Studies on mild catalytic synthesis of methyl acrylate via one‐step aldol reaction

One‐step catalytic synthesis of methyl acrylate from methyl acetate and trioxane, with 90.7% yield and 91.8% selectivity, was realized at 10–25°5. NMR analysis confirmed the ester enolization with generation of [i‐Pr 2 EtN‐H] + [TfO] − in the presence of i‐Pr 2 EtN and Bu 2 BOTf, which was affected by solvent and base. The depolymerization of trioxane into formaldehyde was catalyzed by Bu 2 BOTf. The in‐situ catalytic mechanism and efficiency of [i‐Pr 2 EtN‐H] + [TfO] − was determined and analyzed. Mechanism‐based kinetic and thermodynamic studies were conducted for better understanding of this route. Also the primary process design and product separation simulation were carried out.