CHEMISTRY OF SINGLET OXYGEN—XXVI. PHOTOOXYGENATION OF PHENOLSy†

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Abstract
Abstract— The aerobic dye‐sensitized photooxygenation of monohydric phenols proceeds by way of singlet oxygen under the conditions studied. Various phenols give different proportions of reaction with and quenching of singlet oxygen. Para‐substituted 2,6‐di‐t‐butylphenols show a linear correlation between the log of the total rate of singlet oxygen removal and their halfwave oxidation potentials; the same correlation is given for certain phenol methyl ethers. A Hammett plot using s̀+ gives ρ ‐ 1.72 ± 0.12, consistent with development of some charge in the quenching step. Reaction of photo‐chemically generated singlet oxygen with 2,4,6‐triphenylphenol gives 2,4,6‐triphenylphenoxy radical as an intermediate in singlet oxygen quenching, although no overall reaction occurs. Kinetic analysis indicates that the radical is derived exclusively from the interaction of 2,4,6‐triphenylphenol with singlet oxygen. A charge‐transfer mechanism for quenching of singlet oxygen by phenols is proposed.