活化醇制备羧酸酯.ppt

(3) mostly electron-rich aromatic or heteroaromatic compounds as well as electron-rich alkenes and 1,3-dienes11 are substrates; (4) the transformation is regioselective favoring the less sterically hindered position. 5 Reimer-Tiemann反应 芳香族化合物在碱溶液中与氯仿作用，也能发生芳环氢被甲酰基取代的反应，叫做Reimer-Tiemann反应。 (1) it is the only electrophilic aromatic substitution reaction that occurs under basic conditions in a protic solvent; (2) phenols, naphthols, alkyl-, alkoxy-, and halogenated phenols, salicylic acid derivatives, heterocyclic phenols such as hydroxyquinolin es and hydroxypyrimidines, as well as pyrroles and indoles undergo formylation under the reaction conditions; (3) the regioselectivity is not high, but ortho-formyl products tend to predominate; (4) when the ortho-position is already substituted, para-formyl phenols are obtained (5) when the reaction is conducted in the presence of cyclodextrins, the p-formyl product is formed predominantly. 二、烯烃的C-酰化 加成的方向服从马氏规则,酰基优先进攻氢原子较多的碳原子 机理 三、羰基α位C-酰化 1.活性亚甲基化合物的C-酰化 例 2. Claisen反应和Dieckmann反应 机理 Since the crossed Claisen condensation can potentially give rise to at least four different condensation products, it is a general practice to choose one ester with no α-protons (e.g., esters of aromatic acids, formic acid and oxalic acid). The ester with no α-proton reacts exclusively as the acceptor and this way only a single product is formed. an ester enolate reacts with a ketone or aldehyde to give an β-hydroxyester； a ketone or aldehyde enolate reacts with an ester to give a 1,3-diketone. 3. 酮、腈的a位C-酰化 应用 ①二酮的制备 ②分子内酰化 ③ 腈的酰化 ④烯胺酰化 习题-写出下列反应机理 * 二、芳胺N-酰化 第四节 碳原子上的酰化反应 一、芳烃的C-酰化  1 Friedel-Crafts (F-C )傅-克酰化反应 (1) 反应通式 （2）反应机理 （3）影响因素 ① 酰化剂的影响 I. 酰化剂的影响 acylating agents besides acyl halides are: aromatic and aliphatic carboxylic acids, anhydrides, ketenes and esters. acyl iodides are usually the most reactive, while acyl fluorides are the least