Rangarajan, T.M. and Sathyamoorthi, S. and Velayutham, D. and Noel, M. and Singh, R.P. and Brahma, R. (2011) Products formed at intermediate stages of electrochemical perfluorination of propionyl and n-butyryl chlorides. Further evidence in support of NiF3 mediated free radical pathway. Journal of Fluorine Chemistry, 132 (002). pp. 107-113. ISSN 0022-1139

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Abstract

The partially fluorinated HF soluble intermediates formed during the electrochemical perfluorination of propionyl chloride (PC) and n-butyryl chloride (n-BC) were analyzed after passing 0%, 25%, 50%, 75% and 100% of theoretical charge required for the fluorination of PC and n-BC. The acid fluorides formed were converted to their corresponding sodium salt by alkali treatment and were separated by methanol extraction. The methanol was subsequently removed from the extract by vacuum distillation and the residue containing partially fluorinated sodium carboxylates was analyzed using 19F and 1H NMR spectra. Initial perfluorination on activated electrode surface indicates the operation of ‘zippermechanism’. Formation of partially fluorinated product mixture, initial selectivity towards primary and secondary carbon, carbon chain isomerization and formation of cleaved and coupled products support the general operation of free radical pathway in the overall electrochemical process

Item Type:	Article
Uncontrolled Keywords:	Electrochemical fluorination; Propionyl chloride; n-Butyryl chloride; HF soluble intermediates; Free radical mechanism; Perfluorination
Subjects:	Electroorganic
Divisions:	UNSPECIFIED
Depositing User:	ttbdu cecri
Date Deposited:	19 Nov 2012 10:38
Last Modified:	19 Nov 2012 10:38
URI:	http://cecri.csircentral.net/id/eprint/2906

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