有机化学双语版++Amines.ppt

Chapter17Amines(胺),17.1AmineNomenclature17.2Structuresofamines17.3Basicityofamines17.4Preparationofamines17.4.1Preparationofaminesbyalkylationofammonia17.4.2TheGabrielsynthesisofprimaryamines17.4.3Preparationofaminesbyreduction17.5Reactionsofamines17.5.1Alkylationofamines17.5.2Acylationofamines17.5.3TheHofmannElimination,17.5.4Reactionsofamineswithnitrousacid(A)Reactionsofprimaryaliphaticamineswithnitrousacid(B)Reactionsofprimaryarylamineswithnitrousacid(C)Reactionsofsecondaryamineswithnitrousacid(D)Reactionsoftertiaryamineswithnitrousacid17.5.5Synthetictransformationsofaryldiazoniumsalt(A)ReplacementofthediazoniumgroupbyOH,(B)ReplacementofthediazoniumgroupbyX,CN(c)ReplacementofthediazoniumgroupbyH17.5.6Azocoupling17.6Spectroscopicanalysisofamines,17.1AmineNomenclature,Organicderivativesofammonia,Alkylamines,Arylamines,Methylamine(甲胺）,Isobutylamine(异丁胺)2-Methylpropylamine（2-甲基丙胺）,Benzylamine(苄胺）,Primaryamines（伯胺）:,P380,Aniline(苯胺),Ethylmethylamine（甲乙胺）N-Methylethylamine(N-甲基乙胺）,Diethylamine（二乙胺）,Secondaryamines:(仲胺）,TrimethylamineN,N-Dimethylmethylamine（三甲胺）（N,N-二甲基甲胺）,N,N-Dimethyl-aniline(N,N-二甲基苯胺),Tertiaryamines:（叔胺）,Cyclohexylamine(环己胺),1,2-Ethyldiamine（1,2-乙二胺）,Diamines:,Ammoniumions（铵离子）Aminiumsalts（铵盐）,Aniliniumchloride（盐酸苯胺）,Quaternaryammoniumsalts（季铵盐）,2-Aminoethanol（2-氨基乙醇）,N-Ethyl-N-methylcyclohexylamine(N-甲基-N-乙基环己胺),Heterocyclicamine:(杂环胺),17.2Structuresofamines,sp3-hybrid,Tertiaryamineswith3differentgroups:,Interconversionofamineenantiomers,N:1s22s22px12py12pz1,P383,12.2,Pyramid(棱锥型),17.3Basicityofamines,Quarternaryammoniumsalt:,Weakbases,P384,12.3,Table1Basicstrengthofsomeamines,P385,Table12.1,1.Allaminesareweakbases:,H2ORNH2R3NNH3,Poorersolvation,Separationofaminesfromneutralorganiccompounds,17.4Preparationofamines,17.4.1Preparationofaminesbyalkylationofammonia,P384,12.3,Aniliniumion,17.4.2TheGabrielsynthesisofprimaryamines,Reagent:,PotassiumsaltofPhthalimide（邻苯二甲酰胺钾盐）,Imide（酰亚胺）,Ch.P436,Primaryalkylhalide,SN2,ArX,17.4.3Preparationofaminesbyreduction,LiAlH4,Reductionofnitrilestoamines,GabrielSynthesis.Gabriel,Ber.20,2224(1887).M.S.Gibson,R.W.Bradshaw,Angew.Chem.Int.Ed.7,919(1968);B.Dietrichetal.,J.Am.Chem.Soc.103,1282(1981);O.Mitsunobu,Comp.Org.Syn.6,79-85(1991).Modifiedconditions:S.E.Sen,S.L.Roach,Synthesis1994,756;M.N.Khan,J.Org.Chem.61,8063(1996).Stereoselectivity:A.Kuboetal.,TetrahedronLetters37,4957(1996).,Reductionofnitrocompoundstoarylamines,H2,cat,Reductionofamidestoamines:,P389,Reductiveamination:,Imine（亚胺）,Ch.P435,17.5Reactionsofamines,Unsharedelectronpairofnitrogen:,Basicity:,Nucleophilicity:,17.5.1Alkylationofamines,17.5.2Acylationofamines,Acylatingagents:acylchlorides,carboxylicacidanhydrides,SynthesisofParacetamol（扑热息痛）:,17.5.3TheHofmannElimination,DecreasingtheactivityofarylringorProtectingaminogroups:,MethylationofanaminebyexcessCH3I:,Ch.P448(六),Quaternaryammoniumhydroxides（氢氧化季铵碱）canbepreparedfromQuaternaryammoniumhalides:,Quaternaryammoniumhydroxides,heat,-Elimination,toformalkenesandanamine,Methylenecyclohexane（亚甲基环己烷）(69%),Thebaseattacksthemostacidichydrogenorleasthinderhydrogen.,E2Reaction,Antirelationship,RegioselectivityofHofmannelimination:,Togivealesssubstitutedalkene.,HofmannruleisopposedtotheZaitsevrule.,AugustWilhelmvon18181892,AugustWilhelmvon,18181892,Germanorganicchemist.HewasProfessorattheUniv.ofBerlinfrom1865andwasafounder(1868)oftheGermanChemicalSociety.Hestudiedtheconstitu-tionofanilineandwasthefirsttopreparerosanilineanditsderivatives,therebylayingthebasisfortheanilinedyeindustry.HealsodiscoveredareactionforderivingaminesfromamidesanddevelopedtheHofmannmethodoffindingthevapordensities,andfromthesethemolecularweights,ofliquids.Healsohelpedtopopularizetheconceptofvalence(thewordcomesfromhistermquantivalence,17.5.4Reactionsofamineswithnitrousacid(Nitrosation亚硝化反应),(A)Reactionsofprimaryaliphaticamineswithnitrousacid,Nitrosatingagent:,Primaryaliphaticamines,Nitrousacid,toyieldunstablealiphaticdiazoniumsalt(重氮盐),Diazotization(重氮化反应),Aliphaticdiazoniumsaltsdecomposetoformcarbocationsandnitrogen:,Alkene,alcohol,alkylhalide,(B)Reactionsofprimaryarylamineswithnitrousacid,Primaryarylaminesformdiazoniumsaltonnitrosation:,Aryldiazoniumsaltsarestablebelow5,P390,(C)Reactionsofsecondaryamineswithnitrousacid,Secondaryamines:botharylaminesandalkylaminesreactwithnitrousacidtoyieldN-nitrosoamines（亚硝胺）,N-nitrosoaminesareusuallyseparatedfromthereactionmixtureasoilyyellowliquids,(D)Reactionsoftertiaryamineswithnitrousacid,TertiaryarylaminesreactwithnitrousacidtoformC-nitrosoaromaticcompounds:,Electrophilicaromaticsubstitution,17.5.5Synthetictransformationsofaryldiazoniumsalt,Thediazoniumgroup（重氮基）maybereplacedbyotheratomesorgroups:X,OH,CNandH.,(),P391,:Electron-withdrawinggroup,Aryldiazoniumsaltscanbepreparedfromarene:,(A)ReplacementofthediazoniumgroupbyOH,Aryldiazoniumionisconvertedtophenols(酚),Sulfuricacidisusuallyusedinsteadofhydrochloricacid,Question:Designasynsthesisof,Hydrolysis,(B)ReplacementofthediazoniumgroupbyX,CN,Thepreparationofaryliodides,Thepreparationofarylfluorides:,Treatingthediazoniumsaltwithfluoboricacid(HBF4),(69%),(81%),TheSandmeyerreaction:,Aryldiazoniumsaltsreactwithcuprouschloride,cuprousbromide,cuprouscyanide,(70%overall),(65%overall),BorninWettingennearZurich,andlivedintheZurichareafornearlyallofhislife.Hetrainedasaprecisioninstrument-maker,butbecameinterestedinchemistry.Self-educatedinchemistry,hecarriedoutchemicalexperimentsinhiskitchen.In1881,hebecamealectureassistanttoVictorMeyer(1848-1897).HefollowedMeyertoGttingenin1886,butsoonreturnedtoZurichandworkedforArthurHantzsch(1857-1935).SandmeyerjoinedGeigyasaresearchscientistin1888,andeventuallybecameadirectorofthefirm.HediscoveredthedecompositionofaryldiazoniumChloridestochloroarenesinthepresenceofcopper(I)chloridein1884.Healsoworkedonthetriphenylmethanedyesandthesynthesisofisatin.Manyyearsbefore,hehadsuggestedtoVictorMeyeranimpurityincommericalbenzenewasresponsiblefortheisatinreactionwithsulphuricacid,therebypavingthewayforMeyersdiscoveryofthiophen.,TraugottSandmeyer(1854-1922).,(C)ReplacementofthediazoniumgroupbyH,Aryldiazoniumsaltsreactwithhypophosphorousacid(H3PO2)(次磷酸）orethanoltoyieldtheproduct:,Deamination（脱氨基作用）,(85%),P392,Thevalueofdiazoniumsaltsinsynthesis:Substituentsthatareotherwiseaccessibleonlywithdifficulty,suchasF,I,CN,OH,maybeintroducedontoabenzenering.Compoundsthathavesubstitutionpatternsnotdirectlyavailablebyelectrophilicaromaticsubstitutioncanbeprepared,17.5.6Azocoupling(偶氮偶合反应),Aryldiazoniumsaltsareweakelectrophiles,theyreactwithhighlyreactivearomaticcompounds,toyieldazocompounds,Azodyes（偶氮染料）,OrangeII：,P393,Alkalinesolution,17.6Spectroscopicanalysisofamines,IR：,Strechingvibration,Primaryamine,3000-3500cm-1twopeaks,Secondaryamines,3280cm-1onepeak,Tertiaryamines,Nopeak