60838-91-7Relevant academic research and scientific papers
Functionalization of saturated fluorocarbons with and without light
Chen, Xudong,Lemal, David M.
, p. 1158 - 1167 (2008/09/19)
Photochemical transformation of saturated fluorocarbons into tetrabutylammonium enolates has been improved, and a method employing ketyls as reductants has been developed that accomplishes the same chemistry without light. Enolates have been isolated as enol methyl ethers, from which they can be efficiently regenerated with tetrabutylammonium iodide. In other cases, enolates have been isolated as the corresponding ketone or stable enol. Fluorocarbon LUMO energies correlate with their reactivity and serve as a guide to the choice of ketyl. Use of this chemistry for fluoropolymer surface modification is discussed.
Perfluorinated cyclic and acyclic keto-enol systems: A remarkable contrast
Lindner, Patrick E.,Lemal, David M.
, p. 3259 - 3266 (2007/10/03)
Recent reports from this laboratory have revealed that highly fluorinated 4- and 5-membered-ring enols are comparable in stability to, or more stable thermodynamically than, the corresponding ketones, even in non-Lewis-basic media. Work on perfluorinated
Novel keto-enol systems: Cyclobutane derivatives
Lindner, Patrick E.,Correa, Ricardo A.,Gino, James,Lemal, David M.
, p. 2556 - 2563 (2007/10/03)
3H-Perfluorobicyclo[2.2.0]hexan-2-one (3) has been synthesized from hexafluorobenzene and equilibrated with its enol form (4). In carbon tetrachloride K(e/k) = 0.07 ± 0.01 (25°C), but in Lewis basic solvents (e.g. acetonitrile, ether, and tetrahydrofuran) only enol is detectable at equilibrium because of its strength as a hydrogen bond donor. In the monocyclic counterpart of this keto-enol system, 2H-perfluorocyclobutanone (1) and perfluorocyclobut-1-enol (2), the enol is more stable yet. Here ketone is undetectable under equilibrating conditions in all media examined, including carbon tetrachloride. Among unhindered and unconjugated enols, 2 and 4 are more stable relative to their ketones than any others that have been reported. Ab initio quantum mechanical calculations support the conclusion that destabilization of the ketones, but not stabilization of the enols, by fluorine substitution is responsible for the unique relative stability of these enols.
