Electrosyntheses based on reactions of addition of electrochemically generated radicals to ethylene and its derivatives—II. Mechanism of the reaction

Vassiliev, Yu.B.; Bagotzky, V.S.; Kovsman, E. P.; Гринберг, В. А.; Kanevsky, L.S.; Polishchyuk, V.R.

doi:10.1016/0013-4686(82)80217-x

Cited by 12 publications

(6 citation statements)

References 7 publications

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“…It is of interest that a more normal vaue of @ is actually observed for the acetate Kolbe reaction in completely anhydrous solution (18). Recently, the results of several studies of the Kolbe electrosynthesis under a variety of conditions have been attributed to the surface adsorption of radicals (37)(38)(39).…”

Section: Ch2(nh2)coo(m) + C 0 2 + Nh2ch: + Ementioning

confidence: 94%

Surface electrochemistry of the oxidation of glycine at Pt

Marangoni¹,

Smith²,

Roscoe³

1989

Can. J. Chem.

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The electrochemical oxidation of glycine at a Pt electrode was investigated in aqueous solutions at pH 1 and 13 using steady-state current–potential measurements, cyclic voltammetry, and open circuit potential decay. The capacitance behaviour and the high Tafel slopes suggest the production of free radicals at the surface of the electrode accompanied by a second reaction involving loss of CO2 which is the rate determining step. In the electro-oxidation of glycine, it appears that the adsorbed intermediate species is either hydrolyzed anodically to formaldehyde and ammonia, or is oxidized to a carbonium ion which is subsequently hydrolyzed to formaldehyde and ammonia in solution. This behaviour differs from the dimerization process typical of the radical reactions associated with the Kolbe mechanism. Keywords: glycine, amino acid, electrochemical oxidation, surface electrochemistry, Kolbe mechanism.

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Section: Ch2(nh2)coo(m) + C 0 2 + Nh2ch: + Ementioning

confidence: 94%

Surface electrochemistry of the oxidation of glycine at Pt

Marangoni¹,

Smith²,

Roscoe³

1989

Can. J. Chem.

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“…employed radicals generated from Kolbe electrolysis of carboxylic acids for radical addition to the double bond of ethyl acrylate, methyl vinyl ketone and acrylonitrile with an iron‐based mediator [45] . However, the highly reactive nature of intermediate radicals limited the selectivity to the products of interest, due to the undesired side reactions such as radical self‐coupling, radical‐initiated polymerization or oligomerization, and the reaction of radicals with solvents [39–45] . These studies typically employed high potentials or high current densities that lead to high radical fluxes.…”

Section: Introductionmentioning

confidence: 99%

“…Vassiliev et al. explored the co‐electrolysis of acetic acid and monomethyl adipate with ethylene and butadiene under high pressure [39,40] . Goldschmidt et al.…”

Section: Introductionmentioning

confidence: 99%

“…Previous studies have used carboxylic acids as substrates to electrochemically produce alkenes, [33] ethers, [34] cyclic hydrocarbons, [35] lactones, [36] anhydrides, [37] and amides. [38] Radical addition to alkenes is particularly interesting, [39][40][41][42][43][44][45] as it enables CÀ C coupling that results in asymmetrical products (Scheme 1a). Vassiliev et al explored the co-electrolysis of acetic acid and monomethyl adipate with ethylene and butadiene under high pressure.…”

Section: Introductionmentioning

confidence: 99%

“…Vassiliev et al explored the co-electrolysis of acetic acid and monomethyl adipate with ethylene and butadiene under high pressure. [39,40] Goldschmidt et al performed electrolysis of anhydrous acetic acid with styrene and observed mostly additive dimers. [41] Schaefer et al studied electrolysis of various carboxylic acids in the presence of alkenes.…”

Section: Introductionmentioning

confidence: 99%

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Anodically‐Generated Alkyl Radicals Derived from Carboxylic Acids as Reactive Intermediates for Addition to Alkenes

Ding

Orazov

2023

ChemElectroChem

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Electrochemically driven CÀ C coupling has the potential to reduce the cost and environmental impact of some organic syntheses currently accomplished through thermochemical methods. Here, we use electrochemical oxidation of carboxylic acids as a source of reactive carbon-centered radicals that enable radical addition to alkenes in the anode boundary layer. We demonstrate an optimization of reaction conditions to suppress the thermodynamically favored, but synthetically undesirable radical self-coupling in favor of radical addition to styrene. In methanol solvent, 88 % selectivity and 72 % Faradaic efficiency for targeted functionalized benzenes are achieved. For low current densities, iridium anodes outperform platinum, gold, palladium, and glassy carbon anodes. With constant potential or constant current electrolyses, the deposition of organic by-products on the catalyst surface leads to anode passivation. We show that periodic cathodic current pulses effectively regenerate the catalyst. Lastly, we confirm the role of free radicals in the reaction mechanism with a radical trap.

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Anodic Reactions

Kyriacou¹

1994

Modern Electroorganic Chemistry

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Electrosyntheses based on reactions of addition of electrochemically generated radicals to ethylene and its derivatives—II. Mechanism of the reaction

Cited by 12 publications

References 7 publications

Surface electrochemistry of the oxidation of glycine at Pt

Surface electrochemistry of the oxidation of glycine at Pt

Anodically‐Generated Alkyl Radicals Derived from Carboxylic Acids as Reactive Intermediates for Addition to Alkenes

Anodic Reactions

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