Organic Chemistry

Summary of Reactions 913

b.In acylation reactions:

c.In nucleophilic addition–elimination reactions:

i Reaction of a primary amine with an aldehyde or ketone to form an imine:

ii Reaction of a secondary amine with an aldehyde or ketone to form an enamine:

d.In conjugate addition reactions:

2. Primary arylamines react with nitrous acid to form stable arenediazonium salts (Section 21.4).


3. Oxidation of amines: Primary amines are oxidized to nitro compounds, secondary amines to hydroxylamines, and tertiary amines to
   amine oxides (Section 21.7).


4. Elimination reactions of quaternary ammonium hydroxidesor tertiary amine oxides(Sections 21.5 and 21.7).

RCH 2 CH 2 NCH (^3) Hofmann
elimination
∆
RCH CH 2 + NCH 3 + H 2 O
HO− CH 3

• CH 3
  CH 3
  CH 3
  RCH 2 CH 2 NCH (^3) Cope
  elimination
  ∆
  RCH CH 2 + NCH 3
  O−


• 
  

  CH 3
  OH
  in both eliminations, the proton is removed from the -carbon bonded to the most hydrogens
  CH 3
  RCH 2 CH 2 NCH 3
  H 2 O 2
  CH 3
  RR
  R
  N RR
  R
  O−
  NH+ 2 O
  a tertiary amine a tertiary amine oxide
  R
  R
  NH R
  R
  OH
  NH+ 2 O
  a secondary amine a secondary hydroxylamine

  
  


• 
  

  oxidation
  oxidation
  R
  oxidation
  NH 2 R
  oxidation
  NH OH R
  oxidation
  NO R N
  O−
  O
  NH 2 NNCl–
  HCl +
  NaNO 2
  CHCR R′NH 2 RCH CH 2 CR
  O O
  NHR′
  RCH +
  ON
  R
  R
  RR
  R RR
  RNH H 2 O
  catalytic
  H+
  ++
  O
  R
  R
  RRNH 2 H 2 O
  catalytic
  H+
  ++NCH 2
  R
  R
  Cl
  C 2 R′NH 2 R′NH 3 + Cl–
  R
  O
  NHR′
  C
  R
  O
  ++