Absolute Rate Constants for the Reactions of tert-Butoxyl with Ethers: Importance of the Stereoelectronic Effect

Article abstract of DOI:10.1021/jo00347a015

Absolute rates of hydrogen atom abstraction by tert-butoxyl from variety of cyclic and acyclic ethers, orthoformates, and acetals have been measured at 27 deg C by laser flash photolysis techniques.High rates of abstraction from the C-H bond adjacent to oxygen and forming small dihedral angle (ca. 30 deg) with the ?-type orbital(s) on the oxygen(s) have been observed.For larger dihedral angles (ca. 90 deg) the rate of C-H abstraction is much lower.Arrehenius parameters have also been measured for a few representative cyclic ethers.