Octa, deca, and dodeca(4-nitrophenyl) cage silsesquioxanes via4-trimethylsilylphenyl derivatives

Abstract

Pure octa, deca, and dodeca(4-nitrophenyl) cage silsesquioxanes were obtained by regio-selective 4-nitration of octa, deca, and dodeca(4-trimethylsilylphenyl) cage silsesquioxanes via ipso-substitution of trimethylsilyl-phenyl bonds by fuming nitric acid. 3-Nitration of octa(4-methylphenyl)octasilesquioxane was also described. The starting octa(4-methyl-, 4-isopropyl- and 4-trimethylsilylphenyl)octasilsesquioxanes were selectively formed in 9–21% isolated yield in the presence of hydrochloric acid. Mixtures of octa, deca and dodecasilsesquioxanes, with decasilsesquioxane as the main component, were formed in the presence of tetrabutylammmonium fluoride as a catalyst. All the cage compounds could be separated mainly by crystallization.