全 文 ：团花树中一个新的环烯醚萜苷*
刘玲丽1,2,朱暋锋1,邸迎彤1,郝小江1
**,何红平1**
(1中国科学院昆明植物研究所植物化学与西部植物资源持续利用国家重点实验室,
云南 昆明暋650204;2中国科学院研究生院,北京暋100049)
摘要:从茜草科团花属植物团花树 (Neolamarckiacadamba)枝叶的甲醇提取物中分离得到两个环烯醚萜
苷,其中一个为新的环烯醚萜苷,利用现代波谱学技术鉴定了其结构为 殼13,14灢plumieride,并命名为
plumierideB.
关键词:团花树;茜草科;环烯醚萜苷
中图分类号:Q946暋暋暋暋 暋暋文献标识码:A暋暋暋 暋暋暋暋文章编号:0253灢2700(2010)04灢378灢03
PlumierideB,aNewIridoidfromNeolamarckia
cadamba(Rubiaceae)
LIULing灢Li1,2,ZHUFeng1,DIYing灢Tong1,HAOXiao灢Jiang1** ,HEHong灢Ping1**
(1StateKeyLaboratoryofPhytochemistryandPlantResourcesinWestChina,Kunming
InstituteofBotany,ChineseAcademyofSciences,Kunming650204,China;
2GraduateUniversityofChineseAcademyofSciences,Beijing100049,China)
Abstract:Anewiridoid,namedplumierideB,wasisolatedfromtheleavesofNeolamarckiacadamba,to灢
getherwithaknowniridoid.Thenewstructurewasdeterminedtobe殼13,14灢plumieridebyspectroscopic
methodsespecialy2D灢NMRanalysis.
Keywords:Neolamarckiacadamba;Iridoid;Rubiaceae
暋 ThespeciesNeolamarckiacadamba,previ灢
ously named Anthocephalus chinensis,is a
memberofthetribeNaucleeaeinthefamilyRu灢
biaceaeanddistributedwidelyinthesouthof
China(Luoetal灡,1999;Zhongetal灡,1990).
Ithasbeenusedtraditionalyin“dai暠ethnophar灢
macybythelocalethnicpeopleinYunnanProv灢
inceofChinatotreatinflammation,feverand
pruritus(CompiledgroupofYunnanTraditional
ChineseMedicine,1977).Moreover,inIndia,it
hasbeenusedinAyurvedicmedicineforblooddis灢
easesanddysentery(Takayamaetal灡,2003).So
far,thechemicalconstituentsof N灡cadamba
havebeenextensivelyinvestigatedanddifferent
typesofcompoundshavebeenreported,inclu灢
dingmonoterpenoidindolealkaloidsandiridoids
(Zhouetal灡,2008;Brownetal灡,1976;Handa
etal灡,1984,1983).Aspartofacontinuingefort
todiscovernovelsecondarymetabolitesfrom Yun灢
nanlocalmedicinalplants(Zhouetal灡,2008),a
furtherchemicalinvestigationontheleavesof
N灡cadambawascarriedout,whichledtoobtain
anewiridoid,plumierideB(1)andaknowniri灢
doid,plumieride(2)(Abeetal灡,1988).This
paperreportstheisolationandstructureelucida灢
tionofplumierideB(1).
云 南 植 物 研 究暋2010,32(4):378~380
ActaBotanicaYunnanica暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋DOI:10灡3724/SP灡J灡1143灡2010灡10052
*
**
Foundationitem:TheNationalScienceFoundationofYunnanProvince(2009CD112)
Authorforcorrespondence;E灢mail:haoxj@mail灡kib灡ac灡cn,hehongping@mail灡kib灡ac灡cn;Tel:+86灢871灢5223263.fax:+86灢871灢5223070
Receiveddate:2010灢03灢11,Accepteddate:2010灢05灢17
作者简介:刘玲丽 (1984-)女,硕士研究生,研究方向为天然药物化学。E灢mail:liulingli@mail灡kib灡ac灡cn
ResultsandDiscussion
PlumierideB(1)wasisolatedaswhitesol灢
id.ItsmolecularformulawasdeducedtobeC21
H24O11onthebasisofthepositiveHRESIMSat
m/z475灡1210 [M+Na]+ (calcd475灡1216),
whichindicatedtendegreesofunsaturationin1.
Intensiveabsorptionbandsat1764and1683cm灢1
observedinIRspectrumsuggestedthepresence
ofcarbonylgroups.The13C NMRandDEPT
spectra(Table1)revealed21carbonsignalsdue
tothreequaternarycarbons,thirteenmethines,
two methylenes,twocarbonylsandone me灢
thoxygroup.The13CNMRdataalsoexhibited
characteristicsignalsofiridoids[毮C93灡8(d,C灢
1),152灡3(d,C灢2),111灡3(s,C灢4)].Further灢
more,italsodisplayedasignalofaquaternary
carbon[毮C97灡3(s,C灢8)],atypicalsignalofa
ratherraregroupofiridoidscontainingaspiro灢
lactonering.Inthe1Hand13CNMRspectra,an
anomericprotonsignalat毮H4灡64(1H,d,J=7灡9
Hz,H灢1曚),andcarbonsignals[毮C99灡8(d,C灢1曚),
74灡7(d,C灢2曚),77灡8(d,C灢3曚),71灡4(d,C灢4曚),
78灡4 (d,C灢5曚),62灡5 (t,C灢6曚)],indicatedthe
presenceofaglucosemoietyin1.Anextensive
comparisonof1Hand13C NMRspectraofcom灢
pound1withplumieride(2)(Abeetal灡,1988)
suggestedthattheysharedsimilarplanarstructure
exceptforadoublebondbetweenC灢13andC灢14in
compound1insteadofahydroxylatC灢13inplumi灢
eride(2).
The1H灢1HCOSYrevealedthat1possessed
twofragments,(a):(C灢1toC灢9,C灢9toC灢5,
C灢6andC灢7)and(b):(C灢13toC灢14)(Fig灡1).
IntheHMBCspectrumofcompound1,thecor灢
relationsfrom H灢14toC灢11andC灢12indicated
thelinkageofunitb,theolefiniccarbonandthe
carbonyl.Furthermore,theHMBCcorrelations
ofH灢9/C灢8,andH灢9/C灢10suggestedthefrag灢
mentalinkedtothefragmentbviaaquaternary
carbonandtwoolefiniccarbons.Thesimilar1H
and13CNMRdataofcompounds1and2atC灢6,C灢
7,C灢8,C灢9,C灢10andC灢12indicatedthatcom灢
pound1hadasamespiro灢lactoneringandthesame
relativeconfigurationofC灢8asplumieride(2).In
addition,thecarboxylicmethylestergroupwaspo灢
sitionedatC灢4basedoncorrelationsofH灢3/C灢15
andH3灢16/C灢15intheHMBCspectrum.TheHM灢
BCcorrelationofH灢1/C灢1曚establishedthelinkage
ofglucosesubstituenttoC灢1.Detailed2DNMRa灢
nalysisfurtherestablishedtheplanarstructureof1.
Therelativeconfigurationof1wasdeterminedby
ROESYanalysisandcouplingconstant.Theorien灢
tationsofH灢1,H灢5andH灢9wereassignedtobe
thesameascompound2becauseoftheirapproxi灢
matechemicalshiftsandcouplingconstants.The
couplingconstantofH灢1曚(J=7灡9)deducedthe
glucosetobea毬灢oriented,andtheglucosewas
assignedtobeD灢glucose,thesameasotheriri灢
doisofthistype (Abeetal灡,1984).Thus,
compound1wasdeterminedasshowninFig灡2.
Experimental
GeneralExperimentalProcedures暋1Dand2D NMR
spectrawererecordedonBrukerAM灢400andDRX灢500
spectrometerswithTMSasinternalstandard,respective灢
ly.OpticalrotationsweremeasuredonaJASCODIP灢370
暋暋暋暋 暋暋
Fig灡1暋KeyHMBCandCOSYcorrelationsofcompound1 Fig灡2暋Structuresofcompounds1and2
9733期暋暋暋暋LIULing灢Lietal灡:PlumierideB,aNewIridoidfrom Neolamarckiacadamba(Rubiaceae)暋暋暋 暋
表1暋化合物PlumierideB(1)与Plumieride(2)的氢谱和碳谱数据
Table1暋The1DNMRdataofPlumierideB(1)and
Plumieride(2)inCD3OD
No.
1
毮H 毮C
2
毮H 毮C
1 5灡29(d,4灡4) 93灡8d 5灡26(d,4灡7) 94灡1d
3 7灡47(s) 152灡3d 7灡48(s) 152灡4d
4 111灡3s 111灡0s
5 3灡88(m) 39灡9d 3灡91(m) 40灡3d
6 6灡46(dd,5灡5,2灡9)141灡1d 6灡45(dd,5灡6,2灡5)141灡4d
7 5灡50(dd,5灡5,1灡6)129灡8d 5灡51(dd,5灡6,2灡0)130灡0d
8 97灡3s 97灡9s
9 2灡95(dd,6灡2,3灡6) 50灡9d 2灡93(dd,7灡7,4灡8) 50灡5d
10 7灡36(s) 150灡8d 7灡34(s) 150灡2d
11 130灡1s 138灡6s
12 172灡3s 172灡8s
13 6灡46(m) 126灡7d 6灡45(m) 63灡5d
14 5灡49(dd,14灡4,1灡6)121灡8t 1灡39(d,6灡5) 22灡4q
14 6灡25(dd,14灡4,1灡6)
15 168灡4s 168灡4s
16 3灡74(s) 51灡9q 3灡74(s) 51灡9q
1曚 4灡64(d,7灡9) 99灡8d 4灡66(d,7灡9) 100灡0d
2曚 3灡12(m) 74灡7d 3灡17(m) 74灡6d
3曚 3灡31(m) 77灡8d 3灡33(m) 77灡8d
4曚 3灡23(m) 71灡4d 3灡18(m) 71灡3d
5曚 3灡24(m) 78灡4d 3灡28(m) 78灡4d
6曚 3灡62(dd,10灡5,5灡5) 62灡5t 3灡67(dd,11灡0,5灡5) 62灡5t
3灡84(m) 3灡86(m)
a1Hand13CNMRspectrawereobtainedat400and100MHz,
respectively
bCouplingconstantswerepresentedin Hertz,unlessotherwise
indicated,alprotonsignalsintegrateto1H
digitalpolarimeter.A Tenor27spectrophotometerwas
usedforscanningIRspectroscopy.ESIMSwasrecordedon
afinniganMAT90instrument,HRESIMSspectrumonVG
Auto Spec灢3000 spectrometer.Column chromatography
wasperformedonsilicagel(200-300 mesh;Qingdao
MarineChemicalInc.,Qingdao,People曚sRepublicof
China),SephadexLH灢20(40-70毺m,AmershamPhar灢
maciaBiotechAB,Uppsala,Sweden),andLichroprep
RP灢18gel(40-63毺m,MerckDarmstadt,Germany).
Plantmaterial暋Theair灢driedleavesofN灡cadamba
(25kg)werecolectedinXishuangbanna,YunnanProv灢
inceofChinainJuly,2008.Theplantwasidentifiedby
Prof.XunGong,ChineseAcademyofScience.Aspeci灢
menofthisplant(No.0766725)wasdepositedinthe
KunmingInstituteofBotany,Kunming,China.
Extractionandisolation暋Thedriedandpowdered
leavesofN灡cadamba (25kg)wererefluxedthreetimes
with90% EtOH.Thesolventwasevaporatedinvacuoto
obtainacrudeextract.Aftersuspendinginwater,the
crudeextractwasextractedsuccessivelywithpetroleume灢
ther,EtOAc,andn灢BuOH.Then灢BuOHextract(180
g)wassubjectedonRP(reversephase)灢18elutingwith
H2O灢MeOH (from10暶1to0暶10)toaffordfivefrac灢
tions(I灢V).FractionIV (20g)wasfurtherchromato灢
graphedonsilicagelusingCHCl3灢MeOH [CHCl3灢MeOH
(10暶1),(5暶1)and(3暶2)]togivethreefractionsA,
B,andC.FractionBwaspurifiedbySephadexLH灢20(e灢
lutedwithMeOH)andaseriesofsilicagelcolumnchro灢
matographytoaffordcompounds1(12 mg)and2(53
mg).
PlumierideB(1):C21H24O11,whitesolid;[毩]20D =
-93灡5 (c=0灡12,MeOH);PositiveESIMS m/z475
[M + Na]+ ;HRESIMS m/z475灡1210 [M + Na]+
(calcd475灡1216).IR 毻KBrmax cm灢1:3423,1764,1683,
1639,1444,1294,1178,1081,1035,997,871;1Hand
13CNMRdata,seeTable1.
Plumieride(2):C21H26O12,whitesolid,[毩]24D =-
38灡1[c=0灡32,CHCl3+MeOH (1暶1)];1Hand13C
NMRdata,seeTable1.
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