第九章醛和酮

(AldehydesandKetones)OrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity9.1Structure,NomenclatureandPhysicalPropertiesOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity9.1.1sp2RCHORCROCOδ+δ−sp2Carbonylgroup120120OrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversityOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity9.1.21.„——.„-icacid+-aldehyde.HCHOCH3CHOCH3CH2CHOCH3CH2CH2CHOCHOFormaldehydeAcetaldehydePropoinaldehydeButyraldehydeBenzaldehydeOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity+(ketone)CH3CCH2CH3O()()()Ethylmethylketone-icacid,+-ophenoneCCH3O()AcetophenoneCOBenzophenoneOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity2.„.„.„“”.„“(oxo-)”.OrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversityNomenclatureofaldehydes„Aldehydesarenamedbyreplacingtheterminal–eofthecorrespondingalkanenamewith–al.Thelongestchainselectedasthebasenamemustcontainthe–CHOgroup,andthe–CHOcarbonisalwaysnumberedascarbon1.„Formorecomplexaldehydeinwhichthe–CHOgroupisattachedtoaring,thesuffix-carbaldehydeisused.OrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversityCertainsimpleandwell-knownaldehydeshavecommonnamesthatarerecognizedbyIUPAC.Someofthemoreimportantcommonnamesare:HCHOCH3CHOCH3CH2CHOCH3CH2CH2CHOCHOFormaldehydeAcetaldehydePropoinaldehydeButyraldehydeBenzaldehydeCH3(CH2)3CHOCH2CHCHOPhValeraldehydeAcroleinMethanalEthanalPropanalButanalPentanal2-PropenalBenzenecarbaldehydeOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversityNomenclatureofketones„Ketonesarenamedbyreplacingtheterminal–eofthecorrespondingalkanenamewith–one.Thechainselectedforthebasenameisthelongestonethatcontainstheketonegroup,andthenumberingbeginsattheendnearerthecarbonylcarbon.„CertainketonesareallowedbyIUPACtoretaintheircommonnames,thoughthesearefew:AcetoneAcetophenoneBenzophenoneOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversityCHOCHOCyclohexanecarbaldehyde2-Naphthalenecarbaldehyde2CHOO2'-2'-OxocyclohexanecarbaldehydeCH3CH2CCH2CHOO3-3-OxopentanalOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversityCH3CCH3OCH3CH2CH2CCH2CH3O3-3-HexanonePropanoneAcetoneCH3CHCHCH2CCH3OCH3CH2CCH2CCH3OO4--2-2,4-4-Hexen-2-one2,4-HexanedioneOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversityRCOCH3COHCOCOAcylAcetylFormylBenzoyl9.1.3()OrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity9.2PreparationsOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity9.2.11)2)3)9.2.21)2)OrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity9.2.3CH3CH3CHOCH3MnO2H2SO4,H2OCH2CH3COCH3MnO2H2SO4,H2OCH3NO2CrO3-Ac2OCH(OAc)2NO2CHONO2H2OH+1)OrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity2)Freidel-Crafts3)Gattermann-Koch9.2.49.2.51)COCl+H2Pd-BaSO4CHORosenmundOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity2)RCOClNaCCR'+RCOCCR'(CH3)3CCOCl+(CH3)2CHCH2MgBr-5(CH3)3CCOCH2CH(CH3)294%CH3COCl+Ph2CdCH3COPhCuIOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity9.3ReactionsofAldehydesandKetonesOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversityCHCOHα−HOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity9.3.1(NucleophilicAdditionToTheCarbon-OxygenDoubleBond)Themostcharacteristicreactionofaldehydesandketonesisnucleophilicadditiontothecarbon-oxygendoublebond.CO+COHNuHNuNucleophilicadditiontothecarbon-oxygendoublebondoccursineitheroftwogeneralways.OrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity1)COR'Rδ−δ+NuCOR'RNuHNuCOHR'RNuAdditionofaStrongNucleophiletoanAldehydeorKetoneTheimportantaspectofthisstepistheabilityofthecarbonyloxygenatomtoaccommodatetheelectronpairofthecarbon-oxygendoublebondOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity2)Acid-CatalyzedNucleophilicAdditiontoanAldehydeorKetoneCOH+COHCOHCOHNuHNuSlowHH+COHNuOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity3);„Ingeneral,aldehydearemorereactiveinnucleophilicadditionthanareketones.RCHOδ+δ−RCROδ+δ−AldehydeKetoneCarbonylcarbonismorepositiveCarbonylcarbonislesspositiveOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity4)ƒCRMgX,HCN,RNH2,R2NH,H2N−GH2O.ROHNaHSO3,RSHƒƒƒOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversity1.(1)TheAdditionofGringardReagents(CH3)2CHCCH(CH3)2O+CH3CH2MgBr(1)Et2O(2)H3O+(CH3)2CHCCH(CH3)2OHCH2CH380%OrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversityCORCHCH3CH3CH2Cram1α−CL,M,SOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversityMLSORSLMORNuSLMORSLMORNuOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversitySM—SMLSORMgR'MLSORMgR'XXRMgXOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversityPhEtHCHOHPhEtOH(2)H3O+(1)CH3MgXHPhEtOHHCH3HPhEtHOHCH3PhEtHHOHCH3PhEtHHOHCH3()()CramOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversityCram2α−COH,NH2,OLSORHNuSOrganicChemistryOrganicChemistryXiamenXiamenUniversityUniversityHPhNH2HClCPhOHNPhHOPhHClRMgBrH2NPhHHOPhRR-=HClHClOrganicChem