79976-67-3Relevant academic research and scientific papers
Temperature dependence of the reactions of phenyl radicals with 1,1-diphenylethylene, carbon tetrachloride, and cyclohexene
Weldon, Dean,Holland, Stacey,Scaiano
, p. 8544 - 8546 (1996)
The reaction of phenyl radicals with 1,1-diphenylethylene (DPE), carbon tetrachloride, and cyclohexene has been examined over a range of temperatures using laser flash photolysis techniques. The activation energies are 0.71 ± 0.04, 3.53 ± 0.11 and 2.32 ± 0.33 kcal/mol, and the preexponential factors, expressed as log (A/M-1s-1), are 9.19 ± 0.03, 8.96 ± 0.09, and 9.02 ± 0.26, for DPE, CCl4, and c-C6H10, respectively. In particular the CCl4 data provide a much needed reference for competitive studies.
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.
body text, 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.
