Abstract: Thermolyses of a-azidobenzyl phenyl sulfide (l), sulfoxide (3), and sulfone (2) proceed at markedly different rates. Sulfone 2 requires the highest temperature (> 150" C), whereas sulfide 1 loses nitrogen at 120 OC with neighboring group participation by the sulfur atom to produce N-benzylidenebenzenesulfenamide 4 in 75% yield. Sulfoxide 3 readily decomposes at 70 OC through a radical-pair intermediate, which gives rise to a ...
