Organochalcogenyl Azides and Nitrenes

Sulfinyl azides have higher thermal stability than their divalent counterparts. For example, benzenesulfmyl azides ArS(0)N3 (Ar = Ph, 4-MeCelFt, 4-NO2C6H4), which are obtained by the metathetical reaction of the sulfinyl chloride and sodium azide in acetonitrile, can be stored in the solid state at low temperatures.  

Tribenzenesulfenamide (PhS)3N is obtained as a pale yellow solid by the treatment of the sodium salt of dibenzenesulfenamide, generated in situ, with acetic anhydride (Eq. 10.15). The perfluorinated analogue (C6F5S)3N is prepared by the reaction of (C6F5S)2NH and CeFsSCl in diethyl ether. 

PhSSPh and N2 via the intermediate formation of the purple radical [(PhSlaN], which is readily detected by its five-line (1 2 3 2 1) EPR spectrum. This radical is also generated by the oxidation of (PhSfaNH with lead dioxide.  

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