Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 16, Issue 43, Pages 12962-12969Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201001777
Keywords
heterogeneous catalysis; lactones; oxidation; radical reactions; titanium silicalite
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Funding
- ISA (Institute of Advances Studies), at the University of Bologna
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We demonstrate, for the first time, in the Baeyer-Villiger oxidation of cyclohexanone with aqueous hydrogen peroxide under conditions aimed at obtaining epsilon-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, epsilon-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.
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