Electro-organic reactions. Part II. Mechanism of the kolbe electrolysis of substituted phenylacetate ions

Coleman, James P.; Lines, Robert; Utley, James H. P.; Weedon, B. C. L.

doi:10.1039/p29740001064

Cited by 41 publications

(25 citation statements)

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“…29,[49][50][51][52] Contrary to the Kolbe dimerization reaction, lower current densities lead to the formation of carbenium ions and promote the Hofer-Moest or Non-Kolbe electrolysis. 29,53 The yields are further shifted to Non-Kolbe and Hofer-Moest products when using a carbon electrode. However, various studies reported that the surface shape and functionalization of the electrode have a crucial influence on the activity for Non-Kolbe reactions.…”

Section: Regina Palkovitsmentioning

confidence: 99%

(Non-)Kolbe electrolysis in biomass valorization – a discussion of potential applications

2020

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Section: Regina Palkovitsmentioning

confidence: 99%

(Non-)Kolbe electrolysis in biomass valorization – a discussion of potential applications

2020

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“…W.J. Koehl [34] has reported that electrolysis of butyric acid at carbon anode in aqueous solution gave propene (47%), cyclopropane (25%), and 12% of mixture of n-propyl and isopropyl butyrate (about 1:2 ratio). Moreover, the yield is only based on the products isolated from the reaction mixture.…”

Section: Anodic Decarboxylation Of Sodium Butanoate and Perfluorobutamentioning

confidence: 98%

Anodic oxidation of alkane carboxylates and perfluoroalkane carboxylates at platinum and graphite anodes: product selectivity and mechanistic aspects

Rangarajan

Velayutham

Noel

2011

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Constant current electrolysis of sodium octanoate produced Kolbe and non-Kolbe products. Dimer is the major product at Pt anode and non-Kolbe products were formed on graphite anode. Influence of quantity of electricity, current density, and nature of electrode was studied. Under optimized experimental conditions, butanoate, perfluorooctanoate, and perfluorobutanoate were electrolyzed. Major and minor products were identified based on GC-MS spectra. Isomeric products are due to cationic rearrangement by 1,2-hydride shift and selectivity among them are also rationalized. Anodic decarboxylation of perfluorobutanoate and perfluorooctanoates gave Kolbe dimer on platinum electrode. The role of solvent and criteria for choice of radical or cationic pathway has been discussed.

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“…The oxidative decarboxylation reaction of substituted phenylacetic acids has been studied extensively using peroxodisulfate and other oxidizing agents (19)(20)(21). It is now clear that the side-chain oxidation involves a benzylic radical cation intermediate formed by electron transfer from the carboxylate group (Kolbe reaction) or the n-system of the aromatic ring (pseudo-Kolbe reaction) to the sulfate radical anion.…”

Section: Thermal Electron Transfer Reactions Of Nsaid With Potassium mentioning

confidence: 99%

“…ground state. Oxidative decarboxylation of substituted phenylacetic acids can be mediated by metallic and nonmetallic oxidants or by electrolytic means (19)(20)(21). Naproxen is the only NSAID studied in this type of reaction.…”

Section: Introductionmentioning

confidence: 99%

Electron Transfer Processes in the Reactivity of Nonsteroidal Anti-inflammatory Drugs in the Ground and Excited States

et al. 1998

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The nonsteroidal anti-inflammatory drugs (NSAID), naproxen, sulindac and indomethacin, were shown to donate electrons to nitro blue tetrazolium (NBT) when irradiated with UV light in deoxygenated aqueous buffer solution (pH 7.4, 30 degrees C). The reaction was monitored spectrophotometrically by the appearance of the diformazan reduction product from NBT. The electron transfer process facilitates the decomposition of the drugs. Naproxen in the presence of NBT is photodegraded principally to the alcohol (2-[1-hydroxyethyl]-6-methoxynaphthalene) at a rate approximately 20-fold faster than when irradiated alone in deoxygenated conditions. The photoproduct from naproxen also participates in the electron transfer to NBT but at a much slower rate than naproxen. Irradiation of sulindac or indomethacin in the presence of NBT caused the slow photoreduction of NBT to diformazan. In the absence of NBT, indomethacin and sulindac are essentially unreactive when irradiated in aqueous solution. The ability of a number of NSAID to act as electron donors in their ground state was studied by observing their oxidation by potassium peroxodisulfate in pH 7.0 phosphate buffer at 50 degrees C. The HPLC analysis of the drug remaining showed that the 2-arylpropionic acid NSAID (naproxen, ibuprofen, ketoprofen and suprofen) reacted at a rate equivalent to the thermal decomposition of peroxodisulfate. The major products were the same as detected in the photooxidation of these drugs, resulting from decarboxylation and oxygen addition but also included a dimeric compound. On the other hand, the NSAID that do not contain the propionic acid substituent all reacted more slowly with peroxodisulfate, enabling specific reaction rate constants to be evaluated.

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Electro-organic reactions. Part II. Mechanism of the kolbe electrolysis of substituted phenylacetate ions

Cited by 41 publications

References 0 publications

(Non-)Kolbe electrolysis in biomass valorization – a discussion of potential applications

(Non-)Kolbe electrolysis in biomass valorization – a discussion of potential applications

Anodic oxidation of alkane carboxylates and perfluoroalkane carboxylates at platinum and graphite anodes: product selectivity and mechanistic aspects

Electron Transfer Processes in the Reactivity of Nonsteroidal Anti-inflammatory Drugs in the Ground and Excited States

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