全 文 ：滇产对叶百部中一个新的百部生物碱*
郭暋婕1,2,何红平2,李顺林2,华会明1,郝小江2
**
(1沈阳药科大学中药学院,辽宁 沈阳暋110016;2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)
摘要:从对叶百部 (Stemonatuberosa)根的乙醇提取物中分离鉴定1个新的百部生物碱,命名为去氢异
滇百部碱 (1),以及1个已知化合物:异滇百部碱 (2)。它们的化学结构通过现代波谱解析得以鉴定。
关键词:对叶百部;百部生物碱;去氢异滇百部碱
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)05灢463灢03
ANewAlkaloidfromtheRootsofStemonatuberosa(Stemonaceae)*
GUOJie1,2,HEHong灢Ping2,LIShun灢Lin2,HUAHui灢Ming1,HAOXiao灢Jiang2**
(1DepartmentofNaturalProductsChemistry,ShenyangPharmaceuticalUniversity,Shenyang110016,China;
2StateKeyLaboratoryofPhytochemistryandPlantResourcesinWestChina,Kunming
InstituteofBotany,ChineseAcademyofSciences,Kunming650204,China)
Abstract:OnenewStemonaalkaloid,dehydroisostemotinine(1)alongwithoneknownalkaloidisostemotinine(2),
wereisolatedfromtherootsofStemonatuberosacolectedfromYunnanProvince.Thestructureofthenewalkaloid
wasestablishedonthebasisofone灢andtwo灢dimensionalNMRspectraandotherspectroscopicstudies.
Keywords:Stemonatuberosa;Stemonaalkaloids;Dehydroisostemotinine
暋 Stemonarepresentsthelargestgenuswith灢
inthemonocotyledonfamilyStemonaceaeandis
indigenoustosouthwestAsiaandnorthAustral灢
ia(Greger,2006).Severalspeciesofthisgenus
caledBaibuhavebeenusedasChinesemedicine
particularlyforthetreatmentofrespiratorydis灢
easesandagainstenterichelminthesorectopara灢
sitesonhumanandcattlesinceancienttimes
(JiangsuNew MedicalColege,1977).
Highlyinterestingsecondarymetaboliteshave
beenreportedfrom Stenoma withinthelast20
years.TheStemonaalkaloids,themainconstitu灢
entsofthegenusStemona,wereinterestingnot
onlyduetoitspharmacologicalprofilebutalsodue
tocomplexandunusualmolecularstructures.More
than100derivativeshavebeenidentified,alof
thembearingapyrroloorpyrido [1,2灢毩]az灢
epinebackboneunrealizedinanyotherplant
family(Sturmetal灡,2008).Anumberofstud灢
ieshavebeenperformedtoevaluatethebiologi灢
calactivitiesoftheseuniquealkaloids.
Thespecies S灡tuberosa (Stemonaceae),
distributedwidelyinthesouthernChina,isone
ofthreeauthenticplantresourcesforBaibuin
Chinapharmacopoeia (ChinesePharmacopoeia
Commission,2005). Manyinvestigations on
S灡tuberosaofdifferentlocalitieshaveledtothe
isolationofmorethan60alkaloids,whichare
classifiedintotuberostemonine灢type,stemonin灢
ine灢type,andcroomine灢type.However,thema灢
joralkaloidsofS灡tuberosavarygreatlyinsam灢
plescolectedfrom differentlocations,which
云 南 植 物 研 究暋2010,32(5):463~465
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10084
*
**
Foundationitems:TheMajorStateBasicResearchDevelopmentofChina(973Program)(2009CB940900;2009CB522300)
Authorforcorrespondence;E灢mail:haoxj@mail灡kib灡ac灡cn;Tel:+86灢871灢5223263.Fax:+86灢871灢5223070
Receiveddate:2010灢04灢20,Accepteddate:2010灢08灢06
作者简介:郭婕 (1981-)女,博士,主要从事天然产物活性成分研究。
causesproblemswhenattemptingtodetermine
therelationshipbetweenthespecificmedicinal
useandtheherbalgrowinglocations.Thus,itis
necessarytofurtherinvestigateforthisspecies.
Inourstudiesonthechemicalconstituents
oftherootsofS灡tuberosacolectedfrom Wens灢
hancountry,YunnanProvince,onenewalka灢
loid,dehydroisostemotinine(1)andoneknown
alkaloidisostemotinine(2)wereisolatedandi灢
dentified.Thepresentpaperdescribedtheiriso灢
lationandstructuredetermination.
ResultsandDiscussion
Thestructureofthenewalkaloid11wases灢
tablished by mass灢spectrometricand spectro灢
scopicanalyses,especialy2D灢NMRtechniques
(1H,1H灢COSY,HMBC,NOESY).Compound
2waselucidatedbycomparingitspectroscopic
datawiththedatareportedinliterature(Xuet
al灡,1982).
Fig灡1暋Structureandconfigurationofcompound1
Compound1wasobtainedasanopticaly
active,colorless,amorphouspower.Itsmolecu灢
larformulawasestablishedasC18H23NO5 by
HR灢EI灢MS (m/z 333灡1579 ([M]+ ;calc.
333灡1576),inferringeightdegreesofunsatura灢
tions.The1H NMRspectrumof1showedsig灢
nalsforonemethaneandtwogeminalprotons
attachedtocarbonatoms bearinga nitrogen
functionalityat毮2灡87(1H,dd,J=6灡8,6灡4
Hz,H灢3),3灡28(1H,dd,J=10灡0,15灡0Hz,
H灢5a),and3灡03(1H,dd,J=15灡1,11灡4Hz,
H灢5b),whicharecharacteristicofthepyrido
[1,2灢毩]azepinenucleusoftheStemonaalka灢
loids(Jiangetal灡,2006).Inthe1Hand13C
NMRspectra,thesignalsofasecondarymethyl
at毮1灡26(3H,d,J=7灡5Hz,H灢18)indicated
thepresenceof毩灢methyl灢毭灢lactonering,analyl灢
icmethylat毮1灡93(3H,s,H灢13)andanolef灢
inicprotonat毮7灡31 (1H,s),togetherwith
two olefinic carbon signals at 毮 130灡4 and
150灡4,indicatedthepresenceofanunsaturated
毩灢methyl灢毭灢lactoneinsteadofatypical毩灢methyl灢
毭灢lactonemoiety.Thiswasconfirmedbytwo
pairsoflactonecarbonylandoxygenatedcarbon
signals[毮173灡8 (C灢12,s)and毮87灡9 (C灢9,
s);毮179灡4(C灢17,s)and毮83灡4(C灢14,s)].
Althesedatarevealedthatcompound1shared
thesamebasicskeletonofcroomine.Insucces灢
sion,adetailedanalysisoftheNMRspectrare灢
vealedtheplanarstructureofcompound1.
Fig灡2暋HMBCand1H灢1HCOSYcorrelationsofcompound1
OnthebasisoftheHSQCand1H灢1HCO灢
SYspectraof1,therewerethreespinsystems:
from H灢5toH灢8,H灢1toH灢2andH灢14toMe灢
18.TheHMBCcorrelationsofH灢15,H灢16and
Me灢18toC灢17,H灢3andH灢15toC灢14indicated
thatan毩灢methyl灢毭灢lactoneringislocatedatC灢3.
Inthe HMBC,thecorrelationsfromtheolefinic
protonat毮7灡31(1H,s,H灢10)toC灢8,C灢9,C灢
9a,C灢11,C灢12,andC灢13,suggestedthatC灢9is
spiro灢atomconnectingtheunsaturated毩灢methyl灢毭灢
lactoneandthepyrido [1,2灢毩]azepinenucleus.
Thetetracyclicskeleton,plusthetwolactoniccar灢
bonylsandoneolefinicgroup,accountforsevenof
eightunitsofunsaturationrevealedbythemolecular
formula.Basedonthesedata,compound1should
haveonemorering.TheHMBCcorrelationsbe灢
tweentheprotonat毮4灡68(H灢6)and毮106灡6
(C灢9a)indicatedthatbothC灢6andC灢9awere
linkedbyanO灢atomtoformapyrido[1,2灢毩]
azepinering.Thisstructuralmoiety,theetherfunc灢
tionalitybetweenC灢6andC灢9ahasbeenobserved
before onlyin stemotinine andisostemotinine.
Thus,theplanarstructureof1wasfiguredout.
Therelativeconfigurationof1wasestab灢
lishedbythecomparisonthe1Hand13CNMR
464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
datawithcompound2,andalsoconfirmedbyits
ROESYexperiment.Thesimilarchemicalshifts
andincombination withbiogeneticconsidera灢
tionssuggestedthatthesetwocompoundspos灢
sessthesameconfigurations.Accordingly,the
structureof1wasestablishedasdehydroisoste灢
motininethattheperhydroazaazuleneringhasan
“8灢CH2灢downconformation暠(Xuetal灡,1982).
Experimental
GeneralExperimentalProcedures暋 MPLC:B湽chi
PumpModuleC灢605,andB湽chiPump ManagerC灢615.
Columnchromatography (CC):SilicagelH (10-40
mm;QingdaoMarineChemicalLtd.Co.),aminosilica
gel(90-140mm,FujiSilysiaChemicalLtd.)andSepha灢
dexLH灢20(40-70mm,Pharmacia).TLC:Onsilica灢
gelplates;spots were visualized by spraying with
Dragenoff曚sreagent.Opticalrotations:JASCO DIP灢370
digitalpolarimeter.IRSpectra:Bio灢RadFTS灢135spec灢
trometer,KBrpelets,incm灢1.NMRspectra:Bruker
AM灢400instrument(400/100 MHz),andBrukerDRG灢
500instrument(500/125MHz);毮inppmrel.toTMS
asinternalstandard,JinHz.ESI灢MS:FinniganMAT90
instrument;in m/z.HR灢ESI灢MS:API QstarPulsar
LC/TOFinstrument.
Plantmaterial暋TherootsofS灡tuberosausedinthisin灢
vestigationwerecolectedfrom Wenshancountry,Yunnan
Province,P.R.China,inDecember2008.Theplantspecies
wasauthenticatedbyProf.GunGong,andthevoucherspeci灢
men(BN171)wasdepositedintheHerbariumofKunming
InstituteofBotany,ChineseAcademyofSciences.
ExtractionandIsolation 暋Thedriedandpowdered
rootsofS灡tuberosa(20kg)wereextractedwithMeOH.
Afterevaporationofthecolectedpercolate,thecrudeex灢
tractwasacidifiedwithdiluteHCl(4%)topH1-2and
partitionedbetweenCHCl3andwater.Theaqueouspart
wasbasifiedwithaqueousNH3topH9-10andextrac灢
tedwithCHCl3toafford80gofcrudealkaloids.Then,
thecrudealkaloidswereappliedtoasilicagelCCeluting
withgradientmixturesofpetroleumether灢acetone(from
1暶0to0暶1)togivesevenmajorfractions(Fr灡1灢Fr灡7).
Fr灡3(30g)wassubjectedtoaminosilicagelandsilicagel
CC,elutingwithpetroleumether灢acetone(from10暶1to
3暶1)toaffordfour majorfractions,Fr灡3a灢Fr灡3d.
Fr灡3b(2灡7g)wasfurtherpurifiedbysilicagelCCand
SephadexLH灢20columntoobtain1(19mg).Fr灡4(19
g)wasappliedtoaMPLC,elutedwithCH3OH灢H2Oto
affordthreemajorfractions,Fr灡4a灢Fr灡4c.Fr灡4a(2灡2
g)wasfurtherpurifiedbysilicagelCCandSephadexLH灢
20columntoobtain2(11mg).
Dedrostemotinine(1),C18H23NO5,[毩]20D -7灡6晎(c
0灡50,MeOH),colorlessamorphouspower.13CNMRda灢
taseeTable1.1H NMRdata:1H NMR (CDCl3,500
MHz)毮H 1灡91(1H,m,H灢1a),1灡68(1H,m,H灢1b),
1灡70(1H,m,H灢2a),1灡64(1H,m,H灢2b),2灡87(1H,
dd,J=6灡8,6灡4Hz,H灢3),3灡28 (1H,dd,J=10灡0,
15灡0Hz,H灢5a),3灡03(1H,dd,J=15灡1,11灡4Hz,H灢
5b),4灡68(1H,brs,H灢6),1灡93(1H,m,H灢7a),1灡61
(1H,m,H灢7b),2灡53(1H,m,H灢8a),1灡57(1H,m,H灢
8b),7灡31(1H,brs,H灢10),1灡93(3H,s,H灢13),4灡28
(1H,ddd,J=5灡0,7灡0,1灡6Hz,H灢14),2灡37(1H,m,
H灢15a),1灡47(1H,m,H灢15b),2灡66(1H,dd,J=3灡0,
7灡5Hz,H灢16),1灡26(3H,d,J=7灡5Hz,H灢6).
Table1暋13CNMRdataofcompound1and2
inCDCl3 (13C:125MHz;毮:ppm)
No. 1 2 No. 1 2
1 29灡1(t) 29灡9(t) 10 150灡4(d) 38灡2(t)
2 28灡8(t) 29灡4(t) 11 130灡4(s) 34灡2(d)
3 71灡9(d) 71灡7(d) 12 173灡8(s) 179灡7(s)
5 58灡3(t) 58灡0(t) 13 10灡7(q) 15灡5(q)
6 79灡0(d) 77灡3(d) 14 83灡4(s) 82灡9(s)
7 29灡0(t) 29灡7(t) 15 33灡9(t) 33灡9(t)
8 27灡7(t) 26灡6(t) 16 35灡3(d) 35灡2(d)
9 87灡9(s) 83灡3(s) 17 179灡4(s) 179灡0(s)
9a 106灡3(s) 106灡6(s) 18 14灡8(q) 14灡9(q)
Acknowledgements:Theauthorsaregratefultomembers
ofanalyticalgroupintheStateKeyLaboratoryofPhyto灢
chemistryandPlantResourcein WestChina,Kunming
InstituteofBotany,theChineseAcademyofSciences,for
thespectralmeasurements.
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5645期暋暋暋暋暋GUOJieetal灡:ANewAlkaloidfromtheRootsofStemonatuberosa(Stemonaceae)暋暋暋暋暋暋