18720-62-2Relevant articles and documents
Reactions of partially solvated Grignard reagents with a ketone
Tuulmets, Ants,Sassian, Meeri
, p. 145 - 149 (1999)
Ratios of the yields of addition and reduction products for the reactions of n-butylmagnesium chloride and bromide with diisopropyl ketone in toluene were determined at different THF, diethyl ether and methyl tertbutyl ether (MTBE) contents in the Grignard reagent. The reduction reaction yield is a maximum at the molar ratio 0.1 of THF or diethyl ether to the Grignard reagent. The addition reaction has a maximum in the region of 0.3-0.4 for the same ethers and about 1.5 for MTBE. The ratio Add/Red for conventional Grignard reagents is lower than that for partially solvated reagents. The results were discussed in terms of the solvation of the species in the reaction mixture. The decisive role of the steric requirements of the reagents over their intrinsic acid-base properties was demonstrated. Partially solvated Grignard reagents can serve as tools for the investigation of solvent effects in the Grignard reaction.
Solvation effects in the Grignard reaction with carbonyl compounds
Sassian, Meeri,Tuulmets, Ants
, p. 82 - 90 (2007/10/03)
Ratios of the yields of addition and reduction products for the reactions of butylmagnesium chloride with diisopropyl ketone, methyl 2-methylpropanoate, and isopropyl 2-methylpropanoate in toluene were determined at different THF, diethyl ether, and tert-
Instantaneous SmI2-H2O-mediated reduction of dialkyl ketones induced by amines in THF
Dahlén, Anders,Hilmersson, G?ran
, p. 7197 - 7200 (2007/10/03)
Reduction of various ketones to their corresponding alcohols is shown to be instantaneous, i.e. completed in less than 10 s, by samarium diiodide (2.5 equiv.) in the presence of water (6.25 equiv.) and an amine (5 equiv.) in THF. The rates of reduction of ketones in this mixture exceed by far the rates determined by an amine or water alone. Rate enhancement is at least 100 000 compared to the reduction without a proton source, or at least 100 times faster than the rate of the widely used HMPA/alcohol accelerated reductions. This new method is therefore suggested to be an excellent replacement of the toxic HMPA/alcohol method.