Electrocarboxylation of Dichlorobenzenes on a Silver Electrode in DMF

Abstract

Carbon dioxide (CO 2 ) is the largest contributor to the greenhouse effect, and fixing and using this greenhouse gas in a facile manner is crucial. This work investigates the electrocarboxylation of dichlorobenzenes with the atmospheric pressure of CO 2 in an undivided cell with an Ag cathode and an Mg sacrificial anode. The corresponding carboxylic acids and their derivatives, which are important industrial and fine chemicals, are obtained. To deeply understand this reaction, we investigate the influence of various reaction conditions, such as supporting electrolyte, current density, electric charge, and reaction temperature, on the electrocarboxylation yield by using 1,4-dichlorobenzene as the model compound. The electrochemical behavior of dichlorobenzenes is studied through cyclic voltammetry. The relation among the distinct electronic effects of dichlorobenzenes, the electrochemical characteristics of their reduction, and the distribution law of target products is also established.

Highly Efficient Electrocatalytic Carboxylation of 1-Phenylethyl Chloride at Cu Foam Cathode

“…In fact, lower yields were obtained at both low and high current densities compared with the result at 9 mA/cm 2 (87%, Table 1, entry 8). The results at low current densities 5 mA/cm 2 and 7 mA/cm 2 (73% and 77%, Table 1, entries 1, 6) can probably be ascribed to side reactions such as the reduction of CO2 to C1 or C2 compounds [33,34], while the results at high current densities 11 mA/cm 2 and 13 mA/cm 2 (78% and 75%, Table 1, entries 9, 10) can be ascribed to lower current efficiency with increased ohmic component. The highest yield of 2a was achieved with 9 mA/cm 2 current density and 2.5 F mol −1 charge of 1a (92%, Table 1, entry 13).…”

Comparative Study between Pristine Ag and Ag Foam for Electrochemical Synthesis of Syngas with Carbon Dioxide and Water

“…The exponential increase in anthropogenic carbon dioxide (CO 2 ) emissions to the Earth's atmosphere, has become one of the most urgent problems for the human society [1,2]. Many feasible methods for decreasing the concentration of CO 2 in the atmosphere have been carried out, such as CO 2 capture, utilization and storage [3][4][5][6][7][8][9].…”

Electrochemical CO2 Fixation to α-Methylbenzyl Bromide in Divided Cells with Nonsacrificial Anodes and Aqueous Anolytes

“…16 Consequently, at high negative potentials, the reduction of Mg 2+ to Mg 0 [E°= −2.38 V vs standard hydrogen electrode (SHE)] at the cathode could also facilitate the Grignard reagent formation 28 (Scheme 1, pathway III), in addition to enabling competing CO 2 electroreduction. 29 Other sacrificial anodes (e.g., Al and Zn) have similar reactivity: generated Zn 2+ or Al 3+ can be cathodically reduced to their metal forms, which, in addition to causing cathode passivation, 16 produce organometallic compounds by reacting with organic halides. 30,31 These organometallic compounds can react with CO 2 , producing corresponding carboxylic acids.…”