Synthesis of 2- (perfluoroalkyl)ethyl potassium sulfates based on perfluorinated Grignard reagents

0352163 - ÚOCHB 2011 RIV CH eng J - Článek v odborném periodiku
Paterová, J. - Skalický, M. - Rybáčková, M. - Kvíčalová, Magdalena - Cvačka, Josef - Kvíčala, J.
Synthesis of 2- (perfluoroalkyl)ethyl potassium sulfates based on perfluorinated Grignard reagents.
Journal of Fluorine Chemistry. Roč. 131, č. 12 (2010), s. 1338-1343. ISSN 0022-1139. E-ISSN 1873-3328
Grant ostatní: GA MŠk(CZ) LC06070; GA ČR(CZ) GA203/06/1511
Program: LC
Výzkumný záměr: CEZ:AV0Z40550506; CEZ:AV0Z40320502
Klíčová slova: fluoro Grignard reagent * nucleophilic substitution * DFT
Kód oboru RIV: CC - Organická chemie
Impakt faktor: 1.719, rok: 2010

The first example of nucleophilic substitution with perfluoroalkyl Grignard reagents on the sp3 carbon centre is described. Thus, a series of organometals RF-MgBr, prepared from perfluorinated alkyl iodides reacted with 1,3,2-dioxathiolane-2,2-dioxide to afford the corresponding 2-(perfluoroalkyl)ethyl magnesium sulfates, which were isolated after metathesis to the corresponding potassium salts. In the model reaction, perfluorohexylmagnesium iodide was reacted with methyl triflate yielding polyfluorinated alkane. Polyfluorinated sulfates are easily hydrolyzed with hydrochloric or triflic acid to the corresponding alcohols, which is an alternative to standard transformation of perfluoroalkyl iodides to 2-(perfluoroalkyl)ethanols. Quantum-chemical calculations of the PES of the reaction with both sulfur-containing heterocycles found that the failure of the reaction with 1,3,2-dioxathiane-2,2-dioxide is caused by higher activation energy of the process.
Trvalý link: http://hdl.handle.net/11104/0191740