Electrochemical reduction of decabromodiphenyl ether at carbon and silver cathodes in dimethylformamide and dimethyl sulfoxide

Peverly, Angela A.; Pasciak, Erick M.; Strawsine, Lauren M.; Wagoner, Elizabeth R.; Peters, Dennis G.

doi:10.1016/j.jelechem.2013.07.002

Cited by 30 publications

(16 citation statements)

References 59 publications

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“…Electrochemical debromination by reduction of decabromodiphenyl ether to dimethylformamide and dimethyl sulfoxide can be considered as an example of the synthesis of organics at RVC electrodes [97]. Cyclic voltammetry related the presence of bromine atoms to each of the observed cathodic peaks.…”

Section: Clean Electrosynthesismentioning

confidence: 99%

The continued development of reticulated vitreous carbon as a versatile electrode material: Structure, properties and applications

Walsh

Arenas

León

et al. 2016

Electrochimica Acta

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The limitations of 2-dimensional electrodes can be overcome by using threedimensional materials having sufficient porosity and active area while offering moderate mass transport rates and a relatively low pressure drop at controlled electrolyte flow rate. In concept, a wide variety of metal, ceramic and composite materials are possible but restrictions are imposed by the need to avoid materials degradation, while maintaining adequate electrical conductivity, sufficient robustness and the possibility of facile scale-up. Despite its fragility, one of the traditional electrode materials used as a porous, 3-dimensional electrode is carbon foam, particularly in the 97% vol. porous form of reticulated vitreous carbon, RVC. A timeline indicates that the history of this material dates back over 50 years to the mid1960s, when it was primarily used as an uncoated material in small-scale, laboratory electroanalysis. Surface modification and diverse coatings have considerably extended the use of RVC. Recent applications are found in sensors and monitors, electrosynthesis, environmental processing and energy conversion. This review highlights the fundamental structure and summarises the physicochemical properties of RVC. Fluid flow through various porosity grades of the material, their active electrochemical area and rates of mass transport are quantified. The diverse applications of RVC in energy conversion, environmental treatment and electrosynthesis are illustrated by selected examples from the authors' laboratories and others over the last 30 years. Recent research on coated RVC, energy conversion environmental remediation and sensors is highlighted. Critical areas deserving further research and development are proposed.

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Section: Clean Electrosynthesismentioning

confidence: 99%

The continued development of reticulated vitreous carbon as a versatile electrode material: Structure, properties and applications

Walsh

Arenas

León

et al. 2016

Electrochimica Acta

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“…These observations are fully consistent with our recent studies that reveal the relative ease of reduction of carbon-halogen bonds for numerous substrates at silver cathodes. 30,37,38 On the other hand, it is surprising that reduction of the keto ester moieties of 1 and 2 is more facile at silver than at glassy carbon, a finding that does not seem to have been reported previously. Table I are coulometric data and product distributions pertaining to the exhaustive electroreduction of 5.0 and 10.0 mM solutions of compounds 1 and 2 at silver gauze electrodes in DMF containing 0.10 M TMABF 4 ; all electrolyses were performed at -1.00 V, a potential that ensured the complete reduction of each starting material.…”

Section: Resultsmentioning

confidence: 57%

Electrochemical Reduction of 1-Bromomethyl-2-oxocycloalkane-1-carboxylates at Silver Cathodes in Dimethylformamide: One-Carbon Ring-Expansion Reactions

Wappes

Mubarak

Peters

2014

J. Electrochem. Soc.

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Cyclic voltammetry and controlled-potential (bulk) electrolysis have been employed to investigate the separate electrochemical reductions of methyl 1-bromomethyl-2-oxocyclopentane-1-carboxylate (1) and ethyl 1-bromomethyl-2-oxocyclohexane-1-carboxylate (2) at silver cathodes in dimethylformamide (DMF) containing 0.10 M tetramethylammonium tetrafluoroborate (TMABF 4 ). Oneelectron reductive cleavage of the carbon-bromine bond of each substrate yields a radical intermediate that undergoes a ring-expansion reaction, followed by hydrogen-atom abstraction from the solvent, to afford methyl 3-oxocyclohexane-1-carboxylate (3a) and ethyl 3-oxocycloheptane-1-carboxylate (3b), respectively, in good yield. Each substrate gives rise to three other products: (a) a debrominated analogue of each starting material, (b) a dimeric species formed via radical coupling, and (c) a species possessing an ester group extended by one carbon atom. Electrolyses of 1 and 2 done in the presence of D 2 O have revealed that carbanion intermediates result in small amounts from two-electron cleavage of carbon-bromine bonds. A mechanistic scheme, involving both radicals and carbanions, is proposed to account for the formation of the various products.

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“…4 , GFS Chemicals, 98%) served as the supporting electrolyte; prior to being used, it was recrystallized from methanol-water and stored in a vacuum oven at 90…”

Section: Methodsmentioning

confidence: 99%

“…Shown in Figure 2 is a comparison of the cyclic voltammetric behavior of 2.0 mM solutions of 1 in the absence and presence of a proton donor (1,1,1,3,3,3-hexafluoro-2-propanol, HFIP). Both cyclic voltammograms were recorded at a scan rate of 100 mV s −1 in DMF containing 0.10 M TEABF 4 and either no HFIP (curve A, solid line) or 20 mM HFIP (curve B, dashed line). In the presence of HFIP, all stages in the reduction of 1 are shifted dramatically toward less negative potentials: (a) the first peak shifts from -0.67 to -0.08 V and (b) the second set of cathodic peaks coalesces and shifts from ca.…”

Section: Synthesis Of Ethyl Trans-3-(3 4 -Dimethoxyphenyl)acrylate (mentioning

confidence: 99%

“…Recent publications from our laboratory [3][4][5][6][7][8] and by other research groups [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] have dealt with the electrochemistry of halogenated organic compounds at silver cathodes and have revealed the catalytic effect of silver on the reductive cleavage of carbon-halogen bonds; the cited references lead the way to other earlier papers on this topic. For example, our laboratory discovered quite recently 8 that cleavage of the carbon−chlorine bond of 2-chloro-N-phenylacetamides at a silver cathode occurs at potentials which are 500-600 mV more positive than those seen with a glassy carbon electrode.…”

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confidence: 99%

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Electrochemical Reduction of a Bromo Propargyloxy Ester at Silver Cathodes in Dimethylformamide

Henderson

Buehler

Pasciak

et al. 2014

J. Electrochem. Soc.

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Cyclic voltammograms for the reduction of ethyl 2-bromo-3-(3 ,4 -dimethoxyphenyl)-3-(propargyloxy)propanoate (1) at a silver cathode in dimethylformamide (DMF) containing 0.10 M tetraethylammonium tetrafluoroborate (TEABF 4 ) exhibit several cathodic peaks, the first of which is attributed to reductive cleavage of the carbon-bromine bond. Controlled-potential (bulk) electrolyses of 1 at silver gauze electrodes in DMF-0.10 M TEABF 4 give rise to four products: cis-and trans-isomers of ethyl 3-(3 ,4 -dimethoxyphenyl)-prop-2-enoate (4), ethyl 3-(3 ,4 -dimethoxyphenyl)propiolate (7), and ethyl 3-(3 ,4 -dimethoxyphenyl)-3-(prop-2-yn-1-yloxy)propanoate (8). These products have been identified with the aid of mass spectrometry and nuclear magnetic resonance spectroscopy. We propose that reduction of 1 involves two-electron cleavage of the carbon-bromine bond to form a carbanion. Then the latter species eliminates − OCH 2 C≡CH to afford 4. In addition, − OCH 2 C≡CH can deprotonate 1 to yield (Z)-ethyl 2-bromo-3-(3 ,4 -dimethoxyphenyl)acrylate (5), which is further deprotonated by − OCH 2 C≡CH to give 7. Alternatively, the carbanion resulting from the original two-electron reduction of 1 can gain a proton from the medium to form 8. In two previous projects 1,2 involving collaboration with our laboratory, electrochemical methods were probed as an avenue to the synthesis of building blocks for lignans, which comprise a class of phenylalanine-derived compounds that have attracted considerable attention due to their pharmacological activity and abundance in nature. In the first of those investigations, 1 we examined the reductive intramolecular cyclization of ethyl 2-bromo-3-(3 ,4 -dimethoxyphenyl)-3-(propargyloxy)propanoate (1), catalyzed by electrogenerated nickel(I) tetramethylcyclam, to afford 2-(3 ,4 -dimethoxyphenyl)-3-(ethoxycarbonyl)-4-methylenetetrahydrofuran (2) in good yield (72-85%); the latter species is a desired precursor for the formation of isogmelinol (a furofuran lignan). In addition, a second product, 2-(3 ,4 -dimethoxyphenyl)-3-ethoxycarbonyl-4-methyl-2,5-dihydrofuran (3), was obtained in significant yield (22-30%).A second paper 2 was concerned with the direct reduction of 1 at both glassy carbon and reticulated vitreous carbon cathodes in dimethylformamide (DMF) containing various tetraalkylammonium salts. Interestingly, although 2 was not obtained, 3 (which * Electrochemical Society Student Member.* * Electrochemical Society Fellow. z E-mail: peters@indiana.edu arises via base-promoted rearrangement of 2) was found in modest yield (18-26%). More importantly, the principal product was ethyl trans-3-(3 ,4 -dimethoxyphenyl)acrylate (4), although small amounts of (Z)-ethyl 2-bromo-3-(3 ,4 -dimethoxyphenyl)acrylate (5) and ethyl 3-(3 ,4 -dimethoxyphenyl)-2,3-bis(prop-2-yn-1-yloxy)propanoate (6) were detected.Recent publications from our laboratory 3-8 and by other research groups 9-24 have dealt with the electrochemistry of halogenated organic compounds at silver cathodes and have revealed the catalytic ef...

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Electrochemical reduction of decabromodiphenyl ether at carbon and silver cathodes in dimethylformamide and dimethyl sulfoxide

Cited by 30 publications

References 59 publications

The continued development of reticulated vitreous carbon as a versatile electrode material: Structure, properties and applications

The continued development of reticulated vitreous carbon as a versatile electrode material: Structure, properties and applications

Electrochemical Reduction of 1-Bromomethyl-2-oxocycloalkane-1-carboxylates at Silver Cathodes in Dimethylformamide: One-Carbon Ring-Expansion Reactions

Electrochemical Reduction of a Bromo Propargyloxy Ester at Silver Cathodes in Dimethylformamide

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