50(2H,t,J一7.5Hz,2一mBz),2.34(3H,s,4-OAcCH.).以上数据与文献报道I9对照基本一致,故该化合物鉴定为10一去乙酰基云南红豆杉素.化合物x:无色结晶(P/E),mp229231.ESIMS,IR,HNMR和CNMR数据
32、与文献报道口阳对照基本一致,故该化合物鉴定为1fi.乙酰氧一5一去乙酰基巴卡亭I.化合物:无色结晶,mp298300.ESIMS,IR,HNMR和CNMR数据与文献报道l_3对照基本一致,故该化合物鉴定为巴卡亭I.化合物x:无色结晶,mp265267.IRvKBr(cm一):3512,1740,1374,1228,1031.HNMR(CDC1,500MHz):1.76(1H,overlap,H一1),5.58(1H,d,J一3.3Hz,H一2),2.95(1H,d,J一3.7Hz,H一3),4.22(1H,t,J一3.0Hz,H一5),2.13(1H,m,overlap,H一6/3),1.76
33、(1H,1TI,overlap,H一6a),5.49(1H,dd,J一12.1,4.3Hz,H一7),6.01(1H,d,J一10.9Hz,H一9),6.18(1H,d,Jl1.1Hz,H一10),5.89(1H,dt,J一8.2,1.4Hz,H一13),2.75(1H,ddd,J一15.0,9.4,9.4Hz,H一148),1.44(1H,dd,J=15.2,6.8Hz,H一14a),1.72(3H,s,H一16),1.13(3H,s,H一17),2.25(3H,s,H一18),1.25(3H,s,H一19),3.53(1H,d,J=5.2Hz,H一20a),2.28(1H,d,J一5.2H
34、z,H一20b),2.22,2.12,2.O8,2.04,1.973,1.966(33H,s,6OAcCH3).CNMR(CDC13,125MHz):47.85(C一1),69.96(C一2),39.05(C一3),58.57(C一4),77.60(C一5),31.15(C一6),68.95(C一7),46.50(C一8),75.53(C一9),71.13(C一10),134.45(C一11),137.97(C一12),70.21(C一13),28.79(C一14),38.35(C一15),26.94(C一16),31.28(C一17),15.17(C一18),13.69(C一19),49.6
35、2(C一20),21.49,21.30,21.25,20.93,20.75,2O.52(6OAcCH3),17O.04,169.67,169.60,169.10,168.99,168.14(6OAcCO).以上数据与文献报道I1妇对照基本一致,故该化合物鉴定为taxuchinA.化合物xnl:无色方晶,mp105107.ESI-MS,IR,HNMR和CNMR数据与文献报道1.对照基本一致,故该化合物鉴定为开环异落叶松树脂素.化合物XN:无色结晶,mp229231.ESI-MS,IR,HNMR和CNMR数据与文献报道1.对照基本一致,故该化合物鉴定为aconidendrin.化合物XV:无色结晶
36、,mp171173.ESI-MS,IR,HNMR和CNMR数据与文献报道1.对照基本一致,故该化合物鉴定为异紫杉脂素.化合物XVI:白色针状结晶,mp167169.ESIMS,IR,HNMR和CNMR数据与文献报道对照基本一致,故该化合物鉴定为落叶松脂醇.化合物x:无色结晶,mp232234.ESIMS,IR,HNMR和CNMR数据与文献报道I1对照基本一致,故该化合物鉴定为肌醇甲醚.化合物x:无色针晶,mp140-142.TLC以浓硫酸一香草醛显色呈红色斑点.与谷甾醇对照品TLC对照,Rf值及显色行为一致,且混合斑点为一个点;再将其与一谷甾醇对照品混合后测熔点,混合熔点不下降.因此该化合物确
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