Electrochemical Studies on the Reaction of Superoxide Ion with Halocarbons in Aprotic Media

The reactivity of superoxide ion($O{_2}^{-.}$) with halogenated substrates is investigated by cyclic voltammetry and rotated ring-disk electrode method in aprotic solvents. The more positive the reduction potential of the substituted nitrile, the more facile is nucleophilic displacement by $O{_2}^{-.}$. The reaction rates of halogenonitriles with $O{_2}^{-.}$ vary according to the leaving-group propensity of halide (Br>Cl>F). The relative reaction rates of other substituted nitriles are in the order of electron-withdrawing propensity of the substituent group (CN> $C(O)NH_2$ >Ph, $CH_2CN$). The reaction of $O{_2}^{-.}$ with dihalocarbons indicates that five-membered rings can be rapidly formed by the cyclization of substrate and $O{_2}^{-.}$, and the relative rates of cyclization depend on the number of methylenic carbons {$Br(CH_2)_nBr$, [n=1<2<3>4>5]}. Mechanisms are proposed for the reaction of $O{_2}^{-.}$ with halogenated substrates.