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

Renewable aromatics can be conveniently synthesized from furanics by introducing an intermediate hydrogenation step in the Diels–Alder (DA) aromatization route, to effectively block retro‐DA activity. Aromatization of the hydrogenated DA adducts requires tandem catalysis, using a metal‐based dehydro...

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Autores principales: Thiyagarajan, Shanmugam, Genuino, Homer C., van der Waal, Jan C., de Jong, Ed, Weckhuysen, Bert M., van Haveren, Jacco, Bruijnincx, Pieter C. A., van Es, Daan S.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2015
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4737293/
https://www.ncbi.nlm.nih.gov/pubmed/26684008
http://dx.doi.org/10.1002/anie.201509346
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author Thiyagarajan, Shanmugam
Genuino, Homer C.
van der Waal, Jan C.
de Jong, Ed
Weckhuysen, Bert M.
van Haveren, Jacco
Bruijnincx, Pieter C. A.
van Es, Daan S.
author_facet Thiyagarajan, Shanmugam
Genuino, Homer C.
van der Waal, Jan C.
de Jong, Ed
Weckhuysen, Bert M.
van Haveren, Jacco
Bruijnincx, Pieter C. A.
van Es, Daan S.
author_sort Thiyagarajan, Shanmugam
collection PubMed
description Renewable aromatics can be conveniently synthesized from furanics by introducing an intermediate hydrogenation step in the Diels–Alder (DA) aromatization route, to effectively block retro‐DA activity. Aromatization of the hydrogenated DA adducts requires tandem catalysis, using a metal‐based dehydrogenation catalyst and solid acid dehydration catalyst in toluene. Herein it is demonstrated that the hydrogenated DA adducts can instead be conveniently converted into renewable aromatics with up to 80 % selectivity in a solid‐phase reaction with shorter reaction times using only an acidic zeolite, that is, without solvent or dehydrogenation catalyst. Hydrogenated adducts from diene/dienophile combinations of (methylated) furans with maleic anhydride are efficiently converted into renewable aromatics with this new route. The zeolite H‐Y was found to perform the best and can be easily reused after calcination.
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spelling pubmed-47372932016-02-12 A Facile Solid‐Phase Route to Renewable Aromatic Chemicals from Biobased Furanics Thiyagarajan, Shanmugam Genuino, Homer C. van der Waal, Jan C. de Jong, Ed Weckhuysen, Bert M. van Haveren, Jacco Bruijnincx, Pieter C. A. van Es, Daan S. Angew Chem Int Ed Engl Communications Renewable aromatics can be conveniently synthesized from furanics by introducing an intermediate hydrogenation step in the Diels–Alder (DA) aromatization route, to effectively block retro‐DA activity. Aromatization of the hydrogenated DA adducts requires tandem catalysis, using a metal‐based dehydrogenation catalyst and solid acid dehydration catalyst in toluene. Herein it is demonstrated that the hydrogenated DA adducts can instead be conveniently converted into renewable aromatics with up to 80 % selectivity in a solid‐phase reaction with shorter reaction times using only an acidic zeolite, that is, without solvent or dehydrogenation catalyst. Hydrogenated adducts from diene/dienophile combinations of (methylated) furans with maleic anhydride are efficiently converted into renewable aromatics with this new route. The zeolite H‐Y was found to perform the best and can be easily reused after calcination. John Wiley and Sons Inc. 2015-12-18 2016-01 /pmc/articles/PMC4737293/ /pubmed/26684008 http://dx.doi.org/10.1002/anie.201509346 Text en © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution‐NonCommercial‐NoDerivs (http://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Communications
Thiyagarajan, Shanmugam
Genuino, Homer C.
van der Waal, Jan C.
de Jong, Ed
Weckhuysen, Bert M.
van Haveren, Jacco
Bruijnincx, Pieter C. A.
van Es, Daan S.
A Facile Solid‐Phase Route to Renewable Aromatic Chemicals from Biobased Furanics
title A Facile Solid‐Phase Route to Renewable Aromatic Chemicals from Biobased Furanics
title_full A Facile Solid‐Phase Route to Renewable Aromatic Chemicals from Biobased Furanics
title_fullStr A Facile Solid‐Phase Route to Renewable Aromatic Chemicals from Biobased Furanics
title_full_unstemmed A Facile Solid‐Phase Route to Renewable Aromatic Chemicals from Biobased Furanics
title_short A Facile Solid‐Phase Route to Renewable Aromatic Chemicals from Biobased Furanics
title_sort facile solid‐phase route to renewable aromatic chemicals from biobased furanics
topic Communications
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4737293/
https://www.ncbi.nlm.nih.gov/pubmed/26684008
http://dx.doi.org/10.1002/anie.201509346
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