全 文 ：广 西 植 物 Guihaia　Nov．２０１４,３４(６):８４８－８５３　　　　　　　　　　 http://journal．gxzw．gxib．cn　
DOI:１０．３９６９/j．issn．１０００Ｇ３１４２．２０１４．０６．０２０
徐丽,黎平,唐贵华,等．闭花耳草的化学成分研究[J]．广西植物,２０１４,３４(６):８４８－８５３
XuL,LiP,TangGH,etal．ChemicalconstituentsfromHedyotiscryptantha[J]．Guihaia,２０１４,３４(６):８４８－８５３
ChemicalconstituentsfromHedyotiscryptantha
XULi１,LIPing１,TANGGuiＧHua２,WUShiＧBiao３,
WANGYeＧLing１,EdwardKENNELLY３,LONGChunＧLin１,４∗
(１．CollegeofLifeandEnvironmentalSciences,MinzuUniversityofChina,Beijing１０００８１,China;２．CollegeofPharmaceutical
Sciences,SunYatＧsenUniversity,Guangzhou５１０００６,China;３．LehmanCollege,CityUniversityofNewYork,NewYork
１０４６８,USA;４．KunmingInstituteofBotany,ChineseAcademyofSciences,Kunming６５０２０１,China)
Abstract:ElevenknowncompoundswereisolatedfromthewholeplantofHedyotiscryptantha．Onthebasisof
spectroscopicdata,theirstructureswereidentifiedasasperuloside(１),asperulosidicacid(２),asperulosidicacid
methylester(３),asperulosidicacidethylester(４),３,４ＧdihydroＧ３Ｇmethoxyasperuloside(５),kaempferol(６),
kaempferol３,７ＧdiＧOＧβＧDＧglucoside(７),kaempferol３ＧOＧβＧDＧgalactopyranosylＧ(１→３)ＧβＧDＧgalactopyranoside(８),
ursonicacid(９),stigmasterol(１０),andβＧsitosterol(１１)．Alofthesecompoundswereisolatedfromthisplantfor
thefirsttime,whilecompounds７and８werefoundfromthegenusHedyotisforthefirsttime．
Keywords:Hedyotiscryptantha;iridoidglycosides;flavnoids;triterpenoids;sterols
CLCnumber:Q９４６．９１　　Documentcode:A　　ArticleID:１０００Ｇ３１４２(２０１４)０６Ｇ０８４８Ｇ０６
闭花耳草的化学成分研究
徐　丽１,黎　平１,唐贵华２,吴世标３,王业玲１,EdwardKENNELLY３,龙春林１,４∗
(１．中央民族大学 生命与环境科学学院,北京１０００８１;２．中山大学 药学院,广州５１０００６;３．纽约城市
大学 黎曼学院,纽约１０４６８,美国;４．中国科学院昆明植物研究所,昆明６５０２０１)
摘　要:从闭花耳草(Hedyotiscryptantha)全草中分离得到１１个化合物,经波谱数据分析鉴定为车叶草苷(１),
车叶草苷酸(２),车叶草苷酸甲酯(３),车叶草酸乙酯(４),３,４Ｇ二氢Ｇ３Ｇ甲氧基车叶草苷(５),山奈酚(６),kaempferol
３,７ＧdiＧOＧβＧDＧglucoside(７),kaempferol３ＧOＧβＧDＧgalactopyranosylＧ(１→３)ＧβＧDＧgalactopyranoside(８),乌索酸(９),豆
甾醇(１０),βＧ谷甾醇(１１).所有化合物均为首次从闭花耳草植物中分离得到,其中化合物７和８首次从耳草属
(Hedyotis)植物中分离得到.
关键词:闭花耳草;环烯醚萜;黄酮;三萜;甾醇
　　TheHedyotis(Rubiaceae),alargegenus(ca．６９９
species)ofherbsorsomewhatshrubbyplantsdistribuＧ
tedthroughoutthetropicsandsubtropicsandwith６２
speciesand７varietiesfoundinChina(３８endemic),has
beenwidelyusedasatraditionalmedicineinanumber
ofAsiancountries(Wangetal．,２００１;Ahmadetal．,
２００５)．VariousspeciesofHedyotis wereknownto
havearangeofimportantpharmacologicalefectssuch
asanticancer,antimicrobial,antiＧinflammatory,antiulＧ
cerandimmunomodulatingactivities,andusedtotreat
收稿日期:２０１４Ｇ０１Ｇ１０　　修回日期:２０１４Ｇ０３Ｇ０９
基金项目:国家自然科学基金(３１０７０２８８,３１１６１１４０３４５);科技部科技基础性专项(２０１２FY１１０３００Ｇ７);国家外专局和教育部高等学校学科创新引智计
划(B０８０４４);中央民族大学一流大学一流学科建设项目(YLDX０１０１３０).
作者简介:徐丽(１９８８Ｇ),女,湖北应城人,硕士,主要从事民族植物学、民族药物学研究,(EＧmail)dulinniao１１０２＠１６３．com.
∗通讯作者:龙春林,教授,主要从事民族植物学、民族药物学、植物种植资源和生物多样性研究,(EＧmail)long＠mail．kib．ac．cn.
variousdiseasesincludingsnakebites,sphagitis,bronＧ
chitis,hepatitis,pneumoniainchildren,appendicitis,
pelvitis,tonsilitis,nephritis,rheumaticarthritis,infecＧ
tiousfever,dysentery,andsometumorsinliver,lung
andstomach(Pengetal．,１９９８;Zhangetal．,２０１０,
２０１１)．Previouschemicalinvestigationsofthisgenus
haveledtotheisolationofaseriesofiridoidglycosides
(Pengetal．,１９９９;JiangsuProvincialInstituteofBotaＧ
ny,１９９１),triterpenoids(Sietal．,２０１０;Masataketal．,
１９９８;Huietal．,１９７７),flavonoids(Kimetal．,２００１;
Ju,２００７),anthraquinones(Shietal．,２００８;Yuetal．,
２００９;Rohayaetal．,２００５),phenolicglycosides(Wang
etal．,２０１３)andalkaloids(Pengetal．,１９９７;Phuonget
al．,１９９９),andsomeofthesecompoundshavesignifiＧ
cantbioactivities．
HedyotiscryptanthaisendemictoHainanIsland,
China,whichhasbeenusedasatraditionalmedicineby
Liethnicgroupforthetreatmentofinjury．Itwasfirstly
reportedinethnobotanicalinvestigationinHainanProvＧ
ince(Zhengetal．,２００９a,b)．TothebestofourknowlＧ
edge,thereislittlephytochemicalstudyonthisplant．
Thepresentworkisthefirstdetailedphytochemical
studyonthespeciesH．cryptantha．Intotal１１comＧ
poundswereisolatedfromthewholeplant:asperuloside
(１),asperulosidicacid(２),asperulosidicacidmethylester
(３),asperulosidicacidethylester(４),３,４ＧdihydroＧ３ＧmeＧ
thoxyasperuloside(５),kaempferol(６),kaempferol３,７Ｇ
diＧOＧβＧDＧglucoside(７),kaempferol３ＧOＧβＧDＧgalactopyrＧ
anosylＧ(１→３)ＧβＧdＧgalactopyranoside(８),ursonicacid
(９),stigmasterol(１０),andβＧsitosterol(１１)．
Fig．１　Thechemicalstructuresofcompounds１－１１
　　
１　MaterialandMethod
１．１PlantMaterial
ThewholeplantsofH．cryptanthawerecolectＧ
edfrom LingshuiCounty,Hainan,ChinainAugust
２０１０andidentifiedbyoneofourauthors(Prof．ChunＧ
LinLong)．Thevoucherspecimen(No．２０１００８１４)was
depositedattheHerbariumofMinzuUniversityof
China．
１．２ExperimentalInstruments
１Hand１３CNMRspectrawererecordedonBrukＧ
erAMＧ６００andBrukerDRXＧ５００spectrometersusing
TMSasaninternalstandard．HRＧESIＧMSanalyses
werecarriedoutonanLCTpremierXETOFmass
spectrometer(Waters,Manifold,MA)instrument．Silica
gel(８０－１００and３００－４００mesh,YantaiChemicalInＧ
dustryInstituteCo．,Ltd．,China),MCIgelCHP２０P
(７５－１５０μm,MitsubishiChemicalCorporation,TokyＧ
o,Japan),HSCCC(TBEＧ２０AandTBEＧ３００B,Shanghai
TautoBiotechnique,Shanghai,China),RpＧC１８(２０－４５
９４８６期　　　　　　　　　　　　　　徐丽等:闭花耳草的化学成分研究
μm,BUCHILabortechnicAG,Switzerland)andSephaＧ
dexLHＧ２０(GEHealthcareBioＧXciencesAB)wereused
forcolumnchromatography,andsilicagelGF２５４
(Yantai)wasusedforpreparativeTLCintheformof
precoatedplates．TLCspotswerevisualizedunderUV
lightandbydippinginto５％ H２SO４inEtOHfolＧ
lowedbyheating．
２　ExtractionandIsolation
Driedandpowderedsamples(１０．０kg)ofH．
cryptanthawereextractedwith９０％ EtOHforthree
timesunderrefluxtogiveethanolextract．AfterevapoＧ
rationunderreducedpressure,theextractresiduewas
suspendedinwaterandpartitionedsuccessivelywith
petroleumether,ethylacetate,andnＧbutanol．ThenＧ
butanolextract(５６．０g)wassubjectedtomacroporous
resinTM XAD１６andsuccessfulyelutedwithH２O
anddiferentconcentrationsofEtOHtoobtain５fracＧ
tions(AＧE)．FractionC(５０％)wasfurtherseparated
bysilicagel(２００Ｇ３００mesh)columnchromatography
elutingwithCHCl３ＧMeOHgradient(３５∶１Ｇ４∶１)to
yieldninefractions(Fr．C１ＧFr．C９)．Fr．C２(３．２g)was
chromatographedonHSCCCwithaCHCl３ＧMeOHＧH２
OＧBuOHsolventsystem(４Ｇ３Ｇ２Ｇ０．８)toyieldcomＧ
pounds１(９６mg),３(２１．９mg),and４(１７．１mg)．Fr．
C５(１６１．１mg),Fr．C６(３１．０mg)andFr．C８(２２．０mg)
weresubjectedtotheSephadexLHＧ２０elutingwith
MeOHtoyieldcompounds６(３．１mg),７(９．７mg),and
８(３．４mg)respectively．Fr．B(３０％)wasfurtherseparaＧ
tedbysilicagel(２００－３００mesh)columnchromatograＧ
phyelutingwithCHCl３ＧMeOHgradient(３０∶１→２∶
１)toyieldsevenfractions(Fr．B１ＧFr．B６)．Fr．B１(８．９３
g)wasseparatedby MPLCgradientelutedwitha
MeOHＧH２Osolventsystem(２０∶８０,４０∶６０,６０∶４０,
８０∶２０,and１００∶０)andfurtherpurifiedbygelperＧ
meation chromatography on Sephadex LHＧ２０ in
MeOHtoyieldcompound２(４．４mg),compounds３
(２０．８mg)and５(７．８mg)．Ethylacetateextract(３０g)
wasalsoseparatedonmacroporousadsorptionresin
column(MeOH/H２Ogradient０∶１－０∶１)toaford
fivefractions(F１ＧF５)．FractionF５wassubjectedtoreＧ
peatedcolumnchromatography(silicagel,Sephadex
LHＧ２０(MeOH))toyieldcompound９(６mg)．Fraction
F１wasappliedtocolumnchromatography(silicagel,
CHCl３/MeOH５０∶１;petroleumether(PE)/acetone
９:１)toyieldcompound１０(８．０mg)．FractionF２was
subjectedtorepeatedcolumnchromatography(silica
gel,CHCl３/MeOH５０∶１;EtOH/MeOH/H２O３０∶
１∶１)toyieldcompound１(２０mg)．ThepetroleumeＧ
therextract(５０．０g)wasseparatedwithsilicagelcolＧ
umn(PE/acetonegradient１００∶０－０∶１００)andpuriＧ
fiedbySephadexLHＧ２０(MeOH)andrecrystalizingto
yieldcompound１１(３０mg)．
３　ResultsandIsolation
Asperuloside(１)　Colorlessneedles(methylalcoＧ
hol),ESIＧMSm/z４１５[M＋H]＋,C１８H２２O１１．１H
NMR(６００MHz,MeOD)δ:７．３１(１H,s,HＧ３),５．９６
(１H,s,HＧ１α),５．７３(１H,s,HＧ７),５．５７(１H,d,J＝６．５
Hz,HＧ６β),４．７８(１H,s,HＧ１′),４．６７(２H,t,J ＝１０．７
Hz,HＧ１０),３．９３(１H,m,HＧ６′a),３．６７(２H,m,HＧ６′b,
HＧ５β),３．３７(２H,m,HＧ,HＧ５′),３．２７(２H,m,HＧ,HＧ
４′),３．１９(１H,t,J ＝８．６Hz,HＧ２′),２．０８(３H,s,HＧ
COCH３);１３CNMR(１５０MHz,MeOD)δ:９３．８９９．４(CＧ
１),１５０．８(CＧ３),１０６．７(CＧ４),３８．０(CＧ５),８６．８(CＧ６),
１２９．４(CＧ７),１４４．８(CＧ８),４５．８(CＧ９),６２．４(CＧ１０),１７２．８
(CＧ１１),１７３．１(CＧCOCH３),２１．１(CＧCOCH３),１００．５(CＧ
１′),７５．２(CＧ２′),７８．４(CＧ３′),７２．１(CＧ４′),７８．９(CＧ５′),
６３．３(CＧ６′)．ThiscompoundwasidentifiedbycompariＧ
sonofitsspectraldatawiththosereported(Bergeraet
al．,２０１１)．
Asperulosidicacid(２)　Colorlessneedles(methyl
alcohol),ESIＧMSm/z４３３[M＋H]＋,C１８H２４O１２,１H
NMR(６００MHz,MeOD)δ:７．６３(１H,s,HＧ３),５．９９
(１H,s,HＧ７),５．０３(１H,d,J＝９．０Hz,HＧ１α),４．９１
(１H,d,J＝１４．９Hz,HＧ６β),４．８４Ｇ４．７８(２H,m,HＧ１０),
４．７０(１H,d,J＝７．８Hz,HＧ１′),３．８２(１H,dd,J＝１．５,
１２．０Hz,HＧ６′a),３．５８(１H,dd,J＝１２．０,５．９Hz,HＧ６′
b),３．３６(１H,t,J＝８．５Hz,HＧ５′),３．２４(３H,m,HＧ２′,
HＧ３′,HＧ４′),２．９８(１H,m,HＧ５β),２．６０(１H,m,HＧ９β),
２．０６(３H,s,HＧCOCH３);１３CNMR(１５０MHz,MeOD)
δ:１０１．４(CＧ１),１５５．６(CＧ３),１０８．４(CＧ４),４２．５(CＧ５),
７５．５(CＧ６),１３２．０(CＧ７),１４６．０(CＧ８),４６．３(CＧ９),６３．９
(CＧ１０),１７０．８(CＧ１１),１７２．７(CＧCOCH３),２０．９(CＧ
０５８ 广　西　植　物　　　 　　　　　　　　　　　　　　３４卷
COCH３),１００．７(CＧ１′),７５．０(CＧ２′),７７．９(CＧ３′),７１．７
(CＧ４′),７８．６(CＧ５′),６３．１(CＧ６′)．Thespectraldatawas
consistentwiththosereported(Bergeraetal．,２０１１)．
Asperulosidicacidmethylester(３)　Colorless
needles(methylalcohol),ESIＧMSm/z４４７ [M＋
H]＋,C１９H２６O１２．１HNMR(６００MHz,MeOD)δ:７．６２
(１H,s,HＧ３),５．９９(１H,s,HＧ７),５．０２(１H,d,J＝９．０
Hz,HＧ１α),４．９０(１H,d,J＝１５．６Hz,HＧ６β),４．７７(２H,
m,HＧ１０),４．６９(１H,d,J＝７．８Hz,HＧ１′),３．８２(１H,
dd,J＝１２．０,１．８ Hz,HＧ６′a),３．７１(３H,s,HＧ
COOCH３),３．５８(１H,dd,J＝１２．０,６．０Hz,HＧ６′b),
３．３５(１H,m,HＧ５′),３．２６(２H,m,HＧ２′,HＧ３′),３．２１
(１H,m,HＧ４′),３．００(１H,m,HＧ５β),２．６０(１H,m,HＧ
９β),２．０６(３H,s,HＧCOCH３);１３C NMR(１５０MHz,
MeOD)δ:９９．９(CＧ１),１５４．０(CＧ３),１０８．２(CＧ４),４０．９(CＧ
５),７４．１(CＧ６),１３０．１(CＧ７),１４６．０(CＧ８),４４．８(CＧ９),
６２．２(CＧ１０),１６９．４(CＧ１１),５０．６(CＧCOOCH３),１７２．６
(CＧCOCH３),２０．９(CＧCOCH３),９９．２(CＧ１′),７３．５(CＧ
２′),７７．２(CＧ３′),７０．１(CＧ４′),７６．５(CＧ５′),６１．６(CＧ６′)．
ThespectraldatawasinaccordancewiththosereporＧ
ted(Bergeraetal．,２０１１;Guvenalp,etal．,２００６)．
Asperulosidicacidethylester(４)　ColorlessneeＧ
dles(methylalcohol),ESIＧMSm/z４６１[M＋H]＋,
C２０H２８O１２．１H NMR(６００MHz,DMSOＧd６)δ:７．５８
(１H,s,HＧ３),５．９７(１H,s,HＧ７),５．１４(１H,d,J＝４．２
Hz,HＧ１α),４．９６(１H,d,J＝８．９Hz,HＧ６β),４．７８(１H,
d,J＝１４．８Hz,HＧ１０a),４．７０(１H,d,J＝１４．８Hz,HＧ
１０b),４．１２(２H,q,J＝７．１Hz,HＧCH２CH３),３．６６(１H,
dd,J＝１１．３,２．９Hz,HＧ６′a),３．４３(１H,m,HＧ６′b),３．１６
(２H,dt,J＝１５．３,７．３Hz,HＧ２′,HＧ３′),３．０７(１H,t,J
＝９．１Hz,HＧ４′),３．００(１H,d,J＝８．２Hz,HＧ５′),２．９０
(１H,t,J＝６．７Hz,HＧ５β),２．５３(１H,d,J＝８．７Hz,HＧ
９β),２．０７(３H,s,HＧCOCH３),１．２３(３H,s,HＧCOOCH２
CH３);１３CNMR(１５０MHz,DMSOＧd６)δ:９９．９(CＧ１),
１５３．４(CＧ３),１０７．９(CＧ４),４１．１(CＧ５),７４．１(CＧ６),１３２．３
(CＧ７),１４３．１(CＧ８),４５．１(CＧ９),６２．５(CＧ１０),１６６．８(CＧ
COOCH２CH３),５９．８(CＧCOOCH２CH３),１４．７(CＧ
COOCH２CH３),１７２．６(CＧCOCH３),２１．１(CＧCOCH３),
９９．４(CＧ１′),７３．６(CＧ２′),７７．６(CＧ３′),７０．１(CＧ４′),７７．０
(CＧ５′),６１．５(CＧ６′)．Thespectraldataresembledthose
reported(Pengetal．,１９９９;Bergeraetal．,２０１１)．
３,４ＧdihydroＧ３Ｇmethoxyasperuloside(５)　ColorＧ
lessamorphoussubstance(methylalcohol),ESIＧMS
m/z４４７[M＋H]＋,C１９H２６O１２．１HNMR(６００MHz,
MeOD)δ:６．０１(１H,s,HＧ７),５．３９(１H,d,J＝６．７Hz,
HＧ６β),５．０２(１H,d,J＝６．１Hz,HＧ１α),５．１３(１H,d,J
＝３．６Hz,HＧ３α),４．９８(１H,s,HＧ１０),４．７６(１H,s,HＧ
１０),４．７１(１H,s,HＧ１′),３．８６(１H,m,HＧ６′a),３．６７(１H,
m,HＧ６′b),３．５４(３H,s,HＧOCH３),３．４０(H,dd,J＝
８．５,１７．７Hz,HＧ５β),３．３５(H,dd,J＝８．５,９．１Hz,HＧ
３′),３．２８(２H,m,HＧ４′,HＧ５′),３．２６(１H,dd,J＝３．６,
８．０Hz,HＧ４),３．２２(１H,dd,J＝９．２,８．０Hz,HＧ２′),
３．０５(１H,dd,J＝８．５,６．５Hz,HＧ９β),２．１３(３H,s,HＧ
COCH３);１３CNMR(１５０MHz,MeOD)δ:９８．７(CＧ１),
９６．９(CＧ３),４４．７(CＧ４),３７．８(CＧ５),８７．９(CＧ６),１２６．４(CＧ
７),１５２．２(CＧ８),４５．３(CＧ９),６２．９(CＧ１０),１７７．３(CＧ１１),
１７３．７．１(CＧCOCH３),２０．８(CＧCOCH３),５６．６(CＧ
OCH３),９９．７(CＧ１′),７５．１(CＧ２′),７８．２(CＧ３′),７１．７(CＧ
４′),７８．４(CＧ５′),６２．９(CＧ６′)．Compound５wascharacＧ
terizedas３,４ＧdihydroＧ３ＧmethoxyasperulosidebycomＧ
parisonofthephysicalandspectraldatawiththosereＧ
ported(Quangetal．,２００２;Bergeraetal．,２０１１)．
Kaempferol(６)　Yelowpowder(methylalcoＧ
hol),ESIＧMSm/z２８７ [M＋H]＋,C１５H１０O６,１H
NMR(６００MHz,MeOD)δ:８．１１(２H,d,J＝８．９Hz,HＧ
２′,６′);６．９３(２H,d,J＝８．８Hz,HＧ３′,５′),６．４２(１H,d,
J＝１．９Hz,HＧ８),６．２１(１H,d,J＝２．０Hz,HＧ６);１３C
NMR(１５０MHz,MeOD)δ:１４８．２(CＧ２),１３７．３(CＧ３),
１７７．５(CＧ４),１６５．８(CＧ５),９９．４(CＧ６),１６２．７(CＧ７),９４．６
(CＧ８),１６０．７(CＧ９),１０４．７(CＧ１０),１２３．９(CＧ１′),１３０．８
(CＧ２′,６′),１１６．５(CＧ３′,５′),１５８．４(CＧ４′)．Compound６
wascharacterizedaskaempferolbycomparisonofthe
physicalandchemicalpropertiesandspectraldatawith
thosereported(Ju,２００７)．
Kaempferol３,７ＧdiＧOＧβＧDＧglucoside(７)　Yelow
powder(methylalcohol),ESIＧMSm/z６１１ [M＋
H]＋,C２７H３０O１６．１HNMR(６００MHz,DMSOＧd６)δ:
１２．７(１H,s,HＧ５OH),８．０８(２H,d,J＝８．７Hz,HＧ２′,
６′);６．８９(２H,d,J＝８．６Hz,HＧ３′,５′),６．４４(１H,d,J＝
１．９Hz,HＧ８),６．１９(１H,d,J＝２．０Hz,HＧ６),５．３２(１H,
s,HＧ１″),３．６０(１H,m,HＧ２″),３．４８(１H,m,HＧ３″),３．４１
(１H,m,HＧ４″),３．２６(１H,m,HＧ５″),３．７４(１H,m,HＧ６″
a),３．６０(１H,m,HＧ６″b),４．９３(１H,s,HＧ１‴),３．４８(１H,
m,HＧ２‴),３．７１(１H,m,HＧ３‴),３．２３(１H,m,HＧ４‴),
３．１３(１H,m,HＧ５‴),３．６７(１H,m,HＧ６‴a),３．６０(１H,
m,HＧ６‴b);１３CNMR(１５０MHz,DMSOＧd６)δ:１５７．４
１５８６期　　　　　　　　　　　　　　徐丽等:闭花耳草的化学成分研究
(CＧ２),１３３．５(CＧ３),１７７．９(CＧ４),１６０．４(CＧ５),９８．４(CＧ
６),１６４．８(CＧ７),９３．３(CＧ８),１５７．１(CＧ９),１０３．４(CＧ１０),
１２１．３(CＧ１′),１３１．０(CＧ２′,５′),１１４．９(CＧ３′,６′),１６０．２(CＧ
４′),１００．１(CＧ１″),７８．９(CＧ２″),７６．８(CＧ３″),６８．０(CＧ４″),
７６．３(CＧ５″),６１．２(CＧ６″),１０４．３(CＧ１‴),７３．８(CＧ２‴),８０．９
(CＧ３‴),６９．９(CＧ４‴),７４．１(CＧ５‴),６０．６(CＧ６‴)．This
compoundwascharacterizedaskaempferol３,７ＧOＧβＧdＧ
diglucosidebycomparisonofthephysicalandspectral
datawiththosereported(Kamiyaetal．,１９９７)．
Kaempferol３ＧOＧβＧDＧgalactopyranosylＧ(１→３)ＧβＧ
DＧgalactopyranoside(８)　Yelowpowder(methylalcoＧ
hol),ESIＧMSm/z６３３[M＋Na]＋,C２７H３０O１６．１H
NMR(６００MHz,MeOD)δ:８．０９(２H,d,J＝８．７Hz,HＧ
２′,６′);６．９０(２H,d,J＝８．６Hz,HＧ３′,５′),６．４０(１H,d,
J＝１．９Hz,HＧ８),６．２０(１H,d,J＝２．０Hz,HＧ６),５．３６
(１H,s,HＧ１″),３．８４(１H,m,HＧ２″),３．７０(１H,m,HＧ
３″),４．０６(１H,m,HＧ４″),３．４５(１H,m,HＧ５″),３．５２(１H,
m,HＧ６″a),３．３７(１H,m,HＧ６″b),４．７５(１H,s,HＧ１‴),
３．３８(１H,m,HＧ２‴),３．３５(１H,m,HＧ３‴),３．７９(１H,m,
HＧ４‴),３．３５(１H,m,HＧ５‴),３．６０(１H,m,HＧ６‴a),３．５２
(１H,m,HＧ６‴b);１３CNMR(１５０MHz,MeOD)δ:１５８．７
(CＧ２),１３３．３(CＧ３),１８０．１(CＧ４),１６１．７(CＧ５),１００．０(CＧ
６),１６６．１(CＧ７),９４．９(CＧ８),１５９．０(CＧ９),１０６．２(CＧ１０),
１２３．０(CＧ１′),１３２．８(CＧ２′,５′),１１６．４(CＧ３′,６′),１６３．３(CＧ
４′),１０１．６(CＧ１″),７６．０(CＧ２″),８０．８(CＧ３″),７０．６(CＧ４″),
７８．７(CＧ５″),６２．５(CＧ６″),１０５．０(CＧ１‴),７５．４(CＧ２‴),７７．５
(CＧ３‴),７１．８(CＧ４‴),７８．４(CＧ５‴),６３．１(CＧ６‴)．The
spectraldata wasconsistent withthosereported
(Hirayamaetal．,２０１３)．
Ursolicacid(９)　Colorlessneedles(methylalcoＧ
hol),ESIＧMSm/z４５９[M＋H]＋,C３０H５０O３,１H
NMR(６００MHz,PyrＧd５)δ:１４．７６(１H,brs,ＧCOOH),
５．４８(１H,s,HＧ１２),３．４５(１H,dd,J＝１０．３,５．５Hz,HＧ
３α),２．６３(１H,d,J＝１１．３Hz,HＧ１８),１．２３(６H,d,J＝
９．８Hz,HＧ２３Me,２７Me),１．０４(３H,s,HＧ２６Me),
１．０１(３H,sHＧ２４Me),０．９９(３H,d,J＝６．４Hz,HＧ２９
Me),０．９４(３H,d,J＝６．２Hz,HＧ３０Me),０．８８(３H,s,
HＧ２５Me);１３CNMR(１５０MHz,PyrＧd５)δ:３７．６(CＧ１),
２８．３(CＧ２),７８．３(CＧ３),５６．０(CＧ５),１８．９(CＧ６),３３．７(CＧ
７),３９．６(CＧ８),４８．２(CＧ９),２３．８(CＧ１１),１２５．８(CＧ１２),
２８．３(CＧ１５),２５．１(CＧ１６),１６．７(CＧ２５),１７．６(CＧ２６),２４．１
(CＧ２７),１７．７(CＧ２９),２１．６(CＧ３０)．Thespectraldatawas
inconsistentwiththosereported(Tundisetal．,２００２)．
Stigmasterol(１０)　Colorlessneedles(methylalＧ
cohol),ESIＧMSm/z４１２[M]＋,C２９H４８O．１H NMR
(６００MHz,CDCl３)δ:５．３８(１H,d,J＝３．８Hz,HＧ６),
５．１７(１H,dd,J＝１５．２,８．６Hz,HＧ２２),５．０４(１H,dd,J
＝１５．０,８．５Hz,HＧ２３),３．５５(１H,m,HＧ３)．SixmethＧ
yls:１．０３(３H,s,HＧ１９),０．９５(３H,d,J＝６．５Hz,HＧ
２１),０．８７(３H,m,HＧ２９),０．８５–０．７８(６H,m,HＧ２６,
２７),０．７１(３H,d,J＝１１．２Hz,HＧ１８)．１３CNMR(１５０
MHz,CDCl３)δ:３７．２(CＧ１),３１．６(CＧ２),７１．８(CＧ３),４２．３
(CＧ４),１４０．１(CＧ５),１２１．８(CＧ６),３１．９(CＧ７),３１．９(CＧ８),
５０(CＧ９),３７．２(CＧ１０),２１．１(CＧ１１),４０．６(CＧ１２),４２．２(CＧ
１３),５６．９(CＧ１４),２４．３(CＧ１５),２９．８(CＧ１６),５５．９(CＧ１７),
１２．１(CＧ１８),１９．４(CＧ１９),４２．１(CＧ２０),２１．１(CＧ２１),
１３８．６(CＧ２２),１２９．２(CＧ２３),５１．２(CＧ２４),３１．８(CＧ２５),
２２．２(CＧ２６),１８．９(CＧ２７),２５．４(CＧ２８),１２．２(CＧ２９)．The
spectraldatawasinagreementwiththosereported
(Itohetal．,１９７８)．
βＧSitosterol(１１)　Whitepowder(methylalcoＧ
hol),C２９H５０O．Itwascharacterizedbycomparingit
withanauthenticsampleonTLC．
４　DiscussionsandConclusion
Inthisstudy,１１compoundswereisolatedfrom
thewholeplantofH．cryptantha,inwhichiridoid
glycosides(IGs),especialyasperuloside(１),werethe
majorcompounds．IGsareoneofthemostimportant
typesofnaturalproductswithbioactivitiesofantiＧoxiＧ
dation,antiＧinflammatory and immunomodulatory．
Kaempferolanditsglycosidesarealsoknowntobe
goodantioxidants．Althoughlargelyuntestedforthe
bioactivities,itcouldbeassumedthattheIGsandflaＧ
vonidsfoundinthepresentstudycontributetothe
treatmentofinjureandthusexplainthecurrentuseof
thespeciesinethnomedicine．Inaddition,alofthese
fiveiridoidglycosideshavealsobeenisolatedfromH．
diffusaorotherspeciesinthisgenus．H．diffusa,as
animportanttraditionalChinesemedicine,hasbeen
widelyusedtotreatsnakebite,cancer,appendicitis,
hepatitis,furunculosis,enteritis,andbleedinginChina
andalsofoundtopossessnotableefectonmanytypes
ofcancersinclinicalapplication(JiangsuNewMedical
Colege,１９７７)．TheethanolextractofH．diffusa
２５８ 广　西　植　物　　　 　　　　　　　　　　　　　　３４卷
couldinhibitcolorectalcancergrowthinvivoviainhiＧ
bitionofSHHＧmediatedtumorangiogenesis(Linet
al．,２０１３),induceapoptosisviaactivationofthemitoＧ
chondrionＧdependentpathwayinhumancoloncarcinoＧ
macels(Linetal．,２０１０),exhibitedantileukemiaacＧ
tivityin WEHIＧ３celＧinducedleukemiainvivoand
promotedTＧandBＧCelproliferation(Linetal．,２０１１)
andthewaterextractpossessedhighcytotoxicitytoＧ
wardshumanbreastcancerMCF７cels(Lingetal．,
２０１３)．NotonlytheextractofH．diffusaexhibited
strongantiＧcancerefectbutalsothecompoundsisolaＧ
tedfromgenusofHedyotispresentedpotentbioactiviＧ
ties．Forexample,２ＧhydroxyＧ３Ｇmethylanthraquinone
fromH．diffusainducedTHPＧ１celapoptosisina
timeＧanddoseＧdependentmanner(Wangetal．,２０１０),
６ＧOＧβＧdＧapiofuranosylＧβＧdＧglucopyranosideandgrevilＧ
losideGisolatedfrom H．scandensshowedantiviral
activityagainstrespiratorysyncytialviruswithIC５０
valuesof２０and２５μg􀅰mLＧ１,respectively(Wanget
al．,２０１３)．AsperulosideisolatedfromEucommiaulＧ
moides alsoshowedimportantantiＧobesityefects
(Hirataetal．,２０１１)．Wecandeducethatcompounds
fromH．cryptanthaalsohavesomebioactivitieswhich
aresimilartothosefromH．diffusa．
Furthermore,asanimportantLimedicinalplant
species,H．cryptanthahasonlybeenreportedinthe
ethnopharmacologicalinvestigationsinrecentyears．
Therearetoomanymedicinalplantswhichareonly
knownbythelocalLiethnicgroupbuthavepotential
medicinalvalues,suchasH．ovata(BöjtheＧHorváthet
al．,１９８０)．Ethnobotanicalinvestigationcanplayan
importantroleindiscoveringnewresources．ThetradiＧ
tionalknowledgeoftheseplantsisdisappearingineviＧ
tablyasLipeoplearewithouttheirownwritingcharＧ
acters．WehopemorepeoplewouldengageinthestudＧ
yonethnobotanyofLiethnicgrouptorescuethisculＧ
turaltreasure．Andmorepeoplewouldbeattractedby
thesevaluableplantsandtheirassociatedtraditional
knowledge．
Acknowledgements　Weareverygratefultothe
NMRInstrumentalAnalysisDepartmentofColegeof
LifeandEnvironmentalSciences,MinzuUniversityof
Chinaforthemeasurementofspectra．Specialthanks
gotothelocalLipeople,andDr．SumanNeupanefrom
theOldDominionUniversity,USA．
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(下转第８１５页Continueonpage８１５)
３５８６期　　　　　　　　　　　　　　徐丽等:闭花耳草的化学成分研究