资源描述
文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。COSY:HypotheticalCoupling文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。COSY:1H-1HCoupling文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。Couplingnetworkscanbetracedout,asshowninthefigurebelow.The colored arrows trace out coupling networks,corresponding to:H-3 H-5 H-10 OHH-10-H-9H-3 H-16H-16 H-11COSYSpectrumofCodeine文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。TableofCOSYcorrelationsshiftshiftAssignments 6.66.77-85.75.33-55.72.73-165.74.93-9weak5.34.25-105.32.75-164.94.29-104.22.910-OH3.32.711-163.32.411-143.32.311-183.02.418-143.02.318-182.62.413-132.62.113-172.61.913-172.42.113-172.41.913-172.11.917-17COSYSpectrumofCodeine文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。WhatYouSeeInaNOESY.文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。突出表突出表现NOE效效应的的NOESY谱文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。NOESY.文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。NOESYSpectrumofCodeineThesampleis3.3mgofcodeinein.65mlCDCl3AcontourplotoftheNOESYspectrumisshownbelow.Aswithallhomonuclear2Dplots,thediagonalconsistsofintensepeaksthatmatchthenormalspectrum,asdoprojectionsontoeachaxis.Theinterestinginformationiscontainedinthecross-peaks,whichappearatthecoordinatesof2protonswhichhaveanNOEcorrelation.Forsmallmolecules,theNOEisnegative.ExchangepeakshavetheoppositesignfromNOEpeaks,makingthemeasytoidentify.Thewaterpeakat1.5ppmexchangeswiththeOHat2.9ppm,shownhereinred.Thespectrumisphasedwiththelargediagonalpeaksinverted(showninredhere),sotheNOEcross-peaksarepositive.文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。Expansionoftheupfieldregion:8-7,127-18,183-5,105-11,16,189-10,17,1710-1611-18,16,14,1818-13,1816-14,1713-14,17,1713-17,1717-17NOESYSpectrumofCodeine文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。TableofNOEs:(indicatesthemoreupfieldofgeminalCH2protons)Inadditiontoconfirmingassignments,theNOESYspectrumallowsstereospecificassignmentsofmethyleneHs.The3cross-peaksindicatedinredontheplotbelowdistinguishbetweenthe3CH2pairs:5-1816-1718-13NOESYSpectrumofCodeine文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。2 D C-H相关相关谱(C-H COSY)文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。2 D 远程程C-H COSY文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。HeteronuclearMultipleQuantumCoherence(HMQC)andHeteronuclearMultipleBondCoherence(HMBC):2-D inverse H,C correlation techniques that allow for thedetermination of carbon(or other heteroatom)to hydrogenconnectivity.GradientHMBC(gHMBC)improvestheacquiredspectrabysignificantlyreducingunwantedsignalartifacts.HMQCisselectivefordirectC-HcouplingHMBCwillgivelongerrangecouplings(2-4bondcoupling).HMQCandHMBC文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。HMQC(trans-ethyl 2-butenoate)文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。HMQCHeteronuclearMultiple-QuantumCoherenceExperiment文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。C(9)-HC(9)-HHMQCHeteronuclearMultiple-QuantumCoherenceExperiment文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。HMQC(1-BondCHCorrelation)ofCodeine1H13CAssignment6.611386.512075.713335.312854.89194.266103.856123.359113.0&2.320182.640162.6&2.446132.443142.0&1.83617文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。Thisisa2Dexperimentusedtocorrelate,orconnect,1Hand13Cpeaksforatomsseparatedbymultiplebonds(usually2or3).Thecoordinatesofeachpeakseeninthecontourplotarethe1Hand13Cchemicalshifts.Thisisextremelyusefulformakingassignmentsandmappingoutcovalentstructure.TheinformationobtainedisanextensionofthatobtainedfromanHMQCspectrum,butismorecomplicatedtoanalyze.LikeHMQC,thisisaninversedetectionexperiment,andispossibleonlyonnewermodelspectrometers.AcornNMRsnewJEOLEclipse+400isequippedtoperforminverseexperiments,andusesZ-gradientsforimprovedspectralquality.ThetimerequiredforanHMBCdependsontheamountofmaterial,butismuchgreaterthanforHMQC,andcantakefromanhourtoovernight.HMBC(Multiple-BondCHCorrelation)ofCodeine文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。Peaksoccuratcoordinatesinthe2dimensionscorrespondingtothechemicalshiftsofacarbonandprotonsseparatedby(usually)2or3bonds.Theexperimentisoptimizedforcouplingsof8Hz.Smallercouplingsareobserved,buttheirintensitiesarereduced.Comparetothespectrumobtainedwhentheexperimentisoptimizedfor4Hz.Theexperimentisdesignedtosuppress1-bondcorrelations,butafewareobservedinmostspectra.Inconcentratedsamplesofconjugatedsystems,4-bondcorrelationscanbeobserved.ThereisnowaytoknowhowmanybondsseparateanHandCwhenapeakisobserved,soanalysisisaprocessofattemptingtoassignallobservedpeaks,testingforconsistencyandcheckingtobesurenoneoftheassignmentswouldrequireimplausibleorimpossiblecouplings.Becauseofthelargenumberofpeaksobserved,analysisrequiresseveralexpandedplots.Inthiscase,thespectrumhasbeendividedinto4sections,eachofwhichisdiscussedbelow.HMBC(Multiple-BondCHCorrelation)ofCodeine文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。HMBC(Multiple-BondCHCorrelation)ofCodeine文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。Thediscussionbelowusesthenumberingsystemshownatright.Thenumberswereassignedtopeaksinthe1D13Cspectrum,startingdownfield,movingupfield,andnumberingeachsequentially.ThisgeneratesauniqueidentifierforeachCarbon,evenbeforeknowinganyassignments.HMBC(Multiple-BondCHCorrelation)ofCodeineC9-HC3-HC5-H123456文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。C9-HC3-HC5-H17HMBC(Multiple-BondCHCorrelation)ofCodeine文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。More1Dand2D-SepctraforCodeine文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。1D1Hand13CNMRSpectraofCodeineC18H21NO3,MW=299.4DataacquiredonaJEOLEclipse+400spectrometer1Hspectrum:C3-HC5-HC10-HC7-HC8-HC9-HC12-H3C11-HC16-HC18-HC18-HC17-HC14-HC3-HC5-HC9-HC3-HC5-H文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。13Cspectra18mgsample,1.3hrsacquisitiontime123456791011121314,151617181D1Hand13CNMRSpectraofCodeine文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。PeakAssignmentsforCodeine 13C(ppm)1H(ppm)1 146.3q 2 142.23q 3 133.43CH5.71 4 131.13q 5 128.30CH5.29 6 127.30q 7 119.58CH6.57 8 113.03CH6.66 9 91.39CH4.8910 66.43CH4.1811 58.92CH3.3512 56.40CH33.8413 46.47CH22.59,2.4014 43.12CH32.4415 42.99q16 40.82CH2.6717 35.85CH22.06,1.8818 20.46CH23.04,2.30OH2.99文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。Bothexperimentsareusedtoidentifymultiplicity(quaternary,CH,CH2orCH3)ofpeaksina13Cspectrum.Usually,DEPTispreferredbecausemuchlesstimeisrequired.ForDEPT,1Hmagnetizationisgeneratedfirst,thentransferredto13C.Thispolarizationtransferenhancessensitivity.Also,theexperimentrepetitionrateisdependentonrelaxationof1H,ratherthan13C,soashorterdelayisneeded.DEPTalsocandistinguishbetweenCHandCH3,unlikeAPT,althoughquaternaryCsarenotobservedinDEPT.Thesampleis18mgofcodeinein.65mlCDCl3DEPTandAPTspectraofcodeine文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。DEPT-135CHandCH3peaksup,CH2peaksinvertedDEPT-90CHpeaksonlyDEPT-45allprotonatedcarbonsnormal13Cspectrum 13C(ppm)1 146.3 2 142.23 3 133.43 4 131.13 5 128.30 6 127.30 7 119.58 8 113.03 9 91.3910 66.4311 58.9212 56.4013 46.4714 43.1215 42.9916 40.8217 35.8518 20.46DEPTSpectra文档仅供参考,不能作为科学依据,请勿模仿;如有不当之处,请联系网站或本人删除。
展开阅读全文