Modification of the preparation of a cadmium amalgam reference electrode for use in N,N-dimethylformamide

Hall, Jeffrey L.; Jennings, P. W.

doi:10.1021/ac50007a056

Cited by 54 publications

(31 citation statements)

References 6 publications

(9 reference statements)

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“…• C. [26][27][28] Cells, instrumentation, and procedural details for cyclic voltammetry are described in previous publications. 6,29,30 For controlled-potential (bulk) electrolyses, working cathodes (with geometric areas of approximately 20 cm 2 ) were constructed from silver gauze (Alfa Aesar, 99.9%, 20-mesh, woven from 0.356-mm-diameter wire).…”

Section: Methodsmentioning

confidence: 99%

“…Finally, a very brief cathodic polarization of the electrode, after being inserted into the electrolysis cell, serves to activate the cathode completely. As indicated in the preceding paragraph, the reference electrode was a saturated cadmium amalgam in DMF; [26][27][28] the auxiliary anode was a graphite rod separated from the cathode compartment by a medium-porosity sintered-glass disk backed by a methyl cellulose-DMF-0.10 M TEABF 4 plug. Information about the two-compartment (divided) electrolysis cell, as well as details about instrumentation and procedures for bulk electrolyses, can be found in earlier papers.…”

Section: Methodsmentioning

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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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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

Henderson

Buehler

Pasciak

et al. 2014

J. Electrochem. Soc.

View full text Add to dashboard Cite

show abstract

“…This reference electrode has a reported potential of −0.76 V vs. an aqueous saturated calomel electrode (SCE) at 25°C [40][41][42].…”

Section: Electrodes Cells and Instrumentationmentioning

confidence: 99%

Catalytic reduction of 4,4′-(2,2,2-trichloroethane-1,1-diyl)bis(methoxybenzene) (methoxychlor) with nickel(I) salen electrogenerated at reticulated vitreous carbon cathodes

McGuire

Hansen

Karty

et al. 2016

Journal of Electroanalytical Chemistry

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“…All potentials in this report are given with respect a reference electrode consisting of a cadmium-saturated mercury amalgam in contact with DMF saturated with both cadmium chloride and sodium chloride; this electrode has a potential of À0.76 V versus the aqueous saturated calomel electrode (SCE) at 25°C [22][23][24].…”

Section: Cells Electrodes and Instrumentationmentioning

confidence: 99%

Cyclic voltammetric and spectrophotometric investigation of the catalytic reduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) by electrogenerated cobalt(I) salen in dimethylformamide saturated with carbon dioxide

Skljarevski

Peverly

Peters

2011

Journal of Electroanalytical Chemistry

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Modification of the preparation of a cadmium amalgam reference electrode for use in N,N-dimethylformamide

Cited by 54 publications

References 6 publications

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

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

Catalytic reduction of 4,4′-(2,2,2-trichloroethane-1,1-diyl)bis(methoxybenzene) (methoxychlor) with nickel(I) salen electrogenerated at reticulated vitreous carbon cathodes

Cyclic voltammetric and spectrophotometric investigation of the catalytic reduction of 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) by electrogenerated cobalt(I) salen in dimethylformamide saturated with carbon dioxide

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