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A Rationale of the Baeyer–Villiger Oxidation of Cyclohexanone to ε‐Caprolactone with Hydrogen Peroxide: Unprecedented Evidence for a Radical Mechanism Controlling Reactivity
Author(s) -
Cavani Fabrizio,
Raabova Katerina,
Bigi Franca,
Quarantelli Carla
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201001777
Subject(s) - cyclohexanone , chemistry , hydrogen peroxide , adipic acid , catalysis , reactivity (psychology) , radical , caprolactone , peroxide , solvent , aqueous solution , polymer chemistry , baeyer–villiger oxidation , organic chemistry , polymerization , medicine , polymer , alternative medicine , pathology
We demonstrate, for the first time, in the Baeyer–Villiger oxidation of cyclohexanone with aqueous hydrogen peroxide under conditions aimed at obtaining ε‐caprolactone, that a thermally activated radical reaction leads to the concurrent formation of adipic acid, even when a stoichiometric amount of the oxidant is used. In fact, ε‐caprolactone is the primary reaction product, but it is more reactive than cyclohexanone, and quickly undergoes consecutive transformations. When titanium silicalite‐1 (TS‐1) is used as a catalyst, the high concentration of hydroxy radicals within its pores accelerates the reaction rates, and the consecutive formation of adipic acid (and of lighter diacids as well) becomes largely kinetically preferred. The proper choice of the solvent, which also may act as a radical scavenger, both without catalyst and with TS‐1, is a powerful tool for controlling the rates of the various reactions involved.