59527-21-8Relevant articles and documents
Evaluation of Addition Rates of Thiyl Radicals to Vinyl Monomers by Flash Photolysis. 3. Polar Effects in Addition Reactions of Substituted Benzenethiyl Radicals
Ito, Osamu,Matsuda, Minoru
, p. 5871 - 5874 (1981)
Rate constants for addition (k1) of para-substituted benzenethiyl radicals (p-XC6H4S*) to vinyl monomers (CH2=CHY) such as isobutyl vinyl ether and vinyl acetate (nonconjugated monomers) and acrylonitrile (conjugated one) have been determined by means of flash photolysis.The rate constants for the reverse reaction (k-1) and the equilibrium constants (K = k1/k-1) have been estimated in the forms of k-1/k2 and Kk2, respectively, where k2 is the rate constant for the reaction between p-XC6H4SCH2C*HY and oxygen; oxygen was used as a selective radical trap to the carbon-centered radicals.From the linear correlations obtained in the Hammett plots of log k1, log (k-1/k2), and log Kk2 vs. the substituent constants (?+), the reaction constants (ρ+) were estimated for each vinyl monomer.The ρ+ (Kk2) values were invariant with a change in vinyl monomers (ρ+(Kk2) = 1.37).The ρ+(k1) values increase with an increase in the electron densities of the double bonds in vinyl monomers.This suggests that a part of the polar effects in the reactivities is determined by the polar effect in the thermodynamic stabilities of the p-XC6H4S* and that another part of the polar effects is caused by the polar resonance structures in the transition state of which contribution varies with the electron-donating or -withdrawing ability of vinyl monomers.