Reactivity study of 1,1,2,4,4,5,7,7,8,8,9,9,9-tridecafluoro-5-trifluoromethyl-3,6-dioxanon-1-ene in nucleophilic reactions: fluorination properties of secondary amine adducts |
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Authors: | Ivona DlouháJaroslav Kvi?ala Old?ich Paleta |
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Institution: | Department of Organic Chemistry, Prague Institute of Chemical Technology, Technická 5, 16628 Prague 6, Czech Republic |
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Abstract: | A series of nucleophiles was reacted with 1,1,2,4,4,5,7,7,8,8,9,9,9-tridecafluoro-5-trifluoromethyl-3,6-dioxanon-1-ene (1) as a representative of perfluoro(alkyl vinyl ethers). All reactions were completely regioselective with the nucleophilic attack at the terminal carbon atom. Reactions of hydroxy compounds, thiols and sec-amines afforded addition products, but butyllithium, tributylphosphane or complex hydrides caused displacement of vinylic fluorine: butyllithium afforded cis-derivative, while reactions with hydrides and the phosphane led to mixtures of cis- and trans-derivatives. Diethylamine and piperidine adducts displayed the property to substitute hydroxyl for fluorine in hexadecan-1-ol. Molecular properties of hexafluoropropene and perfluoro(methyl vinyl ether) were calculated by ab initio method at the MP2/6-311G(d,p) level of theory and their impact on relative reactivity was estimated. |
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Keywords: | Perfluoro vinyl ether 1 1 2 4 4 5 7 7 8 8 9 9 9-Tridecafluoro-5-trifluoromethyl-3 6-dioxanon-1-ene Nucleophilic addition Fluorination agent Vinylic fluorine displacement Ab initio calculation Molecular properties LUMO energy Electrostatic potential-derived charge Merz-Kollman-Singh scheme |
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