36960-07-3Relevant articles and documents
Reactivity of α,α′-dichloroketones towards anions electrogenerated at carbonium and oxygen atoms. Electrochemically-induced Favorskii rearrangement. Part 2
Chiarotto, Isabella,Feroci, Marta,Giomini, Claudio,Inesi, Achille
, p. 167 - 175 (2007/10/03)
Electrolyses of solutions containing α,α′-dichloroketones 1a or 2a were carried out, on a mercury pool or glassy carbon cathode, at a potential sufficiently negative to allow two-electron cleavage of the C-Cl bond. The effects of the presence of carboxylic acids 3a,b, phenols 4a-f, or carbon acid 5 in the solutions were evaluated. Depending on the type of acidic substrate, it was possible to isolate from the cathodic solutions the Favorskii-rearrangement products 9m, 10m, 11 and 12, as well as dechlorinated ketones 1b and 2b and the addition products 7m and 8m. The conditions under which it was possible, by electrochemical means, to induce the Favorskii rearrangement between dichloroketones 1a and 2a and the acidic substrates are discussed. Evidence was gained by voltammetric analysis that the rates of formation of the Favorskii adducts 9a-f depend on the structures of the corresponding phenols 4a-f. By employing electrogenerated bases, it was possible to obtain α,β-unsaturated ketones at potentials less negative than required for the direct reduction of 1a and 2a. Elsevier.
