A Facile Solid‐Phase Route to Renewable Aromatic Chemicals from Biobased Furanics

Thiyagarajan, Shanmugam; Genuino, Homer C.; Waal, Jan C. van der; Jong, Ed de; Weckhuysen, Bert M.; Haveren, J. van; Bruijnincx, Pieter C. A.; Es, Daan S. van

doi:10.1002/ange.201509346

Cited by 35 publications

(10 citation statements)

References 25 publications

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“…In the reaction of DMF and maleic anhydride, the full decarboxylation was achieved with 3 % yield of PX. Three products (i.e., PX, 2,5‐DMBA and dimethylphthalic anhydride) obtained in one step at 50 °C in this reaction were identical to those obtained in a solid phase reaction at 200 °C . As the dehydration and decarboxylation of the Diels–Alder adduct of DMF and maleic anhydride hardly occur in traditional solvents because of the retro Diels–Alder reaction, it can be concluded that the Diels–Alder adduct was stabilized and the retro Diels–Alder reaction was prevented through the use of an ionic liquid.…”

Section: Resultssupporting

confidence: 51%

A Simple and Mild Approach for the Synthesis of p‐Xylene from Bio‐Based 2,5‐Dimethyfuran by Using Metal Triflates

Xin

Dong

et al. 2017

ChemSusChem

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The production of aromatic platform chemicals from biomass-derived feedstocks is of considerable importance in biomass conversion. However, the development of effective routes with simple steps and under mild conditions is still challenging. In this work, we report an original route for the direct synthesis of p-xylene from 2,5-dimethylfuran and acrylic acid catalyzed by scandium(III) triflate (Sc(OTf) ) in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim]NTf ) under mild conditions. An overall 63 % selectivity towards p-xylene and 78 % selectivity towards aromatics were obtained at 90 % conversion of 2,5-dimethylfuran by enhancing the dehydration and introducing an extra one-pot decarboxylation step. Furthermore, various dienes and dienophiles were employed as reactants to extend the substrate scope. The aromatic compounds were obtained in moderate yields, which proved the potential of the method to be a generic approach for the conversion of bio-based furanics into renewable aromatics.

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Section: Resultssupporting

confidence: 51%

A Simple and Mild Approach for the Synthesis of p‐Xylene from Bio‐Based 2,5‐Dimethyfuran by Using Metal Triflates

Xin

Dong

et al. 2017

ChemSusChem

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“…In contrast, 2-methylfuran and 2,5-dimethylfuran readily react with maleic anhydride to yield thermally labile unsaturated D-A adducts, which can then be hydrogenated or dehydrated to make tricyclic or phthalic anhydrides, respectively, with a targeted number of methyl substituents (Fig. 1b ) 16 – 18 .…”

Section: Resultsmentioning

confidence: 99%

Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters

Jia

et al. 2018

Nat Commun

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Converting biomass-based feedstocks into polymers not only reduces our reliance on fossil fuels, but also furnishes multiple opportunities to design biorenewable polymers with targeted properties and functionalities. Here we report a series of high glass transition temperature (Tg up to 184 °C) polyesters derived from sugar-based furan derivatives as well as a joint experimental and theoretical study of substituent effects on their thermal properties. Surprisingly, we find that polymers with moderate steric hindrance exhibit the highest Tg values. Through a detailed Ramachandran-type analysis of the rotational flexibility of the polymer backbone, we find that additional steric hindrance does not necessarily increase chain stiffness in these polyesters. We attribute this interesting structure-property relationship to a complex interplay between methyl-induced steric strain and the concerted rotations along the polymer backbone. We believe that our findings provide key insight into the relationship between structure and thermal properties across a range of synthetic polymers.

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“…[1] Notable examples include the synthesis of: p-xylene from dimethylfuran and ethylene, [3][4][5][6][7][8][9][10][11][12][13][14] acrylic acid [15,16] or acrolein; [17] benzene/toluene from furan and ethylene/propylene; [18] and (substituted) phthalic anhydride from (substituted) furan and maleic anhydride. [19][20][21] In general, there are two key considerations that determine how successful these reactions are: 1) the kinetic and thermodynamic efficiency of the DA reaction and 2) the ease with which the resulting DA cycloadduct can be aromatised. Either one can make or break the process and the outcome depends heavily on the diene/dienophile combination used.…”

mentioning

confidence: 99%

Dynamic Trapping as a Selective Route to Renewable Phthalide from Biomass‐Derived Furfuryl Alcohol

et al. 2020

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A novel route for the production of the versatile chemical building block phthalide from biorenewable furfuryl alcohol and acrylate esters is presented. Two challenges that limit sustainable aromatics production via Diels–Alder (DA) aromatisation—an unfavourable equilibrium position and undesired regioselectivity when using asymmetric addends—were addressed using a dynamic kinetic trapping strategy. Activated acrylates were used to speed up the forward and reverse DA reactions, allowing for one of the four DA adducts to undergo a selective intramolecular lactonisation reaction in the presence of a weak base. The adduct is removed from the equilibrium pool, pulling the system completely to the product with a fixed, desired regiochemistry. A single 1,2‐regioisomeric lactone product was formed in up to 86 % yield and the acrylate activating agent liberated for reuse. The lactone was aromatised to give phthalide in almost quantitative yield in the presence of Ac2O and a catalytic amount of strong acid, or in 79 % using only catalytic acid.

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A Facile Solid‐Phase Route to Renewable Aromatic Chemicals from Biobased Furanics

Cited by 35 publications

References 25 publications

A Simple and Mild Approach for the Synthesis of p‐Xylene from Bio‐Based 2,5‐Dimethyfuran by Using Metal Triflates

A Simple and Mild Approach for the Synthesis of p‐Xylene from Bio‐Based 2,5‐Dimethyfuran by Using Metal Triflates

Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters

Dynamic Trapping as a Selective Route to Renewable Phthalide from Biomass‐Derived Furfuryl Alcohol

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