Preparation of Amines 6、羰基化合物的还原胺化( Reductive amination) R-C-H(R)+ R"RNH2-H2/Ni R-CH-NRR H(R) NRR R-C-H(R) H2/NI CH3CH=O NH3 CH3 CH2NH2 1°胺 CH3 CHCHO+ CH3,NH H2/Ni CH3CH2CH2NHCH2CH31° 胺→2°胺 2°胺 3°胺 RNH2+2H2C=O+2 HCOOH—>RN(CH3)21°胺的二甲基化
Preparation of Aamines 6、羰基化合物的还原胺化(Reductive Amination) R C H (R) O + R''R'NH2 H2 /Ni R CH H(R') NR'R'' R C H (R) NR'R'' + H2/Ni CH3CH=O NH3 CH3CH2NH2 NH3 1° 胺 + H2/Ni CH3CH2CHO CH3CH2NH2 CH3CH2CH2NHCH2CH3 1° 胺 2° 胺 2° 胺 3° 胺 RNH2 + 2H2C O + 2HCOOH RN(CH3) 2 1° 胺的二甲基化
Preparation of Amines o Preparation by rearrangements l、 Hofmann rearrangements( Hofmann重排,降解) O ll Br CH3(CH2)4C-NH2 2 CH3(CH2)3CH2-NH2 OH 机理 O BI OH R-C H R一C Br R—C—N-B OH H >0=c=N-R OH-R-NH2 异氰酸酯
Preparation of Aamines Preparation by Rearrangements 1、Hofmann Rearrangements （Hofmann 重排，降解） CH3(CH2) 4C NH2 O Br 2 OH - CH3(CH2) 3CH2 NH2 R C N H H O Br2 OH - R C N H Br O OH - R C N Br O O C N R OH - R NH2 异氰酸酯 机理
Preparation of Amines Stereochemistry H3C CONH2 NH2 HsC2-C HsC Br,/OH H H R-2-甲基丁酰胺 R-2-甲基丁胺 CH O HsC H3C H3C N=C=O C-N—B1 HsC Hs" C Br SN2 三元环过渡态 构型保持
Preparation of Aamines C CONH2 H5C2 H3C H Br 2 /OHC NH2 H5C2 H3C H R-2-甲基丁酰胺 R-2-甲基丁胺 C C H5C2 H3C H O N Br C N O Br C H5C2 CH3 H - - + C N H5C2 H3C H C O SN2 三元环过渡态 构型保持 Stereochemistry
Preparation of Amines 2 Curtius Schmidt Rearrangements Curtius RCOCI NaN O R—C-N—N三N R-N=C=O RCOOH NaN 酰叠氮化合物 HO Schmidt RNH? O C-CI C—N NH260% △ NaN CO2H H,O NH 75%
Preparation of Aamines 2、Curtius & Schmidt Rearrangements RCOCl + NaN3 RCOOH + NaN3 R C N N N O -N2 R N C O H2 O 酰叠氮化合物 RNH2 Curtius Schmidt H2O C Cl O NaN3 C N3 O NH2 60% NaN H3O+ 3 Cl CO2H Cl NH2 75%
Preparation of Amines o Preparation by Mannich reaction 胺甲基化反应 CH3-C-CH3 + CH2O +(C2H5)2NH2 CI CH3CCH2CH2N'H(C2H5h2CI O CCH3 +CH2O +(CH3hNH2CI- CCH2 H(CH3hCI 70% -H酮 甲醛胺盐 β-胺基酮 酸性水、醇溶液
Preparation by Mannich reaction Preparation of Aamines CH3 C CH3 O + CH2O + (C2H5 )2NH2 + Cl - CH3CCH2CH2N + H(C2H5 )2Cl - O 66~75% + CH2O + (CH3 )2NH2 + Cl - CCH3 O CCH2CH2N + H(CH3 )2Cl - O 70% -H 酮 甲醛 胺盐 -胺基酮 酸性水、醇溶液 胺甲基化反应