chapter 7有机化学 高等.pptxVIP

Advanced Organic ChemistryChapter 7Addition, Condensation and SubstitutionReactions of CarbonylCompoundsAddition, Condensation and SubstitutionThree Mechanisms for Additionstructural features of the carbonyl compound; the role of protons or other Lewis acids in activating the carbonyl group toward nucleophilic attack; the reactivity of the nucleophilic species and its influence on subsequent steps; the stability of the tetrahedral intermediate and the extent to which it proceeds to product rather than reverting to starting material.addition of cyanide Hydrolysis The order is Cl OAr OR NR2 O? so that not only is it easier to form the tetrahedral intermediate in the order Cl OAr OR NR2 O?, but the tendency for subsequent elimination to occur is also in the same order.Hydration and Addition of Alcohols to Aldehydes and KetonesAcid-catalyzed mechanismBase-catalyze mechanismAddition of alcohol1. Steric effects result in an order of CH3 ～ C2H5 (CH3)2CH (CH3)3C for acetaldehyde hemiacetals2. Dehydrating reagent or azeotropic distillationhydrolysis reaction is the reverse reaction of addition7.3. Condensation Reactions of Aldehydes and Ketones with Nitrogen Nucleophiles7.4. Substitution Reactions of Carboxylic Acid DerivativesThe order of reactivity as leaving groups is Cl,Br O2CR OR NHR O? N?R. 2.The broad reactivity trends among the carboxylic acid derivatives can be recognized by taking account of the effect of the substituents on the stability of the carbonyl center and the ability of the various substituents to act as leaving groups from the tetrahedral intermediate.7.4.1. Ester Hydrolysis and ExchangeIn acidic solution, the reaction is reversible.In alkaline aqueous solution, ester hydrolysis is essentially irreversible. General mechanism for hydrolysis of esters1. Acid-catalyzed hydrolysis of esters is accompanied by some exchange of oxygen from water into the carbonyl group.2. Alkyl benzoate esters give only a small amount of exchange under basi