Abstract
Regularities of electrochemical carboxylation of carbon tetrachloride in conditions of galvanostatic diaphragmless electrolysis with a soluble zinc anode are studied. It is established that the generation of the CCl 3 − anion at the cathode is accompanied by the discharge of salts of Zn2+, with the deposition of Zn0 at the surface. The interaction between and CCl 3 − and CO2 in experimental conditions leads to the formation of zinc trichloromethylacetate, which proves to be very unstable in the dimethylformamide environment and undergoes fragmentation with the CO2 evolution. It is found that this process competes with currentless reduction of trichloromethylacetate under the action of Zn0 deposited on the cathode surface. As a result, corresponding dichloromethylacetate with a small yield of ≤5.5% forms as the sole product of electrolysis.
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