New methods of free-radical perfluoroalkylation of aromatics and alkenes are reported. n-C4F9I has been utilized as source of C4F9. radical through iodine abstraction by phenyl or methyl radical. The reaction with alkenes, carried out in the presence of catalytic amount of Cu(OAc)2, leads to substitution by a mechanism substantially identical to the aromatic substitution and not to the usual chain addition of perfluoroalkyl group and iodine atom to the double bond. This has allowed to measure for the first time the absolute rate constants and the partial rate factors for the homolytic aromatic perfluoroalkylation by competition kinetics. The C4F9. radical shows a clear-cut electrophilic character in the aromatic substitution, as already reported for the addition to alkenes, but the low regio- and chemoselectivities suggest that the polar effect is not the main factor in determining the high reactivity of perfluoroalkyl radicals toward aromatics (105-106 M-1 s-1, 2-3 orders of magnitude more reactive than alkyl radicals). The enthalpic factor, related to the involved bond energies, appears to be the major cause of the increased reactivity. The polar effect is considered as related more to the polarizability than to the polarity of a radical (the σ-perfluoroalkyl radicals are considered less polarizable and hence less sensitive to polar effects than π-radicals).

(1997). New Methods of Free-Radical Perfluoroalkylation of Aromatics and Alkenes. Absolute Rate Constants and Partial Rate Factors for the Homolytic Aromatic Substitution by n-Perfluorobutyl Radical [journal article - articolo]. In JOURNAL OF ORGANIC CHEMISTRY. Retrieved from https://hdl.handle.net/10446/232753

New Methods of Free-Radical Perfluoroalkylation of Aromatics and Alkenes. Absolute Rate Constants and Partial Rate Factors for the Homolytic Aromatic Substitution by n-Perfluorobutyl Radical

Fontana, Francesca;
1997-01-01

Abstract

New methods of free-radical perfluoroalkylation of aromatics and alkenes are reported. n-C4F9I has been utilized as source of C4F9. radical through iodine abstraction by phenyl or methyl radical. The reaction with alkenes, carried out in the presence of catalytic amount of Cu(OAc)2, leads to substitution by a mechanism substantially identical to the aromatic substitution and not to the usual chain addition of perfluoroalkyl group and iodine atom to the double bond. This has allowed to measure for the first time the absolute rate constants and the partial rate factors for the homolytic aromatic perfluoroalkylation by competition kinetics. The C4F9. radical shows a clear-cut electrophilic character in the aromatic substitution, as already reported for the addition to alkenes, but the low regio- and chemoselectivities suggest that the polar effect is not the main factor in determining the high reactivity of perfluoroalkyl radicals toward aromatics (105-106 M-1 s-1, 2-3 orders of magnitude more reactive than alkyl radicals). The enthalpic factor, related to the involved bond energies, appears to be the major cause of the increased reactivity. The polar effect is considered as related more to the polarizability than to the polarity of a radical (the σ-perfluoroalkyl radicals are considered less polarizable and hence less sensitive to polar effects than π-radicals).
articolo
Bravo, Anna; Bjørsvik, Hans-René; Fontana, Francesca; Liguori, Lucia; Mele, Andrea; Minisci, Francesco
(1997). New Methods of Free-Radical Perfluoroalkylation of Aromatics and Alkenes. Absolute Rate Constants and Partial Rate Factors for the Homolytic Aromatic Substitution by n-Perfluorobutyl Radical [journal article - articolo]. In JOURNAL OF ORGANIC CHEMISTRY. Retrieved from https://hdl.handle.net/10446/232753
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