The Mechanism of Nitration of Phenol and 4-Methylphenol by Nitrogen Dioxide in Solution

Article abstract of DOI:10.1016/S0040-4039(00)73436-8

The quantitative formation of nitrophenols from phenol by reaction with nitrogen dioxide in solution involves stages, the first being the abstraction of a hydrogen atom from the hydroxyl group by NO2^. and the second the reaction of the phenoxy radical formed with NO2.The first stage is ratelimiting at high .>.In the case of 4-methylphenol a similar mechanism leads to both 4-methyl-4-nitrocyclohexa-2,5-dien-1-one and 4-methyl-6-nitrocyclohexa-2,4-dien-1-one intermediates and at high .> the apparent rate of the reaction can become the conversion of the latter intermediate into 4-methyl-2-nitrophenol.