Direct electrochemical detosylation of tetratosylcyclen to cyclen with carbon cathodes

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 observed that the nature of the anolyte and catholyte and the concentrations of the substrate, the supporting electrolyte and the proton donor species dramatically influence the performances of the process.