有机化学 第11章 胺、重氮和偶氮化合物.pptVIP

氯甲酸苄酯 ——保护羟基和氨基 Hofmann Rearrangement and Curtius Reaction N: 缺电子空轨道 中性, 无电荷 在Hofmann 重排反应中，如果发生迁移的烃基碳原子为手性碳，迁移时其构型保持。 ——拜克曼重排（Beckmann rearrangement） N: 缺电子空轨道 离子,正电荷 Curtius Reaction 酰基氮烯 Quiz Compare the basicity of the following compounds： (i) Alkylation of the sulfonamide derivative of a 1o-amine. Gives 2o-amines.?(ii) Reduction of alkyl imines and dialkyl iminium salts. Gives 2o 3o-amines.? (iii) Reduction of amide derivatives of 1o 2o-amines. Gives 2o 3o-amines Preparation of 2o 3o-Amines Reductive Amination The Leuckart Reaction A useful variant of the reductive amination method uses formic acid or formate salts as reductants. Mannich Reaction （曼尼奇反应） 11.6 胺的反应（Reactions of Amines） 11.6.1 烷基化反应（Alkylation of Amines） 11.6.2 胺的酰化（Acylation of Amines） Aza-Michael Addition： Reaction with Benzenesulfonyl chloride (The Hinsberg test) The Hinsberg test is conducted in aqueous base (NaOH or KOH), and the benzenesulfonyl chloride reagent is present as an insoluble oil. Because of the heterogeneous nature of this system, the rate at which the sulfonyl chloride reagent is hydrolyzed to its sulfonate salt in the absence of amines is relatively slow. The amine dissolves in the reagent phase, and immediately reacts (if it is 1o or 2o), with the resulting HCl being neutralized by the base. The sulfonamide derivative from 2o-amines is usually an insoluble solid. However, the sulfonamide derivative from 1o-amines is acidic and dissolves in the aqueous base. Acidification of this solution then precipitates the sulfonamide of the 1o-amine. 11.6.3 胺氧化物（Amine Oxides） Cope Elimination ——occurs when 3o-amine oxides are heated at temperatures of 150 to 200 oC Pyrolytic syn-Eliminations 11.6.4 与亚硝酸的反应（Reaction of Amines with Nitrous Acid） Nitrous acid: HNO2 or HONO A Clear Solution (Ammonium Salt Formation) ??????????????? 3°-Amines + HONO (cold acidic solution) An Insoluble Oil (N-Nitrosoamine) ??????????????? 2°-Amines