Iminyls. Part 8. Intramolecular addition to nitrile groups

Abstract

Evidence for the radical polymerisation of nitrile groups in polyacrylonitrile has been sought using model compounds. No evidence for the cycloaddition of iminyls to nitrile groups has been obtained but nucleophilic addition occurred easily. Thus, 1,8-dicyanonaphthalene reacted with hydroxylamine to give naphthalimide dioxime and with butyl-lithium to give azaphenalene derivatives but adamantyl radicals did not attack the nitrile functions.

3-Benzoyl-1,5-dimethylpimelonitrile and hydroxylamine yielded a piperidine and two decahydro-1,8-naphthyridine derivatives instead of the expected oxime. Reaction of the piperidine with bromoacetic acid gave an oxyacetic acid which was converted by persulphate oxidation into a cis-trans mixture of azopyridines. The structure of one of the decanaphthyridines has been established by X-ray crystallographic analysis.