Hydrophobic vitamin B12. Part 19: Electroorganic reaction of DDT mediated by hydrophobic vitamin B12

Abstract

The controlled-potential electrolysis of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) was carried out at −1.4 V vs. Ag–AgCl in the presence of a hydrophobic vitamin B₁₂, heptamethyl cobyrinate perchlorate. DDT was dechlorinated to form 1,1-bis(4-chlorophenyl)-2,2-dichloroethane (DDD), 1,1-bis(4-chlorophenyl)-2,2-dichloroethylene (DDE), 1-chloro-2,2-bis(4-chlorophenyl)ethylene (DDMU) and 1,1,4,4-tetrakis(4-chlorophenyl)-2,3-dichloro-2-butene (TTDB) (E/Z), and quantitative recovery of the catalyst after the electrolysis was confirmed by electronic spectroscopy. A photo-sensitive intermediate having a cobalt–carbon bond formed during the electrolysis was characterized by electronic spectroscopy. A mechanism for the formation of various dechlorinated products was investigated by using deuterium solvents and various spectroscopic measurements such as UV-VIS and the EPR spin-trapping technique.