The study of the electrochemical oxidation mechanism of diphenylamine derivatives in dipolar aprotic solvents

Saber, T.M.H.; Farsang, G.; Ladányi, L.

doi:10.1016/0026-265x(72)90178-6

Cited by 17 publications

(11 citation statements)

References 15 publications

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“…This result is quite different from that in neutral and HClO 4 -acidic acetonitrile (MeCN). 5,14 The H 2 SO 4 /DMSO solution gives a quite different protonation equilibrium of ADPA and PQDI from that in HClO 4 / MeCN, resulting in different cyclic voltammograms. The current increase at potentials higher than 800 mV is due to the starting formation of an oxide layer on the platinum electrode in DMSO.…”

Section: Resultsmentioning

confidence: 99%

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Kinetics of the p-Aminodiphenylamine Radical in Organic Solution: An Electrochemical and Electron Spin Resonance Study

and

Dunsch

1996

J. Phys. Chem.

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In studying the reaction mechanism of anodic aniline oxidation the dimer p-aminodiphenylamine (ADPA) was found to be the main intermediate product in acidic solution. It is oxidized in both the free amine and the protonated form. The cyclic voltammograms have been simulated by taking into account an electrochemical reaction of both the protonated and the nonprotonated forms. Thus, it was also found that the ADPA concentration is determined by the protonation equilibrium. The oxidation product N-phenylquinone diimine (PQDI) undergoes a symproportionation reaction with ADPA forming the ADPA•+ cation radical. The equilibrium constant for this reaction of PQDI in dimethyl sulfoxide was determined and found to be independent of the concentration of the protons in solution. The ADPA•+ cation radical decay can be described by a rate equation based on a second-order reaction for the radical dimerization and a pre-equilibrium for the radical formation by symproportionation. The reaction mechanisms of the anodic oxidation of p-aminodiphenylamine and its chemical follow-up reactions are given.

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Section: Resultsmentioning

confidence: 99%

“…Their have been several studies on the anodic oxidation of ADPA itself − to follow both the mechanism of the oxidation and the formation of a polymer which is obviously different from polyaniline.…”

Section: Introductionmentioning

confidence: 99%

Kinetics of the p-Aminodiphenylamine Radical in Organic Solution: An Electrochemical and Electron Spin Resonance Study

and

Dunsch

1996

J. Phys. Chem.

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“…There is a vast array of literature surrounding the electrochemical oxidation of aniline in a variety of solvents, much of which stems from the fact that this process is known to yield polyaniline, a very commonly studied and commercially important conducting polymer, with applications in a range of technological fields, such as the development of rechargeable batteries, electronic and electrochromic devices, and pH sensor design. − The complexity of the anodic oxidation of aniline has provoked a number of investigations in which a range of substituents occupy various positions of the aromatic ring in order to probe mechanistic aspects of the electrodimerization and ultimately the polymerization which takes place. − …”

Section: Introductionmentioning

confidence: 99%

In Situ Electrochemical ESR and Voltammetric Studies on the Anodic Oxidation of para-Haloanilines in Acetonitrile

et al. 2005

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An in situ electrochemical electron spin resonance (ESR) study on the electro-oxidation of para-chloroaniline, para-bromoaniline, and para-iodoaniline dissolved in acetonitrile at gold electrodes is reported. ESR spectra obtained using a tubular flow cell reveal the presence of a paramagnetic dimer product derived from para-aminodiphenylamine, during oxidative electrolysis, suggesting the coupling of reactive electrogenerated radical cations with neutral parent haloaniline molecules. The ESR signal intensity behaves in a manner expected for a radical species reacting with second-order kinetics, suggesting the paramagnetic dimer is, itself, unstable. The theory describing the ESR signal intensity flow rate behavior for this reaction mechanism is developed for the tubular arrangement and used to extract mechanistic and kinetic data from the experimental results for the cases of para-chloroaniline and para-bromoaniline. Further mechanistic aspects, including proton and halide ion expulsion during dimerization, are explored voltammetrically and with the aid of digital simulations using Digisim. Comparison of the ESR signal and voltammetric measurements suggests that an additional mechanism operates which does not lead to paramagnetic products. Additionally, the in situ electrolysis of N,N-dimethyl-para-bromoaniline is reported to generate the stable radical cation of N,N,N',N'-tetramethylbenzidine, and a mechanism of electro-oxidation is, thus, proposed.

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“…Electrochemical studies of retinal, the aldehyde of vitamin A, have been numerous (20)(21)(22)(23). Recently, we showed that an optically transparent thin layer electrochemical cell is an ideal tool for examining the spectra of the reduction intermediates of retinal and for determining the reaction pathways of the retinal radical anion (23).…”

mentioning

confidence: 99%

The Electrochemical Activity Determination of Trypsin‐Like Enzymes: VI . The Electrochemical Oxidation of the Marker, p‐aminodiphenylamine in Aqueous Solutions

Nigretto

1981

J. Electrochem. Soc.

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The electrochemical oxidation of p-aminodiphenylamine was investigated in the 0.1 mmol concentration range and in H2804 aqueous solutions. Cyclic voltammetry with slow scan rates at the carbon paste electrode and controlled potential step electrolysis were the techniques followed. Results suggest that the initial oxidation stage produces p-quinodiimine via an ECE process. This two-electron oxidation product further undergoes addition reactions involving the depolarizer. The hydrolysis of the adduct is assumed to yield a quinoidal derivative, aniline and ammonia, as deduced from step coulometry and visible spectroscopy experiments. The sequence of the decomposition which is proposed integrates most of the results available elsewhere. No polymerization of the starting material occurs in the used working conditions. * Electrochemical Society Active Member.

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The study of the electrochemical oxidation mechanism of diphenylamine derivatives in dipolar aprotic solvents

Cited by 17 publications

References 15 publications

Kinetics of the p-Aminodiphenylamine Radical in Organic Solution: An Electrochemical and Electron Spin Resonance Study

Kinetics of the p-Aminodiphenylamine Radical in Organic Solution: An Electrochemical and Electron Spin Resonance Study

In Situ Electrochemical ESR and Voltammetric Studies on the Anodic Oxidation of para-Haloanilines in Acetonitrile

The Electrochemical Activity Determination of Trypsin‐Like Enzymes: VI . The Electrochemical Oxidation of the Marker, p‐aminodiphenylamine in Aqueous Solutions

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