7389-38-0Relevant articles and documents
Evolution Process and Controlled Synthesis of Humins with 5-Hydroxymethylfurfural (HMF) as Model Molecule
Shen, Haiyan,Shan, Haozhe,Liu, Li
, p. 513 - 519 (2019/12/24)
Elucidation of the chemical structure and formation mechanism of humins is a requisite to further improve the efficiency of acid-catalyzed biomass conversion. Through a low-temperature approach, the key intermediates resulting in the formation of 5-hydroxymethylfurfural (HMF)-derived humins were captured, revealing multiple elementary reactions such as etherification, esterification, aldol condensation, and acetalization. Through humin characterization, it was found out that the aldol condensation moiety between aldehyde group and levulinic acid is critical to justify the characteristic IR peaks (1620 and 1710 cm?1) and aromatic fragments from pyrolysis GC–MS. Based on the investigations by means of HPLC–MS/MS, IR, pyrolysis GC–MS, and SEM, the structural models of humins at different temperatures were proposed, which are comprised of the elementary reaction types confirmed by the key intermediates. Humin structures with varying content of aldol condensation could be controllably synthesized under different reaction conditions (temperature and time), demonstrating the evolution process of HMF-derived humins.
Oxidation of 5-Chloromethylfurfural (CMF) to 2,5-Diformylfuran (DFF)
Vicente, Ana I.,Coelho, Jaime A. S.,Simeonov, Svilen P.,Lazarova, Hristina I.,Popova, Margarita D.,Afonso, Carlos A. M.
, (2017/03/08)
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.
Selective oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran by polymer-supported IBX amide
Yoon, Hyo-Jin,Choi, Jung-Woo,Jang, Hyung-Seok,Cho, Jin Ku,Byun, Jang-Woong,Chung, Woo-Jae,Lee, Sang-Myung,Lee, Yoon-Sik
experimental part, p. 165 - 168 (2011/03/20)
5-Hydroxymethyl-2-furfural (HMF) was selectively converted to 2,5-diformylfuran (DFF) under mild conditions by polymer-supported IBX amide reagent, thus providing a new platform for the production of highly valuable chemicals from biomass. Georg Thieme Verlag Stuttgart New York.
