Dioxirane chemistry. Part 25. The effect of solvent on the dimethyldioxirane carbon–hydrogen bond insertion reaction

Abstract

Second order rate coefficients for the insertion reaction of dimethyldioxirane with cis-1,2-dimethylcyclohexane have been measured in several binary solvents. The reaction proceeds stereospecifically with retention to give a single alcohol product as reported earlier. The data were treated with the Kamlet–Taft α parameter taken from the multi-parameter solvent effect equation devised by these authors. The α parameter measures the hydrogen bond donor capacity of the solvent. An excellent correlation was observed between the rate coefficients and the α values indicating that the insertion reaction is facilitated by solvents with hydrogen bond donor properties. A spiro type transition state is proposed for the insertion reaction.