Synthesis and Reactivity oftert‐Butyl‐(2‐aryl‐3‐methyl‐but‐2‐yl) Peroxidestert‐Butyl‐(2‐aryl‐3‐methyl‐but‐2‐yl) peroxides(2a–d)were prepared fromt‐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 of2a–din 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 of2a–dat 80 °C gives the corresponding acetophenones4, epoxides6and hydroperoxides8. The products of the oxidation of2a–2dwere analysed after reduction of the reaction mixtures with LiAlH4. Relative reactivities of the tertiary CH bonds of peroxides2were determined by competitive oxidations