A unique proton coupled electron transfer pathway for electrochemical reduction of acetophenone in the ionic liquid [BMIM][BF4] under a carbon dioxide atmosphere

Zhao, Shufeng; Wu, La-Xia; Wang, Huan; Lu, Jia‐Xing; Bond, Alan M.; Zhang, Jie

doi:10.1039/c1gc15929a

Cited by 28 publications

(56 citation statements)

References 39 publications

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“…This offers an electrochemical route for several commercially relevant α-aryl propionic acids, used as non-steroidal anti-inflammatory drugs (NSAIDs) [80]. Therefore, the electrocarboxylation of aromatic ketones with sacrificial anodes has been extensively investigated [75–77 81–98]. Some researchers focused on replacing toxic and volatile organic solvents with ionic liquids [81–83].…”

Section: Reviewmentioning

confidence: 99%

“…Therefore, the electrocarboxylation of aromatic ketones with sacrificial anodes has been extensively investigated [75–77 81–98]. Some researchers focused on replacing toxic and volatile organic solvents with ionic liquids [81–83]. Their negligible vapor pressure, large electrochemical window, good intrinsic conductivity and high CO 2 solubility make them interesting solvents for electrochemical CO 2 valorization [81–83 99–101].…”

Section: Reviewmentioning

confidence: 99%

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Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

Matthessen¹,

Fransaer²,

Binnemans

et al. 2014

Beilstein J. Org. Chem.

162

130

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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%

Section: Reviewmentioning

confidence: 99%

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

Matthessen¹,

Fransaer²,

Binnemans

et al. 2014

Beilstein J. Org. Chem.

162

130

View full text Add to dashboard Cite

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“…From the thousands of ionic liquids reported so far, those based on the imidazolium cation 20,22 are most commonly used for the electrocarboxylation of organic compounds such as alkenes, 23 alcohols, [24][25][26] ketones 5,16,27,28 and halides [29][30][31] because they are synthesised easily and can dissolve large amounts of many organic compounds and CO 2 . However, when using 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim] [BF 4 ]) as the medium for bulk electrolysis of acetophenone under a CO 2 atmosphere, Zhao et al 28 found that 1-phenylethanol was the main product with a high yield of 97%. It was proposed in that study that the presence of CO 2 enhances the C2-H donating ability in [Bmim] + due to strong complex formation between deprotonated [Bmim] + , N-heterocyclic carbene (NHC), and CO 2 , resulting in a thermodynamically favourable proton coupled electron transfer pathway.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical reduction of aromatic ketones in 1-butyl-3-methylimidazolium-based ionic liquids in the presence of carbon dioxide: the influence of the ketone substituent and the ionic liquid anion on bulk electrolysis product distribution

Zhao

Horne

Bond

et al. 2015

Phys. Chem. Chem. Phys.

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Electrochemical reduction of aromatic ketones, including acetophenone, benzophenone and 4-phenylbenzophenone, has been undertaken in 1-butyl-3-methylimidazolium-based ionic liquids containing tetrafluoroborate ([BF4](-)), trifluoromethanesulfonate ([TfO](-)) and tris(pentafluoroethyl)trifluorophosphate ([FAP](-)) anions in the presence of carbon dioxide in order to investigate the ketone substituent effect and the influence of the acidic proton on the imidazolium cation (C2-H) on bulk electrolysis product distribution. For acetophenone, the minor products were dimers (<10%) in all ionic liquids, which are the result of acetophenone radical anion coupling. For benzophenone and 4-phenylbenzophenone, no dimers were formed due to steric hindrance. In these cases, even though carboxylic acids were obtained, the main products generated were alcohols (>50%) derived from proton coupled electron transfer reactions involving the electrogenerated radical anions and C2-H. In the cases of both acetophenone and benzophenone, the product distribution is essentially independent of the ionic liquid anion. By contrast, 4-phenylbenzophenone shows a product distribution that is dependent on the ionic liquid anion. Higher yields of carboxylic acids (∼40%) are obtained with [TfO](-) and [FAP](-) anions because in these ionic liquids the C2-H is less acidic, making the formation of alcohol less favourable. In comparison with benzophenone, a higher yield of carboxylic acid (>30% versus ∼15%) was obtained with 4-phenylbenzophenone in all ionic liquids due to the weaker basicity of 4-phenylbenzophenone radical anion.

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“…Therefore, 2 may undergo further two-electron transfer to the corresponding carbon anion 8, which would react with another CO 2 to form decarboxylation product 4. Given that a small amount of water is still present in the solvent, the protonation process competes with carboxylation [13,58,59]. Then, dehalogenated monocarboxylation product 3 is formed by either carboxylation following protonation or protonation following carboxylation.…”

Section: Electrocarboxylation Of Other Dichlorobenzenesmentioning

confidence: 99%

“…Although many studies have investigated electroreduction and electrocarboxylation of organic chlorides, most of them focused on monochloride compounds [19,21,22,[40][41][42][43][44]. Only a few studies have examined the electroreduction of polyhalidecompounds [45][46][47][48][49][50][51][52][53][54][55][56][57][58][59], such as dichloromethane, trichloromethane, tetrachloromethane, and hexachlorocyclohexane.…”

Section: Introductionmentioning

confidence: 99%

Electrocarboxylation of Dichlorobenzenes on a Silver Electrode in DMF

et al. 2017

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Carbon dioxide (CO 2 ) is the largest contributor to the greenhouse effect, and fixing and using this greenhouse gas in a facile manner is crucial. This work investigates the electrocarboxylation of dichlorobenzenes with the atmospheric pressure of CO 2 in an undivided cell with an Ag cathode and an Mg sacrificial anode. The corresponding carboxylic acids and their derivatives, which are important industrial and fine chemicals, are obtained. To deeply understand this reaction, we investigate the influence of various reaction conditions, such as supporting electrolyte, current density, electric charge, and reaction temperature, on the electrocarboxylation yield by using 1,4-dichlorobenzene as the model compound. The electrochemical behavior of dichlorobenzenes is studied through cyclic voltammetry. The relation among the distinct electronic effects of dichlorobenzenes, the electrochemical characteristics of their reduction, and the distribution law of target products is also established.

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A unique proton coupled electron transfer pathway for electrochemical reduction of acetophenone in the ionic liquid [BMIM][BF4] under a carbon dioxide atmosphere

Cited by 28 publications

References 39 publications

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

Electrochemical reduction of aromatic ketones in 1-butyl-3-methylimidazolium-based ionic liquids in the presence of carbon dioxide: the influence of the ketone substituent and the ionic liquid anion on bulk electrolysis product distribution

Electrocarboxylation of Dichlorobenzenes on a Silver Electrode in DMF

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