Thermolysis of α-Azido Sulfides, Sulfoxides, and Sulfones: Dependence of Mechanism on Oxidation State of Sulfur

Article abstract of DOI:10.1021/ja00403a043

Thermolyses of α-azidobenzyl phenyl sulfide (1), sulfoxide (3), and sulfone (2) proceed at markedly different rates.Sulfone 2 requires the highest temperature (> 150 deg C), whereas sulfide 1 loses nitrogen at 120 deg C with neighboring group participation by the sulfur atom to produce N-benzylidenebenzenesulfenamide 4 in 75percent yield.Sulfoxide 3 readily decomposes at 70 deg C through a radical-pair intermediate, which gives rise to a CIDNP effect in the reaction products.Kinetic data are presented supporting the suggested reaction mechanisms.