全 文 ：天然产物研究与开发 NatProdResDev2007, 19:584-587
文章编号:1001-6880(2007)04-0584-04
　
　
　ReceivedFebruary6, 2007;AcceptedMarch12, 2007
＊CorrespondingauthorTel:86-871-5223800;E-mail:nhtan@mail.kib.
ac.cn
长舟马先蒿化学成分研究
褚洪标 1, 2 ,谭宁华 1＊ ,熊　江 1 ,张玉梅 1 ,嵇长久 1, 2
1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 , 昆明 650204;
2中国科学院研究生院 , 北京 100039
摘　要:为了进一步研究玄参科长舟马先蒿的化学成分 , 我们从其全草的乙醇提取物中分离得到 1个新环烯醚
萜苷和 12个已知化合物。根据波谱数据(1D, 2D-NMR, HSQC, HMBC, ROESY, MS)分别鉴定为 gardosidemethyl
ester(1)、 7-O-acetylgardosidemethylester(2)、 verbascoside(3)、leucosceptosideA(4)、jionosideD(5)、martynoside
(6)、 2″-O-acetylmartynoside(7)、uridine(8)、adenosine(9)、benzylalcohol-O-β-D-xylopyranosyl-(1※ 2)-β-D-gluco-
pyranoside(10)、2-phenylethylO-β-D-xylopyranosyl-(1※ 2)-β-D-glucopyranoside(11)、apigenin(12)、lariciresinol-4′-
O-β-D-glucopyranoside(13), 其中 7-O-acetylgardosidemethylester(2)为一个新化合物。
关键词:玄参科;长舟马先蒿;环烯醚萜苷;山栀子苷甲基;7β-乙酰基山栀子苷甲基
中图分类号:RR284.2;Q946.91 文献标识码:A
ChemicalConstituentsofPedicularisdolichocymbaHand.-Mazz.
CHUHong-biao1, 2 , TANNing-hua1＊ , XIONGJiang1 , ZHANGYu-mei1 , JIChang-jiu1, 2
1StateKeyLaboratoryofPhytochemistryandPlantResourcesinWestChina,
KunmingInstituteofBotany, theChineseAcademyofSciences, Kunming650204 , China;
2GraduateSchooloftheChineseAcademyofSciences, Beijing100039 , China
Abstract:TostudyfurtherthechemicalconstituentsfromtheethanolextractofthewholeplantsofPedicularisdolicho-
cymbaHand.-Mazz.(Scrophulariaceae), onenewiridoidglycoside, 7-O-acetylgardosidemethylester(2)wasisolated, to-
getherwithtwelveknowncompounds, gardosidemethylester(1), verbascoside(3), leucosceptosideA(4), jionosideD
(5), martynoside(6), 2″-O-acetylmartynoside(7), uridine(8), adenosine(9), benzylalcohol-O-β-D-xylopyranosyl-(1
※ 2)-β-D-glucopyranoside(10), 2-phenylethylO-β-D-xylopyranosyl-(1※ 2)-β-D-glucopyranoside(11), apigenin(12)
andlariciresinol-4′-O-β-D-glucopyranoside(13).Structuresofcompounds1-13 wereelucidatedmainlybasedonNMR
(HSQC, HMBCandROESY)andMSevidence.
Keywords:Scrophulariaceae;Pedicularisdolichocymba;iridoidglycoside;gardosidemethylester;7-O-acetylgardoside
methylester
Introduction
PedicularisL.comprisesabout329 speciesinChi-
na[ 1] .Somespeciesofthisgenusareusedtotreatdis-
ease[ 2] .ManycompoundswereisolatedfromPedicu-
laris, including iridoids, phenylpropanoidsand so
on[ 3] .Amongthem, somecompoundsshowedantioxi-
dantandantitumouractivities[ 4, 5] .Inthepreviouspa-
per, wehavereportedfournewiridoidglycosidesdoli-
chocymbosidesA-DfromP.dolichocymba[ 6] .Hereinwe
reporttwoiridoidglycosidesfromtheplant, gardoside
methylester(1), 7-O-acetylgardosidemethylester(2),
togetherwithotherelevencompounds(Fig.1).
ResultsandDiscussion
Compound1wasobtainedasawhitepowdersolid.The
IRspectrum(KBr)showedthepresenceofhydroxyl
(3422 cm-1), C=O(1693 cm-1), doublebond(1634
cm-1)andC-O-C(1079 cm-1).TheFAB--MSspectrum
gavequasi-molecularionpeakatm/z387 [ M-H] -and
HR-TOF-MSprovidedthemolecularformulaofC17H24O10.
DOI :10.16333/j.1001-6880.2007.04.017
Fig.1　Structuresofcompounds1-13
The1H, 13CNMR(DEPT)spectra(Table1)of1 re
vealedthepresenceof1CH3 , 3CH2 , 1 0CHand3
quaternaryCatoms.The1HNMRsignalat4.66(1H,
d, J=7.9 Hz)suggestedthepresenceofβ-D-glucopyr-
anosyl.HMBCcorelations(Fig.2)ofδH 4.66(1H, d, J
=7.9Hz, H-1′ofGlc)toδC 96.6(CH, C-1), δH 3.70
(3H, s, -COOMe)toδC 169.1(C, CO)suggestedthat
β-D-glucoselinkedatC-1andthemethoxcarboylloca-
tedatC-4.Basedontheseevidence, compound1 was
showntohaveaniridoidstructurecloselyrelatedto
thatofgardosidemethylester[ 7, 8] .
Fig.2　KeycorrelationsinHMBCandROESYspectra
of1
Table1　1H(1:500 MHz;2:400MHz)and13CNMR(100 MHz)dataof1 and2inCD
3
OD
No.1 1
+ 2
δC δH(J, Hz) δC δH(J, Hz)
1 96.6(d) 5.44(d, 1H, 4.8) 96.0(d) 5.43(d, 1H, 6.0)
3 153.5(d) 7.44(s, 1H) 153.6(d) 7.56(d, 1H, 1.1)
4 111.7(s) 110.8(s)
5 31.8(d) 3.15(m, 1H) 33.1(d) 3.26(m, 1H)
6 40.6(t) 1.96(m, 1H) 38.4(t) 2.09-2.25(m, 2H)
2.00(m, 1H)
7 73.8(d) 4.35(m, 1H) 76.3(d) 5.49(m, 1H)
8 152.7(s) 148.3(s)
9 44.9(d) 2.99(m, 1H) 44.4(d) 3.00(m, 1H)
10 113.1(t) 5.36(brs, 2H) 116.6(t) 5.55(brs, 2H)
11 169.1(s) 168.8(s)
-OMe 51.7(q) 3.70(s, 3H) 51.6(q) 3.78(s, 3H)
-OCOCH3 172.3(s)
-OCOCH3 21.0(q) 2.11(s, 3H)
Glucose
1′ 99.9(d) 4.66(d, 1H, 7.9) 99.6(d) 4.76(d, 1H, 7.9)
2′ 74.7(d) 3.19(m, 1H) 74.5(d) 3.28(m, 1H)
3′ 78.4(d) 3.29(m, 1H) 78.3(d) 3.38(m, 1H)
4′ 71.6(d) 3.25(m, 1H) 71.5(d) 3.30(m, 1H)
5′ 78.0(d) 3.35(m, 1H) 77.8(d) 3.41(m, 1H)
6′ 62.8(t) 3.64(dd, 1H, 6.2, 11.9) 62.7(t) 3.69(dd, 1H, 2.8, 11.9)
3.89(dd, 1H, 1.9, 11.9) 3.96(dd, 1H, 2.0, 11.9)
　＊AssignmentfromHSQC, HMBCexperiments.
Therelativeconfigurationof1 wasdeterminedfromits
ROESYexperiment(Fig.2).Thecorrelationsofδ2.99
(H-9)with3.15(H-5), 3.15(H-5)with2.00(H-
6b), 1.96(H-6a)with4.35(H-7), suggestedthatthe
H-5, H-9 andH-6bwereinthesameorientation.The
chemicalshiftofC-1wilbelesthan100 ppmifH-5
585Vol.19 CHUHong-biaoetal:ChemicalConstituentsofPedicularisdolichocymbaHand.-Mazz.
isβ-oriented;whereas, thechemicalshiftofC-1 wilbe
morethan100 ppm iftheH-5 isα-oriented[ 9-13] .
Hence, theH-5, H-9 andH-6bareβ-orientedinview
ofthe13CNMRsignalatδ96.6, butH-6aandH-7are
inα-orientation.Fromtheaboveresults, compound1
wasdeterminedasgardosidemethylester.
Compound2 wasobtainedasacolorlessstickysolid.
TheIRspectrum(KBr)showedthepresenceofhy-
droxyl(3428 cm-1), C=O(1710 cm-1), doublebond
(1635 cm-1)andC-O-C(1076, 1021 cm-1).TheFAB--
MSspectrumgavequasi-molecularionpeakatm/z429
[ M-H] -andHR-TOF-MSsuggestedthemolecularfor-
mulaofC19H26O11.Thespectradataof2(Table1)are
resemblecloselyrelatedtothatof1, butwithanaddi-
tionalsignalatδH 2.11, δC 21.0, 172.3 fromanace-
toxygroup.Comparingwiththoseof1, thesignalsofC-
7 in2wereshifteddownfieldby2.5ppm, andC-6and
C-8 upfield1.8 and4.4ppm.Thus, theacetoxylcould
belocatedatC-7.TheROESYexperimentsuggested
thesamerelativeconfigurationin2 and1.Therefore,
compound2 waselucidatedas7-O-acetylgardoside
methylester.
ByMS, 1Hand13CNMRdata, compounds3-13werei-
dentifiedasfolows:verbascoside(3)[ 14] , leucoscepto-
sideA(4)[ 14] , jionosideD(5)[ 14] , martynoside
(6)[ 15] , 2″-O-acetyl-martynoside(7)[ 15] , uridine
(8)[ 16] , adenosine(9)[ 17] , benzylalcohol-O-β-D-xy-
lopyranosyl-(1※ 2)-β-D-glucopyranoside(10)[ 18] , 2-
phenylethylO-β-D-xylopyranosyl-(1※2)-β-D-gluco-
pyranoside(11)[ 19] , apigenin(12)[ 20] , andlaricires-
inol-4′-O-β-D-glucopyranoside(13)[ 21] .
Experimental
General
OpticalrotationsweremeasuredwithaHorbiaSEAP-
300 polarimeter.IRspectrumwasobtainedonaBio-
RadFTS-135spectrophotometer(KBrdiscs).UVspec-
trumwasrecordedonaShimadzu2401PCspectropho-
tometer.EI, FAB-MSandHR-TOF-MSwerecariedout
onaVGAutoSpec-3000 spectrometer.1Dand2D-
NMRspectrawererecordedonaBrukerAM-400anda
DRX-500spectrometerwithTMSasinternalstandard.
ColumnchromatographywasperformedoverSilicagel
(200-300 mesh, QingdaoMarineChemicalInc., Chi-
na), D101 resin(TianjinAgricultureChemicalCo.,
Ltd., China)andSephedaxLH-20(25-100 μm, Phar-
maciaFineChemicalCo., Ltd., Sweden), respective-
ly.
Plantmaterial
TheplantmaterialwascolectedinZhongDian, Yun-
nanProvinceofChinainAugust2003 andidentifiedby
Prof.WangHong, KunmingInstituteofBotany, Chinese
AcademyofSciences.Thevoucherspecimen(KUN
0556080)wasdepositedintheHerbariumofKunming
InstituteofBotany, ChineseAcademyofSciences.
Extractionandisolation
Thedriedwholeplants(11kg)ofP.dolichocymbawere
extractedwith95% ethanolforthreetimes(eacha
week)atroomtemperature.Afterconcentrationofthe
combinedextractsunderreducedpressure, theresidue
wasdissolvedwithhotwaterandextractedsuccessively
withpetroleumether, EtOAcandn-BuOH.TheEtOAc
portionwasdividedinto5fractions(Frs1-5)oversilica
gelcolumnelutedwithCHCl3-MeOH(20∶1)folowed
byincreasingconcentrationsofMeOH.Fr.1wassepa-
ratedoverSephedaxLH-20 columntogive12(6 mg).
Compound7(8 mg)wasisolatedfromFr.2 oversilica
gelcolumn.Fr.4 wasseparatedfurtheroversilicagel
andSephedaxLH-20 columntogive1(34 mg), 2(7
mg), 6(300 mg), 8(25 mg), 10(16 mg)and11(5
mg).Fr.5 waselutedwithCHCl3-MeOH(20∶1)over
silicagelcolumntogivecompound3(17 mg)anda
mixture, whichwasthenpurifiedbyHPLC(Zorbax
ODS-C18, MeOH-H2O, 1∶4)toafordcompound4(6
mg)and5(9 mg).Then-BuOHfractionwassubjected
toasilicagelcolumnelutedwithCHCl3-MeOH(9∶1)
folowedbyincreasingconcentrationsofMeOHtogive
2fractions(Fr.AandB).Fr.Bwasseparatedover
D101 resinelutedwithMeOH-H2O(3∶7 , 7∶3, respec-
tively), andtheobtainedresiduewasseparatedover
silicagelandSephedaxLH-20 columnsuccessivelyto
givecompounds9(24 mg)and13(6 mg).
Gardosidemethylester(1)　Whitepowdersolid,
C17H24O10 , [ α] 21D -44.6°(c0.65, CH3OH).UVλMeOHmax
nm(logε):202(4.08), 231(4.07).IRνKBrmaxcm-1:
3422, 2924, 1693 , 1634, 1440 , 1297, 1079.1HNMR
586 NatProdResDev　　　　　　　　　　　　　　　　　　　　　 　Vol.19
(500MHz, CD3OD)and13CNMR(100 MHz, CD3OD)
dataareshowninTable1.FAB--MSm/z:387[ M-H] -
(53), 225[ M-Glc] -(91);HR-TOF-MSm/z:[ M-H] -
387.1301(forcalcd.C17H23O10 , 387.1291).
7-Acetylgardosidemethylester(2)　Colorlesssticky
solid, C19 H26 O11 , [ α] 26D -65.8°(c0.66, CH3OH).
UVλMeOHmax nm(logε):203(3.77), 233(4.01).IRνKBrmax
cm-1:3428, 2927, 1734, 1710 , 1635 , 1440, 1374, 1286,
1247, 1157, 1076, 1021.1HNMR(400 MHz, CD3OD)
and13CNMR(100 MHz, CD3OD)aregiveninTable
1.FAB--MSm/z:429[ M-H] -;HR-TOF-MSm/z:[ M-
H] -429.1408(forcalcd.C19H25O11 , 429.1396).
Acknowledgements　Thisworkwassupportedbythe
FoundationofChineseAcademySciences(WestLight
Program)andtheNationalNaturalScienceFoundation
ofChina(30572258).
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