The concurrent formation of furan-2,5- and furan-2,4-dicarboxylic acid under solvent free conditions via a disproportionation reaction is described. By reacting potassium-2-furoate at 260 degrees C in the presence of 22 mol% of (Lewis acidic) catalysts like CdI2 or ZnCl2, potassium-2-furoate is disproportionated to furan and furandicarboxylic acids. Besides furan and furan-2,5-dicarboxylic acid (2,5-FDCA) as the main products, furan-2,4-dicarboxylic acid (2,4-FDCA) is also formed as a by-product. Experimental evidence has been obtained that, under the reaction conditions applied, 2,5-FDCA and 2,4-FDCA are formed by separate reaction pathways. Selectivity towards the different FDCA isomers is affected by the type of catalyst used. Single-crystal X-ray analysis shows that 2,4-FDCA has a more 'linear' character compared to 2,5-FDCA and hence is structurally more comparable to terephthalic acid (TA), making it an interesting monomer for synthetic polyesters.
|Journal||RSC Advances : An international journal to further the chemical sciences|
|Publication status||Published - 2013|
- chiral building-blocks
- renewable resources
- glucose dehydration
- terephthalic acid
Thiyagarajan, S., Pukin, A., van Haveren, J., Lutz, M., & van Es, D. S. (2013). Concurrent formation of furan-2,5-and furan-2,4-dicarboxylic acid: unexpected aspects of the Henkel reaction. RSC Advances : An international journal to further the chemical sciences, 3(36), 15678-15686. https://doi.org/10.1039/c3ra42457j