全 文 ：浆果楝中的新木脂素
宁暋静1,2,李顺林1,郝小江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:从浆果楝 (Cipadessabaccifera)中分离得到两个木脂素,其化学结构通过波谱方法鉴定为:(-)灢9曚灢
O灢(E)灢coumarate灢5,5曚灢dimethoxylariciresinol (1)和 (+)灢9曚灢O灢(E)灢feruloyl灢5,5曚灢dimethoxylariciresinol
(2)。其中化合物1为新化合物。
关键词:浆果楝;木脂素;(-)灢9曚灢O灢(E)灢coumarate灢5,5曚灢dimethoxylariciresinol
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466灢03
LignansfromtheStemofCipadessabaccifera(Meliaceae)
NINGJing1,2,LIShun灢Lin1* ,HAOXiao灢Jiang1*
(1StateKeyLaboratoryofPhytochemistryandPlantResourcesinWestChina,Kunming
InstituteofBotany,ChineseAcademyofSciences,Kunming650204,China;
2GraduateUniversityofChineseAcademyofSciences,Beijing100049,China)
Abstract:Onenewlignan,(-)灢9曚灢O灢(E)灢coumarate灢5,5曚灢dimethoxylariciresinol(1),togetherwithone
knowncompound,(+)灢9曚灢O灢(E)灢feruloyl灢5,5曚灢dimethoxylariciresinol(2)wasisolatedfromthestemofCi灢
padessabaccifera.Thenewstructurewaselucidatedbyspectroscopicmethods.
Keywords:Cipadessabaccifera;Lignan;(-)灢9曚灢O灢(E)灢coumarate灢5
暋 Cipadessabaccifera(Roth.)Miq.(Meliaceae)
iswidelydistributedinsouthwestofChinaandhas
beenusedinfolk medicineforthetreatmentof
rheum,dysentery,andpruritus.Previousefforts
onthisplanthavereportedaseriesoflimonoids
(Luoetal灡,2000;Ganetal灡,2007;Linetal灡,
2008).Asapartofourphytochemicalinvestiga灢
tiononplantsinMeliaceaefamily,twolignans
(1-2)wereisolatedfromthestemofthisplant
(Fig灡1).Ofthem,1isanewcompound.The
knowncompoundwasdeterminedtobe(+)灢9曚灢
O灢(E)灢feruloyl灢5,5曚灢dimethoxylariciresinol(2),
bycomparisonofitsNMRdatawiththoseinthe
literature(Chenetal灡,2008).
Results
Compound1wasisolatedaswhiteamorphous
powder.Itsmolecularformulawasestablishedas
C31 H34 O10 accordingtotheion peak at m/z
589灡2068[M+Na]+ onHR灢ESIMS (calcd.for
589灡2049).Thepresenceofhydroxylgroupin
1wasrevealedbythestrongabsorptionbandat
3432cm灢1intheIRspectrum.The 13C NMR
(DEPT)spectrum (Table1)exhibitedreso灢
nancesforone methyleneat毮33灡8 (t),two
methinesat毮42灡7(d)and49灡1(d),twooxy灢
genatedmethylenesat毮62灡7(t)and72灡7(t),
oneoxygen灢bearingmethineat毮83灡6 (d),as
wel asseveral methoxygroupsat毮56灡3(q,
云 南 植 物 研 究暋2010,32(5):466~468
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10078
* Authorforcorrespondence;E灢mail:haoxj@mail灡kib灡ac灡cn
Receiveddate:2010灢04灢13,Accepteddate:2010灢06灢28
作者简介:宁静 (1985-)女,在读硕士研究生,主要从事植物化学研究。
overlapped)andaseriesofaromaticcarbons.
Theabovespectroscopicfeaturesindicatedthat1
mightbealignan.Adetailedcomparisonofthe
1Hand13CNMRdataof1withthoseof(+)灢9曚灢
O灢(E)灢feruloyl灢5,5曚灢dimethoxylariciresinolsug灢
gestedthattheirstructureswerecloselyrelated
(Chen etal灡,2008),except H灢3曞 [6灡82,d
(8灡5)]of1replacedthe3曞灢OMegroup.This
wassupportedbythe1H灢1HCOSYcorrelations
ofH灢2曞/H灢3曞(=H灢5曞/H灢6曞)andtheapparent
HMBC correlations between H灢2曞 and C灢7曞
(Fig灡2).Therelativeconfigurationof1wasde灢
terminedby ROESYspectrum.Theobserved
correlationsofH灢7曚/H灢9曚aandH灢9曚bsuggested
thatH灢7曚andH灢8曚wereontheoppositeposition
andH灢8曚wasarbitraryassignedas毬orienta灢
tion.WhileH灢8wasdeterminedtobe毬orienta灢
tionduetothepresenceofcorrelationofH灢7曚/
H灢7a.Thus,therelativeconfigurationof1was
fulyestablishedasshown(Fig灡3).
Fig灡1暋LignansfromthestemofCipadessabaccifera
Experimental
GeneralExperimentalProcedures暋Opticalrotations
weredeterminedwithaPerkin灢Elmer241polarimeter.IR
spectrawererecordedonaBio灢RadFTS灢135spectrometer
withaKBrdisk.The1Hand13CNMRspectrawerere灢
cordedonaBrukerAM灢400spectrometer,while2DNMR
spectrawererecordedonandaBrukerDRX灢500instru灢
ment.ESIMSandHRESIMSspectraweremeasuredwith
aFinniganMAT90instrumentandVG AutoSpec灢3000
spectrometer,respectively.Semipreparative HPLC was
performedonaMerckcolumn(i灡d.100-10mm;Mer灢
ck,Darmstadt,Germany),developedwithCH3OH/H2
O (50暶50to58暶42,35min)(flowrate,3灡0ml·min灢1,
detection,UV210nm)at30曟.Columnchromatography
wasperformedonsilicagel(90-150毺m;QingdaoMarine
ChemicalInc.),MCIgel(CHP20P,75-150毺m,Mitsub灢
ishiChemicalIndustriesLtd.),C18reversed灢phasesilicagel
(20-45毺m;Merck,Darmstadt,Germany),andSephadex
LH灢20(40-70毺m;AmershamPharmaciaBiotechAB,Up灢
psala,Sweden).TLCplateswereprecoatedwithsilicagel
GF254andHF254 (QingdaoHaiyangChemicalPlant,Qingd灢
ao,People曚sRepublicofChina).
7645期暋暋暋 暋暋暋NINGJingetal灡:LignansfromtheStemofCipadessabaccifera(Meliaceae)暋暋暋暋暋暋暋暋
暋暋Plantmaterial暋ThestemofC灡bacciferawerecol灢
lectedinXishuangbanna,YunnanProvince,People曚sRe灢
publicofChina,andwereidentifiedbyProf.Jing灢Yun
CuioftheXishuangbannaTropicalBotanicalGarden,Chi灢
neseAcademyofSciences.
暋 暋 Extraction andIsolation暋 Air灢dried stem bark
C灡baccifera(6灡9kg)wasextractedthreetimeswith95%
EtOH.Theextractswerecombinedandconcentrated,
thensuspendedinH2O.Thewaterlayerwasthenextrac灢
tedwithether(PE)andEtOAc.TheEtOAcextracts
(326g)weresubjectedtosilicagelcolumnchromato灢
graph,elutedwithpetroleumether/Acetone(from1暶0
to1暶1),yielding6fractionsA1灢A6.FractionA5(16g)
wasthensubjectedtoC灢18columnchromatograph(eluted
withCH3OH/ H2Ofrom5暶5to10暶0),yielding8
fractionsB1灢B5.FractionB2(1灡5g)wasfirstpurifiedon
SephdexLH灢20,yieldingthreefractionsC1灢C3.Fraction
C2 (210 mg)wassubjectedtosilicagel,eluted with
CHCl3/acetone(10暶1)toafford1 (10mg)and2(15
mg).
(+)灢9曚灢O灢(E)灢coumarate灢5,5曚灢dimethoxylaricires灢
inol(1):whiteamorphouspowder,[毩]25D +5灡3(c0灡4,
MeOH);IR毻KBrmaxcm灢13432,1629,1174;positive灢ionES灢
IMS m/z589 [M+Na]+ ;HR灢ESIMS m/z589灡2068
[M+Na]+ ,calcd589灡2049;1H NMRand13CNMRda灢
ta,seeTable1.
Table1暋1Hand13CNMRdataof1inCDCl3
No. 毮H(mult,J) 毮C No. 毮H(mult,J) 毮C
1 131灡1 6曚 6灡57,s 102灡5
2 6灡40,s 105灡2 7曚 4灡81,d(6灡5) 83灡6
3 147灡0 8曚 2灡65,t(6灡5,7灡4) 49灡1
4 133灡1 9曚a 4灡33,dd(11灡0,3灡5) 62灡7
5 147灡0 9曚b 4灡51,dd(11灡0,6灡5)
6 6灡40,s 105灡2 1曞 126灡7
7a 2灡55,dd(11灡0,2灡0) 33灡8 2曞 7灡37,d(8灡5) 130灡0
7b 2灡87,dd(11灡0,5灡0) 3曞 6灡82,d(8灡5) 115灡9
8 2灡75,m 42灡7 4曞 158灡1
9毩 3灡77,dd(8灡5,1灡5) 72灡7 5曞 6灡82,d(8灡5) 115灡9
9毬 4灡08,dd(8灡5,6灡5) 6曞 7灡37,d(8灡5) 130灡0
1曚 133灡4 7曞 7灡51,d(16灡0) 145灡1
2曚 6灡57,s 102灡5 8曞 6灡23,d(16灡0) 114灡7
3曚 147灡0 9曞 167灡2
4曚 134灡0 OMe 3灡85 56灡3
5曚 147灡0
References:
ChenJJ,WangTY,HwangTL,2008.Neolignans,acoumarin灢
olignan,lignanderivatives,andachromene:anti灢inflam灢
matoryconstituentsfrom Zanthoxylum avicennae [J].
JournalofNaturalProducts,71:212—217
GanLS,WangXN,WuYetal灡,2007.Tetranortriterpenoids
from Cipadessabaccifera[J].JournalofNaturalProducts,
70:1344—1347
LinLG,TangCP,YeYetal灡,2008.Terpenoidsfromthestems
ofCipadessabaccifera[J].JournalofNaturalProducts,71:
628—632
LuoXD,WuSH,MaYB etal灡,2000.ComponentsofCi灢
padessabaccifera[J].Phytochemistry,55:867—872
864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