N-Nitration and C-Nitration by the Nitronium Ion

Abstract

AROMATIC C-nitration through attack by the nitronium ion was kinetically established by the work of Benford and Ingold¹, and of Hughes, Ingold and Reed². The central point in the evidence was the observation of zeroth-order kinetics in the nitration of suitably reactive aromatic compounds, for example, of toluene, by a constant excess of nitric acid, in organic solvents such as nitromethane or acetic acid. All those aromatic compounds which are sufficiently reactive to take up the nitronium ion as fast as it is formed from nitric acid obey this law, and, for the same medium and temperature, can be observed to become nitrated at an identical rate, which is simply the rate of formation of the nitronium ion.