Abstract
The relative rates of decomposition of peroxyesters in cumene at 100° and their activation parameters ΔH≠ (kcal/mol) and ΔS≠ (cal deg−1 mol−1) were tert-butyl perbenzoate (1) 1.0, 34.0, 9.3; tert-butyl pertoluate (7) 1.3, 32.2, 4.8; tert-butyl permesitoate (8) 11, 31.9, 8.4; and tert-butyl 2,4,6-tri-tert-butylperbenzoate (9) 29, 32.9, 13.0. Each peroxyester yielded the corresponding acid as one of the products. The reactions are all interpreted as proceeding through a rate-determining scission of the O—O bond to yield a benzoyloxy radical, which then undergoes competitive decarboxylation and hydrogen abstraction from the solvent. The small rate acceleration due to a para substituent is interpreted as due to a polar factor and the larger rate enhancing effect of the ortho substituents is interpreted as due to destabilization of the ground state due to twisting of the carboxyl group out of conjugation with the ring.
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