Published July 15, 1981 | Version v1
Journal article

Reaction of tert-butoxy radicals with phenols. Comparison with the reactions of carbonyl triplets

  • 1. Univ. of Notre Dame, IN

Description

Tert-butoxy radicals generated in the photodecomposition of di-tert-butyl peroxide react efficiently with phenols to yield the corresponding phenoxy radicals. Typical rate constants in benzene at 220C are 3.3 x 108 and 1.6 x 109 M-1 s-1 for phenol and p-methoxyphenol, respectively. The process is considerably slower in polar solvents; e.g., when pyridine is used as cosolvent, the rate constant for phenol drops to 4.1 x 106 M-1 s-1 as a result of strong hydrogen bonding which decreases the reactivity of the phenolic O-H group. Isotope effects (H/D) are typically in the 3 to 5 range. 5 figures, 4 tables

Additional details

Publishing Information

Journal Title
J. Am. Chem. Soc.
Journal Volume
103
Journal Issue
14
Series
J. Am. Chem. Soc.
Journal Page Range
4162-4166
ISSN
0002-7863