Nitroxide chemistry. Part X. Reactions of NN-bistrifluoromethyl-amino-oxyl with alkyltrihalogenosilanes and vinylsilanes; rearrangement of (1 -NN-bistrifluoromethylamino-oxyalkyl)silanes

Abstract

The reactions of the oxyl (CF3)2N·O˙ with various alkyltrichlorosilanes and alkyltrifluorosilanes show that the α position of the alkyl group is deactivated towards radical attack and the effect is more pronounced with alkyltrichlorosilanes. A novel rearrangement of type N·O·C·Si→N·C·O·Si occurs on heating (1-NN-bistrifluoromethyl-amino-oxyalkyl)silanes, and the ease of rearrangement is in the order (CF3)2N·O·CR2·SiMe3 > (CF3)2N·O·CHR·SiMe3 > (CF3)2N·O·CR2SiCl3 > (CF3)2N·O·CHR·SiCl3. On further heating the rearranged silane (CF3)2N·CMe2·O·SiCl3 eliminates NN-bistrifluoromethylamine to give quantitatively the vinyl compound CH2:CMe·O·SiCl3.