Synthesis of perfluoroaliphatic grignard reagents

作者: D.D. Denson , C.F. Smith , C. Tamborski

DOI: 10.1016/S0022-1139(00)82624-X

关键词: SolventDiethyl etherOrganic chemistryReagentChemistryCyclohexanoneStoichiometryMedicinal chemistryTetrahydrofuranHalideYield (chemistry)

摘要: Abstract Perfluoraliphatic mono- and di-Grignard reagents (R f MgX, XMgR′ MgX) have been conveniently synthesized in excellent yields (90–100%) through metalhalogen exchange reactions. The degree of has found to be subject a number experimental parameters, e.g. the nature solvent (tetrahydrofuran vis-a-vis diethyl ether), type halide displaced, organomagnesium reagent stoichiometry. These sufficient thermal stability at low temperatures (−70°) useful as intermediates for synthesis variety compounds. Various perfluoroaliphatic Grignard reacted with H 3 O + , CO 2 (CF ) cyclohexanone yield R H, OH 1-cyclo-C 6 10 (OH)R compounds, respectively. selection proper reaction conditions, i.e. solvent, temperature time, extremely important preparation derivatives various reagents.

参考文章(12)
Paul. Tarrant, Richard H. Summerville, Ralph W. Whitfield, Preparation and reactions of some trifluorovinyl carbinols containing perhalomethyl groups Journal of Organic Chemistry. ,vol. 35, pp. 2742- 2745 ,(1970) , 10.1021/JO00833A058
R. N. HASZELDINE, Recent Advances in Organic Fluorine Chemistry Nature. ,vol. 168, pp. 1028- 1031 ,(1951) , 10.1038/1681028A0
O. R. Pierce, A. F. Meiners, E. T. McBee, A New Synthesis of n-Heptafluoropropyl Grignard Reagent Journal of the American Chemical Society. ,vol. 75, pp. 2516- 2516 ,(1953) , 10.1021/JA01106A518
Albert L. Henne, William C. Francis, Perfluorinated Grignard Derivatives Journal of the American Chemical Society. ,vol. 73, pp. 3518- 3518 ,(1951) , 10.1021/JA01151A519
E. T. McBee, C. W. Roberts, A. F. Meiners, Reactions of 1-Heptafluoropropylmagnesium Bromide. II.1 The Synthesis of Fluorine-containing Olefins and of 1-Heptafluoropropylbenzene Journal of the American Chemical Society. ,vol. 79, pp. 335- 337 ,(1957) , 10.1021/JA01559A024
E. T. McBee, Robert D. Battershell, H. P. Braendlin, A New Synthesis of Perfluoroalkylmagnesium Halides Journal of Organic Chemistry. ,vol. 28, pp. 1131- 1133 ,(1963) , 10.1021/JO01039A504
O. R. Pierce, M. Levine, Preparation and Some Reactions of n-Hepta-fluoropropylmagnesium Iodide Journal of the American Chemical Society. ,vol. 75, pp. 1254- 1254 ,(1953) , 10.1021/JA01101A515
Albert L. Henne, William C. Francis, Reactions of Perfluorinated Propylmagnesium Iodide Journal of the American Chemical Society. ,vol. 75, pp. 992- 994 ,(1953) , 10.1021/JA01100A510
P.M. Treichel, F.G.A. Stone, Fluorocarbon Derivatives of Metals Advances in Organometallic Chemistry. ,vol. 1, pp. 143- 220 ,(1964) , 10.1016/S0065-3055(08)60067-2
R. N. Haszeldine, Perfluoroalkyl Grignard and Grignard-type reagents. Part IV. Trifluoromethylmagnesium iodide Journal of the Chemical Society (Resumed). pp. 1273- 1279 ,(1954) , 10.1039/JR9540001273