有机化学双语版++Carboxylic+derivatives.ppt

单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,Chapter 14 Carboxylic Acid Derivatives:,Nucleophilic Acyl Substitution,14.1 Carboxylic Acid Derivatives and,Nomenclature,14.2 Structure of carboxylic acid,derivatives,14.3 Preparation of carboxylic acid,derivatives,14.4 Nucleophilic substitution at the acyl,carbon,14.4.1 Hydrolysis,14.4.2 Reactions with alcohols,14.4.3 Reactions with amines,14.5 Reduction,14.5.1 Reduction by LiAlH,4,(LAH)and,its derivatives,14.5.2 Reduction by Na,14.5.3 Reaction with Grignard reagents,14.6 Reactions of amides,14.6.1 Dehydration of amides,14.6.2 The Hofmann Rearrangement,14.7 Spectroscopic analysis of carboxylic,acid derivatives,Propanoyl chloride,丙酰氯,Acyl halides,酰卤,Acetic anhydride,乙酸酐,Carboxylic acid,anhydrides,酸 酐,Propano,ic,acid,Esters,酯,Acetic,acid,Ethyl acetate,乙酸乙酯,Acet,ic,acid,Propano,yl chloride,Acetic,anhydride,Ethyl,acet,ate,P309,10.1,Benzo,ic,acid,Ethyl,benz,oate,（苯甲酸乙酯）,14.1 Carboxylic Acid Derivatives,and Nomenclatures,Acetamide,乙 酰胺,N-Methylbenzamide,N-甲基苯甲 酰胺,N,N-Dimethylform-,amide(DMF),N,N-二甲基甲 酰胺,Amides,酰胺,Acet,ic,acid,Acet,amide,Nitrile,腈,Benzonitrile,苄腈,Phenyl cyanide,苯基氰,Benzo,ic,acid,Benzo,nitrile,4-Methylpentane,nitrile,4-甲基戊腈,R,O,L,A common feature of carboxylic acid,derivatives:,Hydrolysis to carboxylic acids,14.2 Structure of carboxylic acid derivatives,p,-,Conjugation,+C Effect:,14.3 Preparation of Carboxylic Acid,Derivatives,14.3.1 Preparation of Acyl Halides,SOCl,2,(Thionyl chloride),PBr,3,(Phosphorous tribromide),14.3.2 Preparation of Acid Anhydride,14.3.3 Preparation of Esters,14.3.4 Preparation of Amides,14.4 Nucleophilic substitution,at the acyl carbon,14.4.1 Hydrolysis,P318,10.5,Ch.P390,Mechanism:,Saponification,(皂 化 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 anhydrides,Esters,Amides,Catalyzed by a acid,or a base.,P331,Step 2 Elimination of leaving group to restore,carbonyl group:,Step 3 Proton transfer to yield alcohol,and carboxylate ion:,14.4.2 Reactions with alcohols,Acyl halides,Acid anhydrides,Esters,Nitriles,Alcohols or,phenols,Esters,Hydrolysis of Nitriles:,P320,Reactivity of carboxylic acid derivatives:,Benzoyl chloride,Ethyl benzoate,(80%),Esters,Alcohols,Esters,(Exchange,of esters),Salicylic acid,(水杨酸),Asprin,(阿司匹林),Methyl acrylate,（,丙烯酸甲酯）,Butyl alcohol,（丁醇）,Butyl acrylate,(丙烯酸丁酯),(94%),Alcoholysis of Nitriles:,Ch.P391,Benzoyl,chloride,Piperidine,（哌啶）,N-Benzoyl-,Piperidine,（N-苯甲酰哌啶）,（87-91%）,Ethyl,Floroacetate,（氟乙酸乙酯）,Floroacetamide,（氟乙酸酰胺）,(90%),14.4.3 Reactions with amines,Acyl halides,Carboxylic acid anhydrides,Esters,Ammonia,or amines,Amides,14.5 Reduction,14.5.1 Reduction by LiAlH,4,(LAH)and,its derivatives,1)LiAlH(OR),3,Acyl halides,Amides,2)H,2,O,Aldehydes,Amides,Nitriles,Amines,LiAlH,4,Acryl halides,Carboxylic acid,Acid anhydrides,Esters,Primary,alcohols,LiAlH,4,14.4.2 Reduction by Na,Bouveault-Blanc reduction,Esters,Na,Ethanol,Butanol,Pentanol,reflux,Primary alcohols,Ethyl oleate,油酸乙酯,Oleic alcohol,油醇,The unique method for the preparation of,unsaturated primary alcohols in industry,Ch.P393,14.5.3 Reaction with Grignard reagents,1 mol RMgX,Low temperature,RMgX,Ketones,Tertiary,alcohols,Carboxylic acid,derivatives,RMgX,Reactions of nitriles with Grignard reagents,Addition,1.RMgX,Imine,亚胺,Nitriles,2.H,2,O,Hydrolysis,Ketones,RLi reacts in the same way and are often,used instead of RMgX,14.6 Reactions of amides,14.6.1 The dehydration of amides,Amides,Dehydrating agents:P,4,O,10,(P,2,O,5,),（脱水剂）,(CH,3,CO),2,O,Heating,To form nitrils,2-Methylpropanamide,2-甲基丙酰胺,2-Methylpropanenitrile,2-甲基丙腈,（69-86%）,Br,2,/OH,Carbonyl group had been plucked out,14.6.2 The Hofmann Rearrangement,（Hofmann,降解反应,）,N-unsubstituted amides,to form primary amines having one less,carbon atom than amide,Mechanism:,Step 1 Formation of an N-bromo amide,intermediate:,Deprotonation of amide,Amide nitrogen anion,as a nucleophile,Ch.P396,(丙),Step 2 Rearrangement of the N-bromo amide,to an isocyanate,（异氰酸酯）,Deprotonation of N-bromo 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),dissociates to,an amine and CO,2,The features of Hofmann rearrangement:,N-,unsubstituted,amides as substrates,2.Rearrangement proceeds with retention,of configuration at migrating group,(S)-2-Methyl-,3-Phenylpropanamide,(S)-1-Phenyl-2-propanamine,14.7 Spectroscopic analysis of carboxylic,acid derivatives,Table 1.The stretching frequency of C=O,IR:,:,The stretching frequency of,:,22102260 cm,-1,Compounds,Stretching frequency of C=O,(cm,-1,),RCOCl,(RCO),2,ORCO,2,R,RCONH,2,18151785,18501800 and 17801740,1735,16801630,Esters,Carboxylic acid,anhydrides,Stretching frequency of CO:,1310 1050 cm,-1,Amides:Stretching frequency of N H bond:,3500 3200 cm,-1,-H :2 3 ppm,1,H NMR:,13,C NMR:,:120 ppm,Amide:N-H :5 8 ppm,Problems to chapter 14,P 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),10.57,10.58,10.59,10.60,10.61,10.62,