The Hofmann rearrangement is the organic reaction of a primary amide to a primary amine with one fewer carbon atom.

The reaction of bromine with sodium hydroxide forms sodium hypobromite in situ, which transforms the primary amide to an intermediate isocyanate. The intermediate isocyanate is hydrolyzed to a primary amine giving off carbon dioxide.

The reaction is named after its discoverer: August Wilhelm von Hofmann. This reaction is also sometimes called the Hofmann degradation, and should not be confused with the Hofmann elimination.

Variations

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Several reagents can substitute for bromine. N-Bromosuccinimide can effect a Hofmann rearrangement. In the following example, the intermediate isocyante is trapped by methanol forming a carbamate.

A mild alternative to bromine is also (bis(trifluoroacetoxy)iodo)benzene.

References

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1. Hofmann, A. W. v. Ber. 1881, 14, 2725.
2. Wallis, E. S.; Lane, J. F. Org. React. 1949, 3, 267-306. (Review)
3. Shioiri, T. Comp. Org. Syn. 1991, 6, 800-806. (Review)
4. Keillor, J. W.; Huang, X. Organic Syntheses, Coll. Vol. 10, p.549 (2004); Vol. 78, p.234 (2002). (Article)
5. Almond, M. R.; Stimmel, J. B.; Thompson, E. A.; Loudon, G. M. Organic Syntheses, Coll. Vol. 8, p.132 (1993); Vol. 66, p.132 (1988). (Article)

See also

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• Curtius rearrangement
• Iodoform reaction
• Lossen rearrangement
• Schmidt reaction
• Weerman degradation

Organic reactions

Hofmann-Abbau | ホフマン転位