Decomposition of <I>m</I>-Nitrobenzenesulf onyl Peroxide in Several Solvents
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概要
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Rates of decomposition of <I>m</I>-nitrobenzenesulfonyl peroxide in chloroform, nitrobenzene, chlorobenzene, and benzene were determined, and activation parameters were calculated. Products of decomposition in nitrobenzene were <I>m</I>-nitrophenyl <I>m</I>-nitrobenzenesulfonate and <I>m</I>-nitrobenzenesulfonic acid, whereas those in chloroform were <I>m</I>-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-<SUP>18</SUP>O labeled <I>m</I>-nitrobenzenesulfonyl peroxide was decomposed in benzene, about 35–36% of the label was found in the phenolic oxygen of <I>m</I>-nitrophenyl <I>m</I>-nitrobenzenesulfonate. This finding could be accounted for by a mechanism which involves a loose π-complex prior to the formation of a σ-complex.
- 公益社団法人 日本化学会の論文