Renewable production of phthalic anhydride from biomass-derived furan and maleic anhydride

Abstract

A route to renewable phthalic anhydride (2-benzofuran-1,3-dione) from biomass-derived furan and maleic anhydride (furan-2,5-dione) is investigated. Furan and maleic anhydride were converted to phthalic anhydride in two reaction steps: Diels-Alder cycloaddition followed by dehydration. Excellent yields for the Diels-Alder reaction between furan and maleic-anhydride were obtained at room temperature and solvent-free conditions (SFC) yielding 96% exo-4,10-dioxa-tricyclo[5.2.1.0]dec-8-ene-3,5-dione (oxanorbornene dicarboxylic anhydride) after 4 h of reaction. It is shown that this reaction is resistant to thermal runaway because of its reversibility and exothermicity. The dehydration of the oxanorbornene was investigated using mixed-sulfonic carboxylic anhydrides in methanesulfonic acid (MSA). An 80% selectivity to phthalic anhydride (87% selectivity to phthalic anhydride and phthalic acid) was obtained after running the reaction for 2 h at 298 K to form a stable intermediate followed by 4 h at 353 K to drive the reaction to completion. The structure of the intermediate was determined. This result is much better than the 11% selectivity obtained in neat MSA using similar reaction conditions. Scheme 1 Route to renewable phthalic anhydride from biomassderived furan and maleic anhydride. † Electronic supplementary information (ESI) available. See

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

“…[4][5][6] Mahmoud et al addressed the issue of DA adduct instability and furan reactivity by using am ixture of methanesulfonic acid and acetic acid anhydride to synthesize (substituted) phthalic anhydride with high selectivity at 80 8 8C. [8] In an alternative approach, we recently reported on an ew three-step strategy and dealt with this general challenge in DA aromatization by including am ild intermediate hydrogenation step of the oxabicyclic adduct 1. [9] This new route,which is run in the liquid phase,isshown in Scheme 1.…”

“…[8] Related to the challenges associated with controlling such furan-dependent side reactions,careful control over the second catalytic aromatization step is often critical as the intermediate DA adducts are typically unstable and prone to retro-DAreaction, especially at more elevated temperatures. [8,9] Consequently,o ne has to run the aromatization reaction at either low temperature [10] or, if ethylene is the dienophile,a th igh pressure.…”

“…[8] Related to the challenges associated with controlling such furan-dependent side reactions,careful control over the second catalytic aromatization step is often critical as the intermediate DA adducts are typically unstable and prone to retro-DAreaction, especially at more elevated temperatures. [8,9] Consequently,o ne has to run the aromatization reaction at either low temperature [10] or, if ethylene is the dienophile,a th igh pressure. [4][5][6] Mahmoud et al addressed the issue of DA adduct instability and furan reactivity by using am ixture of methanesulfonic acid and acetic acid anhydride to synthesize (substituted) phthalic anhydride with high selectivity at 80 8 8C.…”

Phthalic anhydride production from hemicellulose solutions: Technoeconomic analysis and life cycle assessment

“…7 A path for converting furfural to phthalic anhydrite (PAN) is another recent discovery. 11 It involves the Diels-Alder cycloaddition of furan with MA followed by dehydration of the cycloadduct. 11 It is envisioned as a potentially renewable route as both furan and MA can be produced from furfural.…”

“…11 It involves the Diels-Alder cycloaddition of furan with MA followed by dehydration of the cycloadduct. 11 It is envisioned as a potentially renewable route as both furan and MA can be produced from furfural. The renewable reaction routes used in this work are shown in Figure 1.…”