Chemoselective Synthesis of Stable Phosphorus Ylides from 6-Azauracil and Mechanistic Investigation of the Reaction by UV Spectrophotometry

Abstract

Stable crystalline phosphorus ylides were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine and dialkyl acetylenedicarboxylates, in the presence of NH-acids such as 6-azauracil. 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 automatically drawn, and the values of the second order rate constants (k2) were automatically calculated using standard equations. At the temperature range studied, the dependence of the second order rate constant (Ln k2) on reciprocal temperature was in agreement with the Arrhenius equation. This provided the relevant plots to calculate the activation energy of all the reactions. Furthermore, useful information was obtained from studies of the effect of solvent, structure of reactants (different alkyl groups within the dialkyl acetylenedicarboxylates), and also concentration of reactants on the rate of reactions. The proposed mechanism was confirmed according to the obtained results, and a steady-state approximation and first step (k2) of the reaction was recognized as a rate-determining step on the basis of experimental data.