118716-49-7Relevant academic research and scientific papers
The Grignard reagent formation reaction of 2-chloro-1,1,1-triphenylethane revisited
Bickelhaupt, Friedrich,Newcomb, Martin,DeZutter, Christopher B.,De Boer, Henk J. R.
experimental part, p. 6225 - 6231 (2009/05/31)
The reaction of 2-chloro-1,1,1-triphenylethane (1) with magnesium in THF has been reinvestigated. The reaction produced a dark-red solution and after deuterolysis with D2O, 1,1,1-triphenylethane (2; 16%), 2-D-1,1,1-triphenylethane (3; 52%) and 1,1,2-triphenylethene (4; 26%) were isolated. Rate constants for phenyl migration in the 2,2,2-triphenylethyl radical were measured directly between 23°C and 55°C; the reaction is described by logk = 11.2 - 7.5/2.3 RT [kcal/mol] and the rate constant for rearrangement at 20°C is 4.0 × 105 s-1. The combined results support the intermediate formation of radicals in the reaction of chloride 1 with magnesium. The red colour of the reaction mixture, however, indicates the formation of a carbanionic species, which has not yet been identified. The diffusion model for Grignard formation reactions of Garst et al. is in line with the product distribution. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
