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 , -dichloro derivative which has been isolated. Acid hydrolysis effects conversion to the amine. This laboratory has reported the direct amination of aromatic compounds with N-halamines under Friedel-Crafts conditions leading to basic products of unusual orientation. Thus, when monoalkylbenzenes were allowed to react with trichloramine and aluminum chloride, the corresponding m-alkylanilines were formed.4-7 The proposed addition-elimination mechanism, substitution, accounts for the selective meta orientation. Similar results were obtained with dialkylbenzenes,8 biphenyl,9 and naphthalene9 as substrates.When p-cymene was aminated with trichloramine and aluminum chloride, the presence of 8-amino-p-cy-mene10 in the product stimulated investigation of other aryldialkylmethines in relation to side-chain attack. The efforts were rewarding since various para-substituted alkylbenzenes which possess a tertiary hydrogen afforded the corresponding f-carbinamines.11-13 Further studies showed that alkanes reacted in an analogous fashion, e.g., 1 -methylcyclohexane yielded 1-amino-1 -methylcyclohexane in good yield.14The object of the present work was to investigate amination in the adamantane series in relation to the synthetic and mechanistic aspects. Since 1-aminoadamantane possesses antiviral properties,16 additional (1) Paper XIII: Chemistry of N-Halamines.
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