Oxygenation by Superoxide Ion of CCl4, FCCl3, HCCl3, p,p'-DDT, and Related Trichloromethyl Substrates (RCCl3) in Aprotic Solvents

Article abstract of DOI:10.1021/ja00364a039

In dimethylformamide (DMF) superoxide ion (O2^-) oxygenates compounds with the trichloromethyl group: CCl4, HCCl3, and FCCl3 yield bicarbonate ion; PhCCl3 yields a mixture of PhC(O)OO^- and PhC(O)O^-; CF3CCl3 and HOCH2CCl3 give their carboxylate anions, RC(O)O^-; and p,p'-DDT yields its dechlorinated product, DDE, which in turn reacts with O2^- to give (p-ClPh)2C=O.Alkyl trichloromethyl compounds are unreactive within a 10-min reaction time at millimolar concentrations.The relative rates of reaction have been measured by the rotated ring-disc voltammetric method.On the basis of the relationship between the relative reaction rates and the electrophilic character of the substrates, as measured by the peak reduction potentials (E_p), the initial step is believed to be an electron transfer from the nucleophile to the electrophilic trichloromethyl group (a nucleophilic attack on chlorine with a concerted reductive displacement of Cl^- and formation of RCCl2OO*).