114羧酸衍生物的水解、醇解 氨解反应 Hydrolysis, Alcoholysis and Amonolysis Reactions of Carboxylic Acid Derivatives
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 11.4 羧酸衍生物的水解 醇解 氨解反应 Hydrolysis, Alcoholysis and Amonolysis Reactions of Carboxylic Acid Derivatives
g1.水解反应 E . CH3COCI +h2o CH3 CO,H+HCI (CH3 COhO H2o 2CH2,H CH3CO2C2Hs +H0 OH- CH3CO2H+ C2H5OH H+ CH3 CONH, H,O CH3CO2H+ NH3 或OH
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 1. 水解反应 CH 3CO C l (CH 3CO ) 2 O CH 3CO 2 C 2 H 5 CH 3CO N H 2 + H 2 O + H 2 O + H 2 O + H 2 O CH 3CO 2 H + HC l 2CH 3CO 2H CH 3CO 2 H + C 2 H 5OH CH 3CO 2 H + NH 3 H + 或OH - H + 或OH -
2.醇解反应 碱 CH3COCI C2HsOh CH3 CO C2H5 + hCl CH3 CO)2O C2H5Oh winy CH3CO, C2Hs CH3 cO2H H CH3 CH3 + C2HSOH 或C2H5O CH3CO2 C2H5+ Ch3OH
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 2. 醇解反应 CH 3CO C l (CH 3CO ) 2 O CH 3CO 2CH 3 CH 3CO 2 C 2 H 5 + HC l CH 3CO 2 C 2 H 5 + CH 3CO 2H CH 3CO 2 C 2 H 5 + CH 3OH H + 或 C 2 H 5 O - + C 2 H 5OH 碱 碱 + C 2 H 5OH + C 2 H 5OH
醇解反应实例 O O CHoH ( CH3)3C-C-CI (CH3)3C-C-OC2H5 吡啶 HCI 吡啶 ≈C6H5Co+)o C6H5-C-OC(CH3)3+ HCI CH3CO2 Na (CH3 CO)2o O CH2OH o ChQOCOCH ch coh
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 醇解反应实例: (CH 3 ) 3 C C O Cl C 2 H 5OH 吡啶 (C H 3 ) 3 C C O OC 2 H 5 N HCl + + (CH 3 ) 3COH 吡啶 + N HCl C 6 H 5COCl C 6 H 5 C O OC(CH 3 ) 3 (C H 3CO) 2 O O CH 2OH + O CH 2 OCOCH 3 CH 3CO 2Na + CH 3CO 2 H
O 聚合 可HC≡CH+CH2COH CH3C-OCH= 2 O O-CCH3 COrONa OH CH-CH2 CHOH H—CH2 聚醋酸乙烯 聚乙烯醇 CHoO 维尼纶 部分甲基化
Organic Chemistry Organic Chemistry Xiamen Xiamen University University HC CH + CH 3CO 2 H CH 3 C OCH CH 2 O 聚合 CH CH 2 O C C H 3 O n CH 3ONa CH 3OH CH CH 2 OH n 聚醋酸乙烯 聚乙烯醇 CH 2 O 部分甲基化 维尼纶
酯交换反应的实例 390 CO C2H4 O H O+CHoH CH,OH 人O+ RORO OR (2)CH3 o OH CH3O g(3)CH3C-0-〈 c -och3 +chr oh O ⑨D HO〈 COCH3 CH3 CO2 CH3
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 酯交换反应的实例 CO 2 C 2 H 5 CH 2OH H + O O + C 2 H 5OH CH 3 O O + RO H RO - OR OH O CH 3 C O C O O OCH 3 + CH 3OH CH 3 O - HO C O OCH 3 + CH 3CO 2CH 3 (1) (2) (3 )
关于酰胺的醇解 g■酰胺在酸催化下可发生醇解,在碱条件下 当则较困难,为什么?因为在碱催化下酰胺 的醇解是由较弱的碱交换出一个较强的碱, 这可由下面的机理说明: R-C-NH2 R'O R-C-NH OR R-C-OR'+ NH
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 关于酰胺的醇解 酰胺在酸催化下可发生醇解 在碱条件下 则较困难 为什么 因为在碱催化下酰胺 的醇解是由较弱的碱交换出一个较强的碱 这可由下面的机理说明 R C NH 2 O + R'O R C NH 2 O OR' R C OR' O + NH 2
关于腈的醇解 ■腈在酸性水溶液中醇解也得到酯 O H RCN ROH R-C-OR′+NH+ H2O
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 关于腈的醇解 腈在酸性水溶液中醇解也得到酯 RCN + R' O H H + H 2 O R C OR' O + NH 4 +
Mechanism /RCN、 R'OH R-C≡NH R-C=NH NH NH H,O NH2 R-C-OR'-R-C-OR' R-C-OR H OH NH3 R-C-OR R-C-OR+ NH3 OH OH R-C-OR'+ NH4
Organic Chemistry Organic Chemistry Xiamen Xiamen University University Mechanism RCN H + R C OR' O R C NH + R C N H + R'OH R C OR' NH H + R C OR' NH 2 + H 2 O R C OR' NH 2 +OH 2 R C OR' NH 3 OH + R C OR' +OH + NH 3 + NH 4 +
酯的制备小结 _1.酯化反应 2.羧酸盐+卤代烃 3.羧酸+重氮甲烷 4.羧酸+烯、炔 ■5.羧酸衍生物的醇解 6.腈的醇解
Organic Chemistry Organic Chemistry Xiamen Xiamen University University 酯的制备小结 1. 酯化反应 2. 羧酸盐 + 卤代烃 3. 羧酸 + 重氮甲烷 4. 羧酸 + 烯 炔 5. 羧酸衍生物的醇解 6. 腈的醇解
