Base-Free Oxidative Esterification of HMF Using Mg–Al Hydrotalcite-Supported Gold Catalyst

Guo, Xusheng; Si, Yuxi; Huang, Yuanchao; Zhang, Jiahui; Lyu, Xilei; Cheng, Youwei; Li, Xi

doi:10.1021/acs.iecr.3c02599

Cited by 5 publications

(3 citation statements)

References 38 publications

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“…While there was no difference in MFFC conversion, the MFDC yield without Na 2 CO 3 was higher than those with Na 2 CO 3 (4-10 mol %). The lower MFDC yields are due to base-assisted several side reactions such as the stepwise hydrolysis of MFDC to FDCA [24,40] and the base-catalyzed Cannizaro reaction of MFFC to MHMFC, the latter of which forms the humin-type byproducts via polymerization with the unreacted substrate. [13,23] The base-free oxidative esterification of MFFC with Au/CeO 2 afforded MFDC in an excellent yield of 93 %.…”

Section: Oxidative Esterification Of Mffc To Mfdc (10 Wt %) With Au/ceomentioning

confidence: 99%

A Protection Strategy for High‐yield Synthesis of Dimethyl Furan‐2,5‐dicarboxylate from 5‐Hydroxymethylfurfural Using Methanol as an Acetalizing Agent

Sheet,

Osuga,

Arai

et al. 2024

ChemCatChem

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Developing efficient catalytic processes for obtaining biobased monomers for plastics can significantly contributes to a more sustainable economy. The biomass‐derived and chemical platform 5‐hydroxymethylfurfural (HMF) can be converted to various key intermediates, which is often hampered by side reactions due to the reactive nature of the formyl group in HMF. Here, we present a stepwise approach involving a protecting agent to obtain dimethyl furan‐2,5‐dicarboxylate (MFDC), which is a monomer for polyalkylene furanoates, a new class of biobased polyesters. Methanol is used as a solvent, reactant, and protecting agent for HMF’s formyl group. In the first step, the oxidative esterification of the hydroxymethyl group to methyl carboxylate in HMF‐dimethylacetal catalyzed by Au/CeO2 affords methyl 5‐formylfuran‐2‐carboxylate dimethylacetal (MFFCacetal) in high yields (> 90%) from concentrated methanolic solutions (~ 20 wt%). Without protecting agent, a mixture of methyl‐5hydroxymethylfuran‐2‐carboxylate (MHMFC), MFDC, and humin byproduct was obtained. The deprotection of MFFC‐acetal in the second step proceeded efficiently in acetone with Amberlyst‐15, affording MFFC in a >90% yield. In the final step, oxidative esterification of MFFC in methanol (10 wt%) afforded MFDC in a 93% yield using Au/CeO2. The acetal protection strategy with methanol offers an efficient route toward MFDC in two oxidative esterification steps.

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Section: Oxidative Esterification Of Mffc To Mfdc (10 Wt %) With Au/ceomentioning

confidence: 99%

A Protection Strategy for High‐yield Synthesis of Dimethyl Furan‐2,5‐dicarboxylate from 5‐Hydroxymethylfurfural Using Methanol as an Acetalizing Agent

Sheet,

Osuga,

Arai

et al. 2024

ChemCatChem

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“…This catalytic activity stems from the generation of Lewis acidic site by introducing Mo as proved by pyridine FTIR [133] . Other examples of hydrotalcite utilization in esterification can be found in cited literature [134][135] . Aldol condensation is another example of important organic reactions for biomass upgrading, in particular, to fuels [136] .…”

Section: Biomass Upgradingmentioning

confidence: 99%

Hydrotalcites as Versatile Functional Materials for Renewable Feedstock Upgrading to Value-added Chemicals

Asgar Pour,

Omar Sebakhy

2023

Advanced Materials Science and Technology

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Hydrotalcites are inorganic layered materials which have been used in a wide spectrum of applications from catalysis and adsorption to heavy metals immobilization and polymer stabilization. Apart from this, they can act as drug carriers or acid scavengers. More recently, due to the urgent need for developing functional materials required in the production of renewable fuels and chemicals, hydrotalcites have been increasingly noticed as versatile compounds. For instance, they are applicable in biofuel synthesis, biomass upgrading, plastics degradation, hydrogen storage and so forth. In addition, they are cost-efficient materials and thus beneficial for the realization of the above-mentioned applications on the industrial scale. It is noteworthy that for further development of novel hydrotalcites, validation of their performance and their stability are essential. To elucidate these aspects, the major significance of these materials and their capability for application in various catalytic fields are discussed in this survey. Particular focus is given to their most recent utilization in sustainable and green applications.

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“…Kim et al [14] used a series of gold catalysts supported by hydroxyapatite and achieved an 89.3% yield of FDMC from HMF oxidative esterification in the absence of additional alkali. Recently, Li et al [15] found that the nano-gold catalyst supported by Mg-Al hydrotalcite showed good activity for DFF oxidative esterification, with a 96% yield of FDMC.…”

Section: Introductionmentioning

confidence: 99%

Effect of Support on Oxidative Esterification of 2,5-Furandiformaldehyde to Dimethyl Furan-2,5-dicarboxylate

Ge,

Liu,

Tang

et al. 2023

Catalysts

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One-step oxidative esterification of 2,5-furandiformaldehyde (DFF) derived from biomass to prepare Dimethyl Furan-2,5-dicarboxylate (FDMC) not only simplifies the catalytic process and increases the purity of the product, but also avoids the polymerization of 5-hydroxymethylfurfural (HMF) at high-temperature conditions. Gold supported on a series of acidic oxide, alkaline oxide, and hydrotalcite was prepared using colloidal deposition to explore the effect of support on the catalytic activities. The Au/Mg3Al-HT exhibited the best catalytic activity, with 97.8% selectivity of FDMC at 99.9% conversion of DFF. This catalyst is also suitable for oxidative esterification of benzaldehyde and furfural. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and CO2 temperature programmed desorption (CO2-TPD) were performed to characterize the catalysts. The results indicated that the medium and strong basic sites in the catalysts benefited for the absorption of intermediate agents and facilitated the oxidative esterification of aldehyde groups, while neutral or acidic supports tended to produce an acetal reaction. It is worth noting that basicity on the support surface reduced the electronic state of the Au nanoparticle (Auδ−) and, thus, enhanced the catalytic selectivity of oxidative esterification. This finding demonstrated that the support plays a crucial role in oxidative esterification.

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Base-Free Oxidative Esterification of HMF Using Mg–Al Hydrotalcite-Supported Gold Catalyst

Cited by 5 publications

References 38 publications

A Protection Strategy for High‐yield Synthesis of Dimethyl Furan‐2,5‐dicarboxylate from 5‐Hydroxymethylfurfural Using Methanol as an Acetalizing Agent

A Protection Strategy for High‐yield Synthesis of Dimethyl Furan‐2,5‐dicarboxylate from 5‐Hydroxymethylfurfural Using Methanol as an Acetalizing Agent

Hydrotalcites as Versatile Functional Materials for Renewable Feedstock Upgrading to Value-added Chemicals

Effect of Support on Oxidative Esterification of 2,5-Furandiformaldehyde to Dimethyl Furan-2,5-dicarboxylate

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