Catalytic carbonylation of renewable furfural derived 5-bromofurfural to 5-formyl-2-furancarboxylic acid in oil/aqueous bi-phase system

doi:10.1016/j.mcat.2018.11.021

Molecular Catalysis

Volume 463, February 2019, Pages 94-98

https://doi.org/10.1016/j.mcat.2018.11.021 Get rights and content

Highlights

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Bifunctionalized FFA was synthesized from furfural derived 5-bromofurfural.
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The carbonylation was conducted in oil/aqueous bi-phase with high yield.
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The FFA product can be feasibly separated from catalyst and substrate.

Abstract

Utilizing sustainable biomass to partly replace the fossil feedstock as the carbon source of chemical industry has been well acknowledged because of the scarcity of the fossil resources. This work introduced a novel route for the synthesis of 5-formyl-2-furancarboxylic acid (FFA) from renewable furfural derived 5-bromofurfural, which achieves the transformation of furfural based platform molecule to the products having multifunctional groups, thus opens up its potential market in polymeric applications. Under the optimized conditions, this new catalysis provided up to 99% yield of FFA through oil/aqueous bi-phasic carbonylation. Remarkably, the FFA product could be feasibly separated from the remaining substrate and catalyst because of its aqueous solubility in the biphasic system, giving 95% isolated yield in gram scale synthesis. Currently, FFA is an unstable intermediate in hydroxymethylfurfural (HMF) oxidations; in viewing of that furfural is industrially produced from bulky agroforestrial byproducts, this furfural based route to FFA through catalytic carbonylation has offered an opportunity for its production in large scale.

Graphical abstract

Introduction

Exploring novel catalytic technologies to utilize biomass as the carbon sources of chemical and material industries has attracted much attention than ever because of the rapidly diminishing of fossil resources [[1], [2], [3]]. As one of the top building blocks from biomass, furfural is currently produced in industry from agroforestrial byproducts like corncob, oat, wheat bran and others, which do not compete with the food of human beings [4]. The challenge is that furfural contains only one functional group, which has seriously limited its derivatives for industrial applications; as a result, its current market volume is only approximate to 0.25 M tons per year [5]. On the other side, its analogue, hydroxymethylfurfural (HMF) having two functional groups demonstrates much promising potentials for derivatives of useful molecules. For examples, its sub-chemical 2,5-furandicarboxylic acid (FDCA) is proposed as a bio-based surrogate of terephthalic acid for polymer synthesis, which leads to that exploring new catalytic technologies to synthesize FDCA from HMF becomes greatly attractive [[6], [7], [8]]. Meanwhile, many endeavors have also been paid to explore new catalytic technologies for producing HMF directly from cellulose in place of from glucose and fructose [[9], [10], [11]].

To develop new sub-chemicals having huge market for renewable furfural, we and others even explored catalytic routes for malic acid and anhydride synthesis through furfural oxidation [[12], [13], [14], [15], [16], [17], [18], [19], [20]]. Most recently, we further explored furfural platform based routes to FDCA synthesis through bromination-carbonylation of furoic acid, and to ethyl 5-(acetoxymethyl)furan-2-carboxylate (another HMF derivative) through oxidative carbonylation of furfuryl acetate [[21], [22], [23]]. As the alternative routes to FDCA synthesis, through furoic acid carboxylations with CO₂ in strong base or with carbonate promoter to FDCA, and furoic acid disproportionation to FDCA and furan were even explored [[24], [25], [26], [27]]. Those routes have opened up transforming C5 based furfural to the products having multifunctional groups, thus offering huge potential markets for furfural building blocks. Meanwhile, it provides the alternative routes to synthesize the HMF derivatives from hemicellulose in place of from robust cellulose. Herein, we report a furfural based synthesis of 5-formyl-2-furancarboxylic acid (FFA) from 5-bromofurfural through oil/aqueous bi-phasic carbonylation. Currently, FFA is an unstable intermediate in HMF oxidation to FDCA, and its direct, selective synthesis from HMF was scarcely reported [[28], [29], [30]]. Possibly due to the current challenges in synthesis of FFA from HMF, its industrial applications were not exploited yet. However, because of its multifunctional groups, it has great potentials to function as an intermediate in polymer applications, thus opens FFA-based applications for furfural and HMF based building blocks.

Section snippets

Chemicals

All of the reagents are commercially available. 5-Bromo-furoic acid was purchased from Shandong Youbang Biochemical Technology Co., Ltd. Palladium sources came from different agencies including Pd(OAc)₂ from Strem Chemicals Inc., palladium(II) trifluoroacetate from Energy Chemical, Pd(CH₃CN)₂Cl₂ from Shanghai Boka-Chem Tech Inc., Pd₂(dba)₃ from Adamas Reagent Co., Ltd, PdCl₂ with different bases from Sinopharm Chemical Reagent Co. Ltd. 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene and other

Results and discussion

In literature, palladium is a popularly employed metal for versatile carbonylation reactions [[31], [32], [33], [34]], and we also found that it is an efficient catalyst for 5-bromofuroic acid carbonylation to FDCA [21,23]. In present studies, various palladium sources were also first tested for carbonylation of 5-bromofurfural with different phosphine ligands. The substrate, 5-bromofurfural, is oil-soluble, while after the carbonylation, the generated 5-formyl-2-furancarboxylic acid is

Conclusions

In present studies, a new route to synthesize 5-formyl-2-furancarboxylic acid was explored from renewable furfural derived 5-bromofurfural through oil/aqueous biphasic carbonylation, which offered the quantitative yield (99%) of FFA with palladium catalyst. Remarkably, the generated 5-formyl-2-furancarboxylic acid product can be feasibly separated from the substrate and catalyst, since the product is aqueous soluble under alkaline conditions. In viewing of that furfural is industrially produced

Acknowledgments

The fund from National Natural Science Foundation of China (No. 21872059) is hihgly appreciated. The authors also thank Analytical and Testing Center, Huazhong University of Science and Technology for NMR analysis.

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Catalytic carbonylation of renewable furfural derived 5-bromofurfural to 5-formyl-2-furancarboxylic acid in oil/aqueous bi-phase system

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Chemicals

Results and discussion

Conclusions

Acknowledgments

Coord. Chem. Rev.

Inorg. Chim. Acta

Renew. Sustain. Energy Rev

Catal. Commun.

J. Catal.

Mol. Catal.

J. Organomet. Chem.

J. Organometal. Chem.

J. Mol. Catal. A: Chem.

Chem. Eur. J.

Green Chem.

Chem. Rev.

Eur. Polym. J.

ACS Catal.

ChemSusChem

Sci. China Chem.

J. Phys. Chem. C

Green Chem.

Green Chem.

Green Chem.

Appl. Catal. B-Environ.

RSC Adv.

Green Chem.

ACS Sustain. Chem. Eng.

ChemistrySelect

ARK. J. Org. Chem