The Schmidt reaction uses catalytic acid and hydrazoic acid to convert carboxylic acids, aldehydes, ketones, olefins, and 3° alcohols to amines, nitriles, amides, imines, and imines respectively. In the case of aldehydes, hydrazoic acid attacks the carbonyl group, to form a tetrahedral azidoalkanol intermediate. Water is expelled as nitrogen forms a double bond to carbon, followed by removal of a proton and expulsion of nitrogen gas to make a carbon-nitrogen triple bond.

  • Reagents: Hydrazoic Acid or Alkyl Azide, Acid Catalyst (H2SO4, TFA, PPA, etc.)
  • Reactant: Carboxylic Acid, Aldehyde, Ketone, Olefin, or 3° Alcohol
  • Product: Amine, Nitrile, Amide, or Imine
  • Type of Reaction: Azide Nucleophilic Addition
  • Bond Formation: C-N or C=N, and C≡N

Lab Tips

  • Note that hydrazoic acid is both toxic and explosive, especially in large amounts. It is handled either as a solution in an inert solvent (e.g. CHCl3) or generated in situ by adding NaN3 to the acidic reaction mixture.
  • A possible side reaction for aldehydes is the formation of formamide.
  • If sulfuric acid is used, aromatic aldehydes are preferred as aliphatic aldehydes are unstable in this acid.
  • Lewis acids (TiCl4, TFA, CH3SO3H) are effective catalysts when alkyl azides are used.
  • Unsymmetrical ketones can result in a mixture of amide products since either R group is able to migrate to the nitrogen atom.
Kürti, L., Czakó, B. (2005). Strategic Applications of Named Reactions in Organic Synthesis; Background and Detailed Mechanisms. Burlington, MA: Elsevier Academic.


Top Citations

Original Paper

Related Reactions

  • Curtius Rearrangement

Related Compounds

  • Acid
  • Hydrazoic Acid (CAS 7782-79-8)
By shuhan yang


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