A facile synthesis of stable phosphorus ylides derived from 3,6‐dibromocarbazole and kinetic investigation of the reactions by UV spectrophotometry technique

Abstract

AbstractStable 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‐acid, such as 3,6‐dibromocarbazole. 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 the 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 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 the Arrhenius equation. This provided the relevant plots to calculate the activation energy of all 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 the concentration of reactants on the rate of reactions. The proposed mechanism was confirmed according to the obtained results and a steady‐state approximation and the first step (k2) of reaction was recognized as a rate‐determining step on the basis of the experimental data. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:723–732, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20501