Mixed Tishchenko reaction over solid base catalysts

Catalytic behaviors of solid base catalysts for mixed Tishchenko reactions were investigated to elucidate the activity- and selectivity-determining factors in active sites of the catalysts and molecular structures of the reactants. A mixture containing equal amounts of two kinds of aldehydes was allowed to react at 353 K. The aldehydes used were benzaldehyde, pivalaldehyde, and cyclopropanecarbaldehyde. For all the reactions, the catalytic activity of alkaline earth oxides increased in the order of BaO << MgO < CaO < SrO. As far as the alkaline earth oxides are concerned, it is suggested that a catalyst possessing strong basic sites and high surface area exhibits a high activity. Other solid base catalysts, such as La2O3, ZrO2, ZnO, gamma -alumina, hydrotalcite, KF/alumina, and KOH/alumina, were all inactive for the mixed Tishchenko reaction of benzaldehyde and pivalaldehyde; not only crossed-condensation products but also self-condensation products hardly formed. Quantum chemical calculations of the positive charges on the carbonyl carbon atoms of aldehydes and the structure parameters of the active species for the ester formations account for the observed selectivities to four Tishchenko dimers. The selectivities to four Tishchenko dimers over MgO and CaO are determined primarily in the step of the nucleophilic addition of the active species (PhCH2O-, (BuCH2O-)-Bu-t, and C3H5CH2O-) to the carbonyl carbon atoms of aldehydes. The reaction of the aldehyde having a more positively charged and sterically less-hindered carbonyl carbon atom with the active species having a less-hindered oxygen atom proceeds faster. (C) 2001 Elsevier Science.