全 文 ：天然产物研究与开发 NatProdResDev2009, 21:189-191
文章编号:1001-6880(2009)02-0189-03
ReceivedDecember15, 2008;AcceptedFebruary17, 2009
FoundationItem:ThisworkwasfinancialysupportedbytheNational
NaturalScienceFoundationofChina(No.30270156).
＊CorrespondingauthorE-mail:wangzhen yue@163.com
毛脉酸模根中一新的色原酮苷类化合物
赵海鹏 1, 2 ,王振月 1＊ ,程建蕊 1 ,李瑞明 1 ,王宗权 1, 3
1黑龙江中医药大学研究生院 ,哈尔滨 150040;
2鲁南制药集团股份有限公司 , 临沂 276005;3以岭药业集团股份有限公司 ,石家庄 050035
摘 要:从毛脉酸模根(RumexgmeliniTurcz.)75%乙醇提取物中分离得到 1个新色原酮苷和 5个已知化合物 ,
应用波谱学方法及文献对照分别鉴定为 2, 5-dimethyl-7-hydroxychromone-7-O-β-glucopyranoside(1), nepodin-8-O-
β-D-glucopyranoside(2), 10-hydroxyaloinA(3), 10-hydroxyaloinB(4), 5-methoxyl-1(3H)-benzofuranone-7-O-β-D-
glucopyranoside(5), phenylethyl-O-α-L-arabinopyranosy-(1※ 6)-O-β-D-glucopyranoside(6)。其中化合物 1为新化
合物 , 3～ 6首次从酸模属中分离得到 , 化合物 2首次从该植物中分离得到。
关键词:毛脉酸模;色原酮苷;酸模素苷;10-羟基芦荟苷;苯丙呋喃酮
中图分类号:Q946.91;R284.4 文献标识码:A
NewChromoneGlucosidefromRootsofRumexgmelini
ZHAOHai-peng1, 2 , WANGZhen-yue1＊ , CHENGJian-rui1 , LIRui-ming1 , WANGZong-quan1, 3
1GraduateSchooloftheHeilongjiangUniversityofTraditionalChineseMedicine, Harbin150040 , China;
2LunanPharmaceuticalGroupCorporation, Linyi276005 , China;
3YilingPharmaceuticalGroupCorporation, Shijiazhuang050035 , China
Abstract:Anewchromoneglucoside2, 5-dimethyl-7-hydroxychromone-7-O-β-glucopyranoside(1), wasisolatedfrom
the75% EtOHextractoftherootsofRumexgmeliniTurcz., togetherwithfiveknowncompounds, nepodin-8-O-β-D-glu-
copyranoside(2), 10-hydroxyaloinA(3), 10-hydroxyaloinB(4), 5-methoxyl-1(3H)-benzofuranone-7-O-β-D-glucopy-
ranoside(5), phenylethyl-O-α-L-arabinopyranosy-(1※ 6)-O-β-D-glucopyranoside(6).Theirstructureswereelucidated
mainlybasedonNMR(HSQC, HMBCandH-HCOSY)andMSspectraldata.
Keywords:RumexgmeliniTurcz.;2, 5-dimethyl-7-hydroxychromone-7-O-β-glucopyranoside;nepodin-8-O-β-D-gluco-
pyranoside;10-hydroxyaloin;benzofuranone
Introduction
RumexgmeliniTurcz.(FamilyPolygonaceae)hasbeen
widelyusedasafolkmedicineforcenturiesinChina.
Manyanthraquinones[ 1-3] andstilbenoids[ 4] isolated
fromtherootsshowinterestingbiologicalactivitiessuch
asantifungal, antitumor, antiasthma, antivirusandan-
tioxidation.Duringoursearchforbiologicalactivesub-
stancesfromR.gmeliniTurcz., anewchromonegluco-
side, 2, 5-dimethyl-7-hydroxychromone-7-O-β-glucopyr-
anoside(1), togetherwithfiveknowncompoundswas
isolated(Fig.1).Here, wereporttheisolationand
structureelucidationofthenewcompound.
ResultsandDiscussion
Compound1wasobtainedasamorphouswhiteneedles,
[ α] 25D -4.2°(CH3OH), andgavepositiveresultto
Molishtest.ItsmolecularformulaC17H20O8 wasde-
ducedfromHR-FAB-MS([ M+H] +m/z353.1240,
calcd.353.1236), 13CNMRandMSdata.UVλCH3OHmax
(logε)nm:226(2.29), 249(1.66)and282(1.08).
Theacidhydrolysisof1 afordedglucoseidentifiedon
TLC.The1HNMRdataof1 indicatedthatthiscom-
poundpossesses2-substitutedA-ring, 5, 7-disubstituted
B-ringandtwomethoxygroups(Table1).Thisas-
sumptionwassubsequentlyconfirmedbyits13CNMR
spectraldata.HMBCcorelationswerefoundbetweenC-
Fig.1 Structuresofcompounds1-6
2, C-3andH-11;C-2, C-10 andH-3;C-5, C-6, C-10
andH-12;C-8, C-10andH-6;C-6, C-9andH-8;C-7
andH-1′.HMBCcorelationbetweentheanomericpro-
tonofβ-glucopyranosylgroupatδ5.05(d, 1H, J=7.
5 Hz)andδ162.1(C-7)wasobserved(Fig.2).
Comparisonof13CNMRdataof1 withthoseofthe
known 2, 5-dimethyl-7-hydroxychromone, bothcom-
poundsshowedverysimilar13CNMRdata, but1 pos-
sessesmoresignalsforglucopyranosylgroup[ 5] .There-
fore, compound1 wasidentifiedas2, 5-dimethyl-7-
hydroxychromone-7-O-β-glucopyranoside.
ByMS, 1Hand13CNMRdatacompounds2-6 werei-
dentifiedasfolows:nepodin-8-O-β-D-glucopyranoside
(2)[ 6] , 10-hydroxyaloinA(3)[ 7] , 10-hydroxyaloinB
(4)[ 7] , 5-methoxyl-1(3H)-benzofuranone-7-O-β-D-
glucopyranoside(5)[ 8] , andphenylethyl-O-α-L-arabi-
nopyranosy-(1※6)-O-β-D-glucopyranoside(6)[ 9] .
Table1 NMRspectraldataof1inCD
3
OD(1H 500 MHz;13C125 MHz;δppm, JHz)
No. δH δC No. δH δC
1 10 117.6
2 167.2 1′ 5.05(1H, d, 7.5Hz) 101.6
3 6.06(1H, br.s) 111.8 2′ 3.49(1H, t, 8.5Hz) 74.8
4 182.0 3′ 3.49(1H, t, 8.5Hz) 77.9
5 143.6 4′ 3.40(1H, m) 71.3
6 6.91(1H, d, 1.5Hz) 118.6 5′ 3.52(1H, m) 78.4
7 162.1 6′ 3.71(1H, dd, 6.0, 6.0Hz)
3.92(1H, d, 14.0Hz) 62.5
8 7.02(1H, d, 2.5Hz) 103.0 11 2.35(3H, s) 19.9
9 161.0 12 2.76(3H, s) 23.1
Fig.2 StructuresandkeyHMBCcorrelationsofcom-
pound1
MaterialsandMethods
General
UVspectrumwasrecordedonaShimadzu2401 PC
spectrophotometer.Columnchromatography(CC)was
performedoversilicagel(100-200 mesh, 200-300
mesh, QingdaoMarineChemicalInc., China)andAB-
8 porouspolymerresin(TianjinChemicalInc., Chi-
na), respectively.Prep-HPLC:ODScolumn(Altech
250×10mmi.d., 5 μm), Waters2487 dualλabsor-
bancedetector.NMRspectrawererecordedonaBruk-
erAM-400 andaDRX-500 spectrometerwithTMSas
internalstandard.FAB-MSwerecarriedoutonaAuto-
spec-UltimaETOFspectrometer.
Plantmaterial
TherootsofRumexgmeliniTurcz.werecolectedfrom
MedicinalBotanicalGardenofHeilongjiangUniversity
ofTraditionalChineseMedicineinSeptember2005,
andavoucherspecimenisdepositedatthePlantRe-
190 NatProdResDev Vol.21
sourcesCenterHerbariumofHeilongjiangUniversityof
TCM.Theidentificationoftheplantwasperformedby
Prof.WangZhen-Yue, DepartmentofTraditionalChi-
neseMedicalResourcesinHeilongjiangUniversityof
TCM.
Extractionandisolation
Airdriedroots(5kg)wereextractedat80℃ in75%
EtOH(50kg×3 times, eachfor1 h).The75%EtOH
solutionwasconcentratedat60 ℃underreducedpres-
suretoafordresidue(1kg).Theresidue(1 kg)was
subjectedtoAB-8 macroporousresincolumneluted
withH2O, 30%, 60% and90% EtOHsuccessively.
Thefractionfrom30% EtOH(300 g)wasseparated
oversilicagelcolumngradientlyelutedwithCHCl3-
MeOHtogivesixfractions(Fr.Ⅰ -Fr.Ⅵ ).Fr.Ⅰ was
subjectedtosilicagelcolumnelutedwithCHCl3-
MeOH(25∶1 to10∶1)toafordthreefractionsA-C.
FractionsBandCweresubjectedtosilicagelcolumn
elutedwithCHCl3 -MeOH(10∶1)togive2 (30.5 g)
Fr.Ⅲ wassubjectedtosilicagelcolumnelutedwith
CHCl3-MeOH(10∶1 to6∶1)toafordFr.Ⅲ.1 and
Fr.Ⅲ.2.FractionFr.Ⅲ.1 wasdividedintotwofrac-
tionsII-AandII-Boversilicagelcolumnelutedwith
CHCl3-MeOH(6∶1).II-Awaspurifiedbyprep-
HPLC(ZorbaxODS-C18 , MeOH-H2O=45∶55)togive
3 (6.4mg)and4(6.8 mg).Fr.Ⅲ.2 wasseparated
oversilicagelcolumnelutedwithCHCl3-MeOH(7∶1)
togive2-A, 2-Band2-C.2-Bwaspurifiedbyprep-
HPLC(ZorbaxODS-C18 , MeOH-H2O=40∶60)togive
5 (5.4mg).2-Cwaspurifiedbyprep-HPLC(Zorbax
ODS-C18 , MeOH-H2O=55∶45)toyield1 (5.4 mg)
and6 (4.2 mg).
2, 5-Dimethyl-7-hydroxychromone-7-O-β -glucopyr-
anoside(1) whiteneedles(CH3OH), [ α] 25D-4.2°
(c0.25, CH3OH), C17H20O8.UVλCH3OHmax (logε)nm:
226(2.29), 249(1.66)and282(1.08).NMRdata
areshowninTable1.FAB+-MSm/z:353[ M+H] +
(11%), 375[ M+H+Na] +(17%);HR-FAB-MS
([ M+H] +)m/z:353.1240, calcd.353.1236.
Acknowledgment Thisworkwassupportedbythe
NationalNaturalScienceFoundationofChina(No.
30270156).
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