Synthesis and reactivity of tert-Butyl-(2-aryl-3-methyl-but-2-yl) peroxides

Article abstract of DOI:10.1002/prac.19973390111

tert-Butyl-(2-aryl-3-methyl-but-2-yl) peroxides (2a-d) were prepared from t-BuOOH and corresponding 2-aryl-methyl-butan-2-ols (1a-d) (Ar:p-MeO-C₆H₄ (a); Ph (b); p-Cl-C₆H₄ (c); m-CF₃-C₆H₄ (d)) and characterized by NMR, MS and elemental analysis. Kinetic data for the thermolysis of 2a-d in cumene as the solvent were determined at 110-140°C and the products analyzed. The rate constants satisfy the Hammett equation with σ giving a ρ-value of -0.73. Oxidation of 2a-d at 80°C gives the corresponding acetophenones 4, epoxides 6 and hydroperoxides 8. The products of the oxidation of 2a-2d were analysed after reduction of the reaction mixtures with LiAlH₄. Relative reactivities of the tertiary C-H bonds of peroxides 2 were determined by competitive oxidations. They amount to 0.115-0.275 (with respect to the tertiary C-H bond of cumene). Johann Ambrosius Barth 1997.