Very low pressure pyrolysis of phenyl acetate

Abstract

The kinetics of the unimolecular decomposition of phenyl acetate into phenol and ketene, reaction (1): PhOCOCH_3 → PhOH + CH_2=C=O has been studied under very low-pressure conditions between 950 and 1120 K. In this range alternative processes such as the Fries rearrangement to o-hydroxyacetophenone or bond fission into phenoxyl and acetyl radicals are not observed. Based on present and previous evidence a novel four-center transition state is proposed for reaction (1) which corresponds to the high-pressure Arrhenius expression log (k_1, s^(−1)) = 12.8 – 56.2/θ, θ = 4.575 × 10^(−3)T kcal/mol.

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