Decomposition of m-Nitrobenzenesulf onyl Peroxide in Several Solvents

Publisher Website
Google Scholar
Abstract
Rates of decomposition of m-nitrobenzenesulfonyl peroxide in chloroform, nitrobenzene, chlorobenzene, and benzene were determined, and activation parameters were calculated. Products of decomposition in nitrobenzene were m-nitrophenyl m-nitrobenzenesulfonate and m-nitrobenzenesulfonic acid, whereas those in chloroform were m-nitrobenzenesulfonic acid, hexachloroethane, and phosgene (when air is present). Activation parameters and reaction products indicate that the reaction in chloroform involves homolytic cleavage of the O–O bond, whereas that in nitrobenzene involves electrophilic attack of the peroxide on aromatic nuclei. When sulfonyl-18O labeled m-nitrobenzenesulfonyl peroxide was decomposed in benzene, about 35–36% of the label was found in the phenolic oxygen of m-nitrophenyl m-nitrobenzenesulfonate. This finding could be accounted for by a mechanism which involves a loose π-complex prior to the formation of a σ-complex.

This publication has 3 references indexed in Scilit: