Theoretical, kinetics and mechanism investigation of the reaction between triphenylphosphine, di-tert-butyl acetylenedicarboxilate and OH-acid

Kinetic studies were made of the reaction between triphenylphosphine, di-tert-butyl acetylenedicarboxylate in the presence of OH-acid, such as 2-hydroxy-4-methoxybenzaldehyde. To determine the kinetic parameters of the reaction, it was monitored by UV spectrophotometery. The second order fits were automatically drawn by the software associated with a Cary UV spectrophotometer model Bio-300 at appropriate wavelength. The values of the second order rate constant (k2) were calculated using standard equations within the program. At the temperature range studied the dependence of the second order rate constant (Ln k2) on reciprocal temperature was in a good agreement with Arrhenius equation. This provided the relevant plots to calculate the activation energy of the reaction. Furthermore useful information were obtained from studies of the effect of solvent and concentration of reactants on the rate of reaction. Proposed mechanism was confirmed according to the obtained results and steady state approximation and first step (k2) of reaction was recognized as a rate determining step on the basis of experimental data. In addition, assignment of more stable isomers (Z or E) were investigated using the theoretical study.