Benzidine Rearrangement: A Name Reaction Explained

In 1863, Hofmann reported the rearrangement of diphenylhydrazine to 4,4-diaminobiphenyl (aniline) under acid catalysis, known as the benzidine rearrangement. When diphenylhydrazine contains a para-substituent, the product obtained is para-aminobiphenyl, and this reaction is referred to as the Semidine rearrangement.

Reaction Mechanism

Reaction Examples

References

1. Hofmann, A. W., Proc. Roy. Soc. London, 1863, 12, 576.

2. Benniston, A. C.; Clegg, W.; Harriman, A.; Harrington, R. W.; Li, P.Y. and Sams, C., Tetrahedron Lett.,

2003, 44, 2665.

3. Kisch, H.; Reisser, P. and Knoch, F., Chem. Ber., 1991, 124, 1143.(b) Rhee, E. S. and Shine, H., J. Am. Chem. Soc., 1986, 108, 1000.

4. Subotkowski, W.; Kupczyk-Subotkowska, L. and Shine, H. J., J. Am.Chem. Soc., 1993, 115, 5073.

5. Ritter, J. J. and Ritter, F. O, J. Am. Chem. Soc., 1931, 53, 670.

6. Smith, D. H.; Schwartz, J. R. and Wieland, G. W., J. Am. Chem. Soc.,1952, 74, 2282.

This article is from Name Reactions: A Collection of Detailed Mechanisms

and Synthetic Applications–Fifth Edition, Organic Name Reactions: Mechanisms and Applications Fourth Edition.

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