0000000000103810
AUTHOR
Carmelo Belfiore
showing 14 related works from this author
INFLUENCE OF THE EXPERIMENTAL SYSTEM AND OPTIMIZATION OF THE SELECTIVITY FOR THE ELECTROCARBOXYLATION OF CHLOROACETONITRILE TO CYANOACETIC ACID
2004
The electrocarboxylation of chloroacetonitrile (ClACN) to cyanoacetic acid in undivided cells equipped with sacrificial anodes was investigated both in a bench-scale electrochemical batch reactor and in a continuous batch recirculation reaction system equipped with a parallel-plate electrochemical cell. Selectivity and faradaic yields higher than 90% were obtained by working under anhydrous conditions with low halide concentrations and at more negative potentials. It was found that the instantaneous selectivity in the carboxylate compound depends mainly on the [CO 2 ]/[ClACN] ratio at high substrate concentration and is close to 100% for low ClACN concentration. These results were consisten…
Electrochemical reduction and carboxylation of halobenzophenones
2002
Abstract The electrochemical reduction of a series of halogenated benzophenones XC6H4COC6H4Y (1) was studied in aprotic solvents, in the absence and presence of CO2, by cyclic voltammetry (CV) and controlled-potential electrolysis. The mechanism of electroreduction in dimethylformamide (DMF) has been investigated in some detail. Most of the compounds undergo reductive carbonhalogen bond cleavage in the time window of CV. The radical anions derived from difluorobenzophenones (X=Y=4-F; X=2-F, Y=4-F) as well as from the 3-chloro derivative are quite stable with a cleavage rate constant (kc) of the order of 10−2 s−1 or less. With 4-chloro-, 2-chloro-, 4,4′-dichloro- and 2,4′-dichorobenzophen…
Direct electrochemical detosylation of tetratosylcyclen to cyclen with carbon cathodes
2005
The electrochemical detosylation of tetratosylcyclen to cyclen (1,4,7,10-tetraazacyclododecane) in aprotic solvents at a carbon cathode was investigated both in a bench-scale batch electrochemical reactor and in a continuous batch recirculation reaction system equipped with a parallel-plate electrochemical cell. Yields and faradaic efficiency in cyclen, respectively, of 80 and 55% were obtained in the bench-scale reactor working in acetonitrile. It was found that the faradaic efficiency in cyclen depends on the competition between the reduction of the tetratosylcyclen and parasitic processes as the reduction of the tetraalkylammonium cations present in the supporting electrolyte. We have ob…
An unexpected ring carboxylation in the electrocarboxylation of aromatic ketones
2006
The electrocarboxylation of various aromatic ketones, carried out in N-methyl-2-pyrrolidone (NMP) in a diaphragmless cell equipped with a carbon cathode and an aluminium sacrificial anode, yielded, among the products, the target hydroxy acids, the corresponding alcohols and pinacols and, quite surprisingly, detectable amounts of substituted benzoic acids and cycloexene carboxylic acids. These compounds arise from a never reported before electrocarboxylation on the aromatic ring, respectively, for substitution of an aromatic hydrogen and from an addition reaction. For example, the electrocarboxylation of acetophenone gave rise to the substituted benzoic acids in ortho, para and meta position…