全 文 ：第 27卷增刊
2007年 10月
林　产　化　学　与　工　业
ChemistryandIndustryofForestProducts
Vol.27Supplement
Oct.2007
StudyonGalicAcid, ElagicAcidandHydrolysable
TanninsfromJuglansmandshuricaMaxim.
StemBark
　　Receiveddate:2007-06-08
　　Foundationitems:中国博士后科学基金资助项目(20070410198);天津科技大学引进人才科研启动基金(20060434)
　　Biography:司传领 (1975-), 男 , 山东菏泽人 , 副教授 , 博士 , 主要从事林产化工 、天然产物方面的研究;E-mail:sichli@yahoo.com。
SIChuan-ling　　
SIChuan-ling1 , WANGDan2 , KIMJK3 , KWONDJ3 , BAEYS3
(1.TianjinKeyLaboratoryofPulp＆Paper, TianjinUniversityofScience＆Technology,
Tianjin300222, China;2.InstituteofChemicalIndustryofForestProducts, CAF;Keyand
OpenLab.onForestChemicalEngineering, SFA, Nanjing210042, China;
3.ColegeofForestSciences, KangwonNationalUniversity, Chuncheon200-701, Korea)
Abstract:Galicacid(1), elagicacid(2), and4 hydrolysabletannins, 1, 2, 6-tri-O-galoyl-β-D-
glucose(3), 1, 3, 6-tri-O-galloyl-β-D-glucose(4), 1, 2, 4, 6-tetra-O-galoyl-β-D-glucose(5)and1, 2,
3, 4, 6-penta-O-galoyl-β-D-glucose(6)havebeenisolatedfromtheH2Ofractionofacetone-H2O(7∶3)extractofJuglansmand-
shuricaMaxim.stembarkonthebasisofchemicalevidenceandspectraltechniques.Compounds2, 4 and6 werereportedfor
thefirsttimefromthisspecies.
Keywords:JuglansmandshuricaMaxim.;bark;hydrolysabletannin;NMR
CLCnumbers:TQ943.2　　　　　Documentcode:A　　　　　ArticleID:0253-2417(2007)S0-0008-03
核桃楸树皮的没食子酸 、鞣花酸及水解单宁成分研究
司传领 1 , 王 丹 2 , 金辰奎3 , 权东周 3 , 映寿 3
(1.天津科技大学天津市制浆造纸重点实验室 , 天津 300222;2.中国林业科学研究院
林产化学工业研究所;国家林业局林产化学工程重点开放性实验室 , 江苏 南京 210042;
3.韩国江原大学森林科学学院 , 春川 200-701, 韩国)
摘　要:研究了核桃楸树皮丙酮-水提取物的水溶性萃取部位的化学成分。采用 SephadexLH-20柱色谱及薄层色谱等
方法进行分离 , 经波谱分析及理化性质测定 , 鉴定了 6个化合物:没食子酸(1)、鞣花酸(2)、 1, 2, 6-三没食子酰葡萄糖
(3)、 1, 3, 6-三没食子酰葡萄糖(4)、 1, 2, 4, 6-四没食子酰葡萄糖(5)及 1, 2, 3, 4, 6-五没食子酰葡萄糖(6)。化合物 2、
4、 6为首次从该植物中分得。
关键词:核桃楸;树皮;水解单宁;核磁共振
JuglansmandshuricaMaxim.(Juglandaceae)isafast-growingdeciduoustreewidelydistributedin
China, SiberiaandKoreanPeninsula.Thetreehasbeenusedasafolkmedicinalplantfortreatmentof
esophageal, gastric, cardiacandlungcancer.Itisalsoreportedthatchemicalsvolatilizedfromthespecies
inhibitthegrowthoftheneighboringplantsandcanbedevelopedforchemurgy.Severalnaphthoquinones,
naphthalenylglycosides, α-tertalonylglucopyranosides, flavonoidsanddiarylheptanoylglucopyranosideshave
beenisolatedfromthisplant, andthesecompoundshavebeenshowntohaveanti-HIV-1 activity, cytotoxic
activitytohumancancercellinesandinhibitoryefectsonDNApolymeraseandRNaseHactivitiesofHIV
reversetranscriptase[ 1-3] .Previously, theauthorsisolated11 antioxidantflavonoidsandflavonoidglycosides
fromitsstembark(theresearchpaperwilbetopressinChemistryandIndustryofForestProducts).Asone
增刊 司传领 ,等:核桃楸树皮的没食子酸 、鞣花酸及水解单宁成分研究 9　
chainofasystematicstudyofthistree, inthispaper, wereporttheisolationof6 galicacid-related
compoundsfromitsH2Ofractionofacetone-H2Oextract.
1　Experimental
1.1　Plantmaterials
J.mandshuricastembarkwascolectedinthecampusforestofKangwonNationalUniversity, Koreain
April, 2005 andauthenticatedbyProfessorParkW G, ColegeofForestSciences, KangwonNational
University.AvoucherspecimenisdepositedintheherbariumofDepartmentofWoodScience＆Engineering,
KangwonNationalUniversity.
1.2　Apparatusandreagents
ColumnchromatographywasperformedusingSephadexLH-20 (Merck).Eluentswerecolectedwitha
fractioncolector(GilsonFC204).TLCanalyseswereperformedonDC-PlastikfolienCeluloseF(Merck)
platesanddevelopedwitht-BuOH-HOAc-H2O(3∶1∶1, volumeratio, sameasinfolowing)andHOAc-H2O
(3∶47).VisualizationwasbyUVlight(254and365nm)orbysprayingwith1% FeCl3(inEtOH)solution
folowedbyheating.
The1HNMR, 13CNMR, DEPTandcorelationNMRspectrasuchasHMBC, HMQCandTOCSYwere
recordedinMeOH-d4 withTMSasaninternalstandardusingaBrukerAvanceDPX400 spectrometeratthe
operatingfrequencyof400 MHz(1HNMR)and100 MHz(13CNMR)inCentralLaboratoryofKangwon
NationalUniversity, Korea.PositiveFABMSspectroscopywasperformedwithamicromassautospecM363
spectrometerandMALDI-TOFMSspectroscopywasdoneonaModelVoyager-DESTRspectrometer.Melting
pointsweredeterminedonanElectroThermal9100apparatusandareuncorected.
Alreagents(DaejungCo.Ltd., Korea)usedinthisworkwereofanalyticalgrade.
1.3　Experimentalprocedures
1.3.1　Extractionandfractionation　Thestembark(3.2kg)wasair-dried, groundandextractedin
acetone-H2O(7∶3)forseveraldaysatroomtemperature.Afterfiltrationandconcentrationunderreduced
pressure, theaqueousresiduewassequentialyfractionationedandfreezedriedtogiven-hexane(15.6g,
yield0.5%), CH2Cl2 (20.6g, yield0.6%)EtOAc(130g, yield4.1%)andH2O(337.6g, yield
10.6%)fractions.
1.3.2　Isolation　AportionofH2Ofraction(31.5g)wassubjectedtoaSephadexLH-20 columnwith
MeOH-H2O(1∶1, volumeratio)aselutingsolventtogive4 fractions:W1 (4.5g), W2 (19.3g), W3
(3.8g)andW4(3.9g).WhenaqueousW2 andW4 wereconcentrated, crystalinematerialsidentifiedas
compounds1(17.2g)and6 (251mg), respectively, wereobtainedusingacentrifuge.FractionW3 was
submitedagainonaSephadexcolumnusingMeOH-H2O(1∶3)forfurtherpurificationandyielded4subfrac-
tions.ThethirdsubfractionwasstepwiselyretreatedwithMeOH-H2O(1∶5and1∶7)andEtOH-hexane(2∶1
and1∶2)togivecompounds2(61mg), 3(34mg)and5(110mg).FractionW1 wasreappliedtoa
SephadexcolumnwithMeOH-H2O(1∶3 and1∶5)toisolate72mgofcompound4.
2　Resultsanddiscussion
Galicacid(1, 17.2g), elagicacid(2, 61mg), and4hydrolysabletannins, 1, 2, 6-tri-O-galoyl-β-D-
glucose(3, 34mg), 1, 3, 6-tri-O-galoyl-β-D-glucose(4, 72mg), 1, 2, 4, 6-tetra-O-galoyl-β-D-glucose(5,
110mg)and1, 2 , 3, 4, 6-penta-O-galoyl-β-D-glucose(6, 251mg), asshowninFig.1, wereisolatedas
yelowishpowderswhichshowedphysicalandspectraldatavirtualyidenticaltothosereportedbefore[ 4-8] .
10　 林　产　化　学　与　工　业 第 27卷
Fig.1　CompoundsisolatedfromJ.mandshuricastembark
3　Conclusion
Sixgalicacid-relatedcompoundswereisolatedusingchromatographictechniques(suchasTLCand
columnchromatographyusingSephadexLH-20)andcharacterizedbyspectroscopicanalysesandchemical
evidenceasgalicacid(1), elagicacid(2), 1, 2 , 6-tri-O-galoyl-β-D-glucose(3), 1 , 3, 6-tri-O-galoyl-β-
D-glucose(4), 1, 2 , 4, 6-tetra-O-galoyl-β-D-glucose(5)and1, 2, 3, 4, 6-penta-O-galoyl-β-D-glucose(6)
fromtheJuglansmandshuricaMaxim.stembark.Todate, thiswasisolationofcompounds2, 4 and6 from
thistreeforthefirsttime.
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