ELECTROCHEMISTRY AND ELECTRON SPIN RESONANCE STUDIES OF THE PYRIDINE ALDOXIMES AND DERIVATIVES. I. POLAROGRAPHY OF THE PAM ISOMERS.

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Abstract:

The 2, 3, and 4 positional isomers of pyridine aldoxime and 1-methyl pyridinium aldoxime 1-PAM in dimethyl formamide were examined polarographically. Studies included the effects of concentration, water, acid, and base. Calculations were made of reduction-potential, diffusion-current constant, electrons transferred, shape, slope, and diffusion coefficient. Analysis of the electrochemical-reduction pathways suggested a number of one-electron changes and free-radical intermediates. The use of the electrochemical method of free-radical generation as an adjunct to electron spin-resonance spectroscopy was demonstrated in this study series. The use of the polarographic technique for qualitative and quantitative analyses was established. Electrochemical reduction of each of the above isomers proceeded in at least three steps. The 3 and 4 isomers appeared to have similar pathways, whereas the 2 isomers did not. Author

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