38092-02-3Relevant academic research and scientific papers
Radiation Chemical Production and Lifetimes of Trialkoxymethyl Carbocations in Aqueous Solution
Steenken, S.,Buschek, J.,McClelland, R. A.
, p. 2808 - 2813 (1986)
Trialkoxymethyl radicals were produced in aqueous solution by H abstraction from trialkoxymethanes by OH and H.The radicals were then oxidized by one-electron transfer to give trialkoxymethyl carbocations.The reactions of the cations with water and with OH- were studied by using time-resolved conductance techniques. (CH3O)3C+ hydrolyzes with a rate constant of (1.4 +/- 0.2)E3 s1- and it reacts with OH- with k = (7 +/- 1)E7 M1-s1-.The activation parameters for the reaction with water are EA = 7.6 kcal/mol and ΔS(excit.) = -20.2 eu.Replacement of methoxy in the cation by ethoxy and isopropoxy leads to a pronounced decrease in the rate constants for these processes: the Taft ρ* values for the reaction of (RO)3C+ with H2O and OH- are 5.7 and 3.7, respectively.With cyclic trialkoxymethyl cations that from the six-membered 1,3-dioxane system is more stable than that from 1,3-dioxolane, the five-atom counterpart.Trialkoxymethyl cations are also produced by a β-fragmentation reaction from α-(β-trialkoxy)methoxyalkyl cations.
