A Strategy for the Simultaneous Synthesis of Methallyl Alcohol and Diethyl Acetal with Sn-β

Graphical Mal to Mol and Dal ! Methylallyl alcohol and diethyl acetal are synthesized from methacrolein by using different Sn-modified Beta zeolites (Sn-β) as catalysts. The Sn-β precalcined in Ar followed by sodium-exchange exhibited the highest selectivity toward the desired products. The possible reaction pathways of the reaction between α,β-unsaturated aldehydes and primary alcohols were investigated and proposed. A new strategy was developed to simultaneously produce two important chemicals, namely, methallyl alcohol (Mol) and diethyl acetal (Dal) from methacrolein in ethanol solvent at low temperature with the use of Beta zeolites modified by tin (Sn-β catalysts). All the Sn-β catalysts were prepared by the solid-state ion-exchange method, wherein the calcination step was conducted under different gas atmospheres. The catalyst precalcined in Ar (Sn-β-Ar) had a reduced number of extra-framework Sn species and enabled more Sn species to be exchanged into the framework as isolated tetrahedral Sn IV , enhancing the catalytic activity of the Meerwein–Ponndorf–Verley (MPV) reaction. The sodium-exchanged Sn-β-Ar, with a reduced number of weak Brønsted acid sites, led to an even better selectivity for Mol, owing to the restriction of the side reactions such as acetalization, addition, and etherification. Under optimized catalyst and reaction conditions, the yield of Mol and Dal reached approximately 90 % and 96 %, respectively. The possible reaction pathways, along with a complex network of side products, was proposed after a detailed investigation through the use of different substrates as reactants. The fine-tuning of Sn-β catalysts through different treatments discussed in this work is of great significance toward the understanding and manipulation of complex reactions between α,β-unsaturated aldehydes and primary alcohols.