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（12.3-12.4）

123胺的制备 Preparation of Amines

Organic Chemistry Organic Chemistry Xiamen Xiamen University University 12.3 胺的制备 Preparation of Amines

Alkylation of ammonia or amines NaoH E Nh2 +rX 一RNH3X RNH 2 + Naoh RNH2+RX—-R2NH2x RONH ●● Naoh R2NH+R-X RBNH X R3N ①D ●● R3N+RⅩ RAN X ⑨D RI>RBr>RCl1°RX>2°RX

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Alkylation of ammonia or amines NH 3 + R X RNH 3 X NaOH RNH 2 RNH 2 + R X R 2NH 2 X NaOH R 2NH R 2NH + R X R 3NH X NaOH R 3 N R 3 N + R X R 4N X RI > RBr > RCl 1 R X > 2 R X

a Gabriel Synthesis KOH NH R一X Etoh NK O h or oh COH RNHo t HO CO,H N-R ①D H2NNH2 NH RNH, NH ⑨D Etoh O

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Gabriel Synthesis NH O O KOH EtOH N K O O R X N O O R H + or O H H 2 O H 2NNH 2 EtOH CO 2 H CO 2 H RNH 2 + RNH 2 + NH NH O O

Preparing Amines from Alcohols AlO ROH Nh RNH+ron+ron+ho △,压力 NH3 ROH TsCl ROTS—-RNH2+TsO

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Preparing Amines from Alcohols ROH + Ts C l RNH 2 + Ts O ROH + NH 3 , 压力 RNH 2 + R 2NH + R 3 N + H 2 O ROTs NH 3 Al 2 O 3

Ph Ph nK TSC OH H OTS CH Ph Ph h2nnH2 H HoN H Etoh O CH CH3

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Ph H OH CH 3 TsC l Py. Ph H OTs CH 3 N K O O N O O Ph H CH 3 H 2NNH 2 EtOH H 2 N Ph H CH 3

Reduction of Nitro compounds CH Fe Feso CH NaoH E HOCH2 -C-NOL H20-H2SON HOCHo-C-NH CH CH R一NO R一NH 2 M/H. Zn/Hcl Fe/hcl. Sn/hcl H2/ Catalyst NayS, NaSH, (NH4)HS,(NH4)2S

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Reduction of Nitro compounds HOCH 2 C NO 2 CH 3 CH 3 Fe, FeSO 4 H 2O￾H 2SO 4 NaOH HOCH 2 C NH 2 CH 3 CH 3 R NO 2 R NH 2 [H ] M / H+ : Z n / H Cl , F e / H Cl , S n / H Cl , H 2 / C atalyst Na 2 S , Na S H, ( N H 4)HS , (N H 4 ) 2 S

3 Reduction of Nitriles, Amides and Oximes ERCN R-CONH [H R R—CHNH C-NOH . [H] LiAlH4, B2H6, H2/Catalyst

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Reduction of Nitriles , Amides and Oximes R CN R CONH2 [H] R CH 2NH 2 [H] LiAl H 4 , B 2 H 6 , H 2 / Cataly s t R C R NOH

3 Reductive Amination of Ketones and Aldehydes H/Ni C6H5CHO NH3(excess) C6HS CH2NH Etoh R H,/Ni R 0 + NH3(excess) CH一NH2 R Etoh rt ①D H,/Ni Nh3(excess) Etoh NH ⑨D

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Reductive Amination of Ketones and Aldehydes C 6 H 5CHO + NH 3 ( excess) H 2 / N i R' C R O + NH 3(e x c e s s ) H 2 / N i R' CH R NH 2 NH 2 + NH 3 ( excess) H 2 / N i O EtOH C 6 H 5CH 2NH 2 EtO H EtOH

Mechanism R R C-0 NH3(excess) C=NH R R H/Ni r CH一NH Etoh

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Mechanism Mechanism R' C R O + NH 3(e x c e s s ) R' C R NH H 2 / Ni R' C H R NH 2 EtOH

Leukart reaction Reductive alkylation of ammonium(or amine) salts of formic acid by aldehydes or ketones HCO2NH 4 RCHO RCHONH

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Leukart Leukart Reaction Reaction „ Reductive alkylation of ammonium (or amine) salts of formic acid by aldehydes or ketones: RCHO HCO 2NH 4 RCH 2NH 2