全 文 ：多穗金粟兰中一个新的酚苷*
冉新辉1,2,倪暋伟2,魏暋刚3,陈昌祥2,刘海洋2
**
(1广州中医药大学第一临床医学院,广东 广州暋510405;2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;3广州中医药大学新药研究中心,广东 广州暋510006)
摘要:从多穗金粟兰 (Chloranthusmultistachys)全株的甲醇提取物中分离得到1个新的酚苷,通过波谱
技术鉴定其结构为丁香酸灢4灢O灢毩灢L灢鼠李吡喃糖苷 (1)。同时还首次从该植物中分离得到两个已知倍半萜
内酯和一个已知木脂素:1毬,4毬灢二羟基灢5毩,8毬灢二氢灢7(11)Z灢桉叶烯灢8,12灢内酯 (2),1毬,4毩灢二羟基灢5
毩,8毬灢二氢灢7(11)Z灢桉叶烯灢8,12灢内酯 (3),(–)灢(7S,8R)灢dihydrodehydrodiconiferyalcohol(4)。
关键词:多穗金粟兰;金粟兰科;酚苷;倍半萜内酯
中图分类号:Q946暋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)01灢083灢04
ANewPhenolicGlycosidefromChloranthus
multistachys(Chloranthaceae)
RANXin灢Hui1,2,NIWei2,WEIGang3,CHENChang灢Xiang2,LIU Hai灢Yang2
(1TheFirstAffiliatedHospitalofGuangzhouUniversityofTraditionalChineseMedicine,Guangzhou510405,China;
2StateKeyLaboratoryofPhytochemistryandPlantResourcesinWestChina,KunmingInstituteofBotany,
ChineseAcademyofSciences,Kunming650204,China;3ResearchCenterofNewDrug,
GuangzhouUniversityofTraditionalChineseMedicine,Guangzhou510006,China)
Abstract:Anewphenolicglycoside,namedsyringicacid灢4灢O灢毩灢L灢rhamnopyranoside(1),togetherwith
threeknowncompoundswereisolatedfromtheMeOHextractofthewholeplantsofChloranthusmultistach灢
ys.Theirstructureswereelucidatedonthebasisofextensivespectroscopic.Tothebestofourknowledge,
thethreeknowncompounds,1毬,4毬灢dihydroxy灢5毩,8毬(H )灢eudesm灢7(11)Z灢en灢8,12灢olide(2),1毬,4毩
灢dihydroxy灢5毩,8毬(H )灢eudesm灢7(11)Z灢en灢8,12灢olide(3),and(–)灢(7S,8R)灢dihydrodehydrodiconifery
alcohol(4)werealisolatedfromthisplantforthefirsttime.
Keywords:Chloranthusmultistachys;Chloranthaceae;Phenolicglycoside;Sesquiterpenelactones
暋 TheplantsofgenusChloranthus (Chloran灢
thaceae),comprising15species,aremainlydistrib灢
utedintheeastofAsia(Zhou,1993).Mostof
theseplantshavebeenusingasimportantmedicinal
herbsforthetreatmentoftumors,rheumatisms,
andemmeniopathyintraditionalChinesemedicine
(Jiangsu New MedicalColege,1977).Previous
phytochemicalinvestigationonthisgenusrevealed
thepresenceofmonoterpenoids,sesquiterpenoids,
bisesquiterpenoids,diterpenoids,ligans,andfla灢
voneglycosides (Wu etal灡,2007;Yangand
Yue,2006;Yangetal灡,2007;2008;Wanget
al灡,2008;Xuetal灡,2007;Lietal灡,2008).
Chloranthus multistachysisaperennialherb
云 南 植 物 研 究暋2010,32(1):83~86
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09201
*
**
Foundationitems:ThisworkwasfinancialysupportedbytheYoungAcademicandTechnicalLeaderRaisingFoundationofYun灢
nanProvince(No.2008PY066)
Authorforcorrespondence;E灢mail:haiyangliu@mail灡kib灡ac灡cn;Tel:+86灢871灢5223246
Receiveddate:2009灢10灢12,Accepteddate:2009灢11灢23
作者简介:冉新辉 (1984-)女,在读硕士研究生,主要从事天然药物化学研究。
whichmainlydistributesoverthesouthofChina
anditsrootshasbeenusedtotreatbonefracture
inChinaasfolkmedicine(EditorialCommittee
ofthe Administration Bureauof Tranditional
ChineseMedicine,1998).Onesesquiterpenoid,
threebisesquiterpenoids,andnineent灢kaurane
diterpenoidshavebeenisolatedfromthisplant
(YangandYue,2006;2008).Asapartofour
systematicresearchworksonthegenus(Teng
etal灡,2009),thechemicalconstituents of
C灡multistachys wereinvestigated and a new
phenolicglycoside,syringicacid灢4灢O灢毩灢L灢rh灢
amnopyranoside(1)wasobtained,alongwith
threeknowncompounds,1毬,4毬灢dihydroxy灢
5毩,8毬(H )灢eudesm灢7(11)Z灢en灢8,12灢olide
(2)(Yangetal灡,2007),1毬,4毩灢dihydroxy灢
5毩,8毬(H )灢eudesm灢7(11)Z灢en灢8,12灢olide
(3)(Yangetal灡,2007),and(–)灢(7S,8R)灢
dihydrodehydrodiconiferyalcohol(4)(Zhuet
al灡,2008)(Fig灡1).Inthispaper,wereportthe
isolationandstructuralelucidationofthenew
phenolicglycoside.
Fig灡1暋Structuresofcompounds1灢4
ResultsandDiscussion
Compound1wasisolatedasanamorphous
powderandshowedthemolecularformulaC15
H19O9,with6degreesofunsatuation,bythe
negativeHR灢ESI灢MSatm/z343灡1040[M灢H]灢.
TheIR spectrum displayed peaksindicating
hydroxygengroups(3422cm灢1),benzenerings
(1592,1502,1460cm灢1),andcarboxylgroups
(1700cm灢1).UVabsorptionsat毸max211,254
nmsuggestedthat1hadanexcelentconjugated
system.Analysisofthe 13C灢NMRand DEPT
spectra(Table1)of1indicatedonecarbonyl(毮
C169灡6,s),twomethoxyls(毮C56灡5,q),two
sp2 methines(毮C107灡7,d),andfoursp2qua灢
ternarycarbons[毮C128灡0(s),154灡4(暳2,s),
139灡7(s)],whichshowedthepresenceofsy灢
ringicacid moietyinthiscompound(Shaoet
al灡,2008).Thesignalsat毮H5灡33(d,H灢1曚),
4灡14(m,H灢2曚),3灡89(m,H灢3曚),3灡44(m,H灢
4曚),4灡25(m,H灢5曚),1灡20(d,H灢6曚)inthe1H灢
NMRspectrumandsignalsat毮C103灡3 (d,C灢
1曚),71灡9(d,C灢2曚),72灡1(d,C灢3曚),73灡6(d,
C灢4曚),71灡2 (d,C灢5曚),17灡8 (q,C灢6曚)inthe
13C灢NMRspectrum (Table1)of1showedaL灢
rhamnoseinthiscompound.Theanomericcon灢
figurationoftherhamnopyranosylwasdeter灢
minedas毩灢orientedonthegroundthechemical
shiftvaluesoftheC灢3曚(毮C72灡1)andC灢5曚 (毮C
71灡2)tothoseofthecorrespondingcarbonsof
methyl毩灢and 毬灢rhamnopyranoside (Kasaiet
al灡,1979).TheL灢rhamnosewaslinkedtoC灢4
bytheHMBCcorrelationfrom H灢1曚toC灢4as
showninFig灡2.Basedonabovementionedevi灢
dence,thestructureof1wasidentifiedtobesy灢
ringicacid灢4灢O灢毩灢L灢rhamnopyranoside.
Experimental
Generalexperimentalprocedures暋 Opticalrotation
weretakenonaHoribaSEAP灢300polarimeter.UVspec灢
trawereobtainedonaShimadzuUV灢2401PCspectropho灢
tometer.IRspectraweremeasuredwithaBio灢RadFTS灢
48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
Table1暋1Hand13CNMRdataofcompound1inCD3OD(400MHzand100MHz,毮inppm)
No. 毮H (Multiplicity,JinHz) 毮C HMBC (H曻C)
1 128灡0(s)
2,6 7灡33(2H,s) 107灡7(d) C灢1,3,7,4
3,5 154灡4(s)
4 139灡7(s)
7 169灡6(s)
1曚 5灡33(1H,d,1灡7) 103灡3(d) C灢2曚,4曚
2曚 4灡14(1H,dd,1灡7,3灡3) 71灡9(d) C灢4曚,1曚
3曚 3灡89(1H,dd,3灡3,9灡6) 72灡1(d) C灢4曚
4曚 3灡44(1H,t,9灡6) 73灡6(d) C灢3曚,6曚
5曚 4灡25(1H,m) 71灡2(d) C灢1曚,4曚,6曚
6曚 1灡20(3H,d,6灡3) 17灡8(q) C灢4曚,5曚
3,5灢OMe 3灡87(6H,s) 56灡5(q) C灢3,5
Fig灡2暋KeyHMBCCorrelationsofcompound1
135spectrometerwith KBrpelets.FAB massspectra
wereobtainedonaVGAutospec灢3000spectrometerand
high灢resolutionESImassspectrawererecordedonanAPI
QstarPulsarLC/TOFinstrument.NMRspectra were
measuredinCD3ODandrecordedonaBrukerAM灢400or
aDRX灢500NMRspectrometerwithTMSasaninternal
standard.Separationandpurificationwereperformedby
columnchromatographyonsilicagel(200-300 mesh,
QingdaoMarineChemicalInc.,Qingdao,People曚sRe灢
publicofChina),RP灢18(Merck),andSephadexLH灢20
(AmershamBiosciences,Sweden).Fractionsweremoni灢
toredbyTLC,andspotswerevisualizedbyheatingsilica
gelplatessprayedwith10% H2SO4inEtOH.
Plantmaterial暋ThewholeplantsChloranthusmul灢
tistachyswascolectedinAugust2007fromXinning,Hunan
Province,P.R.China,andidentifiedbyDr.En灢DeLiuof
KunmingInstituteofBotany.A voucherspecimen (No.
HY0001)wasdepositedattheStateKeyLaboratoryofPhy灢
tochemistryandPlantResourcesinWestChina.
Extractionandisolation暋Driedandpoweredwhole
plantsofC灡multistachys (20kg)wereextractedthree
timeswithCH3OHunderreflux.Thefiltratewasevapo灢
ratedunderreducedpressuretogivearesidue,whichwas
suspendedintowaterandpartitionedwithEtOAc.The
EtOAcportion(1300g)wassubjectedtocolumnchro灢
matographyoversilicagelelutedwithpetroleumether灢
Me2CO (1暶0曻1暶1)togivefractionFr灡1-7.Fr灡3(50
g)wasrepeatedlyseparatedonsilicagel,Rp灢18,and
SephadexLH灢20(MeOH)columnchromatographytoaf灢
ford2(19mg),3(40mg),and4(30mg).Fr灡6(45g)
waschromatographedonsilicagelcolumneluting with
CHCl3灢MeOH (30暶1曻1暶1)andRp灢18columneluting
withaMeOH灢H2Ogradientsystem (20%曻60%),fur灢
therpurifiedonSephadexLH灢20usingMeOHassolvent
toyield1(15mg).
syringicacid灢4灢O灢毩灢L灢rhamnopyranoside (1):C15
H19O9,yelowamorphouspowder.[毩]26D = -81灡20曘
(c =0灡12,MeOH).IR毻KBrmaxcm灢1:3422,2936,2851,
1700,1592,1553,1502,1460,1393,1129.UV (CH3
OH)毸max (log毰):211 (4灡38),254 (3灡89)nm.1H灢
NMRand13C灢NMR:seeTable1.NegativeFAB灢MSm/
z(%):343[M灢1]灢 (83),325[M灢18]灢 (100),197[M灢
H灢146]灢 (43);HR灢ESI灢MS m/z:343灡1040 [M灢1]灢
(calcdforC15H18O9cald.343灡1029).
1毬,4毬灢dihydroxy灢5毩,8毬 (H)灢eudesm灢7 (11)
Z灢en灢8,12灢olide(2):C15 H22O4,whitepowder.1H灢
NMR(500 MHz,CD3OD):毮H4灡94 (1H,m,H灢8),
3灡24(1H,dd,J=3灡8,11灡9Hz,H灢1),2灡92(1H,dd,
J=3灡5,14灡1Hz,H灢6毩),2灡64 (1H,dd,J =6灡3,
11灡8Hz,H灢9毬),2灡54(1H,t,J=13灡6Hz,H灢6毬),
1灡90 (1H,m,H灢2毬),1灡81 (3H,m,H灢13),1灡72
581期暋暋暋RANXin灢Huietal灡:ANewPhenolicGlycosidefromChloranthusmultistachys(Chloranthaceae)暋暋暋
(1H,m,H灢3毬),1灡55 (1H,m,H灢2毩),1灡46 (1H,
m,H灢3毩),1灡23(3H,s,H灢15),1灡20(3H,s,H灢14),
1灡16(1H,dd,J=3灡5,13灡1Hz,H灢5),0灡89(1H,t,
J=11灡7Hz,H灢9毩);13C灢NMR (125MHz,CD3OD):
毮C79灡1(d,C灢1),27灡2(t,C灢2),40灡1(t,C灢3),71灡6
(s,C灢4),52灡6(d,C灢5),24灡0(t,C灢6),166灡4(s,C灢
7),80灡4 (d,C灢8),47灡2 (t,C灢9),41灡5 (s,C灢10),
120灡3(s,C灢11),177灡3(s,C灢12),8灡0(q,C灢13),13灡4
(q,C灢14),29灡7(q,C灢15).
1毬,4毩灢dihydroxy灢5毩,8毬 (H)灢eudesm灢7 (11)
Z灢en灢8,12灢olide(3):C15 H22O4,whitepowder.1H灢
NMR(500MHz,CD3OD):毮H4灡66(1H,dd,J=6灡3,
10灡4Hz,H灢8),3灡15(1H,dd,J=4灡3,11灡3Hz,H灢
1),2灡96 (1H,dd,J =3灡3,13灡9 Hz,H灢6毩),2灡55
(1H,dd,J=6灡2,11灡9Hz,H灢9毬),2灡12(1H,m,H灢
6毬),1灡74 (1H,m,H灢3毩),1灡68 (3H,s,H灢13),
1灡57(2H,m,H灢2),1灡48(1H,m,H灢3毩),1灡19(1H,
dd,J=13灡2,3灡4 Hz,H灢5),1灡07 (3H,s,H灢15),
0灡91(3H,s,H灢14),0灡80(1H,t,J=11灡7Hz,H灢9毩
);13C灢NMR(125MHz,CD3OD):毮C77灡3(d,C灢1),
27灡7(t,C灢2),40灡1(t,C灢3),71灡9(s,C灢4),53灡0(d,
C灢5),22灡4(t,C灢6),163灡7(s,C灢7),78灡4(d,C灢8),
46灡8(t,C灢9),39灡9(s,C灢10),119灡4(s,C灢11),175灡7
(s,C灢12),7灡6(q,C灢13),13灡0(q,C灢14),21灡6(q,C灢
15).
(灢)灢(7S,8R)灢dihydrodehydrodiconiferyalcohol
(4):C20H24O6,colorlessoil.1H灢NMR (CD3OD,400
MHz):毮H6灡94(1H,d,J=1灡8,H灢2),6灡82(1H,dd,
J=1灡8,8灡1Hz,H灢6),6灡78(1H,s),6灡75(1H,s,
H灢2曚),6灡72(1H,s,H灢6曚),5灡49(1H,d,J=6灡3Hz,
H灢7),3灡84 (3H,s,OCH3),3灡80 (3H,s,OCH3),
3灡75(1H,m,H灢9),3灡56(2H,t,J=6灡5Hz,H灢9曚),
3灡46(1H,m,H灢8),2灡62(2H,t,J=7灡4Hz,H灢7曚),
1灡83(2H,m,H灢8曚);13C灢NMR(CD3OD,100MHz):
毮C134灡8(C灢1),110灡5(C灢2),147灡5(C灢3),145灡2(C灢
4),116灡1 (C灢5),119灡7 (C灢6),89灡0 (C灢7),55灡4 (C灢
8),64灡9(C灢9),136灡9(C灢1曚),114灡0(C灢2曚),145灡2(C灢
3曚),149灡1 (C灢4曚),129灡8 (C灢5曚),117灡9 (C灢6曚),35灡8
(C灢7曚),32灡9(C灢8曚),62灡2(C灢9曚),56灡3,56灡7 (3,3曚灢
OCH3).
Acknowledgements:Theauthorsaregratefultothemem灢
bersoftheanalyticalgroupoftheStateKeyLaboratoryof
PhytochemistryandPlantResourcesinWestChina,Kun灢
mingInstituteofBotany,ChineseAcademyofSciences
foralofthespectralmeasurements.
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