Electrochemical Behavior of 2 -Chlorocyclohexanone and Derived Imines

Abstract

Polarographic reduction of 2-chlorocyclohexanone results in a single pH-independent, diffusion-controlled, irreversible wave, which is due to:carbon-halogen bond fission. The mechanism probably involves formation of a carbanion which reacts rapidly with the solvent to form cyclohexanone. In ammonia buffer of high pH (high NH3 concentration) a second kinetic-controlled wave appears which is apparently largely due to reduction of the imine present in equilibrium with the 2-ketocyclohexanol formed by hydrolysis of the chloroketone; as the first wave due to the chloroketone decreases with time, the second wave increases.Under the conditions of macroscale electrolysis in solution of high ammonia concentration, as in a coulometric experiment, the reduction product of 2-chlorocyclohexanone, cyclohexanone, reacts with ammonia to give cyclohexanonimine, which is in turn reduced to cyclohexylamine. The hydrolysis product of 2-chlorocyclohexanone, 2-ketocyclohexanol, reacts similarly to form 2-iminocyclohexanol, which is presumably reduced to 2-aminocyclohexanol.In connection with the systematic investigation of the electrochemical behavior of halogenated organic compounds (1), 2:chlorocyclohexanone was studied as a typical cyclic haloketone. Its polarographic behavior was investigated from the viewpoints of (a) the relation of half-wave potential, E1/2 , and diffusion current, id, to pH, ionic

Polarographic Reduction of Epimeric α-Haloketosteroids and Their Vinylogs.

“…Very few studies have been made on the polarographic reduction of -halocarbonyl compounds since Winkel and Proske (17) first examined chloro-, bromo-, and iodoacetones in 1936. The work on alicyclic -halocarbonyls has been especially limited, being confined to -chlorocyclohexanone (5,13), achlorocyclopentanone (5,13), and abromocamphor (IS).…”