5- Hydroxymethyl furfural, oxidation

Bis(hydroxymethyl) furan and 5-hydroxymethyl furfural (available from C6 sugars) have been oxidized to furan-2,5-dicarboxylic acid (44)- Linear polyesters, polyurethanes, and polyamides containing these monomers have been described in the literature (45-43) and have been made via condensation polymerization techniques including bulk, solution, and interfacial mixing procedures. Gandini (5,34) reviewed the poly condensation reactions up to 1986 and... 

Heating a solution of hexoses in a strong non-oxidising acidic conditions, hydroxy methyl furfural is formed. The hydroxymethyl furfural from hexose is usually oxidized further to other products When phenolic compounds such as resorcinol, a-naphthol or enthrone are added, mixture of coloured compounds are formed. ... 

During ageing, the andiocyanins can react with other compounds produced from the yeast like pyruvic acid (Fulcrand et al. 1998), acetaldehyde (Es Safi et al. 1999) or odier aldehydic compounds such as furfural and hydroxymethyl furfural coming from oak wood (Es-Safi et al. 2002). In order to assess the possibility for acetaldehyde to be produced by oxidation of ethanol (Wildenradt and Singleton 1974) and to study the structures of compoimds formed, the model solution previously used for copigmentation studies (Mirabel et al. 1999) were stored for ten weeks in the dark at ambient temperature. Two model solutions (pH3.75) containing 0 or 12% Ethanol were analyzed by LC/MS after 10 weeks of incubation. 

The presence of furfural and hydroxymethyl-furfural, released from grapes affected by Botry-tis cinerea as well as from toasted oak in barrels (Table 13.20, Section 13.8.3), leads to the formation of orange-yellow and brick-red compounds. These xanthylium structures are formed by condensation of the aldehydes with catechin and anthocyanins (malvidin and cyanidin) (Es-Safi et al, 2000 and 2002). Oxidation of tartaric acid results in glyoxylic acid, which then... 

This chapter provides an industrial perspective on several oxidation routes to new bio-based molecules. In particular, it focuses on the use of Co/Mn/Br catalyst systems in air oxidations, based on the Amoco Mid-Century catalyst system used for / r -xylene oxidation (also see Chapter 4), as an efficient methodology for the conversion of 5-(hydroxymethyl)furfural (HMF) and 5-(methoxymethyl)furfural (MMF) to 2,5-furandicarboxylic acid (FDCA) in Avantium s YXY process. In addition, other less-studied conversions, such as methyl levulinate (ML) to succinic acid (SA), lignin to a variety of aromatic and phenolic carboxylic acids, are discussed as well. 

Fig. 2 Putative subcellular localization of HMF oxidizing reactions in P. putida strains S12 HmfH (a), S12 B38 (b), and S12 B97 (c). ADH aldehyde dehydrogenase from either C. basilensis HMF14 (c) or native to P. putida S12 (p). HMF 5-(hydroxymethyl)furfural, HMF acid 5-(hydroxymethyl)furoic acid, FFA 5-formylfuroic acid, FDCA 2,5-furandicarboxylic acid...

Koopman F, Wierckx N, deWindeJH, Ruijssenaars HJ (2010b) Identification and characterization of the furfural and 5-(hydroxymethyl)furfural degradation pathways of Cupriavidus basilensis HMF14. Proc Natl Acad Sci USA 107(11) 4919 924 Kroger M, Prusse U, Vorlop KD (2000) A new approach for the production of 2,5-furandicarboxylic acid by in situ oxidation of 5-hydroxymethylfurfural starting from fructose. Top Catal 13(3) 237-242... 

Sahu and Dhepe (2014) synthesized FDCA by the aerobic oxidation of 5-hydroxymethyl furfural on supported metal catalysts. Supported Ft catalysts were synthesized, characterized, and used in the liquid phase air oxidation of HMF to FDCA. Under the optimum reaction conditions of a gradual increase in the reaction temperature (75°C and 140°C for 12 h each), they attained as high as a 96% FDCA yield in the presence of 1 bar oxygen pressure over Ft/Y Al203. 

Sahu, R., Dhepe, P.L., 2014. Synthesis of 2,5-furandicarboxylic acid by the aerobic oxidation of 5-hydroxymethyl furfural over supported metal catalysts. Reaction Kinetics Mechanisms and Catalysis 112 (1), 173-187. 

E acide 2,5-furan-dicarboxylique E is the end product of the one-step oxidation of - hydroxymethyl furfural. 

Further work by V an Ekenstein and Blanksma7 led to a revision of the formulation of hydroxymethylfurfural. It was found that chitose on dehydration gave hydroxymethylfurfural which when oxidized was converted into hydroxymethylpyromucic acid, identical with the compound obtained by Fischer and Andreae from chitonic and chitaric acids.8 The nature of chitose (a 2,5-anhydrohexose) was such that Kiermayer s original formulation of /J-hydroxy-S-methyl-furfural could not obtain and the accepted formulation, -hydroxymethylfurfural (5-hydroxymethyl-2-furaldehyde (IV)) was assigned to the compound. 

The 3-pyridinols 74 can be prepared from furfural by reductive amination to furfurylamine and oxidation with hydrogen peroxide [135]. The respective 6-hydroxymethyl derivative 75 was prepared from 4-hydroxymethylfurfural by reductive amination followed by exposure to bromine in water/methanol to give a 2,5-dibromo derivative whose hydrolysis, ehmination of water, and cyclization gave 6-hydroxymethyl-3-pyridinol [136]. Similarly, glucosylated furfuryl amine derived from isomaltulose was converted to 76 (Fig. 13). 

Pasini T, Piccinini M, Blosi M, Bonelli R, Albonetti S, Dimitratos N, Lopez-Sanchez JA, Sankar M, He Q, Kiely CJ, Hutchings GJ, Cavani F (2011) Selective oxidation of 5-hydroxymethyl-2-furfural using supported gold-copper nanoparticles. Green Chem 13 2091-2099... 

Casanova O, Iborra S, Corma A (2009) Biomass into chemicals one pot-base free oxidative esterification of 5-hydroxymethyl-2-furfural into 2,5-dimethylfuroate with gold on nanoparticulated ceria. J Catal 265 109-116... 

B. With alumina-supported trimethylammonium chlorochromate 5-Hydroxymethyl-2-furfural (1.26 g, 10 mmol) was adsorbed on neutral aluminum oxide (Merck, activity 1, used as received, 30 g), dried, and the resulting solid was groimd together with molecular sieves 4A (0.4 g, previously dried at 350°C for 48 h) and trimethylammonium chlorochromate (TMACC, 5.85 g, 30 minol). The whole solid mixture was suspended in CH2CI2 (20 mL) and sonicated for 1 h at room temperature. The mixture was filtrated and the solid washed with methylene chloride. The organic phases were evaporated and the solid residue, recrystallized as above, afforded the product as white crystals (0.89 g, 72%), mp 108-109°C, identical to the sample above. 

Chemicals from renewables aerobic oxidation of furfural and hydroxymethyl furfnral over gold catalysts, E. Taaming, I.S. Nielsen, K. Egehlad, R. Madsen, and C.H. Christensen, ChemSusChem, 2008,... 

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