A fast radical chain mechanism in the polyfluoroalkoxylation of aromatics through NO2 group displacement. Mechanistic and theoretical studies
Tejero, I.; Huertas, I.; González-Lafont, A.; Lluch, J.é M.; Marquet, J.
Journal of Organic Chemistry 70(5): 1718-1727
2005
ISSN/ISBN: 0022-3263 PMID: 15730293 DOI: 10.1021/jo048354m
Accession: 048067587
Introduction of polyfluoroalkoxy and polyfluoroalkylthio substituents in aromatic rings can be achieved with mild conditions and short times thorough reaction of concentrated solutions of dinitrobenzenes in DMF with polyfluoro alcohols and polyfluoro thiols in moderate excess, in the presence of excess tetrabutylammonium fluoride as a base. Mechanistic studies suggest that under these conditions a fast radical chain mechanism operates. This mechanism is elicited by oxidation of a Meisenheimer complex and proceeds through a radical aromatic substitution with the polyfluoroalkoxy or the polyfluoroalkylthio radicals as key intermediates. At low concentrations, entrainment can be achieved with superoxide anion. A rationale for this effect is discussed. Answers to particular questions about the proposed mechanism are achieved through a theoretical study at the B3LYP/6-31+G(d,p) level. Specifically, the competition between the radical mechanism and the corresponding polar one (classical S(N)Ar reaction) is studied in that way, with the conclusion that the key steps of the radical mechanism in our reaction conditions (polar aprotic solvent) are at least as efficient as the ones of the polar one, thus justifying the observed kinetic advantage for the chain reaction in the conditions where an efficient initiation occurs.