The conversion of phenols to primary and secondary aromatic amines via a Smiles rearrangement

The conversion of phenols to 2-aryloxy-2-methylpropanamides (1) and the Smiles rearrangement of these to N-aryl-2-hydroxy-2-methyl propanamides are described; hydrolysis of the latter compounds yields anilines. The scope and limitations of reaction are discussed. Routes, some involving α-lactams, from phenols to N-substituted derivatives of (1) have been developed. Under the conditions of the Smiles rearrangement these secondary 2-methylpropanamides can form directly anilides, N-alkylanilines, or benzoxazinones.