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A new anthraquinone from roots of Rumex japonicus

羊蹄根中的一个新的蒽醌类化合物



全 文 :AnewanthraquinonefromrootsofRumexjaponicus
CHENMingxiang,WANGDingyong,FENGYujing,YANGWen
(ColegeofPharmacy,GuangdongPharmaceuticalUniversity,Guangzhou510006,China)
[Abstract] Anewanthraquinone,(1)hydroxymethyl3,6dimethoxyl2,8dihydroxylanthraquinone1,wasisolatedfromthe
rootofRumexjaponicusalongwithsixknowncompounds27.Theirstructureswereelucidatedbyvariousspectroscopicmethodsinclu
ding2DNMRtechniquesorcomparisonwithauthenticsamples.
[Keywords] Rumexjaponicus;anthraquinone;1hydroxymethyl3,6dimethoxyl2,8dihydroxylanthraquinone
[Receiveddate] 20090331
[Correspondingauthor] WangDingyong,Tel:13112243919,E
mail:wdingyong@163.com
[Firstauthor]  Chen Mingxiang, Tel:13244819583,Email:
cmx2003030852@126.com
  TheRumexplantRumexjaponicus,aperennial
herb,iswidelydistributedinChina.Itsresourceisex
tremelyabundant.TherootofR.japonicushasbeen
usedextensivelyforskindiseases,dermatomycosis,
hemorhageandinflammationinTraditionalChinese
herbalmedicinesduetothefunctionofpromotingblood
flow,hematischesis,heatclearing,detoxicatingand
anthelminthic.Previously,anthraquinones,naphtali
numsandflavonoidssuchasemodin,chrysophanol,
musizinandglobulariacitrinwereisolatedfromtheroot
ofR.Japonicus[1].Inacontinuationofourinvestiga
tiontofindactivecompounds,wechemicalystudied
therootsofR.japonicuscolectedinDongkouofHu
nanProvince,andanewanthraquinone,1hydroxym
ethyl3, 6dimethoxyl2, 8dihydroxylanthraquinone
(1),wasisolatedalongwithsixknowncompounds
whichwereidentifiedasβsitosterol(2)[2],quercetin
(3)[3],musizin(4)[4],emodin(5)[4],physcion
(6)[4] andchrysophanol(7)[4] bycomparisionof
theirspectraldatawithliteraturesorauthenticsam
ples.Inthepresentpaper,theisolationandstructural
elucidationofthenewcompound1wasreported.
Compound1 orangeyelowneedlecrystal(ace
tone),mp28852900℃.Themolecularionpeak
atm/z330initsEIMSspectrumsuggestedthemolec
ularweightof1tobe330.Thequasimolecularion
peakatm/z3291initsESIMSspectrumalsosuppor
tedtheaboveresult.ItsmolecularformulaC17H14O7
wasobtainedfrom quasimolecularionpeakatm/z
3290660[M-H]-inHRESIMSspectrum,which
wasfurtherconfirmedby1HNMRand13CNMRspec
trumincludingDEPTdata(Table1).Themaximaab
sorptionsatλ218,289,322,400nmintheUVspec
trum,theIRabsorptionsatν:1586(chelatedquinone
ketone),1625cm-1(unchelatedquinoneketone),
thegenerationofapinkcolorwith05% methanolic
magnesiumacetateandthe1HNMRsignalatδ1302
suggested1wasanαhydroxylanthraquinone[5].The
1HNMRspectrumshowedthreearomaticprotons:δ
655(1H,d,J=18Hz),705(1H,d,J=18
Hz)and765(1H,s).Twomethoxyls:δ402
(3H,s)and331(3H,s).Onehydroxymethyl:δ
497(2H,s)andthreehydroxyls:δ1302(1H,
s),1110(1H,brs),1030(1H,brs).Fromthe
HMBCcorelationsofthetwoaromaticprotons(δ
705,765)withC10(δ1812),δ765and705
inthe1HNMRspectrumcouldbeassignedtoH4and
H5,respectively.TheHMBCcorelationbetweenthe
methoxylprotons(δ402)andC6(δ1644)and
theNOESYcorelationbetweenthemethoxylprotons
(δ402)andH5(δ705)indicatedthismethoxyl
grouptobelocatedatC6.Anothermethoxylprotons
(δ331)waslocatedatC3duetoitsHMBCcorela
tionwithC3(δ1514)andNOESYcorelationwith
H4(δ765).Thehydroxymethylprotons(δ497)
duetothedeshieldingbyneighboringcarbonylgroup
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waslocatedatC1bythecorelationsbetweenthe
hydroxymethylprotons(δ497)andC2(δ1515)
andC8b(δ1256)intheHMBCspectrum.Thus,
thestructureof1wasprosposedas1hydroxymethyl3,
6dimethoxyl2,8dihydroxylanthraquinone(Fig.1).
Table1 NMRdataofcompound1(DMSOd6)
Catom δH(JinHz) δ1)C HMBC
1   1430(s)  
2   1515(s)  
3   1514(s)  
4 765(s) 1088(d)C10,C2,C8b
4a   1341(s)  
4b   1275(s)  
5 705(d,J=18Hz) 1072(d)C10,C7,C8a
6   1644(s)  
7 655(d,J=18Hz) 1077(d)C5,C8a,C6,C8
8   1643(s)  
8a   1101(s)  
8b   1256(s)  
9   1879(s)  
10   1812(s)  
1CH2OH497(s) 639(q)C8b,C2
3OCH3 331(s) 578(q)C3
6OCH3 402(s) 562(s) C6
2OH 1110(brs)    
1CH2OH1030(brs)    
8OH 1302(s)   C8,C8a,C7
  1)MultiplicitywasdeterminedbyDEPT.
Fig.1 thestructureofcompound1
  αMethylanthraquinoneshavebeenobtainedfrom
limitedeightplants,viz.Rhamnusfalax(Rhamnace
ae),Aloesaponaria(Liliaceae),Eleutherineamerica
na(Iridaceae),Rheumsp.(Polygonaceae),Gladio
lussegetum(Iridaceae),Crocussativus(Iridaceae),
Araliorhamnusvaginata(Rhamnaceae)andGladiolus
gandavensis(Iridaceae)[5].Asopposedtotheplant
kingdom,thepresenceofanαsidechainisacommon
featureofanthraquinonesofanimalorigin[6].R.ja
ponicus,therefore,appearstobeanothersourcefor
synthesizingsuchcompounds.αmethylanthraquinone
maybethesignificanttaxonomicfeatureofR.japoni
cusHout.
1 Experimental
MeltingpointsweredeterminedonXRC1mi
cromeltingpointapparatusandwereuncorected.NMR
spectrawererunonaBrukerAM40spectrometer.
MassspectrawereobtainedonFinngenLCQDECA(ES
IMS),VGAutoSpec3000(EIMS)andBioTOFⅢQ
(HRMS)massspectrometer.IRandUVspectrawere
recordedonPerkinElmer599BandShimadzuUV250
spectrometers,respectively.TLCwasperformedonsil
icagelGF254andHRTLConsilicagelH(57μm).
Separationandpurificationwereperformedbycolumn
chromatographyonsilicagel(200300mesh).
TherootofR.japonicuswascolectedfrom
DongkouDistrictofHunanProvinceofChinainOcto
ber2007,andidentifiedbyProf.QiangqingZeng
(ColegeofChineseTraditionalMedicine,Guangdong
PharmaceuticalUniversity).Avoucherspecimenof
thesample(No.20071025)wasdepositedattheHer
bariumofGuangdongPharmaceuticalUniversity.
2 Extractionandisolation
AirdriedandpowderedrootofRjaponicus(2
kg,60mesh)wererefluxedwith95% ethanol(twice,
2heach).Theethanolsolutionwasevaporatedunder
reducedpressuretogivetheresidue,whichwassus
pendedinwarmwaterandextractedwithCHCl3,EtO
AcandnBuOHsaturatedwithwater,respectively,to
givecorespondingfractionsA(35g),B(58g)and
C(85g).FractionAwassubjectedtochromatography
on200300meshsilicagel(300g,100mm×L800
mm)togive2(80mg)[petroleumetherethylacetate
(20∶1)aselute],3(350mg)[petroleumetherethyl
acetate (15∶1) as elute], 6 (86 mg)
[petroleumetherethylacetate(10∶1)aselute],7
(150mg)[petroleumetherethylacetate(10∶1)as
elute],respectively.FractionBwassubjectedtochro
matographyon200300meshsilicagel(500g,100
mm×1000mm)togive5(95mg)[CHCl3MeOH
(20∶1)aselute],1(25mg)[CHCl3MeOH(15∶
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1)aselute]andtheyelowpowder[CHCl3MeOH
(10∶1)aselute].Theyelowpowderwassubjectedto
chromatographyon200300meshsilicagel(200g,50
mm×400mm)elutedwithCHCl3MeOH(12∶1),
thenrecrystalizedinMeOHtogive4(250mg).
Compound1 orangecrystals(MeOH),mp.
28852900℃;UV (MeOH)nm (logε):218
(399),289(415),322(388)and400(386);
IR(KBr)cm-1:3486,3279,2927,1625,
1586,1492,1464,1404,1325,1277,1169,
1119,1088,1019,957;ESIMS(negativemode)
m/z3291[M-H]-;EIMSm/z(%):330(36),
297(14),287(3),272(8),269(20),257(2),
228(3),199(8),184(2),168(1),143(2),
136(2),115(9),101(4),77(10),63(6),57
(13),45(100);HRESIMS(negativemode)m/z
3290660[M-H]-,required:3290661;1H
NMRand13CNMRdataareshowninTable1.
  [Acknowledgements] Thisworkwasfinancial
lysupportedbytheBureauofScienceandTechnology
ofZhongshanMunicipality,Guangdong,China(No.
2007J006).
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entsfromRumexjaponicusHout[J].JChinMedMater,2005,28
(2):104.
[2] ZhangZF,BianBL.Studiesonthechemicalconstituentsin
rootsofJasminumsambac(Ⅱ)[J].NatProdResDev,2007,
19:237.
[3] GaoW,ShenY,ZhangHJ,etal.Thechemicalconstituentsof
Potentilachinensis[J].PharmCareRes,2007,7(4):262.
[4] ZhengSQ,ChenWS,TaoZY,etal.Studyonthechemical
constituentsofRumexjaponicusHout[J].AcadJSecMilMed
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[5] WangDY,YeQ,ZhangGL,etal.Newanthraquinonesfrom
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羊蹄根中的一个新的蒽醌类化合物
陈铭祥,王定勇,冯玉静,杨雯
(广东药学院 药科学院,广东 广州 510006)
[摘要] 目的:对中药羊蹄Rumexjaponicus根进行化学成分研究。方法:用柱色谱法分离,并用各种波谱法对化合物的结构进
行鉴定。结果:从羊蹄根中分离并鉴定了7个化合物,分别为1羟甲基3,6二甲氧基2,8二羟基蒽醌(1)、β谷甾醇(2)、槲皮素(3)、酸模素
(4)、大黄素(5)、大黄素甲醚(6)、大黄酚(7)。结论:1羟甲基3,6二甲氧基2,8二羟基蒽醌(1)为一新的蒽醌类化合物。
[关键词] 羊蹄;蒽醌类化合物;1羟甲基3,6二甲氧基2,8二羟基蒽醌
[责任编辑 王亚君]
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 September,2009