天津大学有机化学双语PPT有机化学部分Chapter 9

9.1IUPACNomenclatureofAlcohols,EthersandPhenols9.1.1NamingAlcohols9.1.2NamingPhenols9.1.3NamingEthers9.2Preparationofalcohols,EthersandPhenols9.2.1PreparationofalcoholsA.Preparationofalcoholsbyreductionofcarbonylcompounds(1)Hydrogenationofaldehydesandketonesbycatalysisofmetals(2)ReductionofcarbonylcompoundsbymetalhydridesB.Preparationofdiols,Chapter9Alcohols,Ethersandphenols,9.2.2PreparationofEthersA.EthersbyintermoleculardehydrationofalcoholsB.WilliamsonSynthesisofEthers9.2.3PreparationofphenolsA.LaboratorysynthesisB.Industrialsynthesis9.3ReactionsofAlcoholsThesitesofreactionsofaAlcohol9.3.1AcidityandBasicityofAlcohols9.3.2Conversionofalcoholstoethers9.3.3OxidationofalcoholsA.OxidationofprimaryalcoholsB.OxidationofsecondaryalcoholsC.Oxidationofvicinaldiols,9.4Reactionsofphenols9.4.1AcidityofPhenols9.4.2Electrophilicaromaticsubstitutions9.4.3AcylationofphenolsFriesrearrangement9.4.4Kolbe-Schmittreaction9.4.5Preparationofarylethers9.4.6Cleavageofarylethersbyhydrogenhalides9.4.7Claisenrearrangementofallylarylethers9.4.8Oxidationofphenols:Quinones,9.5ReactionsofEthers9.5.1Acid-catalyzedcleavageofethers9.5.2PreparationofepoxidesA.EpoxidationofalkenesbyreactionwithperoxyacidsB.Conversionofvicinalhalodrinstoepoxides9.5.3ReactionsofEpoxidesA.Base-catalyzedringopeningB.Acid-catalyzedringopening,CarboxylicCarboxylicacidacidderivatives羧酸羧酸衍生物,CompoundswithO-containingfunctionalgroups,AlcoholEtherPhenolAldehydeKetone醇醚酚醛酮,Theinterplayofthesecompoundsisfundamentaltoorganicchemistryandbiochemistry,AlcoholEtherPhenolAldehydeKetone醇醚酚醛酮,Compoundsthathavehydroxylgroupbondedtoasaturated,sp3-CatomAlcohols.,CompoundsthathavehydroxylgroupbondedtoaaromaticringPhenols.,CompoundsthathaveaoxygenatombondedtotwocarbonatomEthers,ClassofAlcohols:,ClassofEthers:,Ethers,Epoxides,9.1IUPACNomenclatureofAlcohols,EthersandPhenols,P252,8.1,9.1.1NamingAlcohols,Commonname:,Alkyl+alcohol,Substitutivename:,Number:beginattheendnearerthehydroxylgroup.,Benzylalcohol(苄醇),Phenylmethanol(苯甲醇),Allylalcohol(烯丙醇),2-Propen-1-ol(2-丙烯-1-醇),tert-Butylalcohol(叔丁醇),2-Metyl-2-propanol(2-甲基-2-丙醇),ClCH2CH2CH2OH,Glycerol(甘油)1,2,3-Propanetriol,3-Chloro-1-propanol(3-氯-1-丙醇),9.1.2NamingPhenols,Phenolisthebasename:,o-,m-,p-:substitutent,4-Methylphenolp-Methylphenolp-Cresol（甲酚）,1-Naphthol-Naphthol（1-萘酚）,2-Naphthol-Naphthol（2-萘酚）,9.1.3NamingofEthers,CH3CH2OCH3,Ethylmethylether(甲乙醚),P253,tert-Butylphenylether(苯叔丁基醚),Diethylether(乙醚),AnisoleMethylphenylether(茴香醚)(苯甲醚),Tetrahydrofuran(THF)(四氢呋喃),FunctionalclassIUPACnames,SubstitutiveIUPAC,2-Methoxypentane(2-甲氧基戊烷),Alkoxy(烷氧基),1-Ethoxy-4-methylbenzene(4-甲基-1-乙氧基苯),Cyclicethers:,Transformationoftheseveralfunctionalgroupstoalcohols:,A.PreparationofAlcoholsbyReductionofCarbonylCompounds,9.2Preparationofalcohols,EthersandPhenols,9.2.1PreparationofAlcohols,P258,8.4,(1)HydrogenationofaldehydesandketonesbyCatalysisofmetals,AldehydesPrimaryalcohols,KetonesSecondaryalcohols,(2)Reductionofcarbonylcompoundsbymetalhydrides,Metalhydrides:,P259,8.5,ReactionofNaBH4withaldehydesandketones,Anaqueousoralcoholicsolution,ReactionofLiAlH4withAldehydesandKetones,ReactionofLiAlH4withcarboxylicacidsandesters,Characteristicsofreactions:,Selectivereduction:NaBH4doesnotreduceC=C,andCOOH,COOR。LiAlH4doesnotreduceC=C,Methyl2-pentenoate2-Penten-1-ol(91%),LiAlH4reactsviolentlywithwater.,Solvents:,Vicinaldiols,B.Preparationofdiols,KMnO4/OH(cold),OsO4Osmiumtetraoxide(四氧化锇),tert-butylhydroperoxide(叔丁基氢过氧化物),Alkaline(碱性),Hydroxylation,Syn-addition,9.2.2PreparationofEthers,A.Ethersbyintermoleculardehydrationofalcohols,Substrate:PrimaryalcoholsAcid-catalyzedProducts:symmetricethers,B.TheWilliamsonSynthesisofEthers,Sodiumalkoxide,Alkylhalideandderivatives,Mixedethers,P261,8.6,Thereactioncharacteristic:SN2reaction2.Thebestsubstrateisprimaryalkylhalide,AlexanderW.Williamson(1824-1904),AlexanderW.WilliamsonwasBorninLondon,England,andreceivedhisPh.D.attheUniversityofGiessenin1846.Hisabilitytoworkinlaboratorywashamperedbyachildhoodinjurythatcausedthelossofanarm.From1849,utill1887,hewasprofessorofChemistryatUniversityCollege,London.,Bondinginorganiccompoundsatthattimewasthoughttobeofeitherthewatertype,asinalcohols,ROH,oroftheradicaltype,asinetherswhichwouldbegiventheformulaRO.ButWilliamson,byhisethersynthesis,showedthatmixedethers,withtwodifferentalkylgroups,couldbeprepared.Ethersthushastohavethewater-typeformulaROR,andoxygenhadtheequivalentweightof8buttheatomicweightof16.Bythistypeofargumentheestablishedandrationalisedthestructuresofmanyofthefamiliesofsimpleorganiccompounds.Thus,in1850hepredictedtheexistenceofaceticanhydride,whichwaspreparedin1851.Westillhavesomeexamplesofhisearlyapparatus,andhiscopperpelicans,inwhichhepreparedether,areshownatright.Whenyourealisethescaleonwhichthesereactionswerecarriedout,andthefactthatthepelicanwasheatedoveracharcoalbrazier,itisremarkablethatwedonotseemtohaverecordsofcatastrophicaccidentstakingplace.LateronWilliamson,againwithpeoplesuchasLiebig,wasresponsiblefortheintroductionofmuchoftheglasswarewhichwearefamiliarwithtoday,exceptthatitwasusuallyfittedtogetherwithcorksratherthangroundglassjoints.Standardjoints,blowninamould,asweknowthemtodaydidnotcomeintouseuntilthemiddleofthelast(20th)century.TowardstheendofhisperiodasHeadofDepartment,WilliamsonbecameverymuchinvolvedinCollegeandUniversitypolitics,andhisresearchsuffered.ThiswastheperiodwhentheotherLondoncolleges-Kings,Birkbeck,QueenMary,whatisnowImperialCollege,andsoonwerecombinedintoafederaluniversity,andpresumablyWilliamsonfelttheneedtofighttheUniversityCollegecorner.,碱熔法,9.2.3Preparationofphenols,A.Laboratorysynthesis,Fromaniline:,(80%),B.Industrialsynthesis,(1)ReactionofbenzenesulfonicacidwithNaOH,Toluenep-Toluenesulfonicp-methylphenolacid(72%),(2)Hydrolysisofchlorobenzene,3.Fromcumene（枯烯）,Friedel-Craftsalkylation,Cumenehydroperxide(氢过氧化枯烯),卤苯水解,Cumeneisoxidizedtocumenehydroperoxide,9.3.ReactionsofAlcohols,异丙苯法,Weakacidity,Weakbasicity,Protona-tion,Nu:,Oxidation,ThesitesofreactionsofaAlcohol:,Elimination,9.3.1AcidityandBasicityofAlcohols,Likewater,alcoholsarebothweaklybasicandweaklyacidic.,Asaweakbase:,AnalcoholAnoxoniumion,Asaweakacid:,Acid(base)conjugateconjugatebaseacid,AnalcoholAnAlkoxideHydroniumion(烷氧负离子)ion(水合离子),P256,8.3,P257,Table8.1,Inanyproton-transferprocess:,Relativeacidity:,Relativebasicity:,9.3.2ConversionofAlcoholstoEthers,P263.8.7,Dehydration,NaH,NaNH2,Characteristicsofthereaction:Condensation(缩合反应)2.Onlyforprimaryalcohols3.Thetemperatureofcondensationislowerthanelimination.4.SN2mechanism,A.Oxidationofprimaryalcohols,PCCreagentissolubleinCH2Cl2,P263,9.3.3Oxidationofalcohols,B.Oxidationofsecondaryalcohols,PCCdoesntattackC=Cbond,ChromicacidH2CrO4,C.Oxidationofvicinaldiols,VicinaldiolsreactwithHIO4,theC-Cbondisbrokentoformcarbonylcompounds,AgNO3isaddedtoidentifythevicinaldiols,Ch.P225,(3),9.4Reactionsofphenols,Acidity,Acylation,AromaticElectrophilicsubstitution,Formationofarylethers,Thesitesofreactions,9.4.1AcidityofPhenols,TABLE1Theacidityconstantsofphenols,P256,8.3,Substitutedphenols:,Substuentsonthepositiono-orp-,Electrondelocalizationinphenoxideion:,9.4.2Electrophilicaromaticsubstitutions,Ahydroxylgroupisaverypowerfulactivatingsubstituent:,Bromination:,Sulfonation:,Ratecontrol,Equilibriumcontrol,P266;Ch.P322,(2),9.4.3Acylationofphenols,Acylatingagents:acylhalidesandcarboxylicacidanhydrides,Friesrearrangement:,Phenolbenzoate,p-hydroxylbenzopheone（对-羟基二苯酮）(64%),(9%),PhenolicEsters（酚酯）,Conversionofarylesterstoarylketones.,Ch.P319(丙),9.4.4Kolbe-Schmittreaction:,Carboxylaltionofphenols,Sodiumphenoxide,CO2,Heatedunderpressure,Acidified,Salicylicacid,Salicylicacid（水杨酸）(79%),Aspirin（阿斯匹林）（乙酰水杨酸）,9.4.5Preparationofarylethers,WilliamsonMethod,APhenoxideanion,Aalkylhalide,Alkylationofhydroxyloxygenaphenol,Why?,Me2SO4methylatingagent,9.4.6Cleavageofarylethersbyhydrogenhalides,ThebondofORwasbroken!,ThebondofCOinphenolshaspartialdoublebondcharacter,9.4.7Claisenrearrangementofallylarylethers,Heatingallylarylether,Intramolecularreaction,Theproductiso-allylphenol,Transitionstate,ClaisenwasprofessorinAachenin1890,Kielin1897andBerlinin1904.Severalsynthesesespeciallycondensationreactionsbetweenaldehydes,ketones,andesters(1881-1890)areconnectedwithClaisensname.Healsocarriedoutresearchontautomerismandrearrangementreactions(Umlagerungsreaktionen),19thCenturyClaisen,LudwigBorn:Kln(Germany),1851Died:Godesbergnea