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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
- 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.
- Chemoselective Schmidt Reaction Mediated by Triflic Acid: Selective Synthesis of Nitriles from Aldehydes. J. Org. Chem. 2012, 77 (12), 5364–5370.
- Gold(I)-Catalyzed Intramolecular Acetylenic Schmidt Reaction. J. Am. Chem. Soc. 2005, 127 (32), 11260–11261.
- Curtius Rearrangement
- Hydrazoic Acid (CAS 7782-79-8)