Hofmann‐Martius Rearrangement

Abstract

The thermal conversion of hydrohalides of N ‐alkylated aromatic amines to o ‐alkylated and p ‐alkylated aromatic amine derivatives and is generally referred to as the Hofmann–Martius rearrangement. This rearrangement in the solid state mostly gives ortho ‐alkylated products, possibly because of limited diffusion and can be triggered by photo‐irradiation. This rearrangement has proven valuable in the preparation of substituted aromatic amines.