Glycerol as a cheap, safe and sustainable solvent for the catalytic and regioselective β,β-diarylation of acrylates over palladium nanoparticles

Delample, Mathieu; Villandier, Nicolas; Douliez, Jean‐Paul; Camy, Séverine; Condoret, Jean‐Stéphane; Pouilloux, Yannick; Barrault, J.; Jérôme, François

doi:10.1039/b925021b

Cited by 62 publications

(34 citation statements)

References 28 publications

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“…Such systems exhibit a liquid-liquid immiscibility zone at low temperatures and belong to type III of the classification of Scott and Konynenburg [45,46]. The low solubility of glycerol in the CO 2 rich phase is an important characteristic in respect to the development of biphasic reactive systems using glycerol as the catalytic phase and scCO 2 as the reactants and products carrier [12]. Indeed, this insures that low amounts of glycerol are extracted by scCO 2 during the separation step.…”

Section: Tablementioning

confidence: 99%

“…However, drawbacks in the utilization of non-volatile solvents, such as glycerol, are still the uneasy recovery of products and recycling of catalysts. In this context, biphasic systems using supercritical CO 2 (scCO 2 ) as a partner phase make it possible the solubilization of the catalyst in the glycerol phase while products are extracted by scCO 2 [9,11,12].…”

Section: Introductionmentioning

confidence: 99%

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Phase equilibrium of the CO2/glycerol system: Experimental data by in situ FT-IR spectroscopy and thermodynamic modeling

Medina-González

Tassaing

Camy

et al. 2013

The Journal of Supercritical Fluids

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OATAO is an open access repository that collects the work of Toulouse researchers and makes it freely available over the web where possible. This is an author-deposited version published in : http://oatao. a b s t r a c tPhase equilibrium experimental data for the CO 2 /glycerol system are reported in this paper. The measurements were performed using an in situ FT-IR method for temperatures ranging from 40 • C to 200 • C and pressures up to 35.0 MPa, allowing determination of the mutual solubility of both compounds. Concerning the CO 2 rich phase, it was observed that the glycerol solubility in CO 2 was extremely low (in the range of 10 −5 in mole fraction) in the pressure and temperature domains investigated here. Conversely, the glycerol rich phase dissolved CO 2 at mole fractions up to 0.13. Negligible swelling of the glycerol rich phase has been observed. Modeling of the phase equilibrium has been performed using the Peng-Robinson equation of state (PR EoS) with classical van der Waals one fluid and EoS/G E based mixing rules (PSRK and MHV2). Satisfactory agreement was observed between modeling results and experimental measurements when PSRK mixing rules are used in combination with UNIQUAC model, although UNIFAC predictive approach gives unsatisfactory representation of experimental behavior.

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Section: Tablementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Phase equilibrium of the CO2/glycerol system: Experimental data by in situ FT-IR spectroscopy and thermodynamic modeling

Medina-González

Tassaing

Camy

et al. 2013

The Journal of Supercritical Fluids

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“…It has recently gained increased attention as an alternative sustainable solvent for catalytic and noncatalytic organic transformations. [4][5][6][7][8][9] Although its use as a solvent goes back to the middle of the last century, [10] it has only recently been found that glycerol can dissolve many organic and inorganic compounds, including transition-metal complexes. It also allows products to be easily separated by extraction with glycerol-immiscible solvents, such as ethers, esters, [4][5][6][7][8] and supercritical carbon dioxide.…”

Section: Introductionmentioning

confidence: 99%

“…It also allows products to be easily separated by extraction with glycerol-immiscible solvents, such as ethers, esters, [4][5][6][7][8] and supercritical carbon dioxide. [9] Moreover, employing glycerol as a solvent has often resulted in improved product yields and selectivity. [7,8] Glycerol can also be reused and enables transitionmetal complexes to be recycled in a simple way.…”

Section: Introductionmentioning

confidence: 99%

Efficient Synthetic Protocols in Glycerol under Heterogeneous Catalysis

et al. 2011

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The massive increase in glycerol production from the transesterification of vegetable oils has stimulated a large effort to find novel uses for this compound. Hence, the use of glycerol as a solvent for organic synthesis has drawn particular interest. Drawbacks of this green and renewable solvent are a low solubility of highly hydrophobic molecules and a high viscosity, which often requires the use of a fluidifying co-solvent. These limitations can be easily overcome by performing reactions under high-intensity ultrasound and microwaves in a standalone or combined manner. These non-conventional techniques facilitate and widen the use of glycerol as a solvent in organic synthesis. Glycerol allows excellent acoustic cavitation even at high temperatures (70-100 °C), which is otherwise negligible in water.Herein, we describe three different types of applications: 1) the catalytic transfer hydrogenation of benzaldehyde to benzyl alcohol in which glycerol plays the dual role of the solvent and hydrogen donor ; 2) the palladium-catalyzed Suzuki cross-coupling; and (3) the Barbier reaction. In all cases glycerol proved to be a greener, less expensive, and safer alter-native to the classic volatile organic solvents.

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“…Cross-coupling reaction that utilizes palladium catalysts is a versatile tool for CÁC bond formation and, recently, its inventors were awarded the Noble Prize in chemistry (15,21,22). In these reactions, usually an organic polar solvent in a single homogeneous phase is used to dissolve together polar and apolar organic substrates with a strong inorganic base, which activates the reaction and a palladium complex.…”

Section: Resultsmentioning

confidence: 99%

Glycerol derivatives as green reaction mediums

Wolfson

Snezhko

Meyouhas

et al. 2012

Green Chemistry Letters and Reviews

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Representative glycerol derivatives were employed as green solvents for selected organic transformations. In all reactions it was found that both reaction performance and product extraction yields were affected by solvent type and polarity. The solubility of the substrates in the solvent was the key step in product yield determination, while the product solubility in the reaction solvent determined the effectiveness of its extraction.

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Glycerol as a cheap, safe and sustainable solvent for the catalytic and regioselective β,β-diarylation of acrylates over palladium nanoparticles

Cited by 62 publications

References 28 publications

Phase equilibrium of the CO2/glycerol system: Experimental data by in situ FT-IR spectroscopy and thermodynamic modeling

Phase equilibrium of the CO2/glycerol system: Experimental data by in situ FT-IR spectroscopy and thermodynamic modeling

Efficient Synthetic Protocols in Glycerol under Heterogeneous Catalysis

Glycerol derivatives as green reaction mediums

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