Abstract
Polarographic behavior of the methyloximes of testosterone, pregnenolone, estrone, isoandrosterone, and related ketosteroids was examined. Of these compounds, testosterone methyloxime showed two reduction waves, where the half-wave potentials were linearly dependent on pH. With respect to the reduction process of this compound, a mechanism involving two two-electron reductions has been proposed from the result of controlled potential electrolysis and of pH effect on the rate-determining step (Chart 1). The nonconjugated ketosteroid methyloximes also exhibited a reduction wave in acid solution. The half-wave potential and current constant measured at pH 1.00 are collected in Table IV. In addition, the nature of the polarographic wave characteristic to these compounds has been described.