第十七章胺重氮和偶氮化合物.pptVIP

Hofmann Rearrangement and Curtius Reaction 缺电子， 空轨道 N 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。 Curtius Reaction 酰基氮烯 (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 合成2级和3级 胺 Reductive Amination 完成下列转变 The Leuckart Reaction A useful variant of the reductive amination method uses formic acid or formate salts as reductants. Mannich Reaction 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 (磺酰化，Hinsberg test) ⑴ 可用于鉴别：与对甲基苯磺酰氯作用 产物可溶于强碱的为伯胺； 有固体析出的为仲胺； 不反应，出现分层现象的为叔胺。 ⑵ 可用于分离伯、仲、叔胺。在混合物中加入对甲苯磺酰氯，进行作用，然后: 蒸出叔胺； 过滤得到仲胺的磺酰胺，滤液为伯胺的磺酰胺钠盐。 产物经过水解得到原来的胺。 10.6.3胺的氧化和Cope消除 Cope Elimination ——occurs when 3o-amine oxides are heated at temperatures of 150 to 200 oC 消除机理：E2 syn-Eliminations 有两个消除位点时：1）Hofmann产物为主； 2）如有顺反，反式为主 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 + HONO (cold acidic solution) Nitrogen Gas Evolution from a Clear Solution ??????????????? 1°-Amines + HONO (cold acidic solution) (1) Aliphatic Amines Under the acidic conditions of this reaction, all amines undergo reversible salt formation: This happens with 3o-amines, and the salts are usually soluble in water. The reactions of nitrous acid with 1°- and 2°- aliphatic amines may be explained by considering their behavior with the nitrosonium cation (NO+), an electrophilic species present in acidic nitrous acid solutions. 亚硝酰正离子 nitrosonium cation Primary Amines 脂肪族伯胺生成的烷基重氮盐在低温下也会放出氮气生成碳正离子，并按碳正离子的机理继续反应。 N-亚硝基胺 Secondary Amines (2) Aryl Amines 1o-Aryl Amines 芳香族伯胺与亚硝酸反应