DOE OSTI2026
Aldol reactions can follow the classical condensation path and produce an α,β-unsaturated carbonyl compound and water, however in some cases, aldol chemistry may be steered towards a fission that gives an olefin and a carboxylic acid. This investigation examines how the strength of Brønsted acid sites—both in homogeneous and heterogeneous catalysis—controls these two pathways and their kinetics. The cross-aldol reaction between benzaldehyde and 3-pentanone served as test case. Batch reactions, conducted in toluene as solvent at a temperature of 140 °C under autogenous pressure, were analyzed by GC and in situ ATR-FTIR spectroscopy to determine product distributions and rate constants for condensation and fission pathways. A series of soluble acids including a family of sulfonic acids mostly favored the condensation pathway, with formic acid as the weakest in the series by its pKa being inactive for aldol chemistry. Significant amounts of fission products were rare except for the known selectivity of phosphoric acid, and the circumstances were difficult to delineate. For the sulfonic acid family, the logarithm of the first-order condensation rate constants scaled only roughly with pKa (water) values, whereas a good correlation was obtained with calculated deprotonation Gibbs energies in toluene. A series of H-forms of isomorphously substituted beta zeolites, HESiBEA with E = Al, Ga, Fe, or B, favored the fission pathway. Site density and site strength were characterized by calorimetric measurements of the heats of adsorption of isopropylamine, which decreased in the order Al > Ga, Fe > B. The logarithm of the site-normalized first-order fission rate constants scaled roughly with the heats of adsorption and correlated excellently with reported deprotonation energies. In conclusion, acid strength mainly affects activity and can be seen as a pre-requisite for either aldol condensation or fission chemistry, whereas additional, yet to be full clarified catalyst properties and reaction conditions are required to steer aldol chemistry towards fission selectivity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗