Reactions of perfluoroaromatic compounds with ethereal solutions of methylmagnesium iodide in the presence of silver(I) and copper(I) salts

Article abstract of DOI:10.1016/S0022-1139(00)82604-4

The reactions of hexafluorobenzene, octafluorotoluene, decafluorodiphenyl, and octafluoronaphthalene with ethereal solutions of methylmagnesium iodide in the presence of AgCl or CuI gave the products of the methylation and 1-ethoxy-ethylation of the perfluorinated substrates, whose formation has been suggested to occur with participation of free radicals. Substitution of fluorine atoms by the 1-ethoxyethyl radicals in C6F5CF3 and C6F5C6F5 proceeds with predominant para-orientation; in C10F8, 1- and 2-orientations take place to an equal extent, whereas the methyl radicals attack mainly the 1-position of octafluoronaphthalene and show a low selectivity in the reaction with octafluorotoluene.