Chemicals from Biomass: Synthesis of Biologically Active Furanochalcones by Claisen–Schmidt Condensation of Biomass-Derived 5-hydroxymethylfurfural (HMF) with Acetophenones

Arias, Karen S.; Climent, María J.; Corma, Avelino; Iborra, Sara

doi:10.1007/s11244-016-0646-3

Cited by 21 publications

(12 citation statements)

References 33 publications

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“…It was clear to us that catalyst parameters such as acidity, confinement, adsorption-desorption and reactant and product diffusion, together with polarity of the solid, would have to be adapted and optimized to achieve high yields of the acetals. 21 We will show here that this has been possible and yields of 98% have been achieved.…”

Section: Introductionmentioning

confidence: 79%

Mutual Valorization of 5-Hydroxymethylfurfural and Glycerol into Valuable Diol Monomers with Solid Acid Catalysts

Arias

García‐Ortiz

Climent

et al. 2018

ACS Sustainable Chem. Eng.

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Biomass platform molecules such as glycerol and 5-hydroxymethylfurfural have been valorized into diol monomers by acetalization reaction in the presence of tridirectional large pore zeolites (HY and Beta), a laminar zeolite (ITQ-2) and a mesoporous aluminosilicate (MCM-41) and a conventional homogeneous acid catalyst (p-toluenesulfonic acid). The influence of the solvent polarity, pore structure, hydrophobic character and acidity of the catalyst on the activity and selectivity to HMF glyceryl acetals has been studied. Results showed that while the homogeneous catalyst mainly promotes polymerization reactions, tridirectional zeolites are more active catalysts but less selective and deactivate more rapidly than mesoporous MCM-41 and delaminated 2D zeolites. ITQ-2 and MCM-41 catalysts with smaller confinement effects, easy diffusion, and adequate surface polarity provide high yield (98 %) and selectivity (100%) to the target compound. These catalysts are stable and allow regeneration and reuse.

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Section: Introductionmentioning

confidence: 79%

Mutual Valorization of 5-Hydroxymethylfurfural and Glycerol into Valuable Diol Monomers with Solid Acid Catalysts

Arias

García‐Ortiz

Climent

et al. 2018

ACS Sustainable Chem. Eng.

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“…5‐Hydroxymethylfurfural (HMF), obtained by dehydration of hexoses, constitutes one of the most important and versatile platform molecules, owing to its broad range of potential applications in the biofuels and chemical industries. Numerous transformations of HMF, such as, oxidation, reduction, etherification, alkylation, aldol condensation, acetalization, hydration, and reductive amination, have been reported in recent years . Among them, the reduction of the formyl group of HMF to afford the symmetrical diol 2,5‐bis(hydroxymethyl)furan (BHMF), has received much attention .…”

Section: Introductionmentioning

confidence: 99%

Chemoenzymatic Synthesis of 5‐Hydroxymethylfurfural (HMF)‐Derived Plasticizers by Coupling HMF Reduction with Enzymatic Esterification

et al. 2020

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Biobased plasticizers, as substitutes for phthalates, have been synthesized from 5‐hydroxymethylfurfural (HMF) and carboxylic acids (or esters) through a chemoenzymatic cascade process that involves as its first step the reduction of 5‐hydroxymethylfurfural into 2,5‐bis(hydroxymethyl)furan (BHMF), followed by the esterification of BHMF with carboxylic acids (or esters) by using a supported lipase (Novozym 435). The reduction of HMF into BHMF is performed by using monodisperse metallic Co nanoparticles with a thin carbon shell (Co@C) with high activity and selectivity. After optimization of reaction conditions (temperature, hydrogen pressure, and solvent), it is possible to achieve 97 % conversion of HMF with 99 % selectivity to BHMF after 2 h reaction time. The reduction of HMF and esterification of BHMF using carboxylic acids or vinyl esters as acyl donors by lipase are optimized separately in batch and in fixed‐bed continuous reactors. The coupling of two flow reactors (for reduction and subsequent esterification) working under optimized reaction conditions affords the diesters of BHMF in roughly 90 % yield with no loss of activity during 60 h of operation.

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“…Acetone (20 eq. ), zirconium carbonate, H 2 O, 54 °C 7 (92%) [27] Skowronski [28] and Corma [29] independently reported the efficient condensation of acetophenone derivatives with HMF. The reaction, promoted by potassium hydroxide in methanol, produced 5-hydroxymethyl-furfurylideneacetophenone 9, later named furanochalcone, in 82% yield (Scheme 5).…”

Section: Formation Of C=c Bondsmentioning

confidence: 99%

5-Hydroxymethylfurfural (HMF) in Organic Synthesis: A Review of its Recent Applications Towards Fine Chemicals

Fan

Verrier

Queneau

et al. 2019

COS

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Background: 5-Hydroxymethylfurfural (5-HMF) is a biomass-derived platform chemical, which can be produced from carbohydrates. In the past decades, 5- HMF has received tremendous attention because of its wide applications in the production of various value-added chemicals, materials and biofuels. The manufacture and the catalytic conversion of 5-HMF to simple industrially-important bulk chemicals have been well reviewed. However, employing 5-HMF as a building block in organic synthesis has never been summarized exclusively, despite the rapid development in this area. Objective: The aim of this review is to bring a fresh perspective on the use of 5-HMF in organic synthesis, to the exclusion of already well documented conversion of 5-HMF towards relatively simple molecules such as 2,5-furandicarboxylic acid, 2,5-dimethylfuran and so on notably used as monomers or biofuels. Conclusion: As it has been shown throughout this review, 5-HMF has been the object of numerous studies on its use in fine chemical synthesis. Thanks to the presence of different functional groups on this platform chemical, it proved to be an excellent starting material for the preparation of various fine chemicals. The use of this C-6 synthon in novel synthetic routes is appealing, as it allows the incorporation of renewable carbonsources into the final targets.

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Chemicals from Biomass: Synthesis of Biologically Active Furanochalcones by Claisen–Schmidt Condensation of Biomass-Derived 5-hydroxymethylfurfural (HMF) with Acetophenones

Cited by 21 publications

References 33 publications

Mutual Valorization of 5-Hydroxymethylfurfural and Glycerol into Valuable Diol Monomers with Solid Acid Catalysts

Mutual Valorization of 5-Hydroxymethylfurfural and Glycerol into Valuable Diol Monomers with Solid Acid Catalysts

Chemoenzymatic Synthesis of 5‐Hydroxymethylfurfural (HMF)‐Derived Plasticizers by Coupling HMF Reduction with Enzymatic Esterification

5-Hydroxymethylfurfural (HMF) in Organic Synthesis: A Review of its Recent Applications Towards Fine Chemicals

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