全 文 ：广 西 植 物 Guihaia　Jan．２０１４,３４(１):１２６－１２９　　　　　　　　　　 http://journal．gxzw．gxib．cn　
DOI:１０．３９６９/j．issn．１０００Ｇ３１４２．２０１４．０１．０２４
黄永林,陈月圆,颜小捷,等．红背山麻杆叶的化学成分研究(Ⅰ)———酚酸类及相关化合物[J]．广西植物,２０１４,３４(１):１２６－１２９
HuangYL,ChenYY,YanXJ,etal．ChemicalconstituentsfromtheleavesofAlchorneatrewioides(１)．Phenolicacidsandrelatedcompounds[J]．
Guihaia,２０１４,３４(１):１２６－１２９
ChemicalconstituentsfromtheleavesofAlchornea
trewioides(１)．Phenolicacidsandrelatedcompounds
HUANGYongＧLin,CHENYueＧYuan,YANXiaoＧJie,
LIUJinＧLei,YANGZiＧMing,LIDianＧPeng∗
(GuangxiKeyLaboratoryofFunctionalPhytochemicalsResearchandUtilization,
GuangxiInstituteofBotany,Guilin５４１００６,China)
Abstract:８０％acetoneextractsofthefreshleavesofAlchorneatrewioideswassuccessivelyseparatedbySephadex
LHＧ２０,MCIgelCHP２０P,andToyopearlButylＧ６５０Ccolumnchromatographytoyieldtenphenolicacidsandrelated
compounds．Theirstructureswereelucidatedbyspectroscopicanalysesas:salicylicacid(１),pＧhydroxybenzoicacid
(２),２,５Ｇdihydroxybenzoicacid(３),３,４Ｇdihydroxybenzoicacid(４),transＧpＧcoumaricacid(５),cisＧpＧcoumaricacid(６),
caffeicacid(７),cafeicacidmethylester(８),galicacid(９),andmethylgalate(１０)．Compounds１－８,１０wereisolated
fromtheAlchorneaforthefirsttime．
Keywords:Alchorneatrewioides;chemicalconstituents;phenolicacid
GLCNumber:Q９６４．８１　　DocumentCode:A　　ArticleID:１０００Ｇ３１４２(２０１４)０１Ｇ０１２６Ｇ０４
红背山麻杆叶的化学成分研究(Ⅰ)
———酚酸类及相关化合物
黄永林,陈月圆,颜小捷,刘金磊,杨子明,李典鹏∗
(广西植物功能物质研究与利用重点实验室,广西植物研究所,广西 桂林５４１００６)
摘　要:采用８０％丙酮提取石油醚萃取部位,利用凝胶、MCI及ToyopearlButylＧ６５０C柱色谱进行分离纯化
得到１０个酚酸类及相关化合物.根据化合物的波谱数据分析鉴定为水杨酸(１)、对羟基苯甲酸(２)、２,５Ｇ二羟
基苯甲酸(３)、３,４Ｇ二羟基苯甲酸(４)、反Ｇ对香豆酸(５)、顺Ｇ对香豆酸(６)、咖啡酸(７)、咖啡酸甲酯(８)、没食子酸
(９)、没食子酸甲酯(１０).其中化合物１~８、１０均为首次从本属植物中分离得到.
关键词:红背山麻杆;化学成分;酚酸
　　ThegenusAlchorneabelongstothefamilyEuＧ
phorbiaceaeandcontainsapproximately７０species．
Over６specieshavebeenrecordedinChina(Editorial
CommitteeinFloraofChina,１９９６),manyofwhich
havebeenusedfortreatinginflammationoftheprosＧ
tategland,hematuria,shigela,inflammation,lumboＧ
cruralpainand manyotherdiseases(Jiangsu New
MedicalColege,１９７７)．TheA．trewioidesbelongsto
收稿日期:２０１３Ｇ１０Ｇ１５　　修回日期:２０１３Ｇ１１Ｇ２５
基金项目:广西自然科学基金(２０１１GXNSFD０１８０３８);广西科技合作与交流计划项目(桂科合:１２９８０１４Ｇ１０);广西植物研究所基本业务费项目(桂植
业１３００２);广西植物功能物质研究与利用重点实验室开放基金(ZRJJ２０１３Ｇ７).
作者简介:黄永林(１９７４Ｇ),男,广西桂林人,博士,研究员,主要从事天然产物物质基础、生物活性及开发利用研究,(EＧmail)hyl＠gxib．cn.
∗通讯作者:李典鹏,博士,研究员,从事中药、天然药物和植物化学研究,(EＧmail)ldp＠gxib．cn.
thefamilyAlchornea,itwasusedastraditionalmediＧ
cinestoaleviatediseaseanddiscomfort．Previously,
flavonoidglycosides,phenolicacidsandantioxidantacＧ
tivityhavebeenreportedfromthespecies(Lu,２０１２;
Qin,２０１２;Lu,２０１１)．TofurtherresearchforthemaＧ
terialbasisofpharmacologicalefectsfromthespecies
A．trewioides,tenphenolicacidsandrelatedcomＧ
poundswereisolatedfrom８０％acetoneextractsofthe
freshleavesofA．trewioides．Compounds１Ｇ８、１０were
isolatedfromtheAlchorneaforthefirsttime．
１　Materialsandmethods
１HＧand１３CＧNMRspectraweremeasuredinCD３
ODoracetoneＧd６at２７℃usingaBrukerAvance５００
spectrometer(５００MHzfor１Hand１２５MHzfor１３C)
(BrukerBiospinAG,Faelanden,Switzerland)ora
JEOLJNMＧAL４００spectrometer(４００MHzfor１H
and１００MHzfor１３C)(JEOLLtd．,Tokyo,Japan)．
CouplingconstantsareexpressedinHzandchemiＧ
calshiftsaregivenonaδ(mg/L)scale．Column
chromatography wasperformed using MCIgel
CHP２０P(７５－１５０μm;MitsubishiChemical,ToＧ
kyo,Japan),SephadexLHＧ２０(２５－１００mm;GE
HealthcareBioＧScienceAB,Uppsala,Sweden),and
ToyopearlButylＧ６５０C(TOSOH Co．,Tokyo,JaＧ
pan)columns．TLCwasperformedonprecoated
Kieselgel６０F２５４ plates(０．２ mmthick;Merck,
Darmstadt,Germany)with CHCl３ＧMeOHＧH２O
(９∶１∶０．１,８∶２∶０．２,or７∶３∶０．５,v/v)andtoluＧ
eneＧethylformateＧformicacid(１∶７∶１,v/v)asthe
solvent,andspotsweredetectedbyUViluminaＧ
tion(２５４nm)andbysprayingwith２％ethanolic
FeCl３and１０％sulfuricacidreagent,folowedby
heating．
TheleavesofA．trewioideswerecolectedat
GuangxiInstituteofBotany,Guangxi,China,in
August２０１１,andidentifiedbyProf．WEIFaＧNan．
Thevoucherspecimen(２０１１０９２０N)wasdeposited
intheGuangxikeylaboratoryoffunctionalphytoＧ
chemicalsresearchandutilization,GuangxiInstituＧ
teofBotany．
２　Extractionandseparation
ThefreshleavesofA．trewioides(５．３５kg)were
cutintosmalpiecesandextractedwithacetoneＧH２O
(８∶２,v/v)bymacerationatroomtemperature．After
filtration,theplantdebrisremainingonthefilterpaper
wasextractedwiththesamesolventafurthertwo
times．ThefiltratewascombinedandconcentratedunＧ
derreducedpressuretogiveanaqueoussolutionwith
darkgreenprecipitates．Theprecipitantwasmainly
composedofchlorophylsandwaxes,andremovedby
filtration．Thefiltratewasdefattedbypartitioningwith
Et２O,togiveanEt２Ofraction(Fr．E５．４６g)．
TheEt２Ofraction wassubjectedtoSephadex
LHＧ２０columnchromatographywithEtOHcontaining
increasingproportionsofwater(４cmi．d．×４０cm,０－
５０％,１０％stepwiseelution,each４００mL)andfinaly
１００％ MeOH(５００mL)togivefivefractions:frs．EＧ１
(２．３５g),２(０．１５g),３(０．６７g),４(０．５３g),５(１．２８g)．
FractionEＧ１wasfurtherfractionatedbyMCIgelCHP
２０Pcolumnchromatography(３cmi．d．×４０cm)with
０－１００％ MeOH(１０％stepwiseelution,each３００mL)
andthesubfractionswereseparatedbycolumnchroＧ
matographyusingtheToyopearlButylＧ６５０C(２cmi．d．
×３０cm)with０－１００％ MeOH(１０％ stepwise
elution,each２００ml)toyieldcompounds７(４mg),
８(９mg),９(９３７mg),and１０(６７mg)．FractionEＧ３
wassuccessivelyappliedtoaMCIgelCHP２０PcolＧ
umnchromatography(２cmi．d．×３０cm)with０－
１００％ MeOH(１０％stepwiseelution,each１００mL)to
yield３(７mg)．FractionEＧ４wasfurtherfractionated
byMCIgelCHP２０Pcolumnchromatography(２cmi．
d．×４０cm)with１０％－１００％ MeOH(１０％stepwise
elution,each１００ml)toyieldcompounds１(１７mg),
and６(６mg)．FractionEＧ５wasfurtherfractionatedby
MCIgelCHP２０Pcolumnchromatography(２cmi．d．
×４０cm)with１０％－１００％ MeOH(１０％stepwise
elution,each１５０mL),andthesubfractionswerepuriＧ
fiedbyToyopearlButylＧ６５０C(１cmi．d．×３０cm)with
０－１００％ MeOH(１０％stepwiseelution,each１００mL)
togetcompounds２(８mg),４(１７mg),and５(３６mg)．
３　Resultsandanalysis
Salicylicacid(１)　Whiteamorphouspowder,C７
H６O３．１HＧNMR(４００MHz,CD３OD)δ:６．８５(１H,dd,
J＝１．０,８．３Hz,HＧ３),６．８８(１H,m,HＧ５),７．４４(１H,m,
HＧ４),７．８４(１H,dd,J＝１．７,８．３Hz,HＧ６);１３CＧNMR
７２１１期　　　　　　　黄永林:红背山麻杆叶的化学成分研究(Ⅰ)———酚酸类及相关化合物
Fig．１　Chemicalstructuresofcompounds１－１０
(１００MHz,CD３OD)δ:１１４．１(CＧ１),１１８．１(CＧ３),
１２０．０(CＧ５),１３１．５(CＧ６),１３６．５(CＧ４),１６３．２(CＧ２),
１７３．６(CＧ７)(Milenaetal．,２００４)．
pＧHydroxybenzoicacid(２)　BrownamorＧ
phouspowder,C７H６O３．１HＧNMR (４００ MHz,
CD３OD)δ:６．９０(２H,d,J＝８．５Hz,HＧ３,５),７．７７
(２H,d,J＝８．５Hz,HＧ２,６);１３CＧNMR(１００MHz,
CD３OD)δ:１１６．７(CＧ３,５),１２３．６(CＧ１),１３３．８(CＧ２,
６),１６４．２(CＧ４),１７１．３(CＧ７)(Penchometal．,１９９８)．
２,５ＧDihydroxybenzoicacid(３)　Palebrown
amorphouspowder,C７H６O４．１HＧNMR(４００MHz,
CD３OD)δ:６．７４(１H,d,J＝８．９Hz,HＧ３),６．９１
(１H,dd,J＝２．２,８．９Hz,HＧ４),７．２５(１H,d,J＝２．２
Hz,HＧ６);１３CＧNMR(１００MHz,CD３OD)δ:１１３．６
(CＧ１),１１６．２(CＧ６),１１８．４(CＧ３),１２４．２(CＧ４),１５０．１
(CＧ５),１５６．３(CＧ２),１７３．１(CＧ７)(Akiyoetal．,
１９９５)．
３,４ＧDihydroxybenzoicacid(４)　WhiteamorＧ
phouspowder,C７H６O４．１HＧNMR (４００ MHz,
CD３OD)δ:６．７８(１H,d,J＝８．３Hz,HＧ５),７．４１
(１H,dd,J＝２．２,８．３Hz,HＧ６),７．４２(１H,d,J＝２．２
Hz,HＧ２);１３CＧNMR(１００MHz,CD３OD)δ:１１６．２
(CＧ５),１１８．２(CＧ２),１２３．６(CＧ６),１２４．５(CＧ１),１４６．６
(CＧ３),１５１．６(CＧ４),１７０．２(CＧ７)(Banetal．,２００７)．
TransＧpＧcoumaricacid(５)　PalebrownamorＧ
phouspowder,C９H８O３．１HＧNMR (４００ MHz,
CD３OD)δ:６．２９(１H,d,J＝１５．８Hz,HＧ８),６．８０
(２H,d,J＝８．３Hz,HＧ３,５),７．４１(２H,d,J＝８．３
Hz,HＧ２,６),７．５８(１H,d,J＝１５．８Hz,HＧ７);１３CＧ
NMR(１００MHz,CD３OD)δ:１１５．１(CＧ８),１１６．７(CＧ
３,５),１２７．２(CＧ１),１３１．１(CＧ２,６),１４６．８(CＧ７),１６１．３
(CＧ４),１７１．２(CＧ９)(Anetal．,２００８)．
CisＧpＧcoumaricacid(６)　PalebrownamorＧ
phouspowder,C９H８O３．１HＧNMR (４００ MHz,
CD３OD)δ:５．６７(１H,d,J＝１２．７Hz,HＧ８),６．６４
(２H,d,J＝８．５Hz,HＧ３,５),７．７０(１H,d,J＝１２．７
Hz,HＧ７),７．５０(２H,d,J＝８．５Hz,HＧ２,６);１３CＧ
NMR(１００MHz,CD３OD)δ:１１６．５(CＧ３,５),１２６．３
(CＧ８),１３０．１(CＧ７),１３０．２(CＧ２,６),１３１．５(CＧ１),
１５６．６(CＧ４),１７１．７(CＧ８)(Kortetal．,１９９６)．
Caffeicacid(７)　Whiteamorphouspowder,
C９H８O４．１HＧNMR(４００ MHz,CD３OD)δ:６．２０
(１H,d,J＝１５．９Hz,HＧ８),６．７７(１H,d,J＝８．１Hz,
HＧ５),６．９１(１H,dd,J＝２．２,８．１Hz,HＧ６),７．０３
(１H,d,J＝２．２Hz,HＧ２),７．５２(１H,d,J＝１５．９Hz,
HＧ７);１３CＧNMR(１００MHz,CD３OD)δ:１１５．１(CＧ２),
１１５．６(CＧ８),１１６．５(CＧ５),１２２．８(CＧ６),１２７．８(CＧ１),
１４６．７(CＧ３),１４７．０(CＧ７),１４９．４(CＧ４),１７１．１(CＧ９)
(Fukuokaetal．,１９８２)．
Caffeicacidmethylester(８)　WhiteamorＧ
phouspowder,C１０H１０O４．１HＧNMR(４００ MHz,
CD３OD)δ:３．８８(３H,s,OCH３),６．３０(１H,d,J＝
１５．９Hz,HＧ８),６．７９(１H,d,J＝８．１Hz,HＧ５),７．０５
(１H,dd,J＝２．２,８．１Hz,HＧ６),７．１５(１H,d,J＝２．２
Hz,HＧ２),７．５８(１H,d,J＝１５．９Hz,HＧ７);１３CＧNMR
(１００MHz,CD３OD)δ:５６．５(CＧOCH３),１１１．７(CＧ
８),１１６．０(CＧ２),１１６．５(CＧ５),１２４．０(CＧ６),１２７．８(CＧ
１),１４６．８(CＧ７),１４７．３(CＧ３),１５０．６(CＧ４),１６７．９(CＧ
９)(Shinetal．,２００４)．
Galicacid(９)　 Whiteamorphouspowder,
８２１ 广　西　植　物　　　 　　　　　　　　　　　　　　３４卷
C７H６O５．１HＧNMR(５００MHz,acetoneＧd６)δ:７．１４
(２H,s,HＧ２,６);１３CＧNMR(１２５MHz,acetoneＧd６)
δ:１１０．１(CＧ２,６),１２１．９(CＧ１),１３８．７(CＧ４),１４６．０(CＧ
３,５),１６８．１(CＧ７)(Luetal．,１９９９)．
Methylgalate(１０)　WhiteamorphouspowＧ
der,C８H８O５．１HＧNMR(４００MHz,acetoneＧd６)δ:
３．７７(３H,s,OCH３),７．１１(２H,s,HＧ２,６);１３CＧNMR
(１００MHz,acetoneＧd６)δ:５１．９(CＧOCH３),１０９．８
(CＧ２,６),１２１．７(CＧ１),１３８．７(CＧ４),１４５．７(CＧ３,５),
１６７．２(CＧ７)(Maetal．,２００５)．
Acknowledgements　Theauthorsaregrateful
toMr．NINGDeＧSheng(GuangxiKeyLaboratory
ofFunctionalPhytochemicalsResearchandUtiliＧ
zation)forNMRmeasurements．
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(上接第１８页Continuefrompage１８)
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９２１１期　　　　　　　黄永林:红背山麻杆叶的化学成分研究(Ⅰ)———酚酸类及相关化合物