Synthesis of Nitrosobenzene Derivatives via Nitrosodesilylation Reaction

The electrophilic ipso-substitution of trimethylsilyl-substituted benzene derivatives into nitrosobenzene derivatives is reported. The optimization of the reaction conditions was performed for moderately electron-deficient, electron-rich, and sterically hindered starting materials by varying reaction time, temperature, and equivalents of NOBF₄. Also, a stable intermediate of the nitrosation reaction could be characterized by ¹⁹F NMR which can be assigned to a NO⁺ adduct with the nitrosobenzene derivative. This complex decomposes upon aqueous workup and liberates the desired nitrosobenzene derivative.