FLUOROINDENES .11. RADICAL ROUTE FOR THE REACTION OF PERFLUORINATED 3-METHYLINDENE, 1-METHYLENEINDANE, AND 1-ETHYLIDENEINDANE WITH NITRIC-ACID

The reaction of N2O4, and also HNO3 purified from oxides of nitrogen, with perfluoro-3-methylindene and perfluoro-1-methyleneindane takes place at the multiple bond of these compounds and results, after hydrolysis, in mixtures, of similar composition, of the corresponding nitro-1-hydroxy and dinitro derivatives. In contrast, whereas perfluoroindene and HNO3 do not form perfluoro-1,2-dinitroindane, the latter is formed from N2O4. Furthermore, perfluoroindene reacts with HNO3 in acetic acid in the presence of CF3SO3H, but there is no reaction in its absence. From these results one can apparently assume that the reaction of perfluoro-3-methylindene and perfluoro-1-methyleneindene with HNO3 proceeds by a radical route, but that of perfluoroindene with HNO3 is electrophilic. © 1990 Plenum Publishing Corporation.