Chemiluminescence in the Reaction of a Sulfurane with Alkyl Hydroperoxides

Article abstract of DOI:10.1021/ja00530a035

The reaction of Martin's sulfurane 1 with tert-butyl hydroperoxide, in the presence of 9,10-dibromoanthracene, emits light in two stages.The early stage, beginning on warming to about -40 deg C, coincides with the formation of olefin, and is intensified by degassing and quenched by oxygen or by organic sulfides.The later stage, seen on warming from -20 to -10 deg C, occurs during the formation of acetone from the hydroperoxide; this luminescence is eliminated by degassing and quenched by 2,6-di-tert-butyl-p-cresol and organic sulfides.Similar phenomena are observed with cumyl hydroperoxide.Relevant observations are reported on the NMR shifts produced in alcohol proton signals by diphenyl sulphoxide and dimethyl sulfoxide and on the CIDNP signals occurring during the reaction.Some conclusions are drawn concerning the mechanism of the luminescence.