Homolitic Decomposition of tert-Butyl Phenylteracetates.

초록

Substituted t-butyl phenylperacetates were prepared. Thermal decomposition of the peresters were observed in CDCl3 at 60, 70, 80, 90, 100, 110℃. The absolute(kY) and relative rate constants(kY/kH) were measured at the temperatures. Substituent effects have been analyzed in terms of Hammett correlation. ρ＋ gives better correlation than ρ. The temperature studies showed that the selectivity increases with higher temperature, and disobeys the reactivity/selectivity principle. Activation parameters (△H≠, △S≠) and differential activation parameters (△△H≠, △△S≠) were obtained from Eyring equation. The rates are controlled by entropy.