Iron(III) Sulfate-Mediated Synthesis of 2,5-Furandicarboxylic Acid Dimethyl Ester from Galactaric Acid

2,5-furandicarboxylic acid (FDCA) is one of the most studied bio-based monomers, being considered the best substitute for fossil-derived terephthalic acid in plastic production. FDCA is employed in the preparation of polyethylene furanoate (PEF), demonstrating superior mechanical and thermal proprie...

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Bibliographic Details
Main Authors: Giacomo Trapasso, Beatriz Chícharo, Thomas Gherardi, Davide Redolfi-Bristol, Fabio Aricò
Format: Article
Language:English
Published: MDPI AG 2023-07-01
Series:Catalysts
Subjects:
Online Access:https://www.mdpi.com/2073-4344/13/7/1114
Description
Summary:2,5-furandicarboxylic acid (FDCA) is one of the most studied bio-based monomers, being considered the best substitute for fossil-derived terephthalic acid in plastic production. FDCA is employed in the preparation of polyethylene furanoate (PEF), demonstrating superior mechanical and thermal proprieties compared to the widely used polyethylene terephthalate (PET). Nevertheless, FDCA synthesis mostly relies on the oxidation of the bio-based platform chemical hydroxymethyl furfural (HMF), whose notoriously instable nature renders FDCA yield and industrial scale-up production complicated. On the contrary, FDCA esters are less studied, even though they have greater solubility in organic media, which would favor their isolation and potential application as monomers for PEF. On these premises, we report herein an alternative green synthetic approach to FDCA methyl ester (FDME) using galactaric acid as the substrate, dimethyl carbonate (DMC) as the green media, and Fe<sub>2</sub>(SO<sub>4</sub>)<sub>3</sub> as the heterogeneous Lewis acid. Optimization of the reaction conditions allowed the selective production of FDME in a 70% isolated yield; product purification was achieved via flash column chromatography over silica. Furthermore, it was possible to employ up to 5.0 g of galactaric acid in a single reaction, leading to a good isolated yield of FDME.
ISSN:2073-4344