全 文 ：岩芋中的一个新苯丙素苷*
唐贵华1,2,王跃虎1,龙春林1**
(1中国科学院昆明植物研究所,云南 昆明暋650204;2中国科学院研究生院,北京暋100049)
摘要:从岩芋 (Remusatiavivipara)干燥的球茎中分离得到10个化合物,其中一个为新的苯丙素苷,经
波谱学分析及酸水解的方法确定该新化合物的结构为Caffeylalcohol灢3灢O灢b灢D灢glucopyranoside。已知化合
物包括3个苯丙素类 (松柏苷,caffeylalcohol和松柏醇),3个新木脂素 [4,7,9,9灢tetrahydroxy灢3,3灢
dimethoxy灢8灢O灢4灢neolign灢7灢ene,(7R ,8S)灢D7灢3,3灢dimethoxy灢4,7,9,9灢tetrahydroxy灢8灢O灢4灢neoli灢
gnan灢7灢O灢b灢D灢glucopyranoside,以 及 dehydrodiconiferylalcohol灢4灢b灢D灢glucoside],1 个 酰 胺 [(2E,
4E)灢N灢isobutyl灢2,4灢decadienamide],1个甾体皂苷 (methylproto灢taccaoside)和1个三萜皂苷 (saxifra灢
gifolinB)。所有化合物均为首次从岩芋属植物中分离得到。
关键词:岩芋;天南星科;苯丙素苷
中图分类号:Q946暋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)01灢087灢04
ANewPhenylpropanoidGlucosidefrom
Remusatiavivipara(Araceae)
TANGGui灢Hua1,2,WANGYue灢Hu1,LONGChun灢Lin1**
(1KunmingInstituteofBotany,ChineseAcademyofSciences,Kunming650204,China;
2GraduateUniversityofChineseAcademyofSciences,Beijing100049,China)
Abstract:Anewphenylpropanoidglucoside,caffeylalcohol灢3灢O灢b灢D灢glucopyranoside,togetherwithnine
knowncompounds,wasisolatedfromthedrycormsofRemusatiaviviparaSchott.Thestructureofthenew
compoundwasdeterminedbythespectroscopicmethodandacidichydrolysis.Theknowncompoundsinclud灢
edthreephenylpropanoids(coniferin,caffeylalcoholandconiferylalcohol),threeneolignans[4,7,9,9曚灢
tetrahydroxy灢3,3曚灢dimethoxy灢8灢O灢4曚灢neolign灢7曚灢ene,(7R ,8S)灢D7灢3,3曚灢dimethoxy灢4,7,9,9曚灢tetra灢
hydroxy灢8灢O灢4曚灢neolignan灢7灢O灢b灢D灢glucopyranoside,anddehydrodiconiferylalcohol灢4灢b灢D灢glucoside],anamide
[(2E,4E)灢N灢isobutyl灢2,4灢decadienamide],asteroidsaponin(methylproto灢taccaoside)andatriterpenoid
saponin(saxifragifolinB).AlcompoundswereisolatedfromthegenusRemusatiaforthefirsttime.
Keywords:Remusatiavivipara;Araceae;phenylpropanoidglucoside
暋暋Remusatiavivipara(Lodd.)Schott(Arace灢
ae)isaperennialherbmainlyepiphyticonrocks
andcliff灢ledgesinthesubtropicalforestsofAsia
suchasSW China,SriLanka,Nepal,India,
Myanmar,Thailand,Vietnam andIndonesia,
andCameroonin WestAfrica (Li,1979).Its
cormsarestronglypoisonousbutusedexternaly
totreatbreastmastitis,abscesses,acariasisand
云 南 植 物 研 究暋2010,32(1):87~90
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09163
*
**
Foundationitems:ThisworkwerefundedbygrantsoftheMinistryofEducationofChina(B08044& MUC985灢3灢3),theMinis灢
tryofScienceandTechnologyofChina(2008FY110400灢2灢2&2005DKA21006),andtheKnowledgeInnovationProgramof
theChineseAcademyofSciences
Authorforcorrespondence;E灢mail:long@mail灡kib灡ac灡cn;Tel/Fax:+86灢871灢5223233
Receiveddate:2009灢09灢01,Accepteddate:2009灢11灢11
作者简介:唐贵华 (1983-)男,在读硕士研究生,主要从事民族药物化学研究。
so on (Health Bureau of Yunnan Province,
1973).Uptonow,thechemicalconstituentsof
theplanthavenotbeenreportedyet.Soaphy灢
tochemicalinvestigationofthe R灡viviparawas
carriedout,whichledtotheisolationofanew
phenylpropanoidglucoside(1)fromthecorms,
togetherwithnineknowncompounds:coniferin
(2)(Sugiyamaetal灡,1993),caffeylalcohol(3)
(QuideauandRalph,1992),coniferylalcohol(4)
(Quideauand Ralph,1992),4,7,9,9曚灢tetra灢
hydroxy灢3,3曚灢dimethoxy灢8灢O灢4曚灢neolign灢7曚灢ene(5)
(Lourithetal灡,2005),(7R ,8S)灢D7曚灢3,3曚灢
dimethoxy灢4,7,9,9曚灢tetrahydroxy灢8灢O灢4灢ne灢
olignan灢7灢O灢b灢D灢glucopyranoside (6)(Maet
al灡,2008),dehydrodiconiferylalcohol灢4灢b灢D灢gluco灢
side(7)(Yeetal灡,2004),(2E,4E)灢N灢
isobutyl灢2,4灢decadienamide (8)(Yasudaetal灡,
1981),methylproto灢taccaoside(9)(Idakaetal灡,
1991)andsaxifragifolinB (10)(Walthoetal灡,
1986).Thestructureelucidationofthenewcom灢
poundisreported.
ResultsandDiscussion
Compound1wasobtainedaswhiteamor灢
phouspowder.NegativeHRESIMSanalysisof
thecompoundexhibitedaquasimolcularionpeak
atm/z327灡1083 [M灢H]灢 (calcd,327灡1079),
correspondingtothemolecularformulaC15H20
O8for1.ItsIRspectrum showedabsorption
bandsforhydroxygroups (3441cm灢1)anda
phenylring (1631cm灢1,1611cm灢1 and1515
cm灢1).Inthe13C NMRspectrum of1(Table
1),15carbonsignalsincludingtwooxygenated
methylenes[毮C63灡8(C灢9),62灡4(C灢6曚)],ten
methines[毮C131灡5(C灢7),127灡5(C灢8),123灡4
(C灢6),117灡0 (C灢5),116灡5 (C灢2),104灡4 (C灢
1曚),78灡4 (C灢5曚),77灡6 (C灢3曚),74灡9 (C灢2曚),
71灡4(C灢4曚)]andthreequaternarycarbons[毮C
148灡1(C灢4),146灡9(C灢3),130灡8(C灢1)]were
observed.The1H NMRspectrumof1(Table
1)displayedsignalsforanABXbenzenering[毮
H7灡31(1H,d,J=1灡6Hz,H灢2),6灡95(1H,
dd,J=8灡2,1灡6Hz,H灢6)and6灡77(1H,d,J
=8灡2Hz,H灢5)],atrans灢alylicmoiety[毮 H
6灡48(1H,d,J=15灡9Hz,H灢7),6灡20(1H,
dt,J=15灡9,6灡0Hz,H灢8)and4灡18(2H,dd,
J=6灡0,1灡1 Hz,H灢9)].Inaddition,its1H
NMRspectrumshowedananomericprotonsig灢
nalat毮4灡75(1H,d,J=7灡1Hz,H灢1曚),indi灢
catingthepresenceofasugarmoietyin1.Acid
hydrolysisof1yieldedaD灢glucoseanddeter灢
minedbyTLCanditsopticalrotation([毩]26灡3D
= +50灡3(c0灡055,H2O)).Thecouplingcon灢
stant(J =7灡1Hz)ofH灢1曚andH灢2曚deduced
theglucosetobea b灢anomericconfiguration.
Table1暋1H (500MHz)and13C(100MHz)NMRData
of1inCD3OD(毮inppm,JinHz)
No. 毮C 暋暋暋暋毮H
1 130灡8(s)
2 116灡5(d) 7灡31(d,J=1灡6)
3 146灡9(s)
4 148灡1(s)
5 117灡0(d) 6灡77(d,J=8灡2)
6 123灡4(d) 6灡95(dd,J=8灡2,1灡6)
7 131灡5(d) 6灡48(d,J=15灡9)
8 127灡5(d) 6灡20(dt,J=15灡9,6灡0)
9 63灡8(t) 4灡18(dd,J=6灡0,1灡1)
1曚 104灡4(d) 4灡75(d,J=7灡1)
2曚 74灡9(d) 3灡49(m)
3曚 77灡6(d) 3灡47(m)
4曚 71灡4(d) 3灡39(m)
5曚 78灡4(d) 3灡43(m)
6曚 62灡4(t) 3灡91
(dd,J=12灡1,2灡2)
3灡71(dd,J=12灡1,5灡5)
Inthe HMBC spectrum (Fig灡1), H灢7
showedcorrelationstoC灢2andC灢6,and H灢8
showedtoC灢1,meanwhile H灢2and H灢6also
showedcorrelationstoC灢1.Thesecorrelations
indicatedthatthepropenolmoietywasplacedat
C灢1.TheassignmentsofC灢3andC灢4wereas灢
certainedbytheHMBCcorrelationfrom H灢5to
C灢1andC灢3,H灢6toC灢2andC灢4,H灢2toC灢4
andC灢6.Thelinkageoftheb灢D灢glucosesubstit灢
uenttoC灢3wasestablishedbythecorrelation
from H灢1曚toC灢3.Therefore,1waselucidated
ascaffeylalcohol灢3灢O灢b灢D灢glucopyranoside.
88暋暋暋暋暋暋暋暋暋暋暋暋 暋暋暋暋暋暋暋云暋南暋植暋物暋研暋究暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋第32卷
Fig灡1暋 KeyHMBCcorrelationsof1
Experimental
General暋MCIgelCHP20P(75灢150毺m,Mitsubishi
ChemicalCorporation,Tokyo),silicagelG (300灢400
mesh,QingdaoMakal GroupCo.,Ltd),C18silicagel
(40灢75毺m,FujiSilysiaChemicalLtd.),silicagelH (10灢
40毺m),and Sephadex LH灢20 (GE Healthcare Bio灢
XciencesAB)wereusedforcolumnchromatography,and
silicagelGF254 (Qingdao),forpreparativeTLCaspro灢
coatedplates.TheTLCspotswerevisualizedunderUV
lightandbydippinginto5% H2SO4inalcohol,folowed
byheating.SemipreparativeHPLCwascarriedoutonan
Agilent1200seriespumpequippedwithadiodearrayde灢
tectorandaZorbaxSB灢C18column(5灡0毺m,f9灡4暳250
mm).1Dand2DNMRspectrawereobtainedonBRUK灢
ERAM灢400andDRX灢500spectrometerswithTMSasin灢
ternalstandard.MSanalyseswereperformedonaVG
AutoSpec灢3000 massspectrometer.Opticalrotations
weremeasuredwithaHoribaSEPA灢300polarimeter.UV
spectraweredeterminedonaShimadzudouble灢beam210A
spectrometer.IRspectra were measuredonaBio灢Rad
FTS灢135infraredspectrophotometerwithKBrdisks.
Plantmaterial暋ThecormsofR灡viviparawerecol灢
lectedinOctober2008fromLuxiCity,YunnanProvince,
People曚sRepublicofChinaandidentifiedby Dr.Hu
Guang灢Wan(KunmingInstituteofBotany,ChineseA灢
cademyofSciences).Avoucherspecimen(No.LX005)
wasdepositedattheLaboratoryofEthnobotany,Kun灢
mingInstituteofBotany.
Extractionandisolation暋Theair灢dried,powdered
cormsofR灡vivipara(1灡0kg)wasexhaustivelyextracted
with95% EtOH (3times)andthenwithMeOH (twice)
underreflux.Thecrudeextract(68g)wassuspendedin
H2OandthenpartitionedsuccessivelywithEtOAcandn
灢BuOHtoobtaintwofractions:EtOAc(A,13g),andn
灢BuOH (B,6g).Fr.Bwassubjectedtocolumnchroma灢
tographyoverMCIgelCHP20P with MeOH灢H2O (a
gradientelutionofincreasingconcentration)andgained
fivefractions(B1灢B5).Eachfractionwasfurtherpurified
byrepeatedcolumnchromatography(C18silicagel,Seph灢
adexLH灢20,silicagel)andthensemipreparativeHPLC
toobtaincompounds.FromFr.B1,compounds1(4灡2
mg)and2(6灡1mg)wereobtained.Fr.B2 gavecom灢
pound6 (4灡3mg).Fr.B4affordedcompounds9(30灡7
mg)and10(15灡2mg).Fr.Awassubjectedtoreversed灢
phasecolumnchromatographyoverC18silicageleluting
withagradientofincreasingMeOHinH2O (5%灢95%)
andobtainedfivefractions(A1灢A5).Subsequently,Fr.
A2andA4werechromatographedonSephadexLH灢20col灢
umn,repeatedsilicagelcolumnandthenfolowedby
semipreparativeHPLC,togivecompounds3(7灡5mg),
4(4灡6mg),5(5灡6mg),and7(4灡0mg)fromFr.A2
and8(3灡5mg)fromFr.A4.
Acidhydrolysisof1:Asolutionof1(4灡0mg)in2
mol·L灢1 HCl(2ml)washeatedat90曟for4h.Aftere灢
vaporatingtheacidicsolution,thereactionmixturewas
subjected to column chromatography over silica gel
(CHCl3灢MeOH灢H2O,3暶1暶0灡05)toyieldaD灢glucose
(1灡1mg),whichwasdetectedbyTLCcomparingwith
theauthenticsampleanditsopticalrotation,[毩]26灡3D +
50灡3(c0灡055,H2O).
Caffeylalcohol灢3灢O灢b灢D灢glucopyranoside (1):White
amorphouspowder;[毩]25灡5D -35灡2(c0灡125,MeOH);UV
(MeOH)毸 MeOHmax (log毰)263 (3灡54)nm;IR毻 KBrmaxcm灢1:
3441,1631,1610,1515,1283,1074;1Hand13CNMR
(seeTable1);ESIMS m/z363 [M +Cl]灢,327 [M灢
H]灢;HRESIMS m/z327灡1083 [M灢H]灢 (calcdforC15
H19O8,327灡1079).
Caffeylalcohol (3): White amorphous powder
(MeOH);1H NMR (CD3OD,400 MHz)毮H:6灡86
(1H,d,J=1灡7Hz,H灢2),6灡68 (1H,d,J=8灡1
Hz,H灢5),6灡71 (1H,dd,J=8灡1,1灡7 Hz,H灢6),
6灡42(1H,d,J=15灡8Hz,H灢7),6灡10(1H,dt,J
=15灡8,6灡0Hz,H灢8),4灡16(2H,dd,J=6灡0,1灡3
Hz,H灢9);ESIMS m/z165 [M灢H]灢.Thiscompound
wasdeterminedaccordingtoits MSspectrum andby
comparingits1HNMRdatawithcompounds1and4.Its
1HNMRdatawerereportedforthefirsttime.
Acknowledgment:WethankMr.ZhangJia灢Xian,inLuxi
CityofYunnanProvince,forhishelptocolecttheplant
material.
981期暋暋暋TANGGui灢Huaetal灡:ANewPhenylpropanoidGlucosidefrom Remusatiavivipara(Araceae)暋暋暋暋
References:
LiH (李恒),1979.FloraofChina[M].Beijing:SciencePress,
13 (2):58—59
HealthBureauofYunnanProvince(云南省卫生局),1973.Yun灢
nanZhongCaoYaoXuJi(云南中草药续集)[M].Kun灢
ming:YunnanPeoplesPublishingHouse,354—355
IdakaK,HiraiY,ShojiJ,1991.StudiesontheconstituentsofPal灢
maeplants.V.SteroidsapninsandflavonoidsofleavesofPhoe灢
nixrupicolaT.Anderson,P灡loureiriKunth,P灡reclinateN.J.
Jacquin,andArecastrumremanzofianumBeccari[J].Chemical
&PharmaceuticalBuletin,39(6):1455—1461
WalthoJ,WiliamsDH,MahatoSBetal灡,1986.Structureelu灢
cidationoftwotriterpenoidtetrasaccharidesfrom Androsace
saxifragifolia[J].JournaloftheChemicalSociety,Perkin
Transactions1,8:1527—1531
LourithN,KatayamaT,SuzukiT,2005.Stereochemistryand
biosynthesisof8灢O灢4曚neolignansinEucommiaulmoides:
diastereoselectiveformationofguaiacylglycerol灢8灢O灢4曚灢(si灢
napylalcohol)ether[J].JournalofWoodScience,51(4):
370—378
MaJP,TanCH,ZhuDY,2008.Glycosidicconstituentsfrom
CarpesiumcernuumL.[J].JournalofAsianNaturalProd灢
uctsResearch,10(6):565—569
QuideauS,RalphJ,1992.Facilelarge灢scalesynthesisofconifer灢
yl,sinapyl,andp灢coumarylalcohol[J].JournalofAgri灢
culturalandFoodChemistry,40(7):1108—1110
SugiyamaM,NagayamaE,KikuchiM,1993.Lignanandphe灢
nylpropanoidglycosidesfrom Osmanthusasiaticus [J].
Phytochemistry,33(5):1215—1219
YasudaI,TakeyaK,ItokawaH,1981.Structuresofamides
from AsiasarumheterotropoidesMaek.var灡mandshuricum
Maek.[J].Chemical&PharmaceuticalBuletin,29(2):
564—566
YeQH,ZhaoWM,QinGW,2004.Lignansfrom Dendrobium
chrysanthum [J].JournalofAsianNaturalProductsRe灢
search,6(1):39—43
09暋暋暋暋暋暋暋暋暋暋暋暋 暋暋暋暋暋暋暋云暋南暋植暋物暋研暋究暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋暋第32卷