Abstract
Aryliminodimagnesium (ArN (MgBr) 2, aryl-IDMg), derived from arylamines and two molar equivalents of ethylmagnesium bromide, condense with diaryl ketones, nitrosoarenes, and nitroarenes to give the corresponding anils, azoarenes, and azoxyarenes. Types of products and their distributions obtained in the reaction with benzophenones, fluorenones, benzalacetophenones, anthraquinone, and benzils showed that the aryl-IDMg reagents are moderately reactive in terms of electron-transfer as well as condensation ability. The condensation reaction of the reagents with nitroarenes provides a novel method for the independent preparation of isomeric pairs of unsymmetrically substituted azoxyarenes. The isolated azoxyarenes are deoxygenated to give the corresponding azoarenes by the treatment with an excess amount of the reagent. The product distributions obtained in the reaction of nitroarenes with excess reagents are governed mainly by the electronic effect of the substituent on both the substrate and the reagent.
