An investigation of the possibility of synthesising organolithium reagents from electrodeposited lithium powder
An investigation of the possibility of synthesising organolithium reagents from electrodeposited lithium powder
The industrial scale synthesis of organolithium reagents presents a number of problems. An electrochemical process, if possible, may solve some of these problems. To assess the possibility of such an industrial process a variety of lithium salts were investigated to determine (a) their ability to deposit lithium and (b) their effect on the reaction of lithium with bromobenzene. Some attempts at electrosynthesis have also been made. These investigations have also produced further information on the formation of films in lithium battery systems. The prospects of achieving a process have been shown to be poor due to the formation of surface films on lithium which inhibit reaction. However, the investigations have led to a better understanding of film formation in potential lithium battery systems. Strong evidence is presented to suggest that the film formed in the presence of high concentrations of LiAsF6 is due, initially, to the reduction of the anion by lithium. This film is later modified by traces of water introduced with the salt. The study has also provided more information on other reactions in the system. Evidence is presented that the formation of alkoxide species in ether based lithium battery systems is due to base catalysed solvent cleavage rather than electron transfer from lithium to solvent. Electrodeposited lithium powder has been shown as a possible intermediate in the synthesis of acid sensitive esters and Grignard reagents. Preliminary investigation of the deposition of manganese from tetrahydrofuran has been conducted with the ultimate aim of producing organomanganese reagents by an electrosynthetic route. A complex made from MnBr2 and LiBr has been shown to deposit manganese by an instantaneous nucleation mechanism. (DX86439)
University of Southampton
1988
Holding, Alan David
(1988)
An investigation of the possibility of synthesising organolithium reagents from electrodeposited lithium powder.
University of Southampton, Doctoral Thesis.
Record type:
Thesis
(Doctoral)
Abstract
The industrial scale synthesis of organolithium reagents presents a number of problems. An electrochemical process, if possible, may solve some of these problems. To assess the possibility of such an industrial process a variety of lithium salts were investigated to determine (a) their ability to deposit lithium and (b) their effect on the reaction of lithium with bromobenzene. Some attempts at electrosynthesis have also been made. These investigations have also produced further information on the formation of films in lithium battery systems. The prospects of achieving a process have been shown to be poor due to the formation of surface films on lithium which inhibit reaction. However, the investigations have led to a better understanding of film formation in potential lithium battery systems. Strong evidence is presented to suggest that the film formed in the presence of high concentrations of LiAsF6 is due, initially, to the reduction of the anion by lithium. This film is later modified by traces of water introduced with the salt. The study has also provided more information on other reactions in the system. Evidence is presented that the formation of alkoxide species in ether based lithium battery systems is due to base catalysed solvent cleavage rather than electron transfer from lithium to solvent. Electrodeposited lithium powder has been shown as a possible intermediate in the synthesis of acid sensitive esters and Grignard reagents. Preliminary investigation of the deposition of manganese from tetrahydrofuran has been conducted with the ultimate aim of producing organomanganese reagents by an electrosynthetic route. A complex made from MnBr2 and LiBr has been shown to deposit manganese by an instantaneous nucleation mechanism. (DX86439)
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Published date: 1988
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Local EPrints ID: 460961
URI: http://eprints.soton.ac.uk/id/eprint/460961
PURE UUID: bd387797-4695-4e73-ae3a-ce3d25846f6b
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Date deposited: 04 Jul 2022 18:32
Last modified: 04 Jul 2022 18:32
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Author:
Alan David Holding
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