Electrochemical fixation of CO2 to organohalides in room-temperature ionic liquids under supercritical CO2

Tateno, Hiroyuki; Nakabayashi, Koji; Kashiwagi, Tsuneo; Senboku, Hisanori; Atobe, Mahito

doi:10.1016/j.electacta.2015.01.072

Cited by 37 publications

(17 citation statements)

References 39 publications

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“…However, such reaction processes utilize toxic or hazardous reducing agents, as well as generate a large amount of waste regents [6,7]. Electrocarboxylation may use clean electricity for the synthesis of carboxylic acids, providing a worthy alternative [9][10][11][12][13][14][15][16][17][18][19][20][21][22]. The electroreduction of organic halides on different cathodes (Zn, Hg, Cu, Ag, Au, Pt, Sn, Pb, and Bi) have been studied by Bellomunno and coworkers [23], who showed that the group 11 metals have good catalytic properties towards this reduction process.…”

Section: Introductionmentioning

confidence: 99%

Highly Efficient Electrocatalytic Carboxylation of 1-Phenylethyl Chloride at Cu Foam Cathode

Sun

Yang

et al. 2018

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A simple and efficient electrocatalytic carboxylation of benzyl chloride with CO 2 is described. The reaction operates under 1 atm CO 2 and room temperature in a single chamber electrolysis cell with Cu foam cathode and Mg sacrificial anode. No additional catalyst is needed, and noble metal is not necessary. The effects of cathode material, solvent current density, charge amount, and temperature were studied using 1-phenylethyl chloride as a model compound. Under optimal conditions, 99% yield of 2-phenylpropionic acid could be obtained. Moreover, reasonable yields were also achieved with other benzyl chlorides.

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Section: Introductionmentioning

confidence: 99%

Highly Efficient Electrocatalytic Carboxylation of 1-Phenylethyl Chloride at Cu Foam Cathode

Sun

Yang

et al. 2018

Catalysts

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“…After the second electron transfer, 5 is reduced to carbon anion 6, which reacts with CO2 to form halogenated monocarboxylation product 2. The phenomenon in which two successive irreversible cathodic peaks were detected for all the three dichlorobenzenes (Figure 2) is indicative of two two-electron transfer For monoaromatic halide compounds, carboxylated products were normally obtained by the reaction of CO 2 with the anions that were generated by the two-electron transfer of monoaromatic halides [20,25,57,58]. Therefore, the possible electrocarboxylation pathway of dichlorobenzene is Scheme 2.…”

Section: Electrocarboxylation Of Other Dichlorobenzenesmentioning

confidence: 99%

“…To understand this phenomenon, the proposed pathways for the electrocarboxylation of dichlorobenzene were studied, and energy calculations were performed using the Gaussian09W program (Revision A.1, Gaussian, Inc., Wallingford, CT, USA, 2009). For monoaromatic halide compounds, carboxylated products were normally obtained by the reaction of CO2 with the anions that were generated by the two-electron transfer of monoaromatic halides [20,25,57,58]. Therefore, the possible electrocarboxylation pathway of dichlorobenzene is Scheme 2.…”

Section: Electrocarboxylation Of Other Dichlorobenzenesmentioning

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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“…Constant current electrolysis of a solution of 1 a (1 mmol) in DMF (10 mL) containing 0.1 M Bu 4 NBF 4 was carried out using a test‐tube like undivided cell equipped with a platinum plate cathode (2×2 cm 2 ) and a magnesium rod anode (3 mmφ) at 0 °C with bubbling of carbon dioxide through the solution. Platinum cathode was selected by its high reusability and good performances in our previous electrochemical carboxylation even in supercritical CO 2 and in flow microreactor . Effects of current density was studied (entries 1–3).…”

Section: Screening Of Reaction Conditions[a]mentioning

confidence: 99%

Efficient Synthesis of Mandel Acetates by Electrochemical Carboxylation of Benzal Diacetates

et al. 2019

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Efficient synthesis of mandel acetate, 2‐acetoxy‐2‐phenylacetic acid, from benzaldehyde was successfully performed in two steps using electrochemical carboxylation of benzal diacetate as a key step. When benzal diacetate, readily prepared from benzaldehyde and acetic anhydride in one step, in DMF containing 0.1 M Bu4NBF4 was electrolyzed in the presence of carbon dioxide using an undivided cell equipped with a platinum plate cathode and a magnesium rod anode under constant current conditions, reductive cleavage of the C‐OAc bond followed by capture of carbon dioxide took place efficiently at the benzylic position to give mandel acetate in good to high yields. Wide scope, high yields and the use of carbon dioxide as a carbon source of the carboxyl group would provide novel environmentally‐benign synthesis of mandelic acid derivatives.

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Electrochemical fixation of CO2 to organohalides in room-temperature ionic liquids under supercritical CO2

Cited by 37 publications

References 39 publications

Highly Efficient Electrocatalytic Carboxylation of 1-Phenylethyl Chloride at Cu Foam Cathode

Highly Efficient Electrocatalytic Carboxylation of 1-Phenylethyl Chloride at Cu Foam Cathode

Electrocarboxylation of Dichlorobenzenes on a Silver Electrode in DMF

Efficient Synthesis of Mandel Acetates by Electrochemical Carboxylation of Benzal Diacetates

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