Velayutham, D. and Jayaraman, K. and Kulangiappar , K. and Ilayaraja, N. and Rambabu, Y. and Santhanrao, P. and Narayanareddy, S. and Victorbabu, K. and Noel, M. (2006) Free radical and isomerisation processes during the electrochemical fluorination of n-butyryl chloride, i-butyryl chloride and pivaloyl chloride in anhydrous hydrogen fluoride. Journal of Fluorine Chemistry, 127 (8). pp. 1111-1118. ISSN 0022-1139

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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 cyclopropane 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.

Item Type: Article
Uncontrolled Keywords: Electrochemical fluorination; n-Butyryl chloride; i-Butyryl chloride; Pivaloyl chloride; cyclo-Propane intermediate
Subjects: Electroorganic
Depositing User: ttbdu cecri
Date Deposited: 06 Apr 2012 04:08
Last Modified: 06 Apr 2012 04:08

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