15清华大学有机化学李艳梅老师课件第十五章Chapter-15Derivatives-of-Carb

DerivativesofCarboxylicAcids第十五章羧酸衍生物OrganicChemistryA(2)ByProf.LiYan-MeiTsinghuaUniversity15.1Structure&Nomenclature15.2PhysicalProperties&SpectrumData15.3ChemicalReactions15.4Fats,WasandSyntheticdetergent(learnbyyourself)15.5Preparation15.6DerivativesofcarbonicAcid15.7DerivativesofOrtho-Acid15.8peroxyacid15.9Isonitrile15.10SourcesandUsagesofimportantCarboxylicAcidDerivativesContent15.1羧酸衍生物的结构与命名15.2羧酸衍生物物理性质和波谱学性质15.3化学性质15.4油脂、蜡和合成洗涤剂15.5羧酸衍生物的制备15.6碳酸衍生物15.7原酸衍生物15.8过酸和二酰基过酸15.9异腈15.10重要的羧酸衍生物及羧酸衍生物的来源与用途ContentROOHROXROOROOR'RONH2RORCNCarboxylicacidAcidHalideAcidAnhydrideEsterAmideNitrile(X=F,Cl,Br,I)CarboxylicAcidDerivatives羧酸衍生物ROL羧酸衍生物在结构上的共同特点是都含有酰基。-CN可以被水解成羧酸,所以将腈也归入羧酸衍生物。15.1Structure&Nomenclature15.1.1Structure15.1.2Nomenclature15.1.1Structure结构酰基与其所连的基团都能形成p-π共轭体系。C-L具有部分双键性质，双键的程度取决于C的稳定性，C的稳定性随L的变化而不同。ROLROLROLABCAcylhalide:L=Cl电负性大Anhydride:Ester:L=O电负性略小Amide:L=N电负性更小O+CRCRO-OOCRCROOO+CRCROOHROLROLROLABC15.1.2Nomenclature15.1.2.1AcylHalideandAmide15.1.2.2AnhydrideandNitrile15.1.2.3Ester15.1.2.1AcylHalideandAmide酰卤与酰胺中文命名根据分子中酰基所含的碳原子数命名为“某酰卤”或“某酰胺”。CH3COClCH2=CHCOBrCH3CONH2CH2=CHCONH2CH3CONCH3CH2CH3CH3CONHCH3CH3CON(CH3)2乙酰氯乙酰胺丙烯酰溴丙烯酰胺N-甲基乙酰胺N,N-二甲基乙酰胺N-甲基-N-乙基乙酰胺环状酰胺：内酰胺己内酰胺5-甲基己内酰胺123456NHONHOCH3注意：编号沿用羧酸的编号15.1.2.2AnhydrideandNitrile酸酐与腈中文命名根据水解所得的酸命名为“某酸酐”或“某腈”。CH3COCCH2CH3OOOOO乙(酸)丙(酸)酐戊二(酸)酐邻苯二甲酸酐OOO顺序规则！混酐!COCOOH3CH3CCOCOOPhPhCH3CNPhCN乙(酸)酐苯甲(酸)酐乙腈苯甲腈注意计入氰基上的碳原子！若-CN作为取代基，则称为“氰基”。间氰基苯甲酸3-氰基丁磺酸CNCOOHH3CHCH2CH2CSO3HCN中文命名根据水解所得的酸、醇，命名为“某酸某酯”。15.1.2.3Ester酯乙酸乙酯丙二酸二乙酯乙二醇二乙酸酯丙三醇三硝酸酯CH3COCH2CH3OH2CCCOOOCH2CH3OCH2CH3CH2OCOCH3CH2OCOCH3H2CHCH2CONO2ONO2ONO2丁内酯4-甲基丁内酯H2CH2CCOH2COH2CH2CCOCHOCH3123415.2PhysicalPropertiesandSpectrumData15.2.1PhysicalProperties15.2.2SpectrumDataBoilingPoints熔点Even3amideshavestrongattractions.15.2.1PhysicalProperties物理性质MeltingPoints熔点Amideshaveveryhighmeltingpoints.MeltingpointsincreasewithincreasingnumberofN-Hbonds.m.p.-61Cm.p.28Cm.p.79C胺的熔点很高,且随着N-H键的增多而上升.HCNOCH3CH3H3CCNOHCH3H3CH2CCNOHHAcylHalideTobeirritatinganddecomposeinwaterstrongly.具有刺激性，遇水剧烈分解。AnhydrideTodecomposeinwater.遇水分解。NitrileHighlypolarized——Highdipolemomentandhighboilingpoint.高度极化，高的偶极矩与沸点其它性质：CNRCNRNRREsters酯Esterstendtohavesweetsmells.酯一般有芬芳的气息。EsterFormulaFlavour/fragranceMethylbutyrateCH3CH2CH2COOCH3AppleEthylbutyrateCH3CH2CH2COOCH2CH3PineapplePropylacetateCH3COOCH2CH2CH3PearPentylacetateCH3COOCH2CH2CH2CH2CH3BananaPentylbutyrateCH3(CH2)2COOCH2(CH2)3CH3ApricotOctylacetateCH3COOCH2(CH2)6CH3OrangeMethylbenzoateC6H5COOCH3RipekiwiEthylformateHCOOCH2CH3RumMethylsalicylateHOC6H4COOCH3WintergreenBenzylacetateCH3COOCH2C6H5jasmineAmides胺M.W.57387M.P./0C8228-20B.P./0C221204165CH3CNH2OCH3CNHCH3OCH3CN(CH3)2OOCNRHHNOCRR'R'Manyamidescanformintermolecularhydrogenbond.许多胺类化合物可以形成分子间氢键。15.2.2SpectrumData(Learnonyourown)15.2.2.1IRSpectroscopy15.2.2.21HNMRSpectroscopy15.2.2.313CNMRSpectroscopy15.2.2.1IRSpectroscopy红外光谱=15.2.2.21HNMRSpectroscopy1HNMR谱15.2.2.313CNMRSpectroscopy13CNMR谱15.3ChemicalReactions15.3.1HydrolysisofDerivativesofCarboxylAcid15.3.2AlcoholysisofDerivativesofCarboxylAcid15.3.3AmmonolysisofDerivativesofCarboxylAcid15.3.4AcidolysisofDerivativesofCarboxylAcid15.3.5ReactionswithOrganometallicCompounds15.3.6ReductionofCarboxylAcidDerivatives15.3.7OtherReactions15.3.1羧酸衍生物的水解15.3.2羧酸衍生物的醇解15.3.3羧酸衍生物的氨解15.3.4羧酸衍生物的酸解15.3.5与金属有机化合物的反应15.3.6与羧酸衍生物的反应15.3.7其它反应水解、氨解、醇解和酸解反应总论：CRLOCRNuONu-Nu-=-OH,H2O水解反应Nu-=HOR’醇解反应Nu-=NH3氨解反应Nu-=R’COOH酸解反应含义Acylhalide:L=Cl电负性大Anhydride:Ester:L=O电负性略小Amide:L=N电负性更小ROLROLROLABCO+CRCRO-OOCRCROOO+CRCROOH反应性CRClOCROOCORCROR'OCRNH2O10111071.010-2CORZNuH??哪个是更好的离去基团？一般反应过程Reactivitydecreasesasleavinggroupbecomesmorebasic.随着离去基团碱性增大，离去能力降低，反应活性降低。氨解反应：CRLOCRLONH3+NH3L=XL=OCOR’L=OR’’L=NH2离去能力均强于NH2平衡混合物醇解反应：L=XL=OCOR’L=OR’’L=NH2离去能力均强于OR’平衡混合物CRLOCRLOOR'-OR'离去能力弱于OR’水解反应：L=XL=OCOR’L=OR’’L=NH2离去能力均强于OH离去能力弱于OHCRLOCRLOOH-OH离去能力类似于OH15.3.1HydrolysisofDerivativesofCarboxylAcid羧酸衍生物的水解Allcarboxylicacidderivativescanbehydrolysedtotheparentacidandanotherproductwithwater.ReactionConditionsReactionNoCat.HeatingH+orOH-StrongH+orstrongOH-RCOXRCOOHRCOOCORRCOOR'RCONH2(R)RCNR'OHNH3(R)NH4orNH3H2OH2OH2OH2ORCOOHRCOOHRCOOHRCOOH+++H2O+HX所以羧酸衍生物都可以水解成相应的羧酸和另外一种产物。RatesofHydrolysis(forthesameRgroup)RCOClRCOOCORRCOOR’RCONH2RCONR2RelativeRate10111071.010-2L=X,OCOR’,OR’,NH2RCOLOHCORLOHRCOOHRCOO+HL+LAcylHalides酰卤Hydrolysisofacylhalideswithlowmolecularweightoccursquickly,eveninmoistairwithnoacidorbasecatalyst.Reagentsmustbeprotectedfrommoisture.Rateofthereactionslowsdownwiththeincreaseofmolecularweightofacylhalides.OCRClOCROHHCl++H2OMechanism:Nucleophilicacylsubstitution机理：酰基的亲核取代RCClOacidchloride(electrophile)RCOO+Hhydrochloricacidcarboxylicacid+OHHwater(nucleophile)step1RCClOOHHstep2acid-basereactionClstep3HnucleophilicadditioneliminationRCClOOH+Hstep1:nucleophilicadditiontoelectrophiliccarbonofacidchloride...givesatetrahedralintermediatestep3:collapseofthetetrahedralintermediatetoregeneratetheC=O-bondwitheliminationofchlorideanionasleavinggroupstep2:acidbasereaction(depro