Selective oxidations by nitrosating agents

The reactivity of a nitrosating agent (N2O3) on oxidations of alcohols and of acetophenone were tested. Active electrophylic surface nitrosonium ions (NO+) was detected on H2SO4/SiO2 catalysts by Raman spectroscopy, suggesting a surface ionic mechanism of oxidation. Alcohols are selectively oxidized to ketones and aldehydes in high yield, at 25 °C in 1,2-dichlorethane and using sulfonated styrene divinyl benzene resins as catalysts. Under the same reaction conditions, acetophenone is selectively oxidized to benzoyl cyanide in high yield and selectivity. The comparison with oxidation carried out in aqueous solution and the reactivity of the intermediates isolated in such system gives new insight on the mechanism of the heterogeneous reactions.