Solvent-free chromium catalyzed aerobic oxidation of biomass-based alkenes as a route to valuable fragrance compounds.

Chromium containing mesoporous molecular sieves MCM-41 were shown to be an efficient heterogeneous catalyst for the liquid-phase aerobic oxidation of various monoterpenic alkenes under mild solvent-free conditions. The material was prepared through a direct hydrothermal method and characterized by ICP-AES,N2 adsorption?desorption, TEM, XRD, SAXS, andH2-TPR techniques. Characterizations suggest that chromium introduced in MCM-41 is essentially incorporated in the silica framework, with no extraframework chromium oxides being detected. Various oxygenated monoterpenoids important for the flavor and fragrance industry were obtained with high combined selectivities (75?92%) at 30?40% substrate conversions. The oxidation of _-pinene led almost exclusively to allylic mono-oxygenated derivatives, whereas limonene and _-pinene gave both epoxides and allylic oxidation products. The catalyst undergoes no metal leaching and can be easily recovered and re-used. A silica-included chromium catalyst prepared through a conventional sol?gel method showed activity comparable with that of Cr- MCM-41; however, selectivity was much lower