ABSTRACT
Of all aromatic amines, aniline and its derivatives have been most extensively studied electrochemically for many years. The important aim of all those studies was to explain the mechanism of formation of a number of products of this complex oxidation process performed under different electrolysis conditions and using reactants with various substituents. A lot of investigators have focused their interest on understanding the early stages of electrode reactions that yield polyanilines giving rise to many important applications. In view of these, the main part of this chapter is devoted to fundamental results concerning the mechanisms of anodic processes of unsubstituted aniline as well as N-substituted and C-substituted anilines. For the last two groups, monosubstituted anilines in para-, meta-, and ortho-positions are considered šrst, followed by the discussion of di-and tri-substituted anilines. A brief review of the electrochemical reactions of other aromatic amines including polyaminobenzenes follows, and the electrode behavior of azo and azoxy compounds, diazonium salts, as well as aromatic triazenes is reported at the end. In this chapter, only the main routes of the electrode processes and the most important products are considered on the basis of some examples, and only references to the selected examples are cited. A more comprehensive discussion and references to investigations of a number of particular compounds can be found in recent monographic chapters dealing with the electrochemistry of anilines [1] and azo compounds [2]. In earlier monographs, the half-wave and cyclic voltammetric (CV) peak potentials as well as products of electrode processes performed under different conditions are collected in tables for many aniline, diphenylamine, triphenylamine, and phenylenediamine derivatives [3], as well as for azo, diazo, and azoxy compounds [4].
