全 文 ：天然产物研究与开发 NatProdResDev2009, 21:549-552
文章编号:1001-6880(2009)04-0549-04
ReceivedMay19, 2009;AcceptedJuly21, 2009
FoundationItem:Thisworkwassupportedbyfinancialsupportsfrom
theNSFC(30770235)andChineseAcademicofSciences(YZ-06-1).
＊CorrespondingauthorTel:86-871-5216179;E-mail:hjzhu@mail.kib.
ac.cn
藏药臭蚤草的一个新的苯丙素苷类成分
黄圣卓 1, 3 ,蒋思萍 2 ,朱华结 1＊
1中国科学院昆明植物研究所 植物化学与植物资源持续利用国家重点实验室 ,昆明 650204;
2西藏高原生物研究所 ,拉萨 850001;3中国科学院研究生院 ,北京 100049
摘 要:为了研究藏药臭蚤草的活性成分 , 我们利用各种柱色谱技术 , 从藏药臭蚤草甲醇提取物的乙酸乙酯萃
取相分离到 4个化合物 , 通过 1D、 2DNMR、MS和 HRMS等试验 , 鉴定为 2, 4-dihydroxy-6-methyl-ethanone-4-O-β-
D-Glc(1), 4-(3′-hydroxypropyl)-2, 6-dimethoxyphenol-3′-O-β-D-glcoside(2), 4-alyl-2-methoxyphenol-1-O-β-D-glco-
side(3), 2-methyl-1, 3, 6-trihydroxy-9, 10-anthraquinone-3-O-(6′-O-Ac)-α-L-Rha-(1※2)-β-D-Glc(4), 其中化合物 1
～ 3为苯丙素苷类化合物 , 化合物 4为蒽醌苷。化合物 1 ～ 4都是首次从该属植物中分离得到 ,化合物 1为新的
苯丙素苷类化合物。
关键词:藏药;臭蚤草;苯丙素苷;蒽醌苷
中图分类号:Q946.91;R282 文献标识码:A
ANewPhenylpropanoidGlycosidefromTibetanFolkDrugPulicariainsignis
HUANGSheng-zhuo1, 3 , JIANGSi-ping2 , ZHUHua-jie1＊
1StateKeyLaboratoryofPhytochemistryandPlantRescourcesofWestofChina, KunmingInstituteofBotany,
AcademyofSciences, Kunming650204 , China;2PlateauInstituteofBiology, Lhasa850001 , China;
3GraduateUniversityofChineseAcademyofSciences, Beijing100049 , China
Abstract:InordertoinvestigatethebioactivityconstituentsofTibetanfolkdrugPulicariainsignis, fourcompoundswere
isolatedwithchromatographytechniques.Structureswereelucidatedtobe2, 4-dihydroxy-6-methyl-ethanone-4-O-β-D-
Glc(1), 4-(3′-hydroxypropyl)-2, 6-dimethoxyphenol-3′-O-β-D-glcoside(2), 4-allyl-2-methoxyphenol-1-O-β-D-glcoside
(3), 2-methyl-1, 3, 6-trihydroxy-9, 10-anthraquinone-3-O-(6′-O-Ac)-α-L-Rha-(1※ 2)-β-D-Glc(4)onthebasisof
spectroscopicanalysisincluding1D, 2D-NMR, MSandHRMS.FourcompoundswereisolatedfromthegenusPulicaria
forthefirsttime.2, 4-Dihydroxy-6-methyl-ethanone-4-O-β-D-Glc(1)isanewphenylpropanoidglycoside.
Keywords:Tibetanfolkdrug;Pulicariainsignis;phenylpropanoidglycoside;anthraquinoneglycoside
Introduction
PulicariainsignisofthefamilyAsteraceae(Composi-
tae)growsatalpineultimatenaturalenvironmentmore
than4000 mabovesealevel.Thisspeciesareusedtra-
ditionalyinthetreatmentsoffever, painandcough[ 1] .
Thereisnoreportonitschemicalconstitutesstudyin
literatures.
PreviousstudyofchemicalconstituentsforgenusPuli-
cariawerefocusedondiquiterpenoids[ 2-6] andsesquit-
erpenoids[ 7-11] .However, glycosidesfrom thisgenus
werehardlyreported.Tofindmorebioactivecom-
pounds, constituentsinvestigationforP.insigniswas
performed.Herein, wereporttheisolationandidentifi-
cationforonenewphenylpropanoidglycoside, 2, 4-di-
hydroxy-6-methyl-ethanone-4-O-β-D-Glc(1), whichis
diferentfrom2, 4-dihydroxy-6-methyl-ethanone-4-O-α-
L-glcoside(acetophenone)[ 12] , andthreeknowncom-
pounds4-(3′-hydroxypropyl)-2, 6-dimethoxyphenol-3′-
O-β-D-glcoside(2)[ 13] , 4-alyl-2-methoxyphenol-1-O-
β-D-glcoside(3)[ 14-16] andananthraquinoneglycoside
2-methyl-1, 3, 6-trihydroxy-9, 10-anthraquinone-3-O-(6′-
O-Ac)-α-L-Rha-(1※2)-β-D-Glc(4)[ 17] (Fig.1).
DOI :10.16333/j.1001-6880.2009.04.018
Fig.1 Structuresofcompounds1-4
ExperimentalSection
OpticalrotationdeterminationswerecariedonanOA
AA-55polarimeter.IRspectrawererecordedbyaBio-
RadFTS-135 spectrometerwithKBrpelets.1D-and
2D-NMRspectrawererecordedonBurkerAM-400and
DRX-500 instrumentswithTMSasaninternalstand-
ard.TheMSdatawererecordedbyaVGAutoSpec-
3000 Spectrometer.Columnchromatographywasper-
formedonSephadexLH-20(25-100 μm, Phamacia
FineChemicalCo.Ltd.), ChromatorexODS(100-200
μm, YMCCo.Ltd.)andsilicagel(200-300 mesh,
QingdaoMarineChemistryInc.).Thin-layerchroma-
tography(TLC)wascariedoutonsilicagelGpre-coa-
tedplates(QingdaoMarineChemistryInc.)andcom-
poundsweredetectedbybaptizingTLCinsulfuricacid
reagents(5% inethanol)folowedbyheating.
Plantmaterial
TheherbofP.insigniswascolectedinLhasaareaof
Tibet, China, inOctober2007, andidentifiedbyProfes-
sorSi-PingJiang, PlateauInstituteofBiologyLhasaTi-
betofP.R.Chinawherethespecimenwasdeposited.
Extractionandisolation
RowherbpowderofP.insignis(90 kg)wasextracted
withmethanolandtheextraction(2.5kg)wasobtained
andextractedwithpetroleumethertoremoveoils.It
wasthenextractedwithethylester, theextractedfrac-
tionwassubjectedtocolumnchromatographyoversili-
cagel(eludedwithCHCl3 /MeOH1∶0-1∶2), andthe
CHCl3 /MeOH(1∶2)wasthensubjectedtocolumn
chromatographyagainoverODS(eludedwithH2O/
MeOH1∶9 to1∶0), andSephadexLH-20(elutedwith
CHCl3 /MeOH1∶1 or0∶1)repeatedlytoyieldcom-
pounds1 (5mg), 2(3mg), 3(4 mg)and4(41 mg).
Fig.2 KeyHMBCcorrelationsofcompound1
ResultsandDiscussion
Compound1 wasobtainedasayelowoilwithoptical
rotation[ α] 21D -46.8°(c0.00235, MeOH).Itsmolecu-
larformulawasdeductedasC15 H20O8 byHR-ESI-MS
atm/z289.1418([ C15 H22 O4 +Na] + Calcd.m/z:
289.1415).IRabsorptionat3338cm-1 showedtheex-
istenceofhydroxylgroup.Carbonylgroup(1620 cm-1)
andaromaticring(1490, 1430 , 1420 cm-1)werefound.
In1HNMRspectrumof1, twosinglesignals(δ6.46
and6.45)showedthattherewerefoursubstituentson
phenylring, thetwoprotonsmustbeisolatedbythe
foursubstituents.Moreover, theshiftsofprotonat4.90
(m, 1H)[ 4.99(d, 1H, J=7.7 Hz)in(CD3)2CO]
andofcarbonat101.6(d), 74.7(d), 77.9(d), 71.2
(d), 78.2(d)and62.4(t)showedthepresenceofa
O-β-glucosylmoiety[ 13-15] .Onemethyl(δ2.32, s, 3H)
andoneacetylgroup(δ2.54, s, 3H;δ32.7(q)and
207.1(s))werefound.Twobearing-oxygenaromatic
carbons(δ161.0(s)and161.5(s))wereobserved.In
HMBC, therelationshipofmethylofacetylgroupδ
2.54(s, 3H)withthearomaticcarbon[ C-1, δ122.2
(s)] wasfoundandthishintedacetylconnectedtoaro-
maticC-1.Methylgroupδ2.32(s, 3H)hadcorela-
tionstoaromaticcarbonatδ122.2(s), 111.9(d),
140.9(s)inHMBC, thisclearlyexhibitedthismethyl
locatedatC-6(Fig.2).Thecorrelationofaromaticpro-
tonsδ6.46(s, 1H), 6.45(s, 1H)andH-1′ofglucose
δ4.90(m, 1H)[ 4.99(d, 1H, J=7.7 Hz)in
(CD3)2CO] witharomaticcarbonδ161.5(s)revealed
thatglucosyllocatedatC-4 withβ-connection.One
protonconnectedonC-3 δ102.6(d).Ahydroxyl
groupwaslinkedatC-2δ161.0(s).Structureof1was
assignedas2, 4-dihydroxy-6-methyl-ethanone-4-O-β-D-
Glucoside(Fig.2).
TheNMRdataforotherthreecompoundsaresumma-
rizedbelow:
550 NatProdResDev Vol.21
Table1 1HNMR(400 MHz, CD3OD, δ, JHz)and13CNMR(100 MHz, CD3OD, δ)ofcompound1
No. δH δC No. δH δC
1 – 122.2(s) Glc
2 – 161.0(s) 1′ 4.90(m, 1H) 101.6(d)
3 6.46(s, 1H) 102.6(d) 2′ 3.44(m, 1H) 74.7(d)
4 161.5(s) 3′ 3.43(m, 1H) 77.9(d)
5 6.45(s, 1H) 111.9(d) 4′ 3.38(m, 1H) 71.2(d)
6 - 140.9(s) 5′ 3.47(m, 1H) 78.2(d)
C=O - 207.1(s) 6′ 3.90(dd, 1H, J=1.7, 13.7Hz)
3.70(dd, 1H, J=5.5, 12.0Hz) 62.4(t)
CH3(C=O) 2.54(s, 3H) 32.7(q)
CH3 2.32(s, 3H) 21.9(q)
-OH 4.66(s, br)
2, 4-dihydroxy-6-methyl-ethanone-4-O-β -D-Gluco-
side(1) C15 H20 O8 lightyelowoil, [ α] 21D -46.8(c
0.00235, MeOH);IRυKBrmax cm-1:3338, 2930, 2886,
1620, 1490, 1430, 1420, 1377, 1359, 1262, 1222,
1184, 1074, 885, 849, 833, 667;ESI-MS(pos.)m/z:
329 [ M+1] +(2.5), 351 [ M+Na] +(10.0), 567
[ M+K] +(2.0);HRESI-MS(pos.)351.1050([ M
+Na] +, [ C15 H20 O8 +Na] + Calcd.351.1055), For
1Hand13CNMRspectrumdatainCD3ODseetheTa-
ble1.1HNMR((CD3)2CO, 500 MHz)δ:12.1(s,
br), 6.44(s, 1H), 6.43(s, 1H), 5.99(d, 1H, J=7.7
Hz), 4.68(s, br), 4.45(s, br), 4.38(s, br), 3.84
(m, 2H), 3.68(m, 1H), 3.53(m, 1H), 3.48(m,
2H), 2.58(s, 3H), 2.47(s, 3H).
4-(3′-hydroxypropyl)-2, 6-Dimethoxyphenol-3′-O-
β -D-Glc(2) Colourlessoil, [ α] 21D-20.7 (c
0.000159, MeOH), C17H26O9 , ESI-MS(neg.)m/z:409
[ M+Cl] -(110).1HNMR(CD3OD, 400 MHz)δ:6.54
(s, 2H), 4.79(d, 1H, J=7.2Hz), 3.85(s, 1H), 3.83
(s, 6H), 3.77(dd, 1H, J=7.7, 11.9Hz), 3.68(dd,
1H, J=5.1, 6.4 Hz), 3.57(t, 2H, J=12.8 Hz),
3.46(m, 3H), 3.20(s, br, 1H), 2.63(t, 2H, J=15.4
Hz), 1.82(m, 2H);13 CNMR(CD3OD, 100 MHz)δ:
154.1(s), 140.4(s), 135.0(s), 107.4(d), 105.6
(d), 78.3(d), 77.8(d), 75.7(d), 71.3(d), 62.6
(t), 62.1(t), 56.9(q), 35.4(t), 33.4(t).
4-alyl-2-methoxyphenoxy-4-β-D-Glc(3) Colour-
lesoil, [ α] 21D -40.4(c0.00125, MeOH), C16 H22
O7.1HNMR(CD3OD, 400 MHz)δ:7.07(d, 1H, J=
8.2Hz), 6.82(s, 1H), 6.71(d, 1H, J=8.2Hz), 5.95
(m, 1H), 5.05(s, 1H), 5.02(d, 1H, J=9.6 Hz),
4.85(d, 1H, J=7.32Hz), 3.87(s, 1H), 3.84(d, 3H,
J=17.8 Hz), 3.45(dd, 1H, J=6.0, 7.4 Hz), 3.33
(m, 6H);13CNMR(CD3OD, 100 MHz)δ:150.7(s),
146.3(s), 139.0(d), 136.4(s), 122.1(d), 118.2
(d), 115.8(t), 114.1(d), 103.0(d), 78.2(d),
77.8(d), 74.9(d), 71.3(d), 62.5(t), 56.6(q),
40.8(t).
2-methyl-1, 3, 6-trihydroxy-9, 10-anthraquinone-3-
O-(6′-O-Ac)-α-L-Rha-(1※ 2)-β-D-Glc(4) Or-
angeneedlecrystal, [ α] 21D -18.5(c0.0020, MeOH),
C29H32 O15 , ESI-MS(neg.)m/z:619 [ M-1] -(16.0),
655 [ M+Cl] -(1.0), HRESI-MS(neg.)619.1651
([ M-1] -, [ C29H32O15-H] -Calcd.m/z:619.1662).1H
NMR(DMSO-d6 , 400 MHz)δ:13.23(s, br, 1H),
11.10(s, br, 1H), 8.09(d, 1H, J=6.84 Hz), 7.47
(d, 1H, J=1.92 Hz), 7.40(s, 1H), 7.23(dd, 1H, J
=2.0, 6.9 Hz), 5.46(m, 3H), 5.27(s, 1H), 4.68
(d, 1H, J=3.36Hz), 4.48(d, 1H, J=4.7 Hz), 4.33
(s, 1H), 4.31(s, 1H), 3.99(dd, 1H, J=6.4, 9.6
Hz), 3.77(dd, 1H, J=7.6, 7.6 Hz), 3.69(s, 1H),
3.63(m, 3H), 3.20(m, 2H), 2.14(s, 3H), 1.92(s,
3H), 1.07(d, 3H, J=4.92 Hz);13 CNMR(DMSO-
d6 , 100 MHz)δ:186.4(s), 181.7(s), 170.3(s),
163.6(s), 161.3(s), 160.0(s), 135.3(s), 131.9
(s), 129.7(d), 124.5(s), 121.5(d), 120.5(s),
112.5(d), 110.6(s), 105.3(d), 100, 2(d), 97.2
(d), 77.0(s), 76.2(s), 74.0(d), 71.9(d), 70.4
(d), 70.3(d), 70.0(d), 68.5(d), 63.3(t), 20.4
551Vol.21 HUANGSheng-Zhuo, etal:ANewPhenylpropanoidGlycosidefromTibetanFolkDrugPulicariainsignis
(q), 18.1(q), 8.72(q).
参考文献
1 EditorialBoardofFloraofChina, FloraofChina.Beijing:
SciencePress, 1997, Tums75:292-293.
2 NurmukhamedovaMR, KasimovSZ, etal.Diterpenoidsof
Pulicariasalvifolia.I.Structureofsalvinandsalvinin.Khimiya
PrirodnykhSoedineni, 1985, 2:201-205.
3 NurmukhamedovaMR, AbdullaevND, etal.Diterpenoidsof
Pulicariasalvifolia.II.Structureofsalvicin.KhimiyaPrirod-
nykhSoedineni, 1986, 3:299-301.
4 SagitdinovaGV, EtbakovaKA, etal.DiterpenoidsofPulicar-
iasalvifolia.III.Structureofsalvicinin.KhimiyaPrirodnykh
Soedinenii, 1994, 2:246-249.
5 EshbakovaKA, SagitdinovaGV, etal.DiterpenoidsofPuli-
cariasalviifoliaIV.Structuresofsalvicinolideandsalvicinol-
in.ChemistryofNaturalCompounds, 1998, 33:458-461.
6 DasB, ReddyMR, etal.ClerodanediterpenoidsfromPuli-
cariawightiana.Phytochemistry(Elsevier), 2005, 6:633-
638.
7 SanFelicianoA, MedardeM, etal.Sesquiterpenoidsand
phenolicsofPulicariapaludosa.Phytochemistry, 1989, 28:
2717-2721.
8 BohlmannF.ZderoC.Naturallyoccuringterpenederiva-
tives.Part371.Caryophyllenederivativesandahydroxyiso-
comenefromPulicariadysenterica.Phytochemistry, 1981, 20:
2529-2534.
9 RustaiyanA, BohlmannF, etal.Naturallyoccurringterpene
derivatives.Part368.AhardwickicacidderivativefromPu-
licariagnaphalodes.Phytochemistry, 1981, 20:2772-2773.
10 HafezS, BohlmannF, etal.Caryophylenederivativesfrom
Pulicariaarabica.Phytochemistry, 1987, 26:3356-3358.
11 MossaJS, MuhammadI, etal.Bisaboleneandguaianeses-
quiterpenesfromPulicariaglutinosa.Phytochemistry, 1992,
31:575-578.
12 MauthnerN, Constitutionofglucoresacetophenoneandnew
syntheticglucosides.JournalfuerPraktischeChemie(Leip-
zig), 1943, 161:284-288.
13 MulkensA, KapetanidisI.Eugenylglucoside, anewnatural
phenylpropanoidheterosidefromMelissaoficinalis.Journal
ofNaturalProducts, 1988, 51:496-498.
14 SchwabW, SchelerG, etal.Glycosidicalyboundaroma
componentsfromsourcherry.Phytochemistry, 1990, 29:607-
612.
15 UchiyamaT, MiyaseT, etal.Terpenicglycosidesfrom
Plucheaindica.Phytochemistry, 1989, 28:3369-3372.
16 WuTS, HuangSC, etal.Chemicalandantiplateletaggrega-
tiveinvestigationoftheleavesofClausenaexcavate.Phyto-
chemistry, 1993, 32:449-451.
17 ItokawaH, MiharaK, etal.Studiesonanovelanthraquinone
anditsglycosidesisolatedfrom RubiacordifoliaandR.
akane.Chemical＆PharmaceuticalBuletin, 1983, 31:2353-
2358.
552 NatProdResDev Vol.21