Oxidation reactions with new nitrosating reagents

Abstract

It was found that arenesulfonic acid reacted with dinitrogen teroxide at-40$^\circ$C in THF to form arenesulfonyl nitrites which show powerful nitrosating ability on the amino nitrogen. Rapid deamination of aromatic amines or heterocyclic amines to the deaminated products by benzenesulfonyl nitrite occurs in excellent yields. Formation of arenesulfonyl nitrites were observed by UV spectra at low temperature. New efficient methods for the syntheses of $\alpha$-chlorosulfoxides or sulfonyl chlorides using sulfuryl chloride and metal nitrate have been developed. Various sulfides reacted with sulfuryl chloride and metal nitrate to give the correponding $\alpha$-chlorosulfoxides in good yields. The oxidation and chlorination reactions may proceed by an intermediate of sulfuryl chloride nitrate. Various sulfonyl chloride were also obatined by the reaction of thiols with sulfuryl chloride in presence of metal nitrate in aprotic solvents such as $CH_3CN$ and DMF. It was found that trimethylsilyl nitrite generated from the reaction of chlorotrimethyl silane with silver nitrite at low temperature is a new nitrosating reagent ofr the synthesis of N-nitroso amides and $\alpha$-substituted-$\alpha$-diazoesters under neutral condition. Formation of trimethylsilyl nitrite was also observed by UV spectrum at low temperature. The reaction using trmethylsily nitrite are superior to the known methods in terms of the mild, neutral conditions and the high yields.