To mitigate the environmental impact of plastic waste and reduce our dependence on fossil fuels, we must find renewable alternatives with desirable combinations of physical and chemical properties. Recent investigations have shown that bifuran-based polyesters could afford such materials: poly (ethylene bifuranoate), for example, has shown attractive UV blocking and gas barrier properties. To scale up the synthesis of bifuran polymers, alternatives for the selective C-C homocoupling of methyl furanoate via the Heck reaction need to be found. In this poster we will investigate and optimize the oxidative coupling of methyl furoate using homogeneous Pd(II) catalysts. We found that the reaction of methyl furoate, palladium acetate and sodium pivalate as catalyst and additives, in dimethylacetamide (DMAc) solvent under mild conditions (60 to 80 <sup>o</sup>C) generates acceptable yields (~10% in 2 hours) of the product. The reaction kinetics were investigated, and a possible mechanism and rate determine step (RDS) are proposed. We found that the amount of catalyst, the concentration of reactant, and reaction temperature have significant impact on the reaction rate and yield, while oxygen pressure shows no influence, which states that the Reductive elimination is not the RDS. Concentration of sodium pivalate and temperature have an influence on catalyst stability. The transmetalation of two Pd-activated furoates is suggested as the most likely RDS. Ligands with suitable size and nucleophilicity can be chosen to further increases the reaction rate and catalyst stability.

Oxidative coupling of methyl furoate to form 5,5’-dicarboxylic-2,2’-bifuran methyl esters

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.