Samenvatting
5-Hydroxymethylfurfural (HMF) is a platform chemical that can be produced from renewable carbohydrate sources. HMF can be converted to 1,2,4-benzenetriol (BTO) which after catalytic hydrodeoxygenation provides a route to cyclohexanone and cyclohexanol. This mixture, known as KA oil, is an important feedstock for polymeric products such as nylons which use benzene as feedstock that is obtained from the BTX fraction produced in oil refineries. Therefore, the conversion of HMF to BTO provides a renewable, alternative route toward products such as nylons. However, BTO is usually considered an undesired byproduct in HMF synthesis and is only obtained in small amounts. Here, we show that Lewis acid catalysts can be utilized for the selective conversion of HMF to BTO in subsuper critical water. Overall, up to 54 mol % yield of BTO was achieved at 89% HMF conversion using ZnCl2. ZnCl2 and similarly effective Zn(OTf)(2) and Fe(OTf)(2) are known as relatively soft Lewis acids. Other Lewis acid like Hf(OTf)(4) and Sc(OTf)(3) gave increased selectivity toward levulinic acid (up to 33 mol %) instead of BTO, a well-known HMF derivative typically obtained by acid catalysis. Catalytic hydrodeoxygenation of BTO toward cyclohexanone in water was achieved in up to 45% yield using 5 wt % Pd on Al2O3 combined with AlCl3 or Al(OTf)(3) as catalysts. Additionally, a mild selective oxygen induced dimerization pathway of BTO to 2,2',4,4',5,5'-hexahydroxybiphenyl (5,5'-BTO dimer) was identified.
Originele taal-2 | English |
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Pagina's (van-tot) | 3419-3425 |
Aantal pagina's | 13 |
Tijdschrift | ACS Sustainable Chemistry & Engineering |
Volume | 6 |
Nummer van het tijdschrift | 3 |
DOI's | |
Status | Published - 5-mrt.-2018 |
Vingerafdruk
Duik in de onderzoeksthema's van 'Lewis Acid Catalyzed Conversion of 5-Hydroxymethylfurfural to 1,2,4-Benzenetriol, an Overlooked Biobased Compound'. Samen vormen ze een unieke vingerafdruk.Datasets
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CCDC 1565216: Experimental Crystal Structure Determination
Kumalaputri, A. (Contributor), Randolph, C. (Contributor), Otten, E. (Contributor), Heeres, H. J. (Contributor) & Deuss, P. J. (Contributor), University of Groningen, 27-jul.-2017
DOI: 10.5517/ccdc.csd.cc1pjqvs
Dataset