PHOTOLYSIS OF ALKYL 4-NITROBENZENESULFENATES - A NEW AND VERSATILE METHOD FOR THE GENERATION OF FREE-RADICALS

: The irradiation of alkyl 4-nitrobenzene-sulfenates with &300-nm wavelength light in benzene solution results in the homolytic cleavage of the O-S bond. The tertiary alkoxy radicals thus formed undergo 0 scission to produce carbon-centered free radicals in essentially quantitative yields which react with the arylthiyl radical to produce the alkyl aryl sulfide or dimerize. Primary and secondary alkoxy radicals undergo competitive dispro- portionation resulting in lower yields of the sulfide product. © 1990, American Chemical Society. All rights reserved.