Theoretical Study,An Efficient Synthesis Route to,and Kinetic Investigation of,Stable Phosphorus Ylides Derived from Benzamide

Abstract

The synthesis, theoretical study and a kinetics and mechanistic investigation are described as a one-pot condensation reaction between benzamide and acetylenic esters in the presence of triphenyphosphine to generate a novel stable phosphorus ylides. For the first time, theoretical calculations have been employed to assign the most stable isomers (Z or E) of phosphorus ylides 4a-c by AIM and NBO theory, in which Z-4(a,b) are the more stable forms, whereas Z-4c appears as a single isomer. In these cases, the ¹H, ¹³C and ³¹P NMR spectra of these ylides are consistent with the results obtained from theoretical calculations. Kinetic investigation of the new ylides was undertaken by UV. Useful information was obtained from studies of the effect of solvent, structure of reactants (different alkyl groups within the acetylenic esters), and also the concentration of reactants on the rate of reactions. The proposed mechanism was consistent with the results obtained; from the steady-state approximation, the first step (k₂) of the reaction was recognized as the rate-determining step on the basis of the experimental data.