Low-temperature sonoelectrochemical processes Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia
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-chlorinat...
| Hlavní autoři: | , , , , |
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| Médium: | Journal article |
| Jazyk: | English |
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2001
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| _version_ | 1826293376462356480 |
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| author | Del Campo, F Maisonhaute, E Compton, R Marken, F Aldaz, A |
| author_facet | Del Campo, F Maisonhaute, E Compton, R Marken, F Aldaz, A |
| author_sort | Del Campo, F |
| collection | OXFORD |
| description | 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. © 2001 Elsevier Science B.V. |
| first_indexed | 2024-03-07T03:29:09Z |
| format | Journal article |
| id | oxford-uuid:ba166dab-96e7-4a0c-919f-75dc7fe7b5f5 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T03:29:09Z |
| publishDate | 2001 |
| record_format | dspace |
| spelling | oxford-uuid:ba166dab-96e7-4a0c-919f-75dc7fe7b5f52022-03-27T05:07:32ZLow-temperature sonoelectrochemical processes Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammoniaJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:ba166dab-96e7-4a0c-919f-75dc7fe7b5f5EnglishSymplectic Elements at Oxford2001Del Campo, FMaisonhaute, ECompton, RMarken, FAldaz, ADinitrobibenzyls 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. © 2001 Elsevier Science B.V. |
| spellingShingle | Del Campo, F Maisonhaute, E Compton, R Marken, F Aldaz, A Low-temperature sonoelectrochemical processes Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia |
| title | Low-temperature sonoelectrochemical processes Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia |
| title_full | Low-temperature sonoelectrochemical processes Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia |
| title_fullStr | Low-temperature sonoelectrochemical processes Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia |
| title_full_unstemmed | Low-temperature sonoelectrochemical processes Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia |
| title_short | Low-temperature sonoelectrochemical processes Part 3. Electrodimerisation of 2-nitrobenzylchloride in liquid ammonia |
| title_sort | low temperature sonoelectrochemical processes part 3 electrodimerisation of 2 nitrobenzylchloride in liquid ammonia |
| work_keys_str_mv | AT delcampof lowtemperaturesonoelectrochemicalprocessespart3electrodimerisationof2nitrobenzylchlorideinliquidammonia AT maisonhautee lowtemperaturesonoelectrochemicalprocessespart3electrodimerisationof2nitrobenzylchlorideinliquidammonia AT comptonr lowtemperaturesonoelectrochemicalprocessespart3electrodimerisationof2nitrobenzylchlorideinliquidammonia AT markenf lowtemperaturesonoelectrochemicalprocessespart3electrodimerisationof2nitrobenzylchlorideinliquidammonia AT aldaza lowtemperaturesonoelectrochemicalprocessespart3electrodimerisationof2nitrobenzylchlorideinliquidammonia |