连钱草化学成分的研究

连钱草化学成分的研究

椰子林冠色（nakai）是中国的一个步行区，有一个痕迹可追溯性。这是一个循环特征的异常，被认为是一个抽有性的特征，是一个接受性和可追溯性的过程。这是要求绩效评估的。本线政策应明确限制本线政策的积极行为，并向预算中指定绩效补偿。预算中预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算，预算中的预算。h-9和h-12通过h-12日h-13c.和h-13-3.4和h-13-和h-13s和和和和....4和...............4和....和.............................3.3Compound1,colorlessoil,[α]20D-29.3°(c0.30,CHCl3),showedthemolecularformulaasC15H22O3,(HR-ESIMS:m/z251.3481[M+H]+,calcd.forC15H23O3251.3488)anditsIRspectrumindicatedthepresenceofcarbonylandhydroxylgroups.The1Hand13CNMRdataof1(Table1)areverysimilartothatof7,11-dihydroxy-2,9E-bisaboladien,abisabolenesesquiterpenoid,andthedifferenceisthat1hasonelesshydroxymethineandtwomoreketonecarbonylsignals(Figure1).TheprotonscouldbeunequivocallyassignedfromitsNOESY(Table2)andHMBC(Table2)spectraldata.Bycomparisonsofthe1HNMRdataof1withthoseofknownsesquiterpenes,thesignalatδ6.42(d,J=13.8Hz)andδ6.92(d,J=13.8Hz)wereassignedtoH-9andH-10respectively,andbothH-9andH-10correlatedwithH-12(H-13)intheNOESYspectrumof1,sothetwohydrogenatomsaretrans.IntheHMBCspectrumof1,bothH-9andH-10correlatedwithacarbonylcarbon(δ203.3),fromwhichwecouldconcludedthatthecarbonylcarbonisC-8.InHMBCof1,themethylboubletatδ1.01(d,J=7.0Hz),theprotonsignalatδ3.28(dt,J=6.5,6.0Hz)andtheprotonsignalatδ2.78(ddd,J=11,6.5,4.3Hz)allcorrelatedwithC-8,sotheseprotonscanbeassignedtoH-14,H-7andH-6respectively.HMBCof1alsorevealedthecorrelationsofbothH-7andH-6withacarbonylcarbon(δ199.3),whichaccountedthatthecarbonylcarbonisC-1.ThestereochemistryofH-6followedfromthecouplingconstantsobserved,thecouplingconstantsofH-6(J6,5β=11Hz,J6,5α=4.3Hz,J6,7=6.5Hz)indicatedthatH-6isaxialandα-oriented.TherelativeconfigurationofC-7wasdeterminedviaaNOESYexperiment,inNOESYof1,H-7correlatedwiththeprotonsignalatδ1.74(m),H-14correlatedwithboththeprotonsignalatδ1.74(m)andtheprotonsignalatδ2.03(m),whichindicateda7Sconfiguration.InHMBCof1,theprotonsignalatδ2.03(m)correlatedwithC-1,C-6andC-7,thustheprotonsignalatδ1.74(m)canbeassignedtoH-5β,theprotonsignalatδ2.03(m)canbeassignedtoH-5α,C-14isβ-oriented.NOESYof1alsoshowedthecorrelationsbetweenH-6andtheprotonsignalatδ2.46(m),whichsuggestedthatthehydrogenisH-4α.FromNOESYandHMBCof1,wecouldinterpretedthatthesignalatδ2.33(m)isassignedtoH-4β,thesignalatδ5.85(brs)isassignedtoH-2,andthesignalatδ3.05(brs)isassignedtothehydrogenatomofahydroxylgroupatC-11separatively.TheassignmentsofH-12,H-13,H-15aremorelikely.ByHSQCof1andcomparisonsof13CNMRdatawithknownsesquit￣erpenes,thecarbonswereassigned,andHMBCexperimentsalsosupportedalltheseassignments.InHMBCof1bothH-9andH-10correlatedwithacarbonatombearingahydroxylgroup,sothecarboncanbeassignedtoC-11withthesignalatδ70.4.Othercarbonscanbespecifiedanalogically.Bycomparisonswiththespectraldataofbisabolenewithknownstereochemistryandestablishedabsoluteconfiguration,compound1wasidentifiedas(6R,7S)-11-hydroxyl-2,9E-bisaboladien-1,8-dione,namedasglecholone.“双带头人”silca&非价..............................................................3.3.3.GeneralexperimentalproceduresAllmeltingpointsweredeterminedbyaXT-4micromeltingpointapparatusandwereuncorrected.TheopticalrotationsweremeasuredbyaPerkin2Elmer241digitalpolarmeterinCHCl3.IRspectrawererecordedbyanIMPACT400(KBr)spectrometer.1HNMR(300MHz),13CNMR(75MHz),HMQC,HMBCspectrawererunonBrucker300spectrometerwithTMSasinternalstandardandvaluesweregiveninδ.MSspectrawereperformedonVG2Autospec2300massspectrometer.Silicagel(100-200,200-300mesh)(Qingdao)wasusedforCCandsilicagel60254(Qingdao)forTLCandpreparativeTLC.PlantmaterialTheaerialpartsofGlechomalongituba(Nakai)KuprwerecollectedfromXuyicountyofJiangsuprovinceinJuly2003.TheplantmaterialwasidentifiedbyProfessorQianShihui.AvoucherspecimenhasbeendepositedintheHerbariumoftheDepartmentofMedicinalPlants,JiangsuAcademyofTraditionalChineseMedicine.ExtractionandisolationFortykgdriedandcrushedaerialpartsofGlechomalongituba(Nakai)Kuprwereextractedthreetimeswith80%EtOHatreflux.Theextractswerecombinedandconcentratedunderreducedpressure,andtheresiduewasdissolvedinhotwater,andthensuccessivelypartitionedwithpetroleumether,EtOAc,andn-butanol.Thepetro￣leumetherextractwasevaporatedinvacuumtogivearesidue(1012g),whichwaschromatographedoversilicagelcolumnelutingwithpetroleumether-EtOAc(ingradient)toyield13fractions,whichwerecombinedonthebasisofTLC.Compound1(70mg),compound2(10mg),compound3(6mg)andcompound4(8mg)wereisolatedfromFr.8(petroleumether-EtOAc2∶1),andthenpurifiedbypreparationTLC.Compound5(30mg)andcompound8(50mg)wereisolatedfromFr.7(petroleumether-EtOAc3∶1).Compound7(10mg)wasisolatedfromFr.4(petroleumether-EtOAc10∶1).Compound9(30mg)wasisolatedfromFr.3(petroleumether-EtOAc20∶1).TheEtOAcextractwasevaporatedinvacuumtogivearesidue(703g),whichwaschromatographedoversilicagelcolumnelutingwithCHCl3-MeOH(ingradient)toyield11fractions,whichwerecombinedonthebasisofTLC,andcompound6(10mg)wasisolatedfromFr.3(CHCl3-MeOH20∶1).c.4.3ec-5,c-9,3,3,4,3,4.3,4.3,3,4.3,4.3,3,4.3,4.3,3,4.3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,4.3,4.3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,4.3,3,3,3,3,3,3,3,3,3,3,3,4.3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,4.3,3,3,3,4.3,3,4.3,3,4.3,3,3,3,3,3,4.3,3,4.3,3,4.3,3,3,4.3,3,4.3,3,4.3,3,3,3,3,4.3,3,3,3,3,4.3,3,3,3,3,4.3,3,4.3,3,4.3,3,3,3,4.3,3,3,3,4.3,3,4.3,3,4.3,3,4.3,3,4.3,3,3,4.3,3,3,3,3,4.3,3,4.3,3,3,3,4.3,3,3,13,3,3,3,3,3,3,3,3,13.3,3,3,3,3,3,3,3,13.3,3,13.3,3,3,3,13,13,3,3,13.3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,3,4.3,3,13.3,Compound1Colorlessoil,ESI-MS:[M+H]+251(100);[α]20D-29.3°(c0.30,CHCl3);IR(KBr)cm-1:3465,3074,2873,1655,1616,1593,1510,1490,1313,1211,1186,1076;1HNMRand13CNMRdatawerelistedinTable1.Compound2Colorlessoil,ESI-MS:[M-H]-207(100);[α]20D+245°(c0.10,CHCl3);CD(C2H5OH,nm,Δε):243(+137),320(-8);1HNMR(CDCl3),δ:0.97(3H,s,H-12),1.03(3H,s,H-13),1.24(3H,d,J=6.5Hz,H-10),1.90(3H,d,J=0.8Hz,H-11),2.05(1H,d,J=16Hz,H-2α),2.41(1H,d,J=16Hz,H-2β),2.60(1H,d,J=8.6Hz,H-6),4.33(1H,m,H-9),5.56(1H,dd,J=15,8.6Hz,H-7),5.70(1H,dd,J=15.6Hz,H-8),5.90(1H,brs,H-4);13CNMR(CDCl3)δ:36.1(C-1),47.4(C-2),200.2(C-3),125.5(C-4),162.0(C-5),55.4(C-6),126.7(C-7),138.5(C-8),68.1(C-9),23.6(C-10),23.4(C-11),27.8(C-12),27.1(C-13).Thesedatawereidenticaltotheliteraturevaluesof6R,9R-3-oxo-α-ionol.Compound3Colorlessoil,ESI-MS:[M-H]-221(100);[α]20D+143°(c0.75,CH3OH);1HNMR(CDCl3)δ:1.03(3H,s,H-12),1.11(3H,s,H-13),1.89(3H,d,J=0.7Hz,H-11),2.31(3H,s,H-10),2.32(1H,d,J=17Hz,H-2α),2.51(1H,d,J=17Hz,H-2β),5.96(1H,brs,H-4),6.47(1H,d,J=15.9Hz,H-8),6.84(1H,d,J=15.9Hz,H-7);13CNMR(CDCl3)δ:41.4(C-1),49.5(C-2),197.4(C-3),127.8(C-4),160.3(C-5),79.3(C-6),144.9(C-7),130.3(C-8),197.0(C-9),29.1(C-10),18.7(C-11),24.3(C-12),22.9(C-13).ThesedatawereidenticaltotheliteraturevaluesofS(+)-dehydrovomifoliol.Compound4Colorlessoil,ESI-MS:[M-H]-223(100);[α]20D+223°(c0.95,CH3OH);1HNMR(CDCl3)δ:1.03(3H,s,H-12),1.09(3H,s,H-13),1.28(3H,d,J=6.5Hz,H-10),1.89(3H,d,J=0.7Hz,H-11),2.23(1H,d,J=17Hz,H-2α),2.52(1H,d,J=17Hz,H-2β),5.78(1H,dd,J=15.6Hz,H-7),5.86(1H,d,J=15.6,5.5Hz,H-8),5.90(1H,brs,H-4);13CNMR(CDCl3)δ:41.4(C-1),49.7(C-2),199.0(C-3),127.0(C-4),164.1(C-5),80.2(C-6),129.5(C-7),136.4(C-8),68.2(C-9),23.0(C-10),19.1(C-11),24.3(C-12),23.3(C-13).Thesedatawereidenticaltotheliteraturevaluesofvomifoliol.Compound5Whitepowder,