厦门大学化学化工学院：《有机化学》课程教学资源（课件讲稿，双语版）第十二章 胺类（12.5-12.6）

125胺的反应 Reactions of amines

Organic Chemistry Organic Chemistry Xiamen Xiamen University University 12.5 胺的反应 Reactions of Amines

Acylation Primary and secondary (but not tertiary) amines can be acylated by reaction with acid chlorides or acid anhydrides to yield amides. NH 3 RCNH 2 O Pyridine R'NH, R-C-CI R-C-NHR' RCNR 2

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Acylation „ Primary and secondary (but not tertiary) amines can be acylated by reaction with acid chlorides or acid anhydrides to yield amides. NH 3 R'NH 2 R' 2NH R C Cl O + Py r idi n e R C NH 2 O R C NHR' O R C NR' 2 O

9 Hinsberg Reaction g. If a sulfonyl chloride, RSO2Cl, is used as g the acylating agent, a sulfonamide is produced R-S--CI R--S-NHR Sulfonyl chloride Sulfonamide

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Hinsberg Reaction „ If a sulfonyl chloride, RSO 2Cl , is used as the acylating agent, a sulfonamide is produced. R S Cl O O Sul fo nyl chlorid e R S NHR O O Sulfo namid e

RNH Ph--S-NHR O Pyridine R2NH Ph-S-CI Ph--S-NR RoN Ph-S一NR ①D ⑨D Ph-S-oh +rN H2O

Organic Chemistry Organic Chemistry Xiamen Xiamen University University R 3 N RNH 2 R 2NH + Py r idi n e Ph S NHR O Ph S NR 2 O S Cl O O Ph O O Ph S NR 3 O O H 2 O S OH + R 3 N O O Ph

Quaternary Ammonium Compounds g- Quaternary ammonium salt 25 CHsn chal C2H53N CH3 I ether Triethylmethylammonium iodide a Quaternary ammonium hydroxide Ag2o a( C2H5)3N CH3 I (C2H53N CH3 OH Triethylmethy lammonium hydroxide

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Quaternary Ammonium Compounds „ Quaternary ammonium salt (C 2 H 5 ) 3N + CH 3 I 25 ether (C 2 H 5 ) 3 N +CH 3 I - Triethylm ethylam m onium io d i d e „ Quaternary ammonium hydroxide (C 2 H 5 ) 3 N +CH 3 I - Ag 2 O (C 2 H 5 ) 3 N +CH 3 OH - Tri e thylm e thylam m onium hyd r o x i d e

(CH3)4N CI (CH3 CH2 CH2 CH2)4N Br U Tetramethylammonium chloride Tetrabutylammonium bromide 四甲基氯化铵 四丁基溴化铵 (氯化四甲基铵) CH Ch cochochonch2 br CH Acetylcholine bromide 溴化乙酰胆碱

Organic Chemistry Organic Chemistry Xiamen Xiamen University University (C H 3 ) 4 N+ Cl - (C H 3CH 2CH 2CH 2 ) 4 N+ Br - T etramethylam m o nium chlorid e Tetrabutylam m onium b r o mid e CH 3CO 2CH 2CH 2NCH 3 Br CH 3 CH 3 A cetylcholine b r o mid e (氯化四甲基铵 ) 四甲基氯化铵 四丁基溴化铵 溴化乙酰胆碱

Hofmann elimination CHaI CH3(CH2)5 NH2 CH3(CH2)5N(CH3)3 I (excess) Ag,o △ CH3(CH25N(CH3)3 OH 9 CH3CH2CH2CH2CH=CH2+(CH3)3N

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Hofmann Elimination Hofmann Elimination CH 3(CH2 ) 5NH2 CH 3 I (excess) CH 3(CH2 ) 5 N(CH3 ) 3 I Ag 2 O CH 3(CH2 ) 5 N(CH3 ) 3 OH CH 3CH2CH2CH2CH CH2 + ( CH 3 ) 3 N

HO E2 C-C C=C、+N(CH3)3 N(CH3)3 FN(CH3)3 HO CHrCH, CH,CH-CH D CH3CH, CH, CHCH 94:6 CH3 CHO CHFCHCH3 ⑨D

Organic Chemistry Organic Chemistry Xiamen Xiamen University University C C H N(CH 3 ) 3 HO E2 C C + N(CH 3 ) 3 CH 3CH 2CH 2CHCH 3 CH 3CH 2CH 2CH CH 2 N(CH 3 ) 3 HO CH 3CH 2CH CHCH 3 94 : 6

CH3I Ag,O excess N HO H CH CH3 CH CH CH3I Ag,O ①D excess N CH CH ⑨D

Organic Chemistry Organic Chemistry Xiamen Xiamen University University N H CH 3 I (excess) N CH 3 CH 3 I Ag 2 O N CH 3 CH 3 HO N CH 3 CH 3 CH 3 I (ex cess) Ag 2 O

Phase-transfer catalyst CHCI3, 50% Naoh in H,o CI C6Hs NEt3 cl 77% H ①D us hase HgO+NaHO Add R,N CI Hg0+Na HO+CI ⑨D CHCa+R,N HO CHCI+

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Phase-transfer catalyst CHCl 3, 50% NaOH i n H 2 O C 6 H 5CH 2NEt 3 Cl Cl Cl H H 77%