Electrocarboxylation of Chlorinated Aromatic Compounds

Abstract

Chorinated benzenes (1, 4), biphenyls (6, 9), dibenzofurans (10, 15, 17, 18), 2-chlorodibenzo[1,4]dioxine (24) and 1-chloronaphthalene (26) as well as dibenzofuran (12) and naphthalene (27) themselves were transformed into carboxylic acids by galvanostatic electroreduction in the presence of carbon dioxide ("electrocarboxylation"). Dry DMF was used as solvent, zinc or stainless steel as cathode and magnesium as a sacrificial anode in an undivided cell. Hydrogenation of aromatic rings was not observed. However, reductive addition of two molecules of carbon dioxide to form dihydrodicarboxylic acids, e.g. 22 and 29, occurs in the dibenzofuran and naphthalene series.

Electrochemical activation of freons and their joint conversion with sulfur and carbon dioxides

“…Electrochemical carboxylation of various organic substrates has been the subject of a series of papers generally in particular in [8,9,[24][25][26][27]. Interest in this process most of all is that it occurs in a single step under mild conditions to produce a variety of carboxylic acids and/or their esters using carbon dioxide as an accessible and cheap reagent.…”

Electrocarboxylation and related radical coupling processes of aryl and benzyl halides in microemulsion

“…Further improvements in the electrocarboxylation processes employing redox mediators [3][4][5] and silver cathodes [6,7] have been reported. Poly halogenated aromatic compounds [8], iodo aromatic compounds [9] and aliphatic halides [10,11] also undergo facile electrocarboxylation. Al 3?…”

Translating Tactics from Direct CO2 Electroreduction to Electroorganic Coupling Reactions with CO2

“…[ 13 ] In contrast, in aprotic media, the product scope is limited to CO and oxalate. [ 14 ] As EC involves coupling of CO 2 with a large variety of precursors, by its nature, it is characterized by a much wider scope of possible products compared with CO 2 R. When CO 2 is coupled to organic halides, the range of EC products includes aliphatic, [ 15 ] benzylic, [ 16–18 ] aromatic, [ 19–22 ] and heteroaromatic [ 23 ] monocarboxylic acids. In these reactions, a new CCO 2 H bond is formed in place of the CHal (Hal = F, Cl, Br, and I) bond.…”