A new selective route towards benzoic acid and derivatives from biomass-derived coumalic acid

The selective production of aromatics from bio-based sources is an area of interest to expand the potential for greener alternatives to petroleum-derived chemicals. A scalable, efficient route to produce bio-based benzoates is demonstrated by carrying out heterogeneous catalytic reactions in non-toxic bio-based solvents at 180°C obtaining yields of up to 100 mol%. This approach extends the 2-pyrone (coumalic acid/methyl coumalate) Diels-Alder platform by utilizing a bioavailable co-reactant ethylene. A detailed investigation using a combination of kinetic experiments, DFT calculations, and multi-dimensional NMR was carried out to determine the detailed reaction network, and the corresponding activation energies for critical steps. Additionally, a series of experiments were conducted to maximize the yields by comparing different solvents, for both coumalic acid and methyl coumalate. Our results show that the choice of solvent was a significant factor when coumalic acid was the reactant (yields 71-92 mol%), while methyl coumalate was only minimally affected by the solvent (yields 95-100 mol%). Interestingly, the reaction network and kinetic analysis showed that the Diels-Alder reactions were not significantly different between coumalic acid and methyl coumalate, with the rate limiting step for both being decarboxylation with an activation barrier of 141 kJ mol^-1 compared to 77 kJ mol^-1 for the formation of the bicyclic adduct. Finally, the reaction cascade was found to be highly susceptible to by-product formation when as little as 5 vol% water was present in the solvent, which demonstrates that the absence of water is essential for high yielding benzoate production.