REACTIVITY OF CERTAIN HYDROGEN DONORS AND OLEFINS WITH RESPECT TO α,α-DICHLOROALKYL RADICALS

Article abstract of DOI:10.1007/BF00961494

The rate constants of hydrogen splitting from hydrogen donors (DH) by the ClCH2(CH2)3CCl2 radicals (R¹) were determined by the method of competitive kinetics in the temperature range of 413-433 K.As a competing reaction with splitting of hydrogen from the DH, the isomerization of radicals R¹ into ClCH(CH2)3CCl2H with 1,5-migration of hydrogen was chosen, for which log k (sec^-1) = 9.343 - 10.56/2,303RT (kcal/mole) was calculated.It was found that the relative reactivities are similar of R¹ and (CH3)3CO radicals (R⁴) in splitting hydrogen from HD.This makes it possible to predict the values of analogous constants for radicals R¹ from known rate constants of splitting hydrogen from various DH by radicals R⁴.The rate constants of the addition of Cl(CH2)2CCl2 radicals (R²) to α-methylstyrene and methyl methacrylate were determined.Taking into account the data in <7>, where the same constants were determined for styrene, methyl acrylate, acrylonitrile and vinyl methyl ketone, the existence of a linear dependence was shown of the logarithm of the rate constant of the addition of radicals R² to olefins on the polar properties of the above-enumerated olefins.