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Phenolic Hydrogen Transfer by Molecular Oxygen and Hydroperoxyl Radicals. Insights into the Mechanism of the Anthraquinone Process.

ABSTRACT: Hydrogen atom transfer (HAT) by ³O₂ and HO₂^• from arenols (ArOH), aryloxyls (ArO^•), their tautomers (ArH), and auxiliary compounds has been investigated by means of CBS-QB3 computations. With ³O₂, excellent linear correlations have been found between the activation enthalpy and the overall reaction enthalpy. Different pathways have been discerned for HATs involving OH or CH moieties. The results for ArOH + HO₂^• → ArO^• + H₂O₂ neither afford a linear correlation nor agree with the experiment. The precise mechanism for the liquid-phase autoxidation of anthrahydroquinone (AnH₂Q) appears to be not fully understood. A kinetic analysis shows that the HAT by chain-carrying HO₂^• occurs with a high rate constant of ≥6 × 10⁸ M^-1 s^-1 (toluene). The second propagation step pertains to a diffusion-controlled HAT by ³O₂ from the 10-OH-9-anthroxyl radical. Oxanthrone (AnOH) is a more stable tautomer of AnH₂Q with a ratio of 13 (298 K) in non-hydrogen-bonding (HB) solvents, but the reactivity toward ³O₂/HO₂^• is much lower. Combination of the computed free energies and Abrahams' HB donating (α₂^H) and accepting (β₂^H) parameters has afforded an α₂^H(HO₂^•) of 0.86 and an α₂^H(H₂O₂) of 0.50.

SUBMITTER: Korth HG

PROVIDER: S-EPMC7040920 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Phenolic Hydrogen Transfer by Molecular Oxygen and Hydroperoxyl Radicals. Insights into the Mechanism of the Anthraquinone Process.

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