全 文 ：CJNM
ANewGlucopyranosylNaphthalenefrom
ClematishexapetalaPal.
DONGCai-Xia, SHIShe-Po, ZHAOMing-Bo, TUPeng-Fei＊
DepartmentofNaturalMedicines, SchoolofPharmaceuticalSciences, PekingUniversityHealthScienceCenter, Beijing100083 , China
Availableonline20 January2008
【ABSTRACT】　 AIM:TostudythechemicalconstituentsoftherootsandrhizomesofClematishexapetalaPall..METHODS:Thesolventextraction, silicagelcolumnchromatographyandpre-HPLCwereusedtoisolateandpurifytheconstituent, andvarious
spectroscopicanalyseswereusedtoelucidatethestructure.RESULTS:Aglucopyranosylnaphthalene(1)derivative, 5, 8-di-hydro-6-methyl-1, 4-β-D-diglucopyranosylnaphthalenehas(1)beenisolatedfromthisplant.CONCLUSION:Thiscompound
isanewone, andthisstudyenrichedthechemicalconstituentsofClematishexapetala.【KEYWORDS】　Clematishexapetala;GlucopyranosylDihydro-naphthalene;5, 8-dihydro-6-methyl-1, 4-β-D-diglucopyranosylnaphthalene;Chemicalconstituent
【CLCNumber】　R284.1　　【Documentcode】　A　　【AriticleID】　1672-3651(2008)01-0023-03
【Receivedon】　2007-11-12
【FoundationItem】　ThisprojectwassupportedbytheNationalKey
TechnologiesResearchandDevelopmentProgramofChinaduringthe
10thFive-YearPlanPeriod(No.2004AA2Z3730)
【＊Correspondingauther】　TUPeng-Fei:professor, Tel/Fax:86-
10-82802750, E-mail:pengfeitu@bjmu.edu.cn
　　Thereareabout300 speciesofClematisgenusplants(FamilyRanunculacea)overtheworld, and
110ofthemexistinChina, mainlydistributedintheSouthwestofChina.Asoneofthethreeoriginalplantsofawel-knowntraditionalChinesemedicine“weilingxian” , thespeciesofClematishexapetalaPal.hassuchactivitiesasanti-inflammation, anal-gesicandanti-tumoretc, anditismainlydistributedinthenorthernChina, includingInnerMongolia,Heilongjiang, Jilin, Liaoning, Hebei, ShandongandShanxiprovinces.Inourpreviousstudy, wereportedsomeflavonoidsandlignansisolatedfromthisplant,andinthispaper, wewilreporttheisolationandstructuralelucidationofanewglucopyranosylnaph-thalenederivative, 5, 8-dihydro-6-methyl-1, 4-β-D-diglucopyranosylnaphthalene(1).
1　ResultsandDiscussion
Compound1wasobtainedasapaleyelowres-in.InEI-MSspectrum, themolecularionpeakof
aglyconewaspresentas176 [ M-2Glu+2H] +.
Combinedwiththeanalysesof1 HNMR, 13CNMRandDEPTspectra, themolecularformulawasde-ducedasC23H32O12 , with8degreesofunsaturation.The1HNMRspectrumof1 presentedthecharacteris-
ticpaternofABsystem[ δ6.91 (1H, d, J=9.0Hz), 6.88 (1H, d, J=9.0 Hz)] , analkenepro-ton[ δ5.44(1H, t, J=6.5 Hz)] , abroadsin-gletatδ2.10(2H)andatripletatδ3.06 (2H).
Inthe13CNMRspectrum, sixaromaticcarbonsignals(δ 150.0, 148.6, 133.3, 132.2, 114.9 and
114.8)wereobserved, andagroupofsignalsatδ
135.8 , 120.2 , 32.7, 22.7 and25.6 werealsopres-ent, whichwerecomposedofonequaternarycarbon,onetertiarycarbon, twosecondarycarbonsandoneprimarycarbonaccordingtotheDEPTspectrum.Comparingwiththesignalsofisopentenylsuggestedthatamethylcarbonwasreplacedbyamethylenecarbon, andthemethyleneprotons[ δ2.10 (2H)]hadalong-rangecorelationwithC-4a(δ133.3)inHMBC spectrum, indicatingthe methylenewaslinkedtoC-4aofbenzenering.Sotheaglyconewasdeterminedtobe5, 8-dihydro-6-methylnaphthalene.IntheNMRspectra, besidesthesignalsduetotheaglycone, twogroupsofglucosesignalswerealsoobserved, andtheanomericprotonsandcarbonswerelocatedatδ4.57(1H, d, J=8.0 Hz), 4.56(1H,d, J=8.0 Hz), δ103.0 and102.5, respectively.Thecouplingconstant(J=8.0 Hz)suggestedthattheglucopyranosylunitexistedinβ orientation.IntheNOESYspectrum, twoanomericprotonshadevi-dentcorelationswithH-2 andH-3 oftheaglyconerespectively, andtheyalsopresentedalong-rangecorelationwithC-1(δ150.0)andC-4(δ148.6)inHMBCspectrum.Thesedatasuggestedtwogluco-seswerelinkedtoC-1 andC-4 oftheaglycone, re-
CJNM
spectively.Conclusively, thestructureof1 wasidentifiedas5, 8-dihydro-6-methyl-1, 4-β-D-diglu-copyranosylnaphthalene.
Fig1　StructureofCompound1
2　Experimental
2.1　GeneralExperimentalMethodsOpticalrotationsweredeterminedusingaPerkinElmer243Bdigitalpolarimeter.NMRspectrawererecordedonanInova-300andInova-500spectrometerusingTMSasinternalstandardreference.Prep-HPLCwasperformedonanODScolumn(Altech
250mm×10 mmi.d., 5 μm)withaWaters2 487dualλabsorbancedetector.EI-MSspectrawereper-formedonaTrans-MSmassspectrometer.ColumnchromatographywasperformedusingD101 porouspolymerresin(TianjinChem.Ind.Co.)orSepha-dexLH-20 gel(Pharmacia)andsilicagel(QingdaoMarineChemicalFactory)asanabsorbent.TLCwasperformedonsilicagel(QingdaoMarineChemicalFactory).Alsolventswerechemicaloranalyticalpure(BeijingChemicalWorks).
2.2　PlantmaterialTherootsandrhizomesofClematichexapetalaPal.werecolectedfromHailaerintheInnerMongo-lianAutonomousRegionofChina.TheidentificationoftheplantwasperformedbyProf.TuPeng-fei, Pe-kingUniversity.AvoucherspecimenwasdepositedintheherbariumofPekingUniversityModernRe-searchCenterforTraditionalChineseMedicine(No:
200409011).
3　ExtractionandIsolation
Air-driedrootsandrhizomesofC.hexapetala(19kg)wereextractedthreetimes(eachfor1 h)with95% EtOHand50%EtOH, respectively.Thefilteredextractswereconcentratedinavacuumevap-oratortoafordextractAandextractB.ExtractB(3.0 kg)wassuspendedinwaterandextractedsuc-cesivelywithEtOACandn-BuOHtoafordfractionsEtOAcandBuOH.FractionBuOH(256 g)wassub-jectedtoD101 porouspolymerresinandelutedwithH2O, 10, 30, 50 and70% EtOHsuccessively.Thefractionelutedwith10% EtOH wassubjectedtoSephadexLH-20 columnchromatographyandeluted
with10% MeOHtoafordFr.1-2.Fr.2 wassub-jectedtosilicagelcolumnchromatographyandelutedwithCHCl3-MeOH(5∶1), andfinalypurifiedbyprep-HPLC[ MeOH/H2O(35∶65)asmobilephase,
254and280nm, 2.5mL·min-1 ] toafordcompound
1(6.4 mg).
Table1　 NMR(inDMSO-d6)dataofcompound1
No. δH δC HMBC
C(1) 150.0
H-C(2) 6.91(1H, d, J=9.0Hz) 114.9 C(4)
H-C(3) 6.88(1H, d, J=9.0Hz) 114.8 C(1)
C(4) 148.6
C(4a) 133.3
H-C(5) 2.10(2H, brs) 32.7 C(4a)
C(6) 135.8
CH3-C(6) 1.52(1H, s, 6-CH3) 25.6 C(5), C(6), C(7)
H-C(7) 5.44(1H, t, J=6.5Hz) 120.2 C(8a)
H-C(8) 3.06(2H, t, J=9.0Hz) 22.7 C(6), C(4a)
C(8a) 132.2
Glc
H-C(1) 4.57(1H, d, J=8.0Hz) 103.0 C(1)
H-C(2) 3.22(1H, m) 73.5
H-C(3) 3.20(1H, m) 77.0
H-C(4) 3.15(1H, dd, J=7.5, 5.0 Hz) 69.8
H-C(5) 3.43(1H, m) 76.7
H-C(6a) 3.68(1H, dd, J=11.0, 5.5Hz) 60.9
H-C(6b) 3.45(1H, m, J=11.0, 5.5Hz)
Glc′
H-C(1′) 4.56(1H, d, J=8.0Hz) 102.5 C(4)
H-C(2′) 3.22(1H, m) 73.5
H-C(3′) 3.20(1H, m) 76.9
H-C(4′) 3.15(1H, dd, J=7.5, 5.0 Hz) 69.8
H-C(5′) 3.43(1H, m) 76.6
H-C(6′a) 3.68(1H, dd, J=11.0, 5.5Hz) 60.9
H-C(6′b) 3.45(1H, m, J=11.0, 5.5Hz)
＊ThecouplingconstantsofthesugarH-atomswerenotassignedforcurious
overlapping.
5, 8-dihydro-6-methyl-1, 4-β-D-diglucopyrano-sylnaphthalene(1):Paleyelowresin, [ α] 20D -
105.0°(c0.5, DMSO).EI-MS:m/z=176 ([ M-
2Glu+2H] +, C11H9O2).1Hand13CNMRdataseeTable1.
Acknowledgements
WeappreciatethehelpfromMaJi-Yu, HailaerInstitute
forDrugControl, InnerMongoliaAutonomousRegionofChinainthecollectionofplantmaterial.WearealsothankfultoTaoHaiyanandQiaoLiang, analyticalcenterofPekingUniversityHealthSciencesCenter, fortheirhelpintheMSandNMR
measurement.
References
[ 1] 　DongCX, WuKS, ShiSP, etal.FlavanoidsfromClematishex-
apetala[J] .JChinPharmSci.2006, 15(1):15-20.
[ 2] 　DongCX, ShiSP, WuKS, etal.Chemicalconstituentsfrom
therootsandrhizomesofClematishexapetalaPal.[ J] .ChinaJ
ChinMaterMed.2006, 31(20):1696-1699.
[ 3] 　DongCX, ShiSP, WuKS, etal.Chemicalconstituentsfrom
24 DONGCai-Xia, etal:AnewglucopyranosylnaphthalenefromClematishexapetalaPal
CJNM
therootsandrhizomesofClematishexapetalaPal. [ J] .
ZeitschriftfǜrNaturforschungB-ChemicalSciences(inpres).
[ 4] 　YuDQ, YangJS.AnalyticalChemicalHandbook:Vol7 [ M ].
2nded.Beijing:ChemicalIndustryPress, 1999: 367, 799,
902.
棉团铁线莲中新葡萄糖基萘类成分
董彩霞 , 史社坡 , 赵明波 , 屠鹏飞＊
北京大学药学院天然药物学系 ,北京 100083
【摘　要】　目的:研究棉团铁线莲(ClematishexapetalaPal.)的干燥根及根茎的化学成分。方法:利用溶剂提取 、硅胶
柱色谱和高效液相色谱等技术进行分离 、纯化 , 根据理化性质和波谱数据鉴定化合物的结构。结果:从中分离得到 1个葡
萄糖基萘类化合物 ,鉴定为 5, 8-二氢-6-甲基萘-1, 4-二-O-β-D-葡萄糖苷 (1)。结论:该化合物为一新化合物 , 丰富了棉团
铁线莲的化学成分。
【关键词】　棉团铁线莲;葡萄糖基萘;5, 8-二氢-6-甲基萘-1, 4-二-O-β-D-葡萄糖苷;化学成分
【基金项目】　“十五”国家科技攻关计划重点项目(No.2004AA2Z3730)
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25DONGCai-Xia, etal:AnewglucopyranosylnaphthalenefromClematishexapetalaPal