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9701 · 34.1

Primary and secondary amines

Amines contain a nitrogen atom with a lone pair of electrons, making them both basic and nucleophilic. This allows them to react with acids, halogenoalkanes, and acyl chlorides to form a variety of important products.

Need to know

What you need to know

  • **Primary (1°) amines:** One alkyl/aryl group is attached to the nitrogen atom (e.g., ethylamine, CH₃CH₂NH₂). General formula RNH₂.
  • **Secondary (2°) amines:** Two alkyl/aryl groups are attached to the nitrogen atom (e.g., diethylamine, (CH₃CH₂)₂NH). General formula R₂NH.
  • **Tertiary (3°) amines:** Three alkyl/aryl groups are attached to the nitrogen atom (e.g., triethylamine, (CH₃CH₂)₃N). General formula R₃N.

Explanation

Amines: Nitrogen's Nucleophilic Nature

  1. R–NH₂ or R₂NH — lone pair on N is nucleophilic. Basicity order is typically alkyl amines > NH₃ > aryl amines due to electron-donating/withdrawing effects.
  2. With a halogenoalkane, the amine's lone pair attacks the δ+ carbon in a nucleophilic substitution, leading to further alkylation to form 2°/3° amines. Using excess ammonia favours the 1° amine product.
  3. With an acyl chloride, the amine attacks the carbonyl carbon in a nucleophilic addition-elimination reaction. This forms a stable N-substituted amide and hydrogen chloride gas.
  4. As bases, amines react with acids in a neutralisation reaction to form water-soluble ionic salts, called ammonium salts, such as ethylammonium chloride, RNH₃⁺Cl⁻.