کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1315334 976018 2006 8 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Free radical and isomerisation processes during the electrochemical fluorination of n-butyryl chloride, i-butyryl chloride and pivaloyl chloride in anhydrous hydrogen fluoride
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Free radical and isomerisation processes during the electrochemical fluorination of n-butyryl chloride, i-butyryl chloride and pivaloyl chloride in anhydrous hydrogen fluoride
چکیده انگلیسی

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.

ECPF 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 as PowerPoint slide

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Fluorine Chemistry - Volume 127, Issue 8, August 2006, Pages 1111–1118
نویسندگان
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