Publication Date

April 2017


Stewart Novick, Albert Fry




English (United States)


Alkenes, particularly substituted stilbenes, have long been desirable organic substrates for functionalization via anodic oxidation in the presence of nucleophiles. Though the oxidation potentials of such alkenes were relatively low, addition of electrocatalysts described by Steckhan et al proved necessary for selectively oxidizing substrate. However, the possible electrolytic decomposition of triphenyl-based electrocatalysts is demonstrated in the synthesis and electrolyses of various triarylamines. These reactions were accomplished by mixing triarylamine starting materials with nitrating agents in the presence of a weak acid and the washed products were analyzed via Gas Chromatography and Mass Spectrometry, X-ray crystallography, as well as Nuclear Magnetic Resonance Spectroscopy. The desired nitrated electrocatalysts that exhibited appreciably high oxidation potentials, on the order of 1.28 V versus reference, appeared to be quite susceptible to nucleophilic aromatic substitution by trace water in electrolyte solution. Intramolecular ring closure steadily followed via an ECE mechanism, forming N-phenylphenoxazine derivatives. Although the triarylamines were modified following previously described principles of tuning stability and generating high oxidation potentials by attaching various electron-withdrawing substituents, even the most promising electrocatalyst decomposed into a phenoxazine-based product.



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