全 文 ：广东土牛膝的化学成分*
廖彭莹1,2,张颖君1**,王一飞3,王暋东1,杨崇仁1,4
(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广西中医学院,广西 南宁暋530001;3暨南大学,广东 广州暋510632;
4维和生物技术研发中心,云南 玉溪暋653100)
摘要:广东土牛膝为菊科泽兰属植物华泽兰 (Eupatoriumchinense)的干燥根。从其甲醇提取物中共分
离得到11个化合物,其中eupatorinA(1)为一新化合物,经波谱学方法鉴定为 (threo)灢3灢O灢acetyl灢1灢
(4灢hydroxy灢3灢methoxyphenyl)灢2灢[4灢(3灢hydroxy灢1灢(E)灢propenyl)灢2,6灢dimethoxyphenoxy]propyl灢毬灢D灢glu灢
copyranoside。已知化合物分别鉴定为 (threo)灢3灢hydroxy灢1灢(4灢hydroxy灢3灢methoxyphenyl)灢2灢[4灢(3灢hy灢
droxy灢1灢(E)灢propenyl)灢2,6灢dimethoxyphenox灢y]灢propyl灢毬灢D灢glucopyranoside(2),ardisiacrispinA (3),
ardisiacrispinB(4),euparone(5),3灢(2,3灢dihydroxy灢isopen灢tyl)灢4灢hydroxyacetophenone(6),12,13灢di灢
hydroxy灢euparin(7),gymnastone(8),N灢(2曚灢hydroxy灢tetracosanosyl)灢2灢amino灢1,3,4灢trihydroxy灢octa灢
dec灢8灢(E)灢ene(9),stigmasterol(10)和stigmasterol灢3灢O灢毬灢D灢glucopyranoside(11)。化合物2-4为首
次从菊科植物,5-8为首次从泽兰属植物中分离得到。
关键词:广东土牛膝;化学成分;EupatorinA
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)02灢183灢06
ChemicalConstituentsofGuangdongTu灢Niu灢Xi
(Eupatoriumchinense,Compositae)
LIAOPeng灢Ying1,2,ZHANGYing灢Jun1**,WANGYi灢Fei3,
WANGDong1,YANGChong灢Ren1,4
(1StateKeyLaboratoryofPhytochemistryandPlantResourcesinWestChina,KunmingInstituteofBotany,
ChineseAcademyofSciences,Kunming650204,China;2GuangxiTraditionalChineseMedical
University,Nanning530001,China;3JinanUniversity,Guangzhou510632,China;
4WeiheBiotechResearchandDevelopmentCenter,Yuxi653100,China)
Abstract:Onenewcompound,namelyeupatorinA(1),wasisolatedfromthemethanolicextractofGuang灢
dongTu灢Niu灢Xi,thedriedrootsofEupatoriumchinense(Compositae).Itsstructurewasdeterminedtobe
(threo)灢3灢O灢acetyl灢1灢(4灢hydroxy灢3灢methoxyphenyl)灢2灢[4灢(3灢hydroxy灢1灢(E)灢propenyl)灢2,6灢dimethoxy灢
phenoxy]propyl灢毬灢D灢gluco灢pyranosideonthebasisofdetailedspectroscopicanalysis.Inaddition,ten
knowncompounds,including(threo)灢3灢hydroxy灢1灢(4灢hydroxy灢3灢methoxyphenyl)灢2灢[4灢(3灢hydroxy灢1灢(E)灢
propenyl)灢2,6灢dimethoxyphenoxy]propyl灢毬灢D灢glucopyranoside(2),ardisiacrispinA (3),ardisiacrispinB
(4),euparone (5),3灢(2,3灢dihydroxy灢isopentyl)灢4灢hydroxy灢acetophenone (6),12,13灢dihydroxy灢euparin
(7),gymnastone(8),N灢(2曚灢hydroxy灢tetracosanosyl)灢2灢amino灢1,3,4灢trihydroxy灢octadec灢8灢(E)灢ene(9),
stigmasterol(10)andstigmasterol灢3灢O灢毬灢D灢glucopyranoside(11)werealsoobtained.Thiswasthefirst
云 南 植 物 研 究暋2010,32(2):183~188
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09214
*
**
Foundationitems:TheNationalScienceFoundationofChina(U0632010)andtheStateKeyLaboratoryofPhytochemistryand
PlantResourcesinWestChina,KunmingInstituteofBotany,ChineseAcademyofSciences(P2008灢ZZ08)
Authorforcorrespondence:Tel:+86灢871灢5223235.E灢mail:zhangyj@mail灡kib灡ac灡cn
Receiveddate:2009灢11灢02,Aceepteddate:2010灢01灢15
作者简介:廖彭莹 (1984-)女,理学硕士,助教,主要从事中药化学研究。
timethatcompounds2-4werereportedfromCompositaefamily,while5-8wereisolatedfromthegenus
Eupatorium .
Keywords:GuangdongTu灢Niu灢Xi(Eupatoriumchinense);Chemicalconstituents;EupatorinA
暋暋EupatoriumchinenseL.(Compositae)is
mainlydistributedinthesouthpartofChina.
Thedriedroots,caledGuangdongTu灢Niu灢Xi,
havebeenusedmedicinalyforthetreatmentof
coughing,fever,amygdalitis,diphtheriaand
other laryngological diseases in Guangdong
Province,China,foralongtime (Editorial
CommitteeofChinese Materia Medica,State
AdministrationofTraditionalChineseMedicine
oftheP灡R灡C.,1999).Pharmacologicalstudies
showedthatithadanti灢inflammatory,analgesia,
antisepsisandanticancereffects (Liuetal灡,
2004;MeiandWu,2005).Numbersofsesquiter灢
penoidsandsterolswerereportedfromthewhole
plants(YuandKang,1983;Kazuoetal灡,1982;
Yangetal灡,2004;Yangetal灡,2005).Asa
partofourworkonsearchingantiviralnatural
productsfrom medicinalplants,particularly
thoseusedinthesouthpartofChina,adetailed
chemicalinvestigationontheair灢driedrootsof
Eupatoriumchinensewascarriedout,whichled
totheidentificationof11compounds.Their
structureswereidentifiedbyextensive NMR
spectroscopicexperiments,including1Hand13C
NMR,1H灢1HCOSY,HMBC,HMQCandRO灢
SEY.Ofthem,compound1isanewphenylpro灢
panoidalglycosideandnamedaseupatorinA.
Thispaperdescribestheisolationandstructure
determinationofthesecompounds.
1暋 MaterialsandMethods
1灡1暋GeneralExperimentalProcedures
OpticalrotationwasrecordedonaP灢1020Polarime灢
ter(JASCO,Tokyo,Japan).IRspectrumwasmeasured
onaBrukerTensor27spectrometerwithKBrpelets.UV
spectrumwasdeterminedonaShimadzuUV灢2401PCspec灢
trometer.1Hand13CNMR,1H灢1HCOSY,HMQC,HM灢
BC,andROSEYspectrawererecordedwithBrukerAM灢
400and DRX灢500 spectrometers.Coupling constants
wereexpressedinHertz,andchemicalshiftsweregiven
ona毮 (ppm)scalewithTMSasaninternalstandard.
FAB灢MSwererecordedonanAutoSpec3000spectrome灢
terwithglycerolasthematrix,inm/zHRESI灢MSmeas灢
urementwascarriedoutonanAPIQstarPulsaLC/TOF
spectrometer.TLCexperimentswereperformedonsilica
gelHpre灢coatedplates(Qingdao MarineChemicaland
IndustrialFactory,China)andRp灢8orRp灢18pre灢coated
plates(Merck,Germany).Silicagel(200-300mesh)
(QingdaoMarineChemicalandIndustrialFactory,Chi灢
na),MCIgelCHP20P(75-100毺m)(MitsubishiChem灢
icalCo.,Ltd.,Japan),Rp灢8gel,Rp灢18gel(40-60
毺m)(Merck,Germany)andSephadexLH灢20(25-100
毺m)(PharmaciaFineChemicalCo.Ltd)wereusedfor
columnchromatography.Spotsweredetectedbyspraying
withanisaldehyde灢AcOH灢H2SO4灢EtOH (3灡7暶1灡5暶5暶
135)folowedbyheating.
1灡2暋Material
Theair灢driedGuangdongTu灢Niu灢Xiwassuppliedby
BiomedicineResearch & DevelopmentCentreatColege
ofLifeScienceandTechnology,JinanUniversityin2007,
andidentifiedbyProfessorWangYi灢Fei.Avoucherspeci灢
menhasbeendepositedintheBiomedicineResearch &
DevelopmentCentreatColegeofLifeScienceandTech灢
nology,JinanUniversity,Guangzhou,China.
1灡3暋ExtractionandIsolation
Theair灢driedrootsofGuangdongTu灢Niu灢Xi(2灡8
kg)werepowderedandextractedwithmethanolunderre灢
fluxforthreetimes,threehoursatime.Themethanolic
extractwasconcentratedunderreducedpressuretoafford
aresidue(72灡5g).Theresiduewasappliedonasilicagel
column(60暳6灡0cm),elutingwithchloroform灢methanol
(1暶0-0暶1),toafford12fractions(Fr灡1-12).Fr灡1
wasrepeatedlychromatographedoversilicagel(CHCl3/
MeOHorpetroleum ether/acetone),SephadexLH灢20
(MeOH/H2O orCHCl3/MeOH),MCIgelCHP20P
(MeOH/H2O)andRp灢8orRp灢18gel(MeOH/H2O)to
affordcompound5(22mg).Inthesameway,compound
10(55mg)wasobtainedfromFr灡3;compounds6(18
mg)and7(96mg)wereyieldedfromFr灡5;compounds8
(9mg)and9(40mg)wereisolatedfromFr灡6;com灢
pound11(25mg)wasfromFr灡7,compound1(47mg)
wasfromFr灡9,compound2(21mg)wasfromFr灡10,
andcompounds3(20mg)and4(15mg)werebothfrom
Fr灡12.
481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
EupatorinA(1)wasobtainedascolorlessoil,[毩]23D
-20灡8(c0灡24,MeOH),IR毻KBrmax (cm灢1):3432,2934,
2925,1735,1585,1517,1505,1459,1421,1243,
1125,1077,1035;UV毸MeOHmax (log毰)(nm):271(4灡02),
222(4灡53),202(4灡83);ESI灢MS(positive):633[M+
Na]+;HRESI灢MS (positive):633灡2175 [M+Na]+
(calcd.for633灡2159,C29H38O14Na);1H NMR (ace灢
tone灢d6,500 MHz):毮H1灡84(3H,s,COMe),3灡23
(1H,m,H灢3曞),3灡31(1H,m,H灢4曞),3灡32(1H,m,
H灢2曞),3灡40(1H,m,H灢5曞),3灡56(1H,dd,J=9灡5,
5灡5Hz,Hb灢6曞),3灡74(1H,br灡d,J=9灡5Hz,Ha灢6曞),
3灡79(1H,dd,J=12灡0,6灡0Hz,Hb灢9),3灡82(3H,s,
OMe灢3),3灡85(6H,s,OMe灢2曚,6曚),4灡09(1H,dd,J=
12灡0,2灡5Hz,Ha灢9),4灡21(2H,m,H灢9曚),4灡59(1H,
d,J=7灡5 Hz,H灢1曞),4灡60 (1H,m,H灢8),5灡13
(1H,d,J=6灡0Hz,H灢7),6灡35(1H,dt,J=5灡5,
16灡0Hz,H灢8曚),6灡54(1H,d,J=16灡0Hz,H灢7曚),
6灡77(2H,s,H灢3曚,5曚),6灡79(1H,d,J=8灡0Hz,H灢
5),6灡96(1H,dd,J=1灡0,8灡0Hz,H灢6),7灡13(1H,
d,J =1灡0 Hz,H灢2);13C NMR (acetone灢d6,125
MHz):毮C20灡6(q,COMe),56灡3(q,OMe灢3),56灡4
(q,OMe灢2曚,6曚),62灡8(t,C灢6曞),63灡1(t,C灢9曚),64灡7
(t,C灢9),71灡5(d,C灢4曞),75灡2(d,C灢2曞),77灡5(d,C灢
5曞),77灡7(d,C灢3曞),81灡3 (d,C灢7),82灡8 (d,C灢8),
104灡2(d,C灢1曞),104灡4(d,C灢3曚,5曚),112灡1(d,C灢2),
115灡2(d,C灢5),121灡0 (d,C灢6),130灡0 (d,C灢7曚),
130灡5(d,C灢8曚),131灡1 (d,C灢1),134灡1 (d,C灢4曚),
136灡6(d,C灢1曚),147灡0 (d,C灢4),147灡8 (d,C灢3),
154灡0(d,C灢2曚,6曚),170灡9(s,OCOMe).
(threo)灢3灢hydroxy灢1灢(4灢hydroxy灢3灢methoxyphenyl)灢2灢
[4灢(3灢hydroxy)灢1灢(E)灢propenyl)灢2,6灢di灢methoxyphe灢
noxy]propyl灢毬灢D灢glucopyranoside(2)wasobtainedascol灢
orlessoil,C27H36O13,ESI灢MS (positive):591 [M+
Na]+;1H NMR (CD3OD,500MHz):毮H3灡18(1H,
m,H灢3曞),3灡20(1H,m,Hb灢6曞),3灡32(1H,m,H灢
4曞),3灡32(1H,m,H灢2曞),3灡36(1H,m,H灢5曞),3灡60
(1H,m,Ha灢6曞),3灡60(1H,m,Hb灢9),3灡74(1H,dd,
J=2灡5,12灡5Hz,Ha灢9),3灡85(3H,s,OMe灢3),3灡87
(6H,s,OMe灢2曚,6曚),4灡22(2H,dd,J=1灡0,5灡5Hz,
H灢9曚),4灡29(1H,dt,J=3灡5,6灡5Hz,H灢8),4灡59
(1H,d,J=7灡5Hz,H灢1曞),5灡14(1H,d,J=6灡5Hz,
H灢7),6灡34(1H,dt,J=5灡5,16灡0Hz,H灢8曚),6灡55
(1H,d,J=16灡0Hz,H灢7曚),6灡75(1H,d,J=8灡0
Hz,H灢5),6灡77(2H,s,H灢3曚,5曚),6灡92(1H,dd,J
=1灡5,8灡0Hz,H灢6),7灡08(1H,d,J=1灡5Hz,H灢
2);13C NMR (pyridine灢d5,125 MHz):毮C55灡9 (q,
OMe灢3),56灡2(q,OMe灢2曚,6曚),62灡6(t,C灢6曞),61灡6
(t,C灢9),62灡9(t,C灢9曚),71灡6(d,C灢4曞),75灡9(d,C灢
2曞),78灡5(d,C灢5曞),78灡9(d,C灢3曞),80灡8(d,C灢7),
86灡4(d,C灢8),104灡4(d,C灢1曞),104灡5(d,C灢3曚,5曚),
112灡7(d,C灢2),115灡9(d,C灢5),121灡3(d,C灢6),129灡4
(d,C灢8曚),131灡1(d,C灢1),131灡4(d,C灢7曚),134灡0(d,
C灢4曚),136灡7(d,C灢1曚),147灡7(d,C灢4),148灡2(d,C灢
3),153灡9(d,C灢2曚,6曚).(Kensakuetal灡,2002)
ArdisiacrispinA (3)wasobtainedasawhiteamor灢
phouspowder,C52H84O22,FAB灢MS (negative):1059
[M灢1]灢,927[M灢1灢132]灢,765[M灢1灢132灢162]灢;1Hand
13CNMRdata:similartothedatareportedinChaweewan
etal灡 (1987)andGottfriedetal灡 (1989).
ArdisiacrispinB(4)wasobtainedasawhiteamor灢
phouspowder,C53H86O22,FAB灢MS (negative):1074
[M]灢,928[M灢146]灢,765[M灢1灢146灢162]灢;1Hand13C
NMRdata:similartothedatareportedinChaweewanet
al灡 (1987).
Euparone(5)wasobtainedasayelowamorphous
powder,C12H10O4,ESI灢MS(positive):m/z241[M+
Na]+;1HNMR(CDCl3,500MHz):毮H2灡60(3H,s,
H灢13),2灡73(3H,s,H灢11),7灡08(1H,s,H灢7),7灡46
(1H,s,H灢3),8灡17(1H,s,H灢4),12灡56(1H,s,OH灢
6);13CNMR(CDCl3,125MHz):毮C25灡2(q,C灢13),
25灡6(q,C灢11),99灡1(d,C灢7),111灡9(d,C灢3),117灡2
(s,C灢5),118灡5(s,C灢9),125灡7(d,C灢4),152灡5(s,C灢
2),158灡8(s,C灢6),162灡2(s,C灢8),186灡7(s,C灢12),
202灡8(s,C灢10).(Mahmoudetal灡,1974)
3灢(2,3灢dihydroxy灢isopentyl)灢4灢hydroxy灢acetophenone
(6)wasobtainedascolorlessoil,C13H18O4,EI灢MS
(positive):m/z238 [M]+,220 [M灢18]+;1H NMR
(CD3OD,400 MHz):毮H1灡24 (3H,s,H灢12),1灡25
(3H,s,H灢13),2灡55(3H,s,H灢8),2灡55(1H,m,Ha灢
9),3灡05 (1H,dd,J=2灡0,14灡0 Hz,Hb灢9),3灡62
(1H,dd,J=2灡0,10灡5Hz,H灢10),6灡83(1H,d,J=
8灡5Hz,H灢5),7灡75(1H,dd,J=2灡5,8灡5Hz,H灢6),
7灡85(1H,d,J=2灡5Hz,H灢2);13CNMR (CD3OD,
100MHz):毮C25灡1(q,C灢12),25灡7(q,C灢13),26灡3
(q,C灢8),33灡9(t,C灢9),73灡9(s,C灢11),79灡5(d,C灢
10),116灡0(d,C灢5),128灡2(s,C灢3),130灡0(d,C灢6),
130灡1(s,C灢1),133灡7(d,C灢2),162灡4(s,C灢4),199灡8
(s,C灢7).(Soniaetal灡,1992)
12,13灢dihydroxyeuparin(7)wasobtainedasyelow
crystals,C13H14O5,EI灢MS(positive):m/z250[M]+,
219[M灢31]+;1H NMR(CD3OD,400MHz):毮H1灡56
(3H,s,H灢14),2灡66(3H,s,H灢11),3灡74(2H,m,
H灢13),6灡71(1H,s,H灢3),6灡92(1H,s,H灢7),8灡10
(1H,s,H灢4);13CNMR(CD3OD,100MHz):毮C23灡6
(q,C灢14),27灡0(q,C灢11),69灡3(t,C灢13),72灡9(s,C灢
12),99灡9(d,C灢7),103灡8(d,C灢3),118灡0(s,C灢5),
5812期暋暋暋LIAOPeng灢Yingetal灡:ChemicalConstituentsofGuangdongTu灢Niu灢Xi(Eupatoriumchinense)暋暋 暋
122灡7(s,C灢9),125灡4(d,C灢4),160灡9(s,C灢6),161灡9
(s,C灢8),163灡5(s,C灢2),206灡1(s,C灢10).(Hussein,
1992)
Gymnastone(8)wasobtainedasayelowamorphous
powder,C13H14O6,ESI灢MS(positive):289[M+Na]+;
1HNMR(pyridine灢d5,500MHz):毮H2灡58(3H,s,H灢
11),4灡65(2H,d,J=11灡1Hz,H灢13),4灡60(2H,d,J
=11灡2Hz,H灢14),7灡17(1H,s,H灢3),7灡18(1H,s,H灢
4),7灡80 (1H,s,H灢7),12灡63 (1H,s,OH灢5);13C
NMR(CD3OD,125MHz):毮C26灡9(q,C灢11),66灡2
(t,C灢13,14),76灡8(s,C灢12),104灡9(d,C灢3),107灡6
(d,C灢4),113灡1(d,C灢7),116灡4(s,C灢6),137灡3(s,C灢
9),148灡4(s,C灢8),158灡8(s,C灢5),168灡6(s,C灢2),
204灡5(s,C灢2).(Nguyenetal灡,2004)
1灡4暋AcidHydrolysisofCompound1
Compound1(8mg)washydrolyzedwith2mol·L灢1
HCl灢dioxane(1暶1,4ml)underrefluxfor4hat90曟.
ThereactionmixturewaspartitionedbetweenH2Oand
CHCl3 (2ml暳3)aftercooling.Theaqueouslayerwas
neutralizedwith2M NaOH,dried,dissolvedinpyridine
andconcentratedagaintogivethesugarresidue.Thesug灢
arwasanalyzedbycomparing Rfvaluewithauthentic
sampleonsilicagelH pre灢coatedplatesasD灢glucose
([毩]23D+9灡7(c0灡16,H2O)).
2暋ResultsandDiscussion
ThemethanolicextractofGuangdongTu灢
Niu灢Xiwassubjectedtorepeatedcolumnchro灢
matographyoversilicagel,SephadexLH灢20,
MCIgelCHP20P,Rp灢8andRP灢18toyield11
compounds(1-11).Compounds2-11were
determinedtobetheknowncompounds(threo)
灢3灢hydroxy灢1灢(4灢hydroxy灢3灢methoxy灢phenyl)灢2灢
[4灢(3灢hydroxy灢1灢(E)灢propenyl)灢2, 6灢dime灢
thoxy灢phenoxy]propyl灢毬灢D灢glucopyranoside(2)
(Kensakuetal灡,2002),ardisiacrispinA (3)
(Chaweewan etal灡,1987;Gottfried etal灡,
1989),ardisiacrispinB(4)(Chaweewanetal灡,
1987),euparone(5)(Mahmoudetal灡,1974),
3灢(2,3灢dihydroxy灢isopentyl)灢4灢hydroxy灢aceto灢
phenone(6)(Soniaetal灡,1992),12,13灢di灢
hydroxy灢euparin(7)(Hussein,1992),gymnas灢
tone(8)(Nguyenetal灡,2004),N灢(2曚灢hydrox灢
y灢tetracosanosyl)灢2灢amino灢1,3,4灢trihydroxy灢octa灢
dec灢8灢(E)灢ene(9)(Lietal灡,2003),stigmasterol
(10)(Wangetal灡,2004)andstigmasterol灢3灢
O灢毬灢D灢glucopyranoside(11)(Wangetal灡,
2004)onthebasisofdetailedspectroscopicana灢
lyses,togetherwithcomparisonoftheirspectro灢
scopicand physicaldata withreported ones
(Fig灡1).Itwasthefirsttimethatcompounds2-4
wereisolatedfromtheCompositaefamily,while5
-8wereobtainedfromthegenusEupatorium.
暋暋EupatorinA (1)wasobtainedascolorless
oil.Itsmolecularformulawasdeterminedtobe
C29H38O14 by HRESI massspectrum (m/z
633灡2175[M+Na]+),containing15degreesof
unsaturation.TheUVabsorptionsat271,222
and202nmsuggestedthepresenceofconjugated
structureinthemolecule.TheIRspectrumof1
showedcharacteristicabsorptionsat3431and
1735cm灢1,suggestingthepresenceofhydroxyl
groupandcarbonylgroup,andtheabsorptions
at1585,1517,and1505cm–1confirmedtheex灢
istenceofaromatic moiety.The 1H and 13C
NMRspectraldataof1showedtheexistenceof
a1,3,4灢trisubstitutedphenyl[毮H6灡79(1H,
d,J=8灡0Hz,H灢5),6灡96(1H,dd,J=1灡0,
8灡0Hz,H灢6),7灡13(1H,d,J=1灡0Hz,H灢
2)],a1,3,4,5灢tetrasubstitutedphenyl(毮H
6灡77,2H,s,H灢3曚,5曚),aglucopyranosyl[毮H
4灡59(1H,d,J=7灡5Hz,H灢1曞),毮C104灡2,
75灡2,77灡7,71灡5,77灡5(eachd,C灢1曞,C灢2曞,C灢
3曞,C灢4曞,C灢5曞),62灡8(t,C灢6曞)],twotrans灢
coupledolefinicprotons[毮H6灡35(1H,dt,J=
5灡5,16灡0Hz,H灢8曚),6灡54(1H,d,J=16灡0
Hz,H灢7)],threemethoxyls[毮H3灡82 (3H,
s),3灡85(6H,s)],twooxygen灢bearingmethyl灢
enes[毮C63灡1,64灡7(eacht,C灢9曚,9)]andtwo
oxygen灢bearingmethines[毮C81灡3,82灡8(eachd,
C灢7,8)].Inthe1H灢1HCOSYspectrumof1,the
correlationsbetweenH灢7(毮H5灡13)andH灢8(毮H
4灡60),H灢8andHb灢9(毮H3灡78)wereobserved.In
theHMBCspectrumof1,thecorrelationsof毮 H
3灡82(OMe灢3)with毮C147灡8(C灢3)and毮H3灡85
(OMe灢2曚,6曚)with毮C154灡0 (C灢2曚,6曚)con灢
firmedthepositionsofthreemethoxylgroups;
thecorrelationbetween毮H4灡59(1H,d,J=
7灡5Hz,H灢1曞)and毮C81灡3confirmedthatthe
681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Structuresofcompounds1-11
glucopyranosylunitlocatedatC灢7andpossesseda毬
灢anomericconfiguration;thecorrelationofH灢8(毮H
4灡60)withC灢1曚(毮C136灡6)wasalsoobserved.
TheROSEYcorrelationsof毮H5灡13(H灢7)with
毮H7灡13(H灢2)and毮H6灡96(H灢6)assignedC灢7
tobelinkedwiththe1,3,4灢trisubstitutedphe灢
nylgroup,whilecorrelationsof毮H6灡77(H灢3曚,
5曚)with毮H6灡54 (H灢7曚)and毮H6灡35 (H灢8曚)
confirmedthatC灢7曚waslocatedatC灢4曚(Fig灡2).
Comparisonofthe1Hand13CNMRspectra
of1withthoseof2indicatedthatthesetwo
compoundswerequitesimilarwitheachother,
exceptforanadditionalacetylgroup[毮C20灡6,
170灡9;毮H1灡84(3H,s,灢COCH3)]appearedin
compound1.TheESI灢MSalsoshowedthat
compound1had42massunitsmorethan2,cor灢
respondingtoanacetylgroup.TheHMBCcor灢
relationsbetweenH灢9(毮H3灡79and4灡09)and
theacetylcarbonylcarbon(毮C170灡9)indicated
thattheacetylgrouplocatedatC灢9.
Fig灡2暋Thekey2DNMRcorrelationsofcompound1
暋暋Thecouplingconstant(6灡5Hz)between
H灢7andH灢8incompound2indicatedathreo
7812期暋暋暋LIAOPeng灢Yingetal灡:ChemicalConstituentsofGuangdongTu灢Niu灢Xi(Eupatoriumchinense)暋暋 暋
typeofrelativeconfiguration (Yuanand Li,
2003),anditisthesameforcompound1witha
similarcouplingconstantof6灡0Hz.Acidhy灢
drolysisofcompound1gaveD灢glucose([毩]23D+
9灡7)assugarresidue.Theassignmentofthe
protonandcarbonsignalswasachievedbya
combinationof1H灢1HCOSY,HMBC,andRO灢
SEYspectra.Thus,thestructureofcompound
1wasdeterminedtobe(threo)灢3灢O灢acetyl灢1灢
(4灢hydroxy灢3灢methoxyphenyl)灢2灢[4灢(3灢hydroxy灢
1灢(E)灢propenyl)灢2,6灢dimethoxy灢phenoxy]pro灢
pyl灢毬灢D灢glucopyranoside.
Acknowledgements:Theauthorsaregratefultothemembers
oftheAnalyticalGroupofStateKeyLaboratoryofPhyto灢
chemistryandPlantResourcesinWestChina,KunmingIn灢
stituteofBotany,formeasurementsofalspectra.
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