Phenylenediamines anodic oxidation

The anodic oxidation of phenylenediamines parallels that of aminophenols (see Sec. III.A.l) and has been reviewed by Adams [108]. If unsubstituted at the nitrogens, the two-electron oxidation leads to the quinone dimine. This compound either undergoes hydrolysis to the quinone inline and benzoquinone, or a 1,4-addition of a nucleophile, for example, the parent phenylenediamine itself, to the quinoidal systems occurs. Further oxidation of the products may take place. In acetonitrile, the one-electron oxidation to the cation radical predominates [109]. Under these conditions,/7-phenylenediamine also leads to 1,4-coupling products [110,111]. A-Substituted phenylenediamines are forming more stable cation radicals. For example, tetrakis(/7-bromophenyl)/7-phenylenediamine ( °= 0.91V vs. NHE) and tetrakis(2,4-dibromophenyl)-/7-phenylenediamine E° = 0.94 V vs. NHE) in acetonitrile even show reversible behavior for the second oxidation step to the dication [78]. 

Anodic oxidation of substituted hydrazones may induce ring closure. Oxidation of /7flrfl-substituted phenylhydrazones of 2-oxophenylacetonitrile yields derivatives of 1-phenyl-3-cyano-l/7-indazoles [73] p-nitrobenzylidene-o-phenylenediamine is oxidized in MeCN-LiC104 to 2-(pnitrophenyl)benzimidazole [74], chalchone phenylhydrazone in MeCN-C5H5N-LiC104 to 1,3,5-triphenylpyrazol [74], and benzylidene 2-pyridylhydra-zone (XXIV) to 3-phenyl-j -triazolo[4,3-a]pyridine (XXV) oxazoles and imidazoles may be prepared similarly [74] ... 

Platinum electrodes coated with PT and 3-methyU are claimed to work as sensor electrodes for A-phenyl-p-phenylenediamine the mechanism of this anodic oxidation reaction is discussed [214, 215]. 

Anodic conversion of aromatics proceeds in most cases by le-transfer to the anode to form a radical cation (34) (Scheme 9). Oxidation is facilitated by extension of the 7T-system ( 1/2 vs. Ag/Ag+ benzene 2.08 V, pyrene 0.86 V) and by electron donating substituents ( 1/2 vs. Ag/Ag+p-phenylenediamine —0.15 V). Oxidation potentials of polycyclic aromatics and substituted benzenes are collected in Ref [140-142]. 

The mechanism of the reaction that occurs at a platinum anode in CH3CN-Et4NC104 has been elucidated by showing that iV,N,AMriphenyl-o-phenylenediamine (50) is oxidized quantitatively at + 1.3 V versus SCE to give the dication of (49), which then can be reduced to 49 at —0.7 V versus SCE. Selection rules for the conversion of diphenylamines to dihydrophen-azines are given.109... 

Fig. 6.17. Cyclic voltammograms of o-phenylenediamine (101 M) oxidation for W03 thermal-treated (350°C) anodic films (b) and smooth platinum electrode (c) first sweep (curves 1) and repeated sweep (curves 2) scan rate was 80 mV/cm2. The left picture shows a schematic representation of the morphology of thermal-treated anodic W03 film tungsten support, highly defective oxide (including the continuous donor clusters), moderately doped oxide (non-shaded region), poly-o-phenylenediamine deposits.

The electrochemical properties of phenylenediamines, in particular of para-phcnylcnc-diamine (83), have been studied intensively. In aqueous media, the oxidation potentials of these compounds depend upon the pH value, since the amino group can be protonated. In the pH range of 2-6, the radical cation 831 can be generated anodically as demonstrated... 

The imine formed on hydrolysis yields o-phenylenediamine and the corresponding carbonyl compound, and, depending on the pH of the medium, can also undergo further chemical and electrochemical reactions. By this reduction of carbohydrate derivatives of quinoxaline, the corresponding deoxy saccharides would be formed. For 1,2-dihydro-2,3-dimethylquinoxaline in an alkaline medium, the decrease in the height of wave i2 and the appearance of an anodic wave, ia, with increasing pH value prove that only its protonated form is reduced to the corresponding quinoxaline derivative, whereas its nonprotonated form is capable of oxidation to the initial 2,3-dimethylquinoxaline, as shown in Scheme 13. 

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