Influence of butanol isomers on the reactivity of cellulose towards the synthesis of butyl levulinates catalyzed by liquid and solid acid catalysts

Demolis, A.; Eternot, Marion; Essayem, N.; Rataboul, Franck

doi:10.1039/c5nj02493e

Cited by 20 publications

(22 citation statements)

References 28 publications

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“…For comparison, when 2‐butanol was used as reactant, only 9 % of sec ‐butyl levulinate was obtain at 30 % of liquefaction. Moreover the formation of sec ‐butyl levulinate from cellulose and 1‐butene was more efficient than using 2‐butanol as solvent and reactant at higher temperatures, as we observed in a previous study . These points indicate the great interest of using an olefin for this transformation.…”

Section: Resultssupporting

confidence: 81%

“…In γ‐butyrolactone cellulose was finely dispersed as a suspension, and the greater affinity of cellulose for this solvent may explain the higher reactivity at a certain level of temperature. Note that this liquefaction corresponds to that obtained in alcohols . However, this phenomenon is clearly not sufficient to obtain the desired products.…”

Section: Resultsmentioning

confidence: 85%

“…Attempts to suppress this side‐reactivity of iso ‐butene by decreasing temperature and H 2 SO 4 concentration (Table , entries 4–5) were successful: even at 25 °C it was possible to recover a 50 % yield of tert ‐butyl levulinate. Here, we show the possibility to form this compound in a simple manner, which is practically not the case by using tert ‐butanol owing to the fast dehydration of this alcohol …”

Section: Resultsmentioning

confidence: 93%

“…Direct butanolysis of saccharides (and derivatives) or polysaccharides (cellulose or wood) has also been reported, but yields are generally limited. The use of olefins as esterifying agents instead of alcohols is possible to avoid some issues associated with the use of alcohols: side formation of dialkylether and water as byproducts that can limit ester formation . Olefins may also be subjected to self‐reactivity under acidic conditions, leading to higher‐molecular‐mass hydrocarbons .…”

Section: Introductionmentioning

confidence: 99%

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New Insights into the Reactivity of Biomass with Butenes for the Synthesis of Butyl Levulinates

et al. 2017

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This article reports a detailed study on the reactivity of levulinic acid and cellulose with 1-butene and iso-butene for the catalytic formation of sec- and tert-butyl levulinates. The influence of catalyst type and various solvent conditions have been investigated to assess the potential of a sustainable transformation. A very simple and efficient procedure was discovered by using reusable Amberlyst-15 in the absence of solvent to form, from levulinic acid and iso-butene, tert-butyl levulinate (70 % yield), a compound very difficult to prepare by other means. sec-Butyl levulinate (66 % yield) was obtained by using Amberlyst-15 in γ-butyrolactone as a biosourced solvent. The original procedure was also extended notably by directly using cellulose as a reactant. In the presence of a catalytic amount of H SO , it was possible to form sec-butyl levulinate (19 % yield) from 1-butene in a more efficient way than by using the alcohol as an esterifying agent.

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Section: Resultssupporting

confidence: 81%

Section: Resultsmentioning

confidence: 85%

Section: Resultsmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

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New Insights into the Reactivity of Biomass with Butenes for the Synthesis of Butyl Levulinates

et al. 2017

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“…Besides 2‐MeTHF and GVL, alkyl levulinates form a family of compounds having the advantage to be possibly obtained via a more straightforward procedure through a one‐step alcoholysis of biomass. To date methyl to butyl levulinates have been obtained directly from (ligno)cellulose …”

Section: Introductionmentioning

confidence: 99%

First Example of the Use of Biosourced Alkyl Levulinates as Solvents for Synthetic Chemistry: Application to the Heterogeneously Catalyzed Heck Coupling

et al. 2019

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Modern organic synthesis is highly demanding for environmentally friendly biosourced solvents. In this area, alkyl levulinates, that can be obtained directly from lignocellulose, represent serious candidates. This was demonstrated for the first time in this study, using Heck C−C coupling in the presence of various heterogeneous Pd‐catalysts. In most cases quantitative conversions of aryl halides were observed within short reaction time, associated with good to high isolated yields (30‐95%). In addition to be suitable solvents for this application, alkyl levulinates can be recovered and reused, offering when associated to heterogeneous catalysts facile work‐up procedure for easy obtaining of pure products.

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Preparation of Carbon‐Supported Tungsten Carbides: Comparative Determination of Surface Composition and Influence on Cellulose Transformation into Glycols

et al. 2023

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The chemical valorization of lignocellulosic biomass is of fundamental importance for the sustainable production of chemicals. Among them ethylene and propylene glycols are useful products that can be obtained from lignocellulose using heterogeneous catalysts. It has been reported that catalysts composed of supported Ni and W carbides promote this transformation. We intend in this article to bring new insights by reporting a deep investigation of Ni-W x C/AC (x = 1 or 2) materials, including the preparation modes, the comparison of the surface species composition and their impact on the catalytic cellulose hydrogenolysis into ethylene and propylene glycol. The composition of materials obtained by the preparation mode consisting in the co-impregnation of W and Ni on the carbon support was influenced by the amount of W and Ni. It appears that a catalyst composed of 5 wt% Ni and 30 wt% of W allowed the formation of a material presenting only the W 2 C phase and two alloys Ni 3 W 17 and Ni 6 W 6 C. The preparation mode consisting in forming W x C phases on the carbon support before Ni impregnation allowed the selective formation of W 2 C/AC or WC/AC depending on the carburization conditions. The catalyst prepared by the co-impregnation showed the most important synergetic effect between Ni and W sites leading to high yields into ethylene and propylene glycol from cellulose, hemicellulose or pine wood. In addition, this catalyst showed a much higher stability with a good reusability.

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Influence of butanol isomers on the reactivity of cellulose towards the synthesis of butyl levulinates catalyzed by liquid and solid acid catalysts

Abstract: SSCI-VIDE+CDFA+ADO:MET:NES:FRAInternational audienc

Cited by 20 publications

References 28 publications

New Insights into the Reactivity of Biomass with Butenes for the Synthesis of Butyl Levulinates

New Insights into the Reactivity of Biomass with Butenes for the Synthesis of Butyl Levulinates

First Example of the Use of Biosourced Alkyl Levulinates as Solvents for Synthetic Chemistry: Application to the Heterogeneously Catalyzed Heck Coupling

Preparation of Carbon‐Supported Tungsten Carbides: Comparative Determination of Surface Composition and Influence on Cellulose Transformation into Glycols

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