A scalable carboxylation route to furan-2,5-dicarboxylic acidElectronic supplementary information (ESI) available: Experimental procedures, additional data, NMR spectra. See DOI: 10.1039/c7gc01059a

Furan-2,5-dicarboxylic acid (FDCA) is a biomass-derived diacid that can be used to make polymers including polyethylene furandicarboxylate (PEF), a highly attractive substitute for petroleum-derived polyethylene terephthalate (PET). Current FDCA syntheses require edible fructose as the feedstock, en...

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Hauptverfasser: Dick, Graham R, Frankhouser, Amy D, Banerjee, Aanindeeta, Kanan, Matthew W
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Sprache:eng
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Zusammenfassung:Furan-2,5-dicarboxylic acid (FDCA) is a biomass-derived diacid that can be used to make polymers including polyethylene furandicarboxylate (PEF), a highly attractive substitute for petroleum-derived polyethylene terephthalate (PET). Current FDCA syntheses require edible fructose as the feedstock, entail a difficult oxidation step that generates undesirable aldehyde impurities, and have moderate yields. As an alternative, carbonate-promoted C-H carboxylation enables the synthesis of FDCA from 2-furoic acid and CO 2 . This route is potentially advantageous because 2-furoic acid is made from furfural, a feedstock produced commercially from inedible lignocellulosic biomass, and it obviates late-stage oxidation. In the carboxylation reaction, salt mixtures composed of alkali furan-2-carboxylate (furoate) and alkali carbonate (M 2 CO 3 ) are heated under CO 2 in the absence of solvent or catalysts to form furan-2,5-dicarboxylate (FDCA 2− ), which is subsequently protonated to produce FDCA. Previously, high yields were achieved on small-scale reactions using caesium furoate and Cs 2 CO 3 . In this work, we investigate the carboxylation reaction using alkali furoate/M 2 CO 3 salts containing cation blends and describe reaction conditions that provide high yields on a preparative scale. We show that the carboxylation proceeds efficiently with K + /Cs + blends that have a high K + content (up to 4 : 1 K +  : Cs + ). Removing H 2 O, which is a by-product of the reaction, is important for suppressing decomposition pathways. The accumulation of the FDCA 2− product inhibits the reaction. Integrating these lessons, we demonstrate the carboxylation of furoate on a 1 mol scale using a fixed-bed flow reactor with 89% isolated yield of pure FDCA upon protonation. 2-Furoic acid is converted to furan-2,5-dicarboxylic acid in high yield on a mole scale using carbonate-promoted C-H carboxylation.
ISSN:1463-9262
1463-9270
DOI:10.1039/c7gc01059a