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Molecules 2017, 22(2), 329; doi:10.3390/molecules22020329

Oxidation of 5-Chloromethylfurfural (CMF) to 2,5-Diformylfuran (DFF)

1
Research Institute for Medicines (iMed.ULisboa), Faculty of Pharmacy, Universidade de Lisboa, Av. Prof. Gama Pinto, 1649-003 Lisboa, Portugal
2
Institute of Organic Chemistry with Centre of Phytochemistry Bulgarian Academy of Sciences, Acad. G. Bonchev str., bl. 9, 1113, Sofia, Bulgaria
*
Author to whom correspondence should be addressed.
Academic Editor: Artur Silva
Received: 15 January 2017 / Revised: 10 February 2017 / Accepted: 14 February 2017 / Published: 20 February 2017
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Abstract

2,5-Diformylfuran (DFF) is an important biorenewable building block, namely for the manufacture of new polymers that may replace existing materials derived from limited fossil fuel resources. The current reported methods for the preparation of DFF are mainly derived from the oxidation of 5-hydroxymethylfurfural (HMF) and, to a lesser extent, directly from fructose. 5-Chloromethylfurfural (CMF) has been considered an alternative to HMF as an intermediate building block due to its advantages regarding stability, polarity, and availability from glucose and cellulose. The only reported method for the transformation of CMF to DFF is restricted to the use of DMSO as the solvent and oxidant. We envisioned that the transformation could be performed using more attractive conditions. To that end, we explored the oxidation of CMF to DFF by screening several oxidants such as H2O2, oxone, and pyridine N-oxide (PNO); different heating methods, namely thermal and microwave irradiation (MWI); and also flow conditions. The combination of PNO (4 equiv.) and Cu(OTf)2 (0.5 equiv.) in acetonitrile was identified as the best system, which lead to the formation of DFF in 54% yield under MWI for 5 min at 160 °C. Consequently, a range of different heterogeneous copper catalysts were tested, which allowed for catalyst reuse. Similar results were also observed under flow conditions using copper immobilized on silica under thermal heating at 160 °C for a residence time of 2.7 min. Finally, HMF and 5,5′-oxybis(5-methylene-2-furaldehyde) (OBMF) were the only byproducts identified under the reaction conditions studied. View Full-Text
Keywords: 5-chloromethylfurfural; 2,5-diformylfuran; 5-hydroxymethylfurfural; oxidation; heterogeneous catalysis; catalyst reuse; flow chemistry 5-chloromethylfurfural; 2,5-diformylfuran; 5-hydroxymethylfurfural; oxidation; heterogeneous catalysis; catalyst reuse; flow chemistry
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Vicente, A.I.; Coelho, J.A.S.; Simeonov, S.P.; Lazarova, H.I.; Popova, M.D.; Afonso, C.A.M. Oxidation of 5-Chloromethylfurfural (CMF) to 2,5-Diformylfuran (DFF). Molecules 2017, 22, 329.

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