Predicting the Solvent Effect on Esterification Kinetics

Lemberg, Max; Sadowski, Gabriele

doi:10.1002/cphc.201700507

Cited by 15 publications

(36 citation statements)

References 22 publications

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“…Rather, the molecular interactions caused by the solvents are the reason for higher yield and faster kinetics of the reaction. This has been found for diverse reactions in the literature (Lemberg and Sadowski, 2017; Voges et al, 2017; Wangler et al, 2019).…”

Section: Resultssupporting

confidence: 64%

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Catalytic Low-Temperature Dehydration of Fructose to 5-Hydroxymethylfurfural Using Acidic Deep Eutectic Solvents and Polyoxometalate Catalysts

2019

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HMF synthesis typically requires high temperature and is carried out in aqueous solutions. In this work, the low-temperature dehydration of fructose to HMF in different deep eutectic solvents (DES) was investigated. We found a very active and selective reaction system consisting of the DES tetraethyl ammonium chloride as hydrogen bond acceptor (HBA) and levulinic acid as hydrogen bond donor (HBD) in a molar ratio of 1:2 leading to a maximum HMF yield of 68% after 120 h at 323 K. The DES still contained a low amount of water at the initial reaction, and water was also produced during the reaction. Considering the DES properties, neither the molar ratio in the DES nor the reaction temperature had a significant influence on the overall performance of the reaction system. However, the nature of the HBA as well as the acidity of the HBD play an important role for the maximum achievable HMF yield. This was validated by measured yields in a DES with different combinations of HBD (levulinic acid and lactic acid) and HBA (choline chloride and tetra-n-alkyl ammonium chlorides). Moreover, addition of vanadium containing catalysts, especially the polyoxometalate HPA-5 (H8PV5Mo7O40) leads to drastically increased reaction kinetics. Using HPA-5 and the DES tetraethyl ammonium chloride—levulinic acid we could reach a maximum HMF yield of 57% after only 5 h reaction time without decreasing the very high product selectivity.

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Section: Resultssupporting

confidence: 64%

“…Kinetics and yield of chemical and biochemical reactions strongly depend on the reaction solvent (Lemberg and Sadowski, 2017; Voges et al, 2017; Wangler et al, 2019). Figure 1 shows that this was also observed for the reaction under consideration in the present study.…”

Section: Resultsmentioning

confidence: 99%

Catalytic Low-Temperature Dehydration of Fructose to 5-Hydroxymethylfurfural Using Acidic Deep Eutectic Solvents and Polyoxometalate Catalysts

2019

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“…Overall, very promising results could be achieved. Moreover, esters were modeled using PC-SAFT in various other previous works. − Also, SAFT-γ Mie was applied to represent pure-component properties such as vapor pressures and various properties of binary mixtures for a broad range of esters. , …”

Section: Introductionmentioning

confidence: 99%

Thermodynamic Properties of Systems Comprising Esters: Experimental Data and Modeling with PC-SAFT and SAFT-γ Mie

Haarmann

Siewert

Samarov

et al. 2019

Ind. Eng. Chem. Res.

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In this work, new experimental vapor-pressure data of 14 esters were obtained using the transpiration method. Besides dimethyl fumarate, dimethyl maleate, diethyl maleate, benzyl ethanoate, benzyl propanoate, and benzyl butanoate, eight representatives of the homologous series of ethyl alkanoates were investigated. The pure-component vapor pressures and liquid densities were modeled by means of Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) and SAFT-γ Mie. Satisfying modeling results could be achieved with both equations of state. Furthermore, the molar excess enthalpies of 12 binary mixtures benzyl ethanoate + n-alkane were modeled. Only one binary interaction parameter was fitted for PC-SAFT to quantitatively predict the molar excess enthalpies of all binary mixtures under study, while SAFT-γ Mie predicts these properties in qualitative agreement with the experimental data. Finally, the liquid–liquid equilibria of three binary mixtures ester (benzyl ethanoate, dimethyl maleate, and diethyl maleate) + water were investigated. These systems show a very low and almost temperature-independent solubility of the ester in the aqueous phase, whereas the moderate solubility of water in the organic phase is temperature-dependent. Promisingly, both PC-SAFT and SAFT-γ Mie predicted broad and unsymmetrical miscibility gaps for these mixtures, which is in qualitative agreement with the experimental data.

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“…Thus, further investigations concerning the solute-solvent interactions of pharmaceuticals are still necessary in this regard. To this end, the solute-solvent interactions and their corresponding effects have been investigated utilizing various experimental and computational methods 34–41 . Indeed, combination of experimental and computational represents an inimitable opportunity for observing such kind of interactions, where the experimental results can be molecularly interpreted using various computational approaches 36 .…”

Section: Introductionmentioning

confidence: 99%

Probing the Solute-Solvent Interaction of an Azo-Bonded Prodrug in Neat and Binary Media: Combined Experimental and Computational Study

Bani-Yaseen

Aljaber

Ali

2019

Sci Rep

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Preferential solvation has significant importance in interpreting the molecular physicochemical properties of wide spectrum of materials in solution. In this work, the solute-solvent interaction of pro-drug Sulfasalazine (SSZ) in neat and binary media was investigated experimentally and computationally. The solute-solvent interactions of interest were spectrophotometrically probed and computationally investigated for providing insights concerning the molecular aspects of SSZ:media interaction. Experimentally, the obtained results in 1,4-dioxane:water binary mixture demonstrated a dramatic non-linear changes in the spectral behavior of SSZ indicative of the dependency of its molecular behaviors on the compositions of the molecular microenvironment in the essence of solute-solvent interaction. Computationally, geometry optimization and simulation of the absorption spectra of SSZ in media of interest were performed employing DFT and TD-DFT methods, respectively, where the solvent effects on the absorption were examined implicitly using IEFPCM method. Obtained results revealed a nonpolar nature of the molecular orbitals that are directly involved in the SSZ:medium interaction. As in good correspondence with the experimental results, these simulations demonstrated that these orbitals are of non-polar nature and hence minimally affected by polarity of the media and in turn favoring the non-polar molecular environments. On the other hand, the molecular origin of SSZ:media interaction was demonstrated explicitly through complexation of SSZ with water molecules revealing a cooperative hydrogen bonding stabilization with an average length of 1.90 Å. The findings of this work demonstrate the significance of the preferential solvation and composition of the molecular microenvironment on the physicochemical properties of molecules of pharmaceutical importance.

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Predicting the Solvent Effect on Esterification Kinetics

Cited by 15 publications

References 22 publications

Catalytic Low-Temperature Dehydration of Fructose to 5-Hydroxymethylfurfural Using Acidic Deep Eutectic Solvents and Polyoxometalate Catalysts

Catalytic Low-Temperature Dehydration of Fructose to 5-Hydroxymethylfurfural Using Acidic Deep Eutectic Solvents and Polyoxometalate Catalysts

Thermodynamic Properties of Systems Comprising Esters: Experimental Data and Modeling with PC-SAFT and SAFT-γ Mie

Probing the Solute-Solvent Interaction of an Azo-Bonded Prodrug in Neat and Binary Media: Combined Experimental and Computational Study

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