Acetalization of Alkyl Alcohols with Benzaldehyde over Cesium Phosphomolybdovanadate Salts

In this work, vanadium-substituted cesium phosphomolybdate salts with general formulae Cs3+nPMo12-nVnO40 (n = 0, 1, 2, and 3) were synthesized and evaluated in the acetalization of benzaldehyde with alkyl alcohols. All the catalysts were characterized through Raman, infrared, and ultraviolet-visible spectroscopies, powder X-ray diffraction patterns, isotherms of N2 desorption/adsorption, and measurements of acidity strength. The catalytic activity of cesium phosphomolybdovanadate salts was evaluated in the acetalization reactions of benzaldehyde with alkyl alcohols. Among the salts tested, the Cs4PMo11V1O40 was the most active and selective catalyst in the conversion of benzaldehyde to methyl benzyl acetal and benzoic acid, which was obtained without the use of an oxidant agent. The impact of the main reaction parameters on the conversion and selectivity was evaluated by varying the content of vanadium per heteropolyanion, catalyst load, temperature, and alkyl alcohols. The greatest activity of the Cs4PMo11V1O40 salt was assigned to the highest Bronsted acidity strength, as demonstrated by the acidity measurements and analysis of their surface properties. This solid catalyst has advantages over traditional liquid homogenous catalysts, such as low corrosiveness, a minimum generation of residues and effluents, and easy recovery/reuse. In addition, its synthesis route is easier and quicker than solid-supported catalysts and comprises a potential alternative route to synthesize acetals.

Automated summary

In this study, vanadium-substituted cesium phosphomolybdate salts were synthesized and evaluated as catalysts for the acetalization of benzaldehyde with alkyl alcohols. The Cs4PMo11V1O40 salt exhibited the highest activity and selectivity, converting benzaldehyde into methyl benzyl acetal and benzoic acid without the need for an oxidant. The catalytic activity was found to be influenced by the Bronsted acidity of the catalyst. This solid catalyst offers advantages over liquid homogeneous catalysts, including low corrosiveness, minimal waste generation, and easy recovery/reuse, and provides a potential alternative route for acetal synthesis.