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1、Chapter 14 Carboxylic Acid Derivatives:Nucleophilic Acyl Substitution14.1 Carboxylic Acid Derivatives and Nomenclature14.2 Structure of carboxylic acid derivatives14.3 Preparation of carboxylic acid derivatives14.4 Nucleophilic substitution at the acyl carbon14.4.1 Hydrolysis14.4.2 Reactions with al
2、cohols 14.4.3 Reactions with amines14.5 Reduction 14.5.1 Reduction by LiAlH4(LAH)and its derivatives14.5.2 Reduction by Na14.5.3 Reaction with Grignard reagents14.6 Reactions of amides14.6.1 Dehydration of amides14.6.2 The Hofmann Rearrangement14.7 Spectroscopic analysis of carboxylic acid derivativ
3、esPropanoyl chloride丙酰氯丙酰氯Acyl halides酰卤酰卤Acetic anhydride乙酸酐乙酸酐Carboxylic acid anhydrides酸酸 酐酐Propanoic acidEsters酯酯Acetic acidEthyl acetate乙酸乙酯乙酸乙酯Acetic acidPropanoyl chlorideAcetic anhydrideEthyl acetateP309,10.1Benzoic acidEthyl benzoate（苯甲酸乙酯）（苯甲酸乙酯）14.1 Carboxylic Acid Derivatives and Nomencl
4、atures Acetamide乙乙 酰胺酰胺N-MethylbenzamideN-甲基苯甲甲基苯甲 酰胺酰胺N,N-Dimethylform-amide(DMF)N,N-二甲基甲二甲基甲 酰胺酰胺Amides酰胺酰胺Acetic acidAcetamideNitrile腈腈Benzonitrile苄腈苄腈Phenyl cyanide苯基氰苯基氰Benzoic acidBenzonitrile4-Methylpentanenitrile4-甲基戊腈甲基戊腈ROLA common feature of carboxylic acid derivatives:Hydrolysis to carbo
5、xylic acids14.2 Structure of carboxylic acid derivativesp-Conjugation+C Effect:14.3 Preparation of Carboxylic Acid Derivatives14.3.1 Preparation of Acyl HalidesSOCl2(Thionyl chloride)PBr3(Phosphorous tribromide)14.3.2 Preparation of Acid Anhydride14.3.3 Preparation of Esters14.3.4 Preparation of Ami
6、des14.4 Nucleophilic substitution at the acyl carbon14.4.1 HydrolysisP318,10.5Ch.P390Mechanism:Saponification(皂皂 化化 反应反应)Step 1 Nucleophilic addition of hydroxide ion to carbonyl group.Base-promoted hydrolysis of ester Hydrolysis of Acyl halides is catalyzed by a base.Hydrolysis of Acid anhydridesEs
7、tersAmidesCatalyzed by a acid or a base.P331Step 2 Elimination of leaving group to restore carbonyl group:Step 3 Proton transfer to yield alcohol and carboxylate ion:14.4.2 Reactions with alcoholsAcyl halidesAcid anhydridesEstersNitrilesAlcohols orphenolsEstersHydrolysis of Nitriles:P320Reactivity o
8、f carboxylic acid derivatives:Benzoyl chlorideEthyl benzoate(80%)EstersAlcoholsEsters(Exchange of esters)Salicylic acid(水杨酸水杨酸)Asprin(阿司匹林阿司匹林)Methyl acrylate（丙烯酸甲酯）丙烯酸甲酯）Butyl alcohol（丁醇）丁醇）Butyl acrylate(丙烯酸丁酯丙烯酸丁酯)(94%)Alcoholysis of Nitriles:Ch.P391BenzoylchloridePiperidine（哌啶）哌啶）N-Benzoyl-Piper
9、idine（N-苯甲酰哌啶）苯甲酰哌啶）（87-91%）Ethyl Floroacetate（氟乙酸乙酯）氟乙酸乙酯）Floroacetamide（氟乙酸酰胺氟乙酸酰胺）(90%)14.4.3 Reactions with aminesAcyl halidesCarboxylic acid anhydridesEstersAmmoniaor aminesAmides14.5 Reduction14.5.1 Reduction by LiAlH4(LAH)and its derivatives1)LiAlH(OR)3Acyl halidesAmides2)H2OAldehydesAmidesNi
10、trilesAminesLiAlH4Acryl halidesCarboxylic acidAcid anhydridesEstersPrimaryalcoholsLiAlH414.4.2 Reduction by NaBouveault-Blanc reductionEsters NaEthanolButanolPentanolreflux Primary alcoholsEthyl oleate油酸乙酯油酸乙酯Oleic alcohol油醇油醇 The unique method for the preparation of unsaturated primary alcohols in
11、industryCh.P39314.5.3 Reaction with Grignard reagents1 mol RMgXLow temperatureRMgXKetonesTertiaryalcoholsCarboxylic acidderivativesRMgXReactions of nitriles with Grignard reagents Addition1.RMgX Imine亚胺亚胺Nitriles2.H2OHydrolysisKetonesRLi reacts in the same way and are often used instead of RMgX 14.6
12、 Reactions of amides14.6.1 The dehydration of amidesAmidesDehydrating agents:P4O10(P2O5),（脱水剂）脱水剂）(CH3CO)2O Heating To form nitrils2-Methylpropanamide2-甲基丙酰胺甲基丙酰胺2-Methylpropanenitrile2-甲基丙腈甲基丙腈（69-86%）Br2/OHCarbonyl group had been plucked out 14.6.2 The Hofmann Rearrangement （Hofmann 降解反应降解反应）N-uns
13、ubstituted amidesto form primary amines having one less carbon atom than amideMechanism:Step 1 Formation of an N-bromo amide intermediate:Deprotonation of amideAmide nitrogen anionas a nucleophileCh.P396,(丙丙)Step 2 Rearrangement of the N-bromo amide to an isocyanate（异氰酸酯）异氰酸酯）Deprotonation of N-brom
14、o amide,the group R migrates from C atom to N atom to form an isocyanate.Step 3 Hydrolysis of isocyanate by base-catalyzed Carbamic acid(异氰酸异氰酸)dissociates to an amine and CO2The features of Hofmann rearrangement:1.N-unsubstituted amides as substrates2.2.Rearrangement proceeds with retention3.of con
15、figuration at migrating group(S)-2-Methyl-3-Phenylpropanamide(S)-1-Phenyl-2-propanamine14.7 Spectroscopic analysis of carboxylic acid derivativesTable 1.The stretching frequency of C=OIR:The stretching frequency of:22102260 cm-1CompoundsStretching frequency of C=O(cm-1)RCOCl(RCO)2ORCO2RRCONH21815178
16、518501800 and 17801740173516801630EstersCarboxylic acidanhydridesStretching frequency of CO:1310 1050 cm-1Amides:Stretching frequency of N H bond:3500 3200 cm-1 -H :2 3 ppm1H NMR:13C NMR:120 ppmAmide:N-H :5 8 ppmProblems to chapter 14P 346 10.31(a),(d),(e)10.32(c)(g)10.33(b),(d),(g)10.37 10.39 10.41 10.42(a),(c)10.45 10.46(a),(c)10.47 10.55 10.56(b)10.5710.5810.5910.6010.6110.62