Article ID Journal Published Year Pages File Type
1315334 Journal of Fluorine Chemistry 2006 8 Pages PDF
Abstract

Electrochemical perfluorination (ECPF) of the title compounds containing primary, secondary and tertiary carbon atoms was carried out in anhydrous hydrofluoric acid (AHF). Detailed analysis of major and minor products suggest that carbon chain isomerisation involving cyclo-propane intermediate is more prevalent during ECPF of i-butyryl chloride when compared to n-butyryl chloride. Simple statistical probability involving free radical intermediates also support this observation. ECPF involving cyclo-propane intermediate is even more prevalent in pivaloyl chloride containing three methyl substituents. In this case, perfluorinated cyclo-propane intermediates were also observed in the product sample. Distribution of minor perfluorinated and partially fluorinated products also suggest the predominant role of normal free radical pathway involving single-electron transfer.

Graphical abstractECPF proceeds via free radical pathway (Scheme 2) as well as diradical cyclo-propane intermediate pathway (Scheme 3). As the branching in alkyl chain increases the contribution from the latter cyclo-propane intermediate pathway becomes significant. Figure optionsDownload full-size imageDownload as PowerPoint slide

Related Topics
Physical Sciences and Engineering Chemistry Inorganic Chemistry
Authors
, , , , , , , , ,