Synthesis of Itaconic Acid Ester Analogues via Self-Aldol Condensation of Ethyl Pyruvate Catalyzed by Hafnium BEA Zeolites

Wang, Yuran; Lewis, Jennifer D.; Román‐Leshkov, Yuriy

doi:10.1021/acscatal.6b00561

Cited by 57 publications

(42 citation statements)

References 45 publications

(110 reference statements)

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“…According to, Hf‐BEA performance in ethyl pyruvate self‐condensation was characterized by TOF value ca. 0.65 s −1 at 393 K. Close TOF values found for Hf‐BEA and Zr‐BEA could be attributed to the similarity of these two cations in zeolite structure.…”

Section: Resultsmentioning

confidence: 99%

“…[21] Thus, the significant differences in condensation TOF values for Zr-sites described here provide a possible explanation for previous results. [47] According to, [48] Hf-BEA performance in ethyl pyruvate selfcondensation was characterized by TOF value ca. 0.65 s À 1 at 393 K. Close TOF values found for Hf-BEA and Zr-BEA could be attributed to the similarity of these two cations in zeolite structure.…”

Section: Intrinsic Activity Of Open and Closed Sitesmentioning

confidence: 99%

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Selective Self‐Condensation of Butanal over Zr‐BEA Zeolites

2019

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Butanal conversion has been studied over Zr‐BEA zeolites with different amount of partially hydrolyzed open Zr‐sites and fully condensed closed sites. The kinetic study pointed that the main reaction pathway of butanal conversion involves its self‐condensation into 2‐ethyl‐2‐hexenal (2‐EN), the selectivity to 2‐EN being within 80–85 %. Besides, small amounts of 1‐butanol and butanoic acid are formed via Cannizzaro disproportionation of butanal. Secondary reactions include butanoic acid ketonization to 4‐heptanone and esterification to butyl butanoate and tandem hydrogenation/dehydration of 2‐EN into octadienes. A number of techniques, including FTIR spectroscopy of adsorbed CO, pyridine, 2,6‐di‐tert‐butylpyridine (DTBPy), TPD of isopropylamine and selective poisoning with DTBPy were applied for characterization of Zr‐sites and elucidation of their activity. Open Zr‐sites were found to be more active with respect to closed Zr‐sites in butanal condensation: the TOF values estimated at 433 K being 1.4 s−1 for open Zr‐sites and 0.6 s−1 for closed sites. On the contrary, selectivity into 2‐EN was similar for open and closed sites. The results point that Zr‐BEA catalysts with enhanced content of open sites are perspective catalysts for the selective synthesis of 2‐EN.

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Section: Resultsmentioning

confidence: 99%

Section: Intrinsic Activity Of Open and Closed Sitesmentioning

confidence: 99%

Selective Self‐Condensation of Butanal over Zr‐BEA Zeolites

2019

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“…15 After hydrolysis with a heterogeneous Brønsted acid resin catalyst, DHHDA was recovered with a 93% yield (by weight) and appeared as a hard pale yellow powder in high purity (97%, based on 1 H-NMR). The reverse reaction sequence to obtain DHHDA, i.e.…”

Section: Synthesis Of New Diester and Diacid Building Blocks Through mentioning

confidence: 99%

“…12 The rich functionality within the carbohydrate molecule (having indeed a high atomic O to C ratio) presents a great opportunity to particularly focus on novel synthesis routes to (drop-in or novel) chemicals with a variety of functional groups, as their atom economy is usually high. [13][14][15] Moreover, in contrast to biofuels, such high-value chemicals and materials operate in niche markets with high profit margins. 16 From this perspective, α-hydroxy acids, and lactic acid (LA) in particular, are interesting molecules as they can be derived very efficiently from sugary biomass, while they have exciting commercial value both in existing and new applications.…”

Section: Introductionmentioning

confidence: 99%

“…The reported co-polymerization of VGA with LA by polycondensation (PC) is also shown. 21,25,[30][31][32][33]37 Although literature describing the synthesis of diacids (mainly succinic and muconic acid recently) from biomass is numerous, 15,38,39 synthesis routes via olefin metathesis are scarce and mostly limited to reacting unsaturated fatty acids (or esters) to obtain long-chain diacids (or esters). 6, [40][41][42][43] The synthesis of the above symmetric α-OH C 6 diacids (and their esters) is, to the best of our knowledge, not reported.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Novel Renewable Polyesters and Polyamides with Olefin Metathesis

Dewaele¹,

Meerten²,

Verbelen³

et al. 2016

ACS Sustainable Chem. Eng.

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Unsaturated and hydroxyl-functionalized C6-dicarboxylic acids were successfully synthesized via olefin metathesis from methyl vinyl glycolate (MVG), a renewable α-hydroxy C4-ester product from Lewisacid carbohydrate conversion. Addition of a second-generation Hoveyda-Grubbs catalyst to neat MVG leads to a near quantitative yield of dimethyl-2,5-dihydroxy-3-hexenedioate (DMDHHD). Additional hydrolysis and hydrogenation steps form interesting polymer building blocks like 2,5-dihydroxy-3hexenedioic acid (DHHDA) and 2,5-dihydroxyadipic acid (DHAA). Their use in polyester and polyamide synthesis is demonstrated after determination of their physical and spectroscopic characteristics. Copolymerization of DHHDA with L-lactic acid for instance produces a crosslinked poly(L-lactic acid-co-DHHDA) polyester. Proof of crosslinks is ascertained by NMR and FT-IR. Substantial impact on the melting, thermal and polar properties of PLA are observed already at low amounts of DHHDA (0.1 mol%) in accord with the presence of crosslinks in the polymer. Bio-based polyamides were also synthesized by equimolar reaction of DHHDA with hexamethylenediamine, producing a renewable polyamide analogue of the petroleum-based nylon 6,6. Interestingly, the assynthesized polyamide (α-bishydroxylated unsaturated polyamide, HUPA) possesses similar thermal stability as nylon 6,6 but shows different chemical properties as a result of the double bond and αhydroxy functionality.

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hafnium in catalysis

Thiel¹

2020

Catalysis From a to Z

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Synthesis of Itaconic Acid Ester Analogues via Self-Aldol Condensation of Ethyl Pyruvate Catalyzed by Hafnium BEA Zeolites

Cited by 57 publications

References 45 publications

Selective Self‐Condensation of Butanal over Zr‐BEA Zeolites

Selective Self‐Condensation of Butanal over Zr‐BEA Zeolites

Synthesis of Novel Renewable Polyesters and Polyamides with Olefin Metathesis

hafnium in catalysis

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