1104041-73-7Relevant academic research and scientific papers
Mechanism of α-ketol-type rearrangement of benzoin derivatives under basic conditions
Karino, Masahiro,Kubouchi, Daiki,Hamaoka, Kazuki,Umeyama, Shintaro,Yamataka, Hiroshi
, p. 7194 - 7198 (2013)
The mechanism of base-catalyzed rearrangement of ring-substituted benzoins in aqueous methanol was examined by kinetic and product analyses. Substituent effects on the rate and equilibrium constants revealed that the kinetic process has a different electron demand compared to the equilibrium process. Reactions in deuterated solvents showed that the rate of H/D exchange of the α-hydrogen is similar to the overall rate toward the equilibrium state. A proton-inventory experiment using partially deuterated solvents showed a linear dependence of the rate on the deuterium fraction of the solvent, indicating that only one deuterium isotope effect contributes to the overall rate process. All these results point to a mechanism in which the rearrangement is initiated by the rate-determining α-hydrogen abstraction rather than a mechanism with initial hydroxyl hydrogen abstraction as in the general α-ketol rearrangement.
