AMINATION OF ADAMANTANES AND THEIR PRECURSORS WITH TRICHLORAMINE-ALUMINUM CHLORIDE

The reaction of trichloramine and aluminum chloride with adamantane and alkyladamantanes gave excellent yields of the corresponding bridgehead amines. Various tricyclic alkanes upon treatment with trichloramine under Friedel-Crafts conditions underwent rearrangement and amination in one step to the corresponding aminoadamantanes. This represents the first case in which rearrangement of an adamantane precursor is accompanied by the introduction of a functional group. Synthetically, the trichloramine amination route provides a simple, one-step method of obtaining aminoadamantanes in high yields. The postulated mechanism involves hydride abstraction by positive chlorine from the adamantane nucleus. Subsequent attack by a nitrogen-containing nucleophile affords the N,N-dichloro derivative which has been isolated. Acid hydrolysis effects conversion to the amine. © 1969, American Chemical Society. All rights reserved.