A DFT study of the acid-catalyzed conversion of 2,5-dimethylfuran and ethylene to p-xylene

Nikbin, Nima; Phuong, T.; Caratzoulas, Stavros; Lobo, Raúl F.; Dauenhauer, Paul J.; Vlachos, Dionisios G.

doi:10.1016/j.jcat.2012.09.017

Cited by 145 publications

(221 citation statements)

References 48 publications

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“…A recent computational study using density functional theory (DFT) experiments to elucidate the role of different acid sites in the Diels-Alder dehydration reaction between DMF and ethylene has suggested that Lewis acids can coordinate with ethylene to catalyze the [4 + 2]-DielsAlder reaction, but there is no prior experimental evidence of the catalysis of ethylene in Diels-Alder cycloadditions (20). Additionally, the DFT study also suggested the usefulness of Lewis acids in the dehydration of cycloadducts between ethylene and furans.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural

Pacheco

Davis

2014

Proc. Natl. Acad. Sci. U.S.A.

265

237

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Terephthalic acid (PTA), a monomer in the synthesis of polyethylene terephthalate (PET), is obtained by the oxidation of petroleumderived p-xylene. There is significant interest in the synthesis of renewable, biomass-derived PTA. Here, routes to PTA starting from oxidized products of 5-hydroxymethylfurfural (HMF) that can be produced from biomass are reported. These routes involve DielsAlder reactions with ethylene and avoid the hydrogenation of HMF to 2,5-dimethylfuran. Oxidized derivatives of HMF are reacted with ethylene over solid Lewis acid catalysts that do not contain strong Brønsted acids to synthesize intermediates of PTA and its equally important diester, dimethyl terephthalate (DMT). The partially oxidized HMF, 5-(hydroxymethyl)furoic acid (HMFA), is reacted with high pressure ethylene over a pure-silica molecular sieve containing framework tin (Sn-Beta) to produce the Diels-Alder dehydration product, 4-(hydroxymethyl)benzoic acid (HMBA), with 31% selectivity at 61% HMFA conversion after 6 h at 190°C. If HMFA is protected with methanol to form methyl 5-(methoxymethyl)furan-2-carboxylate (MMFC), MMFC can react with ethylene in the presence of Sn-Beta for 2 h to produce methyl 4-(methoxymethyl) benzenecarboxylate (MMBC) with 46% selectivity at 28% MMFC conversion or in the presence of a pure-silica molecular sieve containing framework zirconium (Zr-Beta) for 6 h to produce MMBC with 81% selectivity at 26% MMFC conversion. HMBA and MMBC can then be oxidized to produce PTA and DMT, respectively. When Lewis acid containing mesoporous silica (MCM-41) and amorphous silica, or Brønsted acid containing zeolites (Al-Beta), are used as catalysts, a significant decrease in selectivity/yield of the DielsAlder dehydration product is observed.cycloaddition | dehydrative aromatization | heterogeneous catalysis

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Section: Resultsmentioning

confidence: 99%

Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural

Pacheco

Davis

2014

Proc. Natl. Acad. Sci. U.S.A.

265

237

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“…It was assumed that this structure actually contains an epoxide, rather than a ketone, based on computational results of the most stable structure of a similar intermediate in the 2,5-dimethylfuran/ethylene system. 32 A species was identified by GC-MS as the dimer formed from the cycloaddition of two 2-methylfuran molecules. Similarly, a 2-methylfuran trimer, 5,5-bisylvyl-2-pentanone, is formed by the hydrolysis of 2-methylfuran to form 4-oxopentanal followed by alkylation with two additional 2-methylfuran molecules.…”

Section: Methodsmentioning

confidence: 99%

Diels–Alder cycloaddition of 2-methylfuran and ethylene for renewable toluene

Green

Patet

Nikbin

et al. 2016

Applied Catalysis B: Environmental

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112

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“…[30] Untersuchungen mittels Dichtefunktionaltheorie (DFT) legen nahe,d ass,o bwohl der [4+ +2]-Cycloadditionsschritt thermisch mçglich ist, die Lewis-Säure-Zentren die Aktivierungsanforderungen weiter verringern kçnnen, indem der HOMO-LUMO-Abstand der wechselwirkenden Moleküle reduziert wird. [31] Es hat sich gezeigt, dass das Ausmaß dieser katalytischen Wirkung von der Anordnung der Addenden am Katalysezentrum abhängt:w enn Ethylen an die Lewis-Säure gebunden ist, wird das Ethylen noch elektronenärmer;w enn jedoch das DMF an die Lewis-Säure geSchema 3. Diels-Alder-Cycloaddition/Dehydratisierung für die Umwandlung von DMF und Ethylen in p-Xylol.…”

Section: Diels-alder-cycloadditionen/dehydratisierungenunclassified

“…[33] [31,33] In Übereinstimmung mit experimentellen Ergebnissen [31] tritt die erforderliche Öffnung der Sauerstoffbrücke nur in Gegenwart von Brønsted-oder Lewis-Säure-Katalysatoren bei Te mperaturen im Bereich von 200 bis 300 8 8Cauf.W ie in Schema 4a dargestellt ist, wird der Brønsted-Säure-katalysierte Mechanismus durch einen schnellen Protonentransfer vom aktiven Zentrum des Zeoliths zum Brückensauerstoffatom ausgelçst, was zur Öffnung der Oxanorbornen-Sauerstoffbrücke und zur Bildung von Wasser führt, weil ein Proton vom C5-Kohlenstoff-zum Sauerstoffatom transferiert wird. [33] .…”

Section: Zeolithkatalyseunclassified

Metalloenzymartige Zeolithe als Lewis‐Säure‐Katalysatoren für die C‐C‐Bindungsbildung

Vyver

Román‐Leshkov

2015

Angewandte Chemie

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In den letzten Jahren wurde der Verwendung von metalloenzymartigen Zeolithen als Lewis‐Säure‐Katalysatoren für C‐C‐Kupplungen zunehmende Aufmerksamkeit geschenkt. Insbesondere die Beobachtung, dass hydrophobe Zeolithe mit isolierten Metallzentren im Gerüst direkte Aldolkondensationen ermöglichen, hat die Entwicklung von Katalyseverfahren für die Herstellung von Chemikalien ausgehend von aus Biomasse stammenden Verbindungen angestoßen. Die Entdeckung von neuen Diels‐Alder‐Cycloadditions‐/Dehydratisierungswegen sowie experimentelle und rechnerische Untersuchungen von Lewis‐Säure‐katalysierten Carbonyl‐En‐Reaktionen haben die Entwicklung dieses schnell wachsenden Forschungsgebietes weiter vorangetrieben.

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A DFT study of the acid-catalyzed conversion of 2,5-dimethylfuran and ethylene to p-xylene

Cited by 145 publications

References 48 publications

Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural

Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural

Diels–Alder cycloaddition of 2-methylfuran and ethylene for renewable toluene

Metalloenzymartige Zeolithe als Lewis‐Säure‐Katalysatoren für die C‐C‐Bindungsbildung

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