Low-temperature sonoelectrochemical processes - Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia
F. J. Del Campo, E. Maisonhaute, R. G. Compton, F. Marken, A. Aldaz
Institute for Sustainable Energy and the Environment
Centre for Sustainable and Circular Technologies (CSCT)
EPSRC Centre for Doctoral Training in Statistical Applied Mathematics (SAMBa)
Water Innovation and Research Centre (WIRC)
Centre for Nanoscience and Nanotechnology
Centre for Biosensors, Bioelectronics and Biodevices (C3Bio)
Dinitrobibenzyls are key intermediate species in certain drug syntheses. They can be formed by the electrochemical reduction of nitrobenzyl halides (in this work, 2-nitrobenzylchloride) in various solvents. In liquid ammonia at - 60°C, the mechanism involves a one-electron reduction and de-chlorination followed by the coupling of the neutral radical intermediate species. Exhaustive voltammetric studies, including fast scan cyclic voltammetry, of the starting material are presented prior to preparative electrolysis experiments. Electrolysis under both potentiostatic and galvanostatic conditions are compared. Under conditions of severe dryness, potentiostatic reduction at platinum gauze set at a voltage of - 0.30 V (vs. Ag wire) in the presence of ultrasound yields the dimer 2, 2-dinitrobibenzyl (> 95%) and no detectable side products. Water and oxygen have been found to decrease both the current efficiency and product yield of the process. Ultrasound is beneficial by: (i) enhancing the dissolution kinetics of the starting material; (ii) mass transport from the bulk towards the electrode, and vice versa, is greatly enhanced, thus considerably reducing the reaction times and optimising the current efficiency and product yields.
Journal of Electroanalytical Chemistry
Cryoelectrochemistry
Dinitrobibenzyl
Electrodimerisation
Electrosynthesis
Fast scan voltammetry
Liquid ammonia
Mass transport
Sonoelectro-chemistry
Chemical Engineering(all)
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Ammonia Chemical Compounds
Electrolysis Chemical Compounds
Liquids Chemical Compounds
Ultrasonics Chemical Compounds
Dimers Chemical Compounds
Chlorination Chemical Compounds
Cyclic voltammetry Chemical Compounds
Del Campo, F. J., Maisonhaute, E., Compton, R. G., Marken, F., & Aldaz, A. (2001). Low-temperature sonoelectrochemical processes - Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia. Journal of Electroanalytical Chemistry, 506(2), 170-177. https://doi.org/10.1016/S0022-0728(01)00501-0
Low-temperature sonoelectrochemical processes - Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia. / Del Campo, F. J.; Maisonhaute, E.; Compton, R. G.; Marken, F.; Aldaz, A.
In: Journal of Electroanalytical Chemistry, Vol. 506, No. 2, 29.06.2001, p. 170-177.
Del Campo, FJ, Maisonhaute, E, Compton, RG, Marken, F & Aldaz, A 2001, 'Low-temperature sonoelectrochemical processes - Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia', Journal of Electroanalytical Chemistry, vol. 506, no. 2, pp. 170-177. https://doi.org/10.1016/S0022-0728(01)00501-0
Del Campo FJ, Maisonhaute E, Compton RG, Marken F, Aldaz A. Low-temperature sonoelectrochemical processes - Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia. Journal of Electroanalytical Chemistry. 2001 Jun 29;506(2):170-177. https://doi.org/10.1016/S0022-0728(01)00501-0
Del Campo, F. J. ; Maisonhaute, E. ; Compton, R. G. ; Marken, F. ; Aldaz, A. / Low-temperature sonoelectrochemical processes - Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia. In: Journal of Electroanalytical Chemistry. 2001 ; Vol. 506, No. 2. pp. 170-177.
@article{15f0b909094d4afd81b0e28eb53c5735,
title = "Low-temperature sonoelectrochemical processes - Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia",
abstract = "Dinitrobibenzyls are key intermediate species in certain drug syntheses. They can be formed by the electrochemical reduction of nitrobenzyl halides (in this work, 2-nitrobenzylchloride) in various solvents. In liquid ammonia at - 60°C, the mechanism involves a one-electron reduction and de-chlorination followed by the coupling of the neutral radical intermediate species. Exhaustive voltammetric studies, including fast scan cyclic voltammetry, of the starting material are presented prior to preparative electrolysis experiments. Electrolysis under both potentiostatic and galvanostatic conditions are compared. Under conditions of severe dryness, potentiostatic reduction at platinum gauze set at a voltage of - 0.30 V (vs. Ag wire) in the presence of ultrasound yields the dimer 2, 2-dinitrobibenzyl (> 95%) and no detectable side products. Water and oxygen have been found to decrease both the current efficiency and product yield of the process. Ultrasound is beneficial by: (i) enhancing the dissolution kinetics of the starting material; (ii) mass transport from the bulk towards the electrode, and vice versa, is greatly enhanced, thus considerably reducing the reaction times and optimising the current efficiency and product yields.",
keywords = "Cryoelectrochemistry, Dinitrobibenzyl, Electrodimerisation, Electrosynthesis, Fast scan voltammetry, Liquid ammonia, Mass transport, Sonoelectro-chemistry, Ultrasound",
author = "{Del Campo}, {F. J.} and E. Maisonhaute and Compton, {R. G.} and F. Marken and A. Aldaz",
journal = "Journal of Electroanalytical Chemistry",
T1 - Low-temperature sonoelectrochemical processes - Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia
AU - Del Campo, F. J.
AU - Maisonhaute, E.
AU - Compton, R. G.
AU - Marken, F.
AU - Aldaz, A.
N2 - Dinitrobibenzyls are key intermediate species in certain drug syntheses. They can be formed by the electrochemical reduction of nitrobenzyl halides (in this work, 2-nitrobenzylchloride) in various solvents. In liquid ammonia at - 60°C, the mechanism involves a one-electron reduction and de-chlorination followed by the coupling of the neutral radical intermediate species. Exhaustive voltammetric studies, including fast scan cyclic voltammetry, of the starting material are presented prior to preparative electrolysis experiments. Electrolysis under both potentiostatic and galvanostatic conditions are compared. Under conditions of severe dryness, potentiostatic reduction at platinum gauze set at a voltage of - 0.30 V (vs. Ag wire) in the presence of ultrasound yields the dimer 2, 2-dinitrobibenzyl (> 95%) and no detectable side products. Water and oxygen have been found to decrease both the current efficiency and product yield of the process. Ultrasound is beneficial by: (i) enhancing the dissolution kinetics of the starting material; (ii) mass transport from the bulk towards the electrode, and vice versa, is greatly enhanced, thus considerably reducing the reaction times and optimising the current efficiency and product yields.
AB - Dinitrobibenzyls are key intermediate species in certain drug syntheses. They can be formed by the electrochemical reduction of nitrobenzyl halides (in this work, 2-nitrobenzylchloride) in various solvents. In liquid ammonia at - 60°C, the mechanism involves a one-electron reduction and de-chlorination followed by the coupling of the neutral radical intermediate species. Exhaustive voltammetric studies, including fast scan cyclic voltammetry, of the starting material are presented prior to preparative electrolysis experiments. Electrolysis under both potentiostatic and galvanostatic conditions are compared. Under conditions of severe dryness, potentiostatic reduction at platinum gauze set at a voltage of - 0.30 V (vs. Ag wire) in the presence of ultrasound yields the dimer 2, 2-dinitrobibenzyl (> 95%) and no detectable side products. Water and oxygen have been found to decrease both the current efficiency and product yield of the process. Ultrasound is beneficial by: (i) enhancing the dissolution kinetics of the starting material; (ii) mass transport from the bulk towards the electrode, and vice versa, is greatly enhanced, thus considerably reducing the reaction times and optimising the current efficiency and product yields.
KW - Cryoelectrochemistry
KW - Dinitrobibenzyl
KW - Electrodimerisation
KW - Electrosynthesis
KW - Fast scan voltammetry
KW - Liquid ammonia
KW - Mass transport
KW - Sonoelectro-chemistry
KW - Ultrasound
JO - Journal of Electroanalytical Chemistry
JF - Journal of Electroanalytical Chemistry