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Schmidt Reaction

(Schmidt Rearrangement)

Published Online: 15 SEP 2010

DOI: 10.1002/9780470638859.conrr566

Comprehensive Organic Name Reactions and Reagents

Comprehensive Organic Name Reactions and Reagents

How to Cite

2010. Schmidt Reaction. Comprehensive Organic Name Reactions and Reagents. 2503–2510.

Publication History

  1. Published Online: 15 SEP 2010

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Abstract

The reaction between a hydroazoic acid (i.e., azoimide) and a carboxylic acid or a carbonyl compound via an 1,2-migration to form a nitrogen-containing molecule such as primary amine or amide is generally known as the Schmidt reaction. In particular, the reaction between a hydroazoic acid and a carboxylic acid to yield a primary amine with one less carbon atom by decarboxylation is referred to as the Schmidt rearrangement. Currently, the scope of the Schmidt reaction has been extended to include reactions between hydroazoic acid or alkyl azide and other molecules that can form carbocation intermediates under acidic conditions, such as olefins, tertiary alcohols, and some secondary alcohols (e.g., benzhydrols). Schmidt reaction is very versatile and has many advantages. Furthermore, the aryl group is preferred over the alkyl group for the migration from minodiazonium ion, and the migrating tendency correlates well with the Hammett substituent constant. The reaction with carbonyl compounds has an even wider application in organic synthesis.

Keywords:

  • carboxylic acid;
  • bicyclic lactams;
  • hydroazoic acid;
  • Hammett substituent constant