DIOXIRANE CHEMISTRY .25. THE EFFECT OF SOLVENT ON THE DIMETHYLDIOXIRANE CARBON-HYDROGEN BOND INSERTION REACTION

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 alpha parameter taken from the multi-parameter solvent effect equation devised by these authors. The alpha parameter measures the hydrogen bond donor capacity of the solvent. An excellent correlation was observed between the rate coefficients and the alpha 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.