63121-56-2Relevant academic research and scientific papers
Thermolysis of aryl-tert-alkyl-tert-butylmethanols: substituent effects and benzyl stabilization of strained radicals
Lomas, John S.,Adenier, Alain,Boussad, Nadjib
, p. 395 - 400 (2007/10/02)
Rate constants and products of the thermolysis of a series of ortho-tolyl-tert-alkyl-tert-butylmethanols have been determined with particular attention to the homolytic scission of the t-Bu-C bond.By means of molecular mechanics calculations an attempt is made to interpret the effects of varying the second tert-alkyl group upon the reactivity.It is found that the secondary alcohol model, used successfully for tri-tert-alkylmethanols, is unsuitable for aryl-substituted alcohols.Thermolysis rates of ortho-tolyldi-tert-butylmethanols appear, surprisingly, to be reduced by spin-delocalizing para or meta substituents, with a ρα. value of -3.9 or a ρ+ of 0.1.A tentative explanation in terms of stretching of the sp2-sp3 CAr-COH bond in the initial state is proposed.
