7.6.1 Production of Amines

• Primary amines are organic compounds that have an -NH₂ functional group attached to an alkyl or aryl group
• Secondary amines have two alkyl or aryl groups attached to an -NH group

Primary and secondary amines

• Primary and secondary amines can be prepared from different reactions including:
  • The reaction of halogenoalkanes with ammonia
  • The reaction of halogenoalkanes with primary amines
  • The reduction of amides
  • The reduction of nitriles

Reaction of halogenoalkanes with ammonia

• This is a nucleophilic substitution reaction in which the nitrogen lone pair in ammonia acts as a nucleophile and replaces the halogen in the halogenoalkane
• When a halogenoalkane is reacted with excess, hot ethanolic ammonia under pressure a primary amine is formed

Formation of primary amine

Reaction of halogenoalkanes with primary amine

• This is also a nucleophilic substitution reaction in which the nitrogen in the primary amine acts as a nucleophile and replaces the halogen in the halogenoalkane
• When a halogenoalkane is reacted with a primary amine in ethanol and heated in a sealed tube, under pressure a secondary amine is formed

Formation of secondary amine

Reduction of amides

• Amines can also be formed from the reduction of amides by LiAlH₄ in dry ether
• Whether a primary or secondary amine is formed depends on the nature of the amide

Amides can be reduced by LiAlH₄ to form amines

Reduction of nitriles

• Nitriles contain a -CN functional group which can be reduced to an -NH₂ group
• The nitrile vapour and hydrogen gas are passed over a nickel catalyst or LiAlH₄ in dry ether can be used to form a primary amine

Nitriles can be reduced with LiAlH₄ or H₂ and Ni catalyst