5‐(Chloromethyl)furfural is the New HMF: Functionally Equivalent But More Practical in Terms of its Production From Biomass

Mascal, Mark

doi:10.1002/cssc.201500940

Cited by 88 publications

(55 citation statements)

References 35 publications

(62 reference statements)

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“…Nonetheless, numerous challenges exist with the HMF chemical properties that make it unattractive as a liquid fuel, i. e. instability in a non‐neutral solvent system, low energy‐density and high reactivity. An interesting platform molecule, 5‐(chloromethyl)furfural, has been suggested as a functional substitute of HMF with a more practical approach for its production process ,…”

Section: Catalytic Production Of Platform Chemicals From Lignocellulomentioning

confidence: 99%

Recent Advances in the Catalytic Production of Platform Chemicals from Holocellulosic Biomass

et al. 2019

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This Review discusses novel catalytic pathways of lignocellulosic biomass to value‐added chemicals including biomass‐derived sugar alcohols, organic acids, furans and biohydrocarbons. These production approaches are undertaken by biological, chemical and thermochemical transformations or a combination of them. Nevertheless, the majority of research in this area is focused on the design of heterogeneous catalysts to convert value‐added products from holocellulosic biomass. Biorefineries represent the peak of biomass processes in order to produce valuable chemicals and liquid fuels avoiding the utilization of corroding and toxic elements. The aim of the present Review is to offer the readers a broad overview of recent holocellulosic‐based chemical and fuels production technologies via heterogeneous catalysis. There is also an overview of the economic aspects to efficiently produce these platform chemicals at industrial scale. To summarize this Review, an outlook and conclusions of the reported processes to date is provided.

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Section: Catalytic Production Of Platform Chemicals From Lignocellulomentioning

confidence: 99%

Recent Advances in the Catalytic Production of Platform Chemicals from Holocellulosic Biomass

et al. 2019

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“…Besides the intensive research and remarkable achievements regarding the production of HMF, there are still limitations that arise from the specific nature of HMF, namely, its thermal and chemical instability, high solubility in water, and low melting point. On the other hand, as highlighted by the Mascal group, 5-chloromethylfurfural (CMF) is an appealing alternative to HMF, due to its higher stability, lower polarity and higher accessibility from glucose and cellulose [ 12 , 13 , 14 ].…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2017

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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.

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“…5‐(Chloromethyl)furfural (CMF) 1 is a carbohydrate‐derived renewable platform molecule that is considered to be a disruptive innovation in the field of green chemistry . Equivalent to 5‐(hydroxymethyl)furfural (HMF) 2 in its synthetic versatility, CMF 1 can be produced in high yield directly from raw biomass, while HMF 2 is only practically derived from fructose …”

Section: Methodsmentioning

confidence: 99%

Butenolide Derivatives of Biobased Furans: Sustainable Synthetic Dyes

Mascal

Saska

et al. 2019

Angewandte Chemie

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The dye and pigment manufacturing industry is one of the most polluting in the world. Each year, over one million tons of petrochemical colorants are produced globally, the synthesis of which generates a large amount of waste. Naturally occurring, plant‐based dyes, on the other hand, are resource intensive to produce (land, water, energy), and are generally less effective as colorants. Between these two extremes would be synthetic dyes that are fully sourced from biomass‐derived intermediates. The present work describes the synthesis of such compounds, containing strong chromophores that lead to bright colors in the yellow to red region of the visible spectrum. The study was originally motivated by an early report of an unidentified halomethylfurfural derivative which resulted from hydrolysis in the presence of barium carbonate, now characterized as a butenolide of 5‐(hydroxymethyl)furfural (HMF). The method has been generalized for the synthesis of dyes from other biobased platform molecules, and a mechanism is proposed.

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5‐(Chloromethyl)furfural is the New HMF: Functionally Equivalent But More Practical in Terms of its Production From Biomass

Cited by 88 publications

References 35 publications

Recent Advances in the Catalytic Production of Platform Chemicals from Holocellulosic Biomass

Recent Advances in the Catalytic Production of Platform Chemicals from Holocellulosic Biomass

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

Butenolide Derivatives of Biobased Furans: Sustainable Synthetic Dyes

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