All ring compounds-XXIX. Thermal decomposition of t-butyl per (trans-2-substituted cyclopropyl) acetates

Article abstract of DOI:10.1016/S0040-4020(01)97355-7

Three kinds of t-butyl per (trans-2-substituted cyclopropyl) acetates (RH, CH₃, C₆H₅) were synthesized from the corresponding acyl chlorides and thermally decomposed in cyclohexane to investigate the chemical stability and behaviour of the cyclopropylcarbinyl radical. Clean first-order kinetics were obtained in all of the thermal decomposition reactions. The experimental fact that the decompositoin rates and activation parameters of these three t-butyl peresters are similar to each other may indicate the absence of the ionic character in the transition state suggesting the almost complete homolytic decomposition of these peresters. Although the typical concerted decomposition might be invalid for these peresters in view of the activation parameters, it would be suggested from the product studies that the decomposition of these peresters was characterized by a considerable loss of their acyl-alky] bonds at the time of the fission of their OO bonds. The products yielded from the thermal decomposition of t-butyl per (trans-2-phenylcyclopropyl) acetate in various hydrogen donating solvents consisted of three hydrocarbons and two t-butyl ethers. The formation of these t-butyl ethers, possibly cage products, was significant.