Structure and Reactivity of Nitroso Oxides

Article abstract of DOI:10.1021/ja00011a035

Abstract: The presence of nitroso oxide intermediates has been studied in the photooxidation of phenyl azide. The hydroxylation of benzenes occurred and was accelerated by electron-donating groups. Sulfides were oxidized to sulfoxides, but the oxygenation and deoxygenation of sulfoxides proceeded concurrently; these reactions were facilitated by electron-donating substituents. Trapping of the intermediates by added nitrosobenzenes was most efficient, approaching 80% O transfer. The relative reactivity order (styrenes, PhN=O ? Ph₂S < Ph₂SO < PhH), substituent effects, and the stereochemistry of hydroxylation of C-H bonds characterized the electrophilic radical nature of nitroso oxides. An ¹⁸O-tracer study revealed that a unimolecular isomerization of nitroso oxides to nitro compounds proceeds competitively with the O transfers. The reactivity of XOO species is discussed on the basis of electronegativity of X.