Rearrangement in the Reaction of Chlorobenzene-1-C^(14) with Potassium Amide

No satisfactory explanation has been published for the rearrangements which often occur in the amination of "non-activated" aryl halides with alkalimetal amides. The pattern of the rearrangements shows a considerable disregard for the influences governing the usual aromatic substitutions and is well illustrated by the products obtained from the amination of the methoxy- and trifluoromethylhalobenzenes. Although the methoxy- and trifluoromethyl groups orient oppositely in aromatic nitration, o- and m-methoxy- and trihoromethylhalobenzenes with alkali-metal amides yield exclusively m-substituted anilines, while the p-isomers yield mixtures containing roughly equal amounts of m- and p-substituted aniline.