142706-75-0Relevant academic research and scientific papers
Facile access to fluorinated aryl and vinyl ethers through copper-catalysed reaction of fluoro alcohols
Vukga, Daniela,Legros, Juelien,Crousse, Benoit,Bonnet-Delpon, Daniele
experimental part, p. 3513 - 3518 (2009/12/01)
Fluorinated alcohols react with aryl and vinyl halides by copper-catalysed cross-coupling reactions to afford the corresponding ethers. With trifluoroethanol (TFE) the reaction proceeds with both iodides and bromides and a wide range of aromatic substituents are tolerated. When higher fluorinated homologues such as C7P15CH2OH were used, the corresponding products were obtained in good yields, thus of-fering an interesting entry to fluorous tagging.
A fast radical chain mechanism in the polyfluoroalkoxylation of aromatics through NO2 group displacement. Mechanistic and theoretical studies
Tejero, Ismael,Huertas, Imma,Gonzalez-Lafont, Angels,Lluch, Jose M.,Marquet, Jordi
, p. 1718 - 1727 (2007/10/03)
(Chemical Equation Presented) Introduction of polyfluoroalkoxy and polyfluoroalkylthio substituents in aromatic rings can be achieved with mild conditions and short times thorough reaction of concentrated solutions of dinitrobenzenes in DMF with polyfluoro alcohols and polyfluoro thiols in moderate excess, in the presence of excess tetrabutylammonium fluoride as a base. Mechanistic studies suggest that under these conditions a fast radical chain mechanism operates. This mechanism is elicited by oxidation of a Meisenheimer complex and proceeds through a radical aromatic substitution with the polyfluoroalkoxy or the polyfluoroalkylthio radicals as key intermediates. At low concentrations, entrainment can be achieved with superoxide anion. A rationale for this effect is discussed. Answers to particular questions about the proposed mechanism are achieved through a theoretical study at the B3LYP/6-31+G(d,p) level. Specifically, the competition between the radical mechanism and the corresponding polar one (classical SNAr reaction) is studied in that way, with the conclusion that the key steps of the radical mechanism in our reaction conditions (polar aprotic solvent) are at least as efficient as the ones of the polar one, thus justifying the observed kinetic advantage for the chain reaction in the conditions where an efficient initiation occurs.
Various synthetic approaches to fluoroalkyl p-nitrophenyl ethers
Preschera, Dietrich,Thiele, Thomas,Ruhmann, Ralf
, p. 145 - 148 (2007/10/03)
Homologous 1H,1H-perfluoroalkyl p-nitrophenyl ethers (alkyl = C2-C8) were synthesized using different methods. The results are discussed in context with contradictory comments of the literature. The fluoroalkoxylation of p-chloronitrobenzene occurs in only one step, but it is limited to small fluoroalkyl groups. The fluoroalkylation of p-nitrophenol via sulphonic acid esters is a better synthetic route. Differences in reactivity and yield between tosylates, mesylates and inflates are found and discussed. The preferred synthesis includes the use of trifluoromethane sulphonic acid esters.
