Kinetics and mechanism of the reaction of substituted benzyl chlorides with copper in dimethylformamide

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The reaction of copper metal with various substituted benzyl chlorides in dimethylformamide was studied. The kinetic and thermodynamic parameters of the reaction was clarified. Hammett plots of log(k/k0) vs the substituent constant σ gave a good correlation (ρ = 0.43, Sρ = 0.05, r = 0.960). The structure of the organic group has little effect on the rate of reaction of substituted benzyl chlorides with copper. In the absence of atmospheric oxygen, the oxidative dissolution of copper proceeded via a single‐electron transfer mechanism with formation of 1,2‐diphenylethanes and copper(I) complexes. The stereochemistry and intermediate compound were also studied. The reaction mechanism is discussed.