(The) synthesis of α-chlorosulfoxides with sulfuryl chloride nitrate & deamination of aromatic amines with benzene sulfonyl nitrite

Abstract

The reaction of sulfuryl chloride with silver- or potassium nitrate affored sulfuryl chloride nitrate intermediate together with quantitative precipitation of silver- or potassium chloride in anhydrous acetonitrile. Though sulfuryl chloride nitrate has not been isolated, it was found to be a new oxidative chlorinating agent: various sulfides reacted readily with sulfuryl chloride nitrate to give the corresponding $\alpha$ -chlorosulfoxides under mild conditions in high yields. Benzene sulfonic acid was found to react with dinitrogen tetroxide at $-40\,^\circ\!C$ to form a new nitrosating agent, benzene sulfonyl nitrite, which is stable enough to be used for nitrosation at low temperature. Aromatic amines reacted with benzene sulfonyl nitrite to give the corresponding deaminated products in high yields. The deamination reaction were carried out by benzene sulfonyl nitrite generated in situ from the benzene sulfonic acid and dinitrogen tetroxide at $-40\,^\circ\!C$ in the presence of catalytic amount of copper (II) chloride. Formation of benzene sulfonyl nitrite was confirmed by comparring it``s UV spectra with that from dinitrogen tetroxide at $-20\,^\circ\!C$.