On the phase behaviour of oxetane-CO 2 and propargylic alcohols-CO 2 binary mixtures by in situ infrared micro-spectrometry

Zaky, Mohamed F.; Boyaval, Amélie; Grignard, Bruno; Méreau, Raphaël; Detrembleur, Christophe; Jérôme, Christine; Tassaing, Thierry

doi:10.1016/j.supflu.2017.03.009

Cited by 3 publications

(5 citation statements)

References 33 publications

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“…Some of us reported on the phase behaviour of propargylic alcohols/CO 2 biphasic systems and highlighted that the concentration of CO 2 dissolved in the propargylic alcohol phase decreased with a decrease in pressure at a constant temperature . This effect is reflected in the results we obtained (Table , entries 1–6).…”

Section: Resultssupporting

confidence: 69%

“…The temperature can impact the reaction in two ways, that is, by affecting the rate of the reaction and by changing the solubility of CO 2 in the propargylic alcohol phase. We showed that at a constant pressure, the concentration of CO 2 dissolved in the alcohol phase decreases with a decrease in the temperature . The results obtained for experiments performed at 60 °C and 50 bar for 6 h using n Bu 4 NOAc, ( n Bu 4 N) 2 Ox and n Bu 4 NOPh are summarised in Table , entries 7–9.…”

Section: Resultsmentioning

confidence: 89%

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Boosting the Catalytic Performance of Organic Salts for the Fast and Selective Synthesis of α‐Alkylidene Cyclic Carbonates from Carbon Dioxide and Propargylic Alcohols

et al. 2018

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The synthesis of α‐alkylidene cyclic carbonates (αCCs) by the carboxylative coupling of CO2 with propargylic alcohols is receiving increasing interest but requires the use of catalysts that are most often added in large quantities and/or lack selectivity. Herein, we describe the fine‐tuning of the structure of organocatalysts of the ammonium‐type that enables us to identify the important structural parameters that dictate their catalytic performance. Tetrabutylammonium oxalate was revealed to be one of the most attractive organocatalysts with a remarkably fast, complete and selective production of αCCs at a low catalyst loading (2.5 mol %) under solvent‐free conditions. This study opens new avenues for the facile and selective synthesis of libraries of αCCs from CO2 and propargylic alcohol by using simple organocatalysts.

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Section: Resultssupporting

confidence: 69%

Section: Resultsmentioning

confidence: 89%

Boosting the Catalytic Performance of Organic Salts for the Fast and Selective Synthesis of α‐Alkylidene Cyclic Carbonates from Carbon Dioxide and Propargylic Alcohols

et al. 2018

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“…Interestingly, increasing the pressure sped up the reaction and improved the selectivity. This can be explained by the higher CO 2 concentration dissolved in the alkynol phase at a higher pressure, which favors the reaction . Thus, in the pressure range investigated, that is, 1–5 MPa, the optimal conditions to maximize the yield of 1 under solvent‐free conditions are obtained at T =353 K, P=5 MPa, and 5 mol % TBAOAc.…”

Section: Methodsmentioning

confidence: 95%

“…As ag eneral rule, we observed that increasing the temperature and the catalystl oading increased the rate of the reactionb ut had ad etrimental effect on the selectivity.I nterestingly,i ncreasing the pressure sped up the reaction and improved the selectivity.T his can be explained by the higherC O 2 concentrationd issolved in the alkynol phase at ah igherp ressure, which favors the reaction. [22] Thus, in the pressurer ange investigated, that is, 1-5 MPa,t he optimal conditions to maximize the yield of 1 under solventfree conditions are obtained at T = 353 K, P = 5MPa, and 5mol %T BAOAc.…”

mentioning

confidence: 99%

Tetrabutylammonium Salts: Cheap Catalysts for the Facile and Selective Synthesis of α‐Alkylidene Cyclic Carbonates from Carbon Dioxide and Alkynols

et al. 2018

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n‐Tetrabutylammonium organic salts were used for the first time as catalysts for the coupling of CO2 with 2‐methyl‐3‐butyn‐2‐ol to form an α‐methylene cyclic carbonate. Final yields up to 98 % were reached in less than 10 h at 353 K and 3 MPa under solvent‐free conditions. A particular synergistic effect between the cation and the anion of the organocatalyst was demonstrated through catalyst screening. Online kinetic studies by Attenuated Total Reflectance (ATR) IR spectroscopy correlated to DFT calculations revealed compelling evolution of solvation of the catalyst during the reaction that provided insight into the underlying reason for the observed unique kinetics and selectivity. Such in‐depth fundamental mechanistic and kinetic studies enabled determination and comprehension of the key parameters favoring the design of novel, highly active and selective catalysts for valorization of CO2 as a chemical feedstock.

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“…8 On the other hand, infrared (IR) absorption spectroscopy is currently one of the most relevant methods for the qualitative and quantitative analysis of products such as food, medicines, polymers, and textile materials generally under ambient conditions of temperature and pressure. In our team, we implemented this method using homemade optical (IR) cells to determine phase equilibria for model binary mixtures such as CO 2 –epoxide, 9 CO 2 –alcohols, 10–12 or CO 2 –water 13,14 in the presence of sodium chloride (NaCl) 15 under high pressure (25 MPa) and high temperature (350 °C). Recent work has also shown the possibility of using a near-IR probe inserted in a high-pressure cell for the determination of CO 2 –hydrocarbon phase equilibrium under pressure (up to 20 MPa) at temperatures below 80 °C.…”

Section: Introductionmentioning

confidence: 99%

Co-Localized Infrared–Raman Spectroscopy: An Innovative Approach for the Quantitative In Situ Analysis of Gas Mixtures at High Pressures

Boé,

Bruneel,

Tassaing

2024

Appl Spectrosc

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This article spotlights the interest in using co-localized infrared (IR)–Raman spectroscopy as an innovative approach for the in situ monitoring of complex gas mixtures, e.g., hydrogen (H2), nitrogen (N2), carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4), at elevated pressures. Thus, by combining the IR and Raman spectra of CH4, we proposed a new methodology for the calibration of the Raman spectra to circumvent the fact that Raman intensities are arbitrary (laser power, instrument response, integration time, and fluorescence). Applying our methodology to scale several consecutive experiments, the concentrations of all gases were determined with a relative uncertainty lower than 10%. These original results highlight the interest in co-localized IR–Raman spectroscopy analysis in a single cell for the quantitative analysis of solutes by Raman spectroscopy without the use of an internal standard.

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On the phase behaviour of oxetane-CO 2 and propargylic alcohols-CO 2 binary mixtures by in situ infrared micro-spectrometry

Cited by 3 publications

References 33 publications

Boosting the Catalytic Performance of Organic Salts for the Fast and Selective Synthesis of α‐Alkylidene Cyclic Carbonates from Carbon Dioxide and Propargylic Alcohols

Boosting the Catalytic Performance of Organic Salts for the Fast and Selective Synthesis of α‐Alkylidene Cyclic Carbonates from Carbon Dioxide and Propargylic Alcohols

Tetrabutylammonium Salts: Cheap Catalysts for the Facile and Selective Synthesis of α‐Alkylidene Cyclic Carbonates from Carbon Dioxide and Alkynols

Co-Localized Infrared–Raman Spectroscopy: An Innovative Approach for the Quantitative In Situ Analysis of Gas Mixtures at High Pressures

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