Investigation of intermolecular proton exchange of 3,6-di-tert-butyl-2-oxyphenoxyl with N-phenylanthranilic acid by ESR spectroscopy method

Abstract

In this work we studied the intermolecular proton exchange (IPE) reaction between the spin probe of 3,6-ditert- butyl-2-hydroxyphenoxyl (I) and the aromatic amino acid N-phenylanthranilic acid (N-PhAA). The experimental spectra of the 3,6-di-tert-butyl-2-hydroxyphenoxyl-N-phenylanthranilic acid system were recorded using dynamic EPR spectroscopy. The studies were carried out in a non-aqueous indifferent solvent toluene in a wide temperature range. The theoretical EPR spectra of the radical I — N-PhAA system corresponding to various process rates were successfully simulated using the ESR-EXHANGE program. This program is written in the modern version of the algorithmic language Fortran 90. The general line-form equation for the four-jump model have been derived from the modified Bloch equations. The second-order rate constants for the intermolecular proton exchange process between radical I and N-PhAA were determined by comparison of the experimental and simulated EPR spectra. The iterative least squares procedure was used for computer analysis of the kinetic data of intermolecular proton exchange and for obtaining activation parameters of the reaction. From kinetic data it follows that N-phenylanthranilic acid has the lowest value of protolytic ability in comparison with aminobenzoic acids.