EVIDENCE FOR RADICAL CATIONS IN LINKED MECHANISMS OF N,N-DIALKYL AROMATIC AMINE NITRATION AND NITROSATIVE DEALKYLATION

N,N-Dialkyl aromatic amines react rapidly with nitrous acid to competi tively produce a nitrosamine and a nitro compound. The mechanism of ni tro compound formation involves a reaction of an amine radical cation with NO2, while the nitrosamine is produced by two competing pathways, one of which involves N-alpha-CH deprotonation of a radical cation wi th subsequent oxidative generation of an imminium ion, and the other o f which occurs through NOH elimination of a nitrosammonium ion (R3N-N= O+). All three pathways are linked through the reversible homolysis of R3N-N=O+ to NO and a radical cation.