Electrosynthesis of Trichloroacetic Acid by Electrochemical Carboxylation of Carbon Tetrachloride

Olloqui‐Sariego, José Luis; Molina, Víctor M.; González-Arjona, D.; Roldán, Emilio; Domí­nguez, Manuel

doi:10.1149/1.2971028

Cited by 8 publications

(7 citation statements)

References 33 publications

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“…The exact anodic reaction(s), however, are not really specified. Oxidation of chloride, which itself originates in the CCl 4 reactant, likely results in partial chlorination of the acetonitrile solvent, releasing protons which in turn cause the formation of chloroform by attacking the cathodically formed carbanions [ 143 ].…”

Section: Reviewmentioning

confidence: 99%

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

Matthessen¹,

Fransaer²,

Binnemans

et al. 2014

Beilstein J. Org. Chem.

154

127

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SummaryThe near-unlimited availability of CO2 has stimulated a growing research effort in creating value-added products from this greenhouse gas. This paper presents the trends on the most important methods used in the electrochemical synthesis of carboxylic acids from carbon dioxide. An overview is given of different substrate groups which form carboxylic acids upon CO2 fixation, including mechanistic considerations. While most work focuses on the electrocarboxylation of substrates with sacrificial anodes, this review considers the possibilities and challenges of implementing other synthetic methodologies. In view of potential industrial application, the choice of reactor setup, electrode type and reaction pathway has a large influence on the sustainability and efficiency of the process.

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Section: Reviewmentioning

confidence: 99%

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

Matthessen¹,

Fransaer²,

Binnemans

et al. 2014

Beilstein J. Org. Chem.

154

127

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“…To evaluate the performance of the process in terms of efficiency and yield of desired product and main by-products, samples of 1 mL were periodically taken from the cell during the electrolysis and were analyzed via GC-ECD, as previously described. 23 Chloroacetic acids were isolated after electrolyses by the following procedure: ACN was evaporated, and the residue was acidified with an aqueous solution of sulfuric acid and extracted twice with methyl tert-butyl ether. Finally, the chloroacetic acids were recovered after evaporation of the solvent, recrystallized, and analyzed by GC.…”

Section: Methodsmentioning

confidence: 99%

“…As a result of this, a decrease in the current efficiency of the electrocarboxylation process is to be expected. In a previous work, 23 the electrochemical carboxylation of CT was studied using different electrodes by cyclic voltammetry and some electrolysis protocols. We showed that silver exhibits a remarkable electrocatalytic activity toward the reduction of CT in the presence of CO 2 , and its use as a cathode gives both high faradaic and trichloroacetate ͑TCA͒ yields.…”

mentioning

confidence: 99%

An Efficient Electrochemical Carboxylation of Polychloromethanes at Zinc Cathode in Acetonitrile

Olloqui‐Sariego¹,

Molina²,

González-Arjona³

et al. 2010

J. Electrochem. Soc.

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An efficient and selective electrochemical carboxylation process of some polychloromethanes was developed to synthesize chloroacetic acids using a zinc cathode and sacrificial anodes under a galvanostatic regime. The electrochemical behavior of carbon tetrachloride ͑CT͒, chloroform ͑CF͒, and its carboxylated products was studied by cyclic voltammetry in acetonitrile using tetrabutylammonium perchlorate as a supporting electrolyte in the presence and absence of CO 2 . Galvanostatic electrolyses of CT and CF in the presence of CO 2 were carried out in an undivided cell. The influence of some operative parameters on the performance of the process was studied. The electrochemical carboxylation of CT resulted in high faradaic yields and in the selective formation of trichloroacetate ͑TCA͒. The electrocarboxylation of CF led to high current efficiencies and a good dichloroacetate yield. TCA and dichloromethane ͑DCM͒ were obtained as by-products in this process. The formation of TCA and DCM suggests that the electrocarboxylation reaction of CF competes with the self-protonation of the carbanion CHCl 2 − generated in its reduction process.The polychloromethanes are considered to be among the most harmful pollutants due to their high toxicity and carcinogenic character. In fact, the Montreal Protocol, now signed into a treaty, recommended a complete ban on chlorofluorocarbon refrigerants that are synthesized using carbon tetrachloride ͑CT͒ and chloroform ͑CF͒ once their role in ozone layer depletion was recognized. Furthermore, the existing regulation ͑European Community͒ no. 1907/ 2006 of the European Parliament and Council considers CT and CF to be hazardous substances, and the U.S. Environmental Protection Agency classifies these chemicals as possible human carcinogens. Thus, the use of CT and CF has been restricted or at least reduced significantly, their main application being as organic solvents. Despite these restrictions, CT and CF are still being indirectly produced mainly in two processes: in the industrial synthesis of chloromethanes and in the disinfection of drinking water with chlorine. 1,2 A wide range of techniques aimed at the elimination of CT is under development. 3-7 However, all of them have in common the formation of unexploitable substances and pollutants.In previous work, one of the methods proposed for the elimination of CT was based on its electrochemical reduction under mild conditions, 8,9 the main product of this reduction being CF. However, this does not constitute a solution because the use of CF itself is being drastically limited for the reasons given above.However, carbon dioxide is one of the main greenhouse gases. In light of these considerations, we propose the electrochemical carboxylation of polychloromethanes as a synthetic process toward carboxylic acids and as a "green" process for the conversion of these pollutants.Many studies have been devoted to the electrocarboxylation of aromatic organic halides as a way to prepare carboxylated products. 10-21 However, studies of electrocarb...

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“…Another thought‐provoking research topic is asymmetric electro‐carboxylation via CO 2 [116–188] . The notable point is that, in the production of new chiral centres, both the carbon and oxygen atoms of CO 2 might be involved.…”

Section: Electrochemical Carboxylation With Different Functional Groupsmentioning

confidence: 99%

“…Chloride, which originates from the CCl 4 reactant, underwent oxidation resulting in partial chlorination of the acetonitrile solvent, in addition to attacking the cathodically formed carbanions, resulting in the formation of chloroform. [140] Furthermore, for the CO 2 fixation into aliphatic halides, an undivided electrosynthesis system with a stable anode can be used. In the electro-carboxylation of 1-bromo-2-methylpentane, the anodic oxidation of tetraethylammonium oxalate is used, leading to the formation of 3-methylhexanoic acid.…”

Section: Electro-carboxylation Of Organic Halidesmentioning

confidence: 99%

Renewable Electricity Enables Green Routes to Fine Chemicals and Pharmaceuticals

Murtaza

Qamar

Saleem

et al. 2022

The Chemical Record

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Syntheses of chemicals using renewable electricity and when generating high atom economies are considered green and sustainable processes. In the present state of affairs, electrochemical manufacturing of fine chemicals and pharmaceuticals is not as common place as it could be and therefore, merits more attention. There is also a need to turn attention toward the electrochemical synthesis of valuable chemicals from recyclable greenhouse gases that can accelerate the process of circular economy. CO2 emissions are the major contributor to human‐induced global warming. CO2 conversion into chemicals is a valuable application of its utilisation and will contribute to circular economy while maintaining environmental sustainability. Herein, we present an overview of electro‐carboxylation, including mechanistic aspects, which forms carboxylic acids using molecular carbon dioxide. We also discuss atom economies of electrochemical fluorination, methoxylation and amide formation reactions.

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Electrosynthesis of Trichloroacetic Acid by Electrochemical Carboxylation of Carbon Tetrachloride

Cited by 8 publications

References 33 publications

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

An Efficient Electrochemical Carboxylation of Polychloromethanes at Zinc Cathode in Acetonitrile

Renewable Electricity Enables Green Routes to Fine Chemicals and Pharmaceuticals

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