Reilly-Rickinbottom rearrangement

What is Reilly-Rickinbottom rearrangement?

The Reilly-Hickinbottom rearrangement, discovered by Reilly and Hickinbottom in 1920, is a thermal rearrangement of N-alkyl anilines into aryl-substituted anilines under the influence of Lewis acids. During this reaction, an alkyl group migrates from the nitrogen atom to the aromatic nucleus, resulting in intermolecular rearrangement.

This reaction is an extension of the Hofmann-Martius Rearrangement and generally produces para-alkylated aromatic amine derivatives without the formation of alkyl halides. The use of ZnCl2 as a catalyst often leads to a higher yield of the alkylated product, except in the case of CoCl2-catalyzed rearrangement of N-benzylaniline, which produces a significant amount of the ortho isomer. Additionally, this rearrangement can result in the formation of multi-alkylated products.

Reilly-Hickinbottom rearrangement
Reilly-Hickinbottom rearrangement


XV.—Intramolecular rearrangement of the alkylarylamines: formation of 4-amino-n-butylbenzeneJ. Chem. Soc., Trans., 1920, 117, 103-137
DOI: 10.1039/CT9201700103