Transfer Hydrogenation of Furfural to Furfuryl Alcohol Under Microwave Irradiation Using Mixed Oxides.

The reaction to obtain furan alcohols is one of the most important in the upgrading of furan derivates. An attractive route is the transfer hydrogenation of furfural using acidic-basic catalysts. In this work, mixed oxides derived from ternary hydrotalcites were employed to obtain furfuryl alcohol from furfural assisted by microwave irradiation. These materials were characterized via X-ray diffraction (XRD), N2 adsorption-desorption isotherms, Fourier-transform infrared (FTIR) and the CO2 temperature-programmed desorption (CO2 -TPD) analyses. The lamellar structure of hydrotalcite-type materials collapses during the calcination process, resulting in the loss of carbonate anions and hydroxyl groups, present in the interlayer space. This leads to the formation of mixed oxides that exhibit larger surface areas. Furthermore, these changes alter the basic nature of these materials, giving rise to the formation of strong basic sites. The reaction was studied using containing Co2+ and Ni2+ in their structure and was then optimized using distinct primary and secondary alcohols as hydrogen donor sources, as well as distinct temperatures and initial concentrations of furfural. The yields to furfuryl alcohol are strongly dependent on the type of Me2+ in layered oxides mainly due to higher basicity and to the donor employed in the reaction. The mixed oxide containing Co2+ showed complete conversion of furfural and higher yields to furfuryl alcohol (>95 %) at short times of reaction (<1 h).

Valorization of Oleuropein via Tunable Acid-Promoted Methanolysis.

The acid-promoted methanolysis of oleuropein was studied using a variety of homogeneous and heterogeneous acid catalysts. Exclusive cleavage of the acetal bond between the glucoside and the monoterpene subunits or further hydrolysis of the hydroxytyrosol ester and subsequent intramolecular rearrangement were observed upon identification of the most efficient catalyst and experimental conditions. Furthermore, selected conditions were tested using oleuropein under continuous flow and using a crude mixture extracted from olive leaves under batch. Formation of (-)-methyl elenolate was also observed in this study, which is a reported precursor for the synthesis of the antihypertensive drug (-)-ajmalicine.