Carboxylation of Acetylene without Salt Waste: Green Synthesis of C-4 Chemicals Enabled by a CO2-Pressure Induced Acidity Switch

The inherent formation of salt waste in C-H carboxylations is a key obstacle precluding the utilization of CO2 as C-1 building block in the industrial synthesis of base chemicals. This challenge is addressed in a circular process for the production of the C-4 base chemical dimethyl succinate from CO2 and acetylene. At moderate CO2 pressures, acetylene is doubly carboxylated in the presence of cesium carbonate. Hydrogenation of the C-C triple bond stabilizes the product against decarboxylation. By increasing the CO2 pressure to 70 bar, the medium is reversibly acidified, allowing an esterification of the succinate salt with methanol. The cesium base and the hydrogenation catalyst are regenerated and can be reused. This provides the proof of concept for a salt-free route to C-4 chemicals from biogas (CH4/CO2). The origin of this reversible acidity switch and the critical roles of the cesium base and the NMP/MeOH solvents were elucidated by thermodynamic modeling.