Free Radical Reactions in the Electrolysis of Organic Compounds

Томилов, А. П.; Fioshin, M. Ya.

doi:10.1070/rc1963v032n01abeh001291

Cited by 22 publications

(8 citation statements)

References 104 publications

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“…The Kolbe reaction,1 in general, refers to anodic oxidation of a carboxylate structure with subsequent decarboxylation and coupling to yield a hydrocarbon or a substituted derivative corresponding to the alkyl function in the carboxylate reactant. The best known example is the reaction of acetate which may be represented in terms of the over-all process as 2CH3COO-->-C2H6 + 2C02 + 2e Many variations of this reaction involving substituted carboxylate structures have been reported, and the general phenomenology (1,13,48,56,88,109,150,152,158,160,168,169,174) of this reaction, based on mainly empirical approaches, has been well established from the point of view of synthetic organic chemistry. The production of hydrocarbons from mixtures of aliphatic carboxylates was performed by Wurtz.…”

Section: General Introductionmentioning

confidence: 99%

Electrode Kinetic Aspects of the Kolbe Reaction

Vijh¹,

Conway²

1967

Chem. Rev.

279

169

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Section: General Introductionmentioning

confidence: 99%

Electrode Kinetic Aspects of the Kolbe Reaction

Vijh¹,

Conway²

1967

Chem. Rev.

279

169

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“…The well-known net reaction that resembles the Kolbe electrolysis [ 22 , 23 ] is given in Figure 4 . For neutral alanine, we observed a very similar reaction ( Figure 5 ).…”

Section: Resultsmentioning

confidence: 99%

Ab-Initio Molecular Dynamics Simulation of Condensed-Phase Reactivity: The Electrolysis of Amino Acids and Peptides

2020

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Electrolysis is a potential candidate for a quick method of wastewater cleansing. However, it is necessary to know what compounds might be formed from bioorganic matter. We want to know if there are toxic intermediates and if it is possible to influence the product formation by the variation in initial conditions. In the present study, we use Car–Parrinello molecular dynamics to simulate the fastest reaction steps under such circumstances. We investigate the behavior of amino acids and peptides under anodic conditions. Such highly reactive situations lead to chemical reactions within picoseconds, and we can model the reaction mechanisms in full detail. The role of the electric current is to discharge charged species and, hence, to produce radicals from ions. This leads to ultra-fast radical reactions in a bulk environment, which can also be seen as redox reactions as the oxidation states change. In the case of amino acids, the educts can be zwitterionic, so we also observe complex acid–base chemistry. Hence, we obtain the full spectrum of condensed-phase chemistry.

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“…In the light of this we studied the effect of the nature of the solvent on the electrochemical activation of fluorine-containing imines (1) and (2) and their carboxylation. The polar aprotic solvents DMF, CH 3 CN, MP, and DMSO most often used for electrochemical carboxylation [10,11] and the less polar THF were chosen as solvents.…”

Section: Effect Of the Nature Of The Solvent On The Electrochemical Amentioning

confidence: 99%

Effect of the nature of the solvent and the supporting electrolyte on the electrochemically activated insertion of CO2 into fluorine-containing aromatic imines with the production of amino acids

et al. 2010

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CO 2 was studied for the case of pand m-fluorobenzylideneaniline. It was shown that factors promoting the formation of intimate ion pairs between the radical-anions of the imines -the initial products of the processes in the electrochemical activation of the imines -and the cations of the supporting electrolyte (decrease of the polarity of the medium and decrease of the radius of the cation in the supporting electrolyte) significantly reduce the effectiveness of electrochemical carboxylation right down to its complete cessation. Key words: electrochemical reduction and carboxylation, fluorine-containing aromatic imines and amino acids, carbon dioxide.Earlier we demonstrated the possibility of producing a series of fluorine-containing amino acids [1] by the electrochemically activated insertion of carbon dioxide into fluorine-containing imines and studied the effect of the electronic structure of the imines on the processes of their electrochemical activation [2] and the yields of the respective amino acids [1,2]. Here it was established that the key intermediates in the electrochemical carboxylation of fluorine-containing imines are their radical-anions, the reactivity of which can largely determine one or the other reaction paths of the process and the yields of the amino acids. As known [3][4][5], the effectiveness of the electrochemical generation of radical-anions and their reactivity can depend substantially not only on the electronic structure of the electrochemically activated substrate but also on many other factors: the nature of the solvent, the supporting electrolyte, temperature, etc. In view of this in the present work we studied the effect of the nature of the solvent and the supporting electrolyte on the electrochemical activation of fluorine-containing imines and their carboxylation by CO 2 with the formation of the corresponding fluorine-containing amino acids for the case of paraand meta-fluorobenzylideneanilines in order to optimize the conditions for the realization of these new processes. The choice of the fluorobenzylideneanilines as subjects for investigation was governed by the fact that among the fluorine-containing imines that we had studied [2] these compounds give fairly high yields of fluorine-containing amino acids during electrochemical carboxylation and their radical-anions are relatively stable.8 0040-5760/10/4601-0008

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Free Radical Reactions in the Electrolysis of Organic Compounds

Cited by 22 publications

References 104 publications

Electrode Kinetic Aspects of the Kolbe Reaction

Electrode Kinetic Aspects of the Kolbe Reaction

Ab-Initio Molecular Dynamics Simulation of Condensed-Phase Reactivity: The Electrolysis of Amino Acids and Peptides

Effect of the nature of the solvent and the supporting electrolyte on the electrochemically activated insertion of CO2 into fluorine-containing aromatic imines with the production of amino acids

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