Rn. Loeppky et al., EVIDENCE FOR RADICAL CATIONS IN LINKED MECHANISMS OF N,N-DIALKYL AROMATIC AMINE NITRATION AND NITROSATIVE DEALKYLATION, Journal of the American Chemical Society, 120(21), 1998, pp. 5193-5202
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.