The Reaction of Anthracene with Nitrogen Dioxide Revisited

Article abstract of DOI:10.1021/jo00301a022

The primary products of the reaction of anthracene (AN) with nitrogen dioxide are cis- and trans-9,10-dinitro-9,10-dihydroanthracene, identified by NMR and single-crystal X-ray analysis.The chemical literature contains conflicting product analyses for this reaction, and the discrepancies are rationalized in terms of the thermal and chemical lability of these primary products.These products are rationalized in terms of a radical reaction of AN with NO2, rather than an electrophilic reaction mechanism.Analysis of the reaction kinetics reveal the formation of an intermediate, apparently of the charge-transfer type, between AN and one molecule of nitrogen dioxide.This intermediate precedes the formation of the 9-nitro-9,10-dihydroanthryl radical that readily couples with a molecule of nitrogen dioxide to yield cis- and trans-9,10-dihydroanthracene in a 1:1 ratio.