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Durham e-Theses
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New methodology for nucleophilic fluorination

Murray, Christopher B. (2003) New methodology for nucleophilic fluorination. Doctoral thesis, Durham University.



This work describes the development of three methods for the fluorination of electrophilic substrates:1.) The reaction of caesium fluoride with perfluoro(2-methylpent-2-ene) leads to the formation of perfluoro(2-methylpentan-2-yl)caesium. This perfluoroalkyl carbanion has been shown to undergo significant fluoride ion exchange at temperatures above 60 C. Thus, reaction of a solution of the carbanion with a suitable electrophile resulted in the selective formation of a carbon-fluorine bond or perfluoroalkylation of the electrophile.2.) Caesium fluoride has been developed as a moderately effective nucleophilicfluorinating agent in the Room Temperature Ionic Liquid (RTIL) solvent [BMIM][PF(_6)]. The fluorination of a range of volatile substrates was studied, and fluorination in the absence of a conventional organic solvent was demonstrated. Recycling of the solvent has been investigated, as has the decomposition of [BMLM] [PF(_6)] in the presence of caesium or potassium fluoride at elevated temperatures.3.) Reaction of a highly fluorinated azaheterocycle with DMAP leads to the formation of a fluoride salt. This salt, formed in situ, was used as a source of nucleophilic fluoride ion for the fluorination of a range of electrophiles. Several of the fluoride salts were converted to their more stable tetrafluoroborate or triflate analogues and characterised.

Item Type:Thesis (Doctoral)
Award:Doctor of Philosophy
Thesis Date:2003
Copyright:Copyright of this thesis is held by the author
Deposited On:26 Jun 2012 15:20

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