Synthesis of Stable Phosphorus Ylides from 6-Chloro-2-Benzoxazolinone and Kinetic Investigation of the Reactions by Uv Spectrophotometry

Abstract

Stable crystalline phosphorus ylides were obtained in excellent yields from the 1:1:1 addition reactions between triphenylphosphine and dialkyl acetylenedicarboxylates, in the presence of an NH-acid, such as 6-chlorobenzoxazolinone. These stable ylides exist in solution as a mixture of two geometrical isomers as a result of restricted rotation around the carbon-carbon partial double bond resulting from conjugation of the ylide moiety with the adjacent carbonyl group. To determine the kinetic parameters of the reactions, they were monitored by UV spectrophotometry. The second order fits were drawn and the values of the second order rate constant ( k2) were calculated automatically using standard equations within the program. Over the temperature range studied, the dependence of the second order rate constant (Ln k2) on reciprocal temperature was in a good agreement with the Arrhenius equation, leading to the activation energies of all reactions. Furthermore, useful information was obtained from studies of the effect of solvent, the structure of reactants (different alkyl groups within the dialkyl acetylenedicarboxylates) and also the concentration of reactants on the rate of reactions. The proposed mechanism is consistent with the results obtained and the steady state approximation, and the first step ( k2) of reaction was recognized as the rate-determining step on the basis of experimental data.