A rationale of the Baeyer-Villiger oxidation of cyclohexanone to ε-caprolactone with hydrogen peroxide: unprecedented evidence for a radical mechanism controlling reactivity.
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.
Cavani
Fabrizio
F
Dipartimento di Chimica Industriale e dei Materiali, ALMA MATER STUDIORUM Università di Bologna, Viale Risorgimento 4, 40136 Bologna, Italy.
Raabova
Katerina
K
Bigi
Franca
F
Quarantelli
Carla
C
D002208:Caproates / Q000737:chemistry*; D002384:Catalysis; D003512:Cyclohexanones / Q000737:chemistry*; D016166:Free Radical Scavengers / Q000737:chemistry; D006861:Hydrogen Peroxide; D007783:Lactones / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D017640:Silicates / Q000737:chemistry; D013237:Stereoisomerism; D013816:Thermodynamics; D014025:Titanium / Q000737:chemistry; D014867:Water / Q000737:chemistry
D002208:Caproates; D003512:Cyclohexanones; D016166:Free Radical Scavengers; D007783:Lactones; D017640:Silicates; D014867:Water; C103828:titanium silicide; C121056:caprolactone; C036468:cyclohexanone; D006861:Hydrogen Peroxide; D014025:Titanium