title: Substituted Phthalic Anhydrides from Biobased Furanics: A New Approach to Renewable Aromatics.
abstract: A novel route for the production of renewable aromatic chemicals, particularly substituted phthalic acid anhydrides, is presented. The classical two-step approach to furanics-derived aromatics via Diels-Alder (DA) aromatization has been modified into a three-step procedure to address the general issue of the reversible nature of the intermediate DA addition step. The new sequence involves DA addition, followed by a mild hydrogenation step to obtain a stable oxanorbornane intermediate in high yield and purity. Subsequent one-pot, liquid-phase dehydration and dehydrogenation of the hydrogenated adduct using a physical mixture of acidic zeolites or resins in combination with metal on a carbon support then allows aromatization with yields as high as 84 % of total aromatics under relatively mild conditions. The mechanism of the final aromatization reaction step unexpectedly involves a lactone as primary intermediate.
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht (The Netherlands).|Food & Bio-based Research, Wageningen University and Research Centre, P.O. Box 17, 6700 AA Wageningen (The Netherlands).
authors.forename: Shanmugam
authors.initials: S
authors.lastname: Thiyagarajan
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht (The Netherlands).
authors.forename: Homer C
authors.initials: HC
authors.lastname: Genuino
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht (The Netherlands).
authors.forename: Michał
authors.initials: M
authors.lastname: Śliwa
authors.affiliation: Avantium Chemicals, Zekeringstraat 29, 1014 BV Amsterdam (The Netherlands).
authors.forename: Jan C
authors.initials: JC
authors.lastname: van der Waal
authors.affiliation: Avantium Chemicals, Zekeringstraat 29, 1014 BV Amsterdam (The Netherlands). ed.dejong@avantium.com.
authors.forename: Ed
authors.initials: E
authors.lastname: de Jong
authors.affiliation: Food & Bio-based Research, Wageningen University and Research Centre, P.O. Box 17, 6700 AA Wageningen (The Netherlands).
authors.forename: Jacco
authors.initials: J
authors.lastname: van Haveren
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht (The Netherlands).
authors.forename: Bert M
authors.initials: BM
authors.lastname: Weckhuysen
authors.affiliation: Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht (The Netherlands). p.c.a.bruijnincx@uu.nl.
authors.forename: Pieter C A
authors.initials: PC
authors.lastname: Bruijnincx
authors.affiliation: Food & Bio-based Research, Wageningen University and Research Centre, P.O. Box 17, 6700 AA Wageningen (The Netherlands). daan.vanes@wur.nl.
authors.forename: Daan S
authors.initials: DS
authors.lastname: van Es
mesh_terms: D018533:Biomass; D005663:Furans / Q000737:chemistry*; D055772:Green Chemistry Technology / Q000379:methods*; D006865:Hydrogenation; D010796:Phthalic Anhydrides / Q000737:chemistry*
chemical_list: D005663:Furans; D010796:Phthalic Anhydrides; C043103:phthalic anhydride
keywords: Diels-Alder reaction; aromatics; aromatization; furans; hydrogenation