Investigation of the Synthetic and Mechanistic Aspects of the Highly Stereoselective Transformation of α‐Thioamides to α‐Thio‐β‐chloroacrylamides.

Murphy, Maureen E.; Lynch, Denis; Schaeffer, Marcel; Kissane, Marie; Chopra, Jay; O'Brien, Elisabeth; Ford, Alan; Ferguson, George; Maquire, Anita R.

doi:10.1002/chin.200733082

Cited by 2 publications

(3 citation statements)

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“…Spectral data of the obtained product matched that reported in the literature. 1 1 HNMR (300 MHz, CDCl 3 ): δ 8.21 (s, 1H), 7.42 (d, J = 8.2 Hz, 2H), 7.15 (d, J = 8.2 Hz, 2H), 4.54 (q, J = 7.1 Hz, 1H) 2.13 (s, 3H), 1.83 (d, J = 7.1 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ): δ 166.9, 134.4, 134.0, 129.1, 119.7, 55.…”

Section: ■ Introductionmentioning

confidence: 99%

Experimental and Modeling Studies on the Solubility of 2-Chloro-N-(4-methylphenyl)propanamide (S1) in Binary Ethyl Acetate + Hexane, Toluene + Hexane, Acetone + Hexane, and Butanone + Hexane Solvent Mixtures Using Polythermal Method

et al. 2017

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The solubility of 2-chloro-N-(4-methylphenyl)propanamide (S1) in ethyl acetate + hexane mixtures between the temperatures of 273.43 to 327.67 K, in toluene + hexane mixtures from 273.24 to 331.62 K, in acetone + hexane mixtures from 269.81 to 318.8 butanone + hexane mixtures between 267.10 and 322.92 were determined using the polythermal method. In situ focused beam reflectance measurement (FBRM) was used to characterize the dissolution properties and to provide S1's saturation temperature profile as a function of concentration. It was demonstrated that the solubility of S1 increases with increasing temperature at constant solvent composition. The experimental solubility data were correlated using Apelblat, λh, and phase equilibria with NRTL (nonrandom two liquid) model equations, and the predicted solubility data obtained agree sufficiently with the experimental data based on the relative deviation (RD%) and average relative deviation (ARD%) values. The Apelblat and λh model equation provides a convenient operational model of engineering interest to calculate the solubility of S1 quickly and easily, although it does not take the solvent composition into account, therefore needing separate parameters for each different solvent compositions. Therefore, the phase equilibria with NRTL model equation is used to provide a more comprehensive model that illustrates the effect of solvent composition on the solubility more apparently. One general set of NRTL parameters has the capability of describing all solvent compositions. Additionally, the melting temperature, T m and the molar fusion enthalpy, Δ fus H, (394.83 K and 26.77 kJ mol −1 respectively) of S1 were determined by differential scanning calorimetry (DSC).

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Section: ■ Introductionmentioning

confidence: 99%

Experimental and Modeling Studies on the Solubility of 2-Chloro-N-(4-methylphenyl)propanamide (S1) in Binary Ethyl Acetate + Hexane, Toluene + Hexane, Acetone + Hexane, and Butanone + Hexane Solvent Mixtures Using Polythermal Method

et al. 2017

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“…9 1 H-and 13 C-NMR spectra in addition to IR and mass spectra for Z-1 have already been reported. 2 Powder X-ray diffraction was used in order to confirm the crystal structure of the synthesized material as being that of Z-1. In addition, 1 H NMR and 13 C NMR spectroscopy was used to confirm the molecular structure of Z-1 (Supporting Information, Figure S1 and Figure S2).…”

Section: Wilson Modelmentioning

confidence: 99%

“…The flexible synthetic utility of these heavily functionalized acrylamide compounds is well documented. 1 Specifically, a wide array of transformations have been successfully applied to these compounds including nucleophilic substitution, 2 Diels−Alder reactions, 3 1,3-dipolar cycloadditions, 4,5 and oxidation of the sulfide group 6,7 as summarized in Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

Solubility Measurement and Thermodynamic Modeling of N-(4-Methylphenyl-Z-3-chloro-2-(phenylthio)propenamide in 12 Pure Solvents at Temperatures Ranging from 278.15 to 318.15 K

et al. 2018

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α-Thio-β-chloroacrylamides are of considerable synthetic utility due to their versatile reactivity profile enabling a diverse range of useful transformations. Availability of accurate and extensive solubility data and models is a prerequisite for advanced process optimization of such valuable pure synthetic intermediate compounds, in particular facilitating their isolation with a high degree of efficiency and control. As an illustrative example the solubility of one such derivative, N-(4methylphenyl-Z-3-chloro-2-(phenylthio)propenamide (Z-1), is described in the present work. Solubility data is reported in 12 pure solvents specifically selected for their potential utility in synthesis and isolation at scale. Solubility data are determined using the gravimetric method across a range of temperatures T= (278.15 to 318.15) K under pressure of 0.1 MPa. On a molar basis, the solubility of Z-1 at temperature T = 298.15 K was observed to follow the order: tetrahydrofuran > 1,2-dichloroethane > 2-methyltetrahydrofuran > butanone > acetone > ethyl acetate > methyl acetate > toluene > tert-butyl methyl ether > acetonitrile > 2-propanol > 2-methyl-2-butanol. The experimental solubility data were correlated by the modified Apelblat, Margules, Van-Laar, Wilson, and nonrandom two-liquid (NRTL) models. The NRTL model was found to result in the lowest error for 8 of the 12 solvents tested. In the case of acetonitrile, the Wilson model had a slightly lower mean square error of 3.52 × 10 −4 while for methyl acetate and 1,2-dichloroethane the Van-Laar model had the smallest mean square error of 1.47 × 10 −3 and 3.54 × 10 −4 , respectively. The provision of solubility data and models for such a prized and versatile compound will assist with further development of continuous isolation strategies.

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Investigation of the Synthetic and Mechanistic Aspects of the Highly Stereoselective Transformation of α‐Thioamides to α‐Thio‐β‐chloroacrylamides.

Cited by 2 publications

References 1 publication

Experimental and Modeling Studies on the Solubility of 2-Chloro-N-(4-methylphenyl)propanamide (S1) in Binary Ethyl Acetate + Hexane, Toluene + Hexane, Acetone + Hexane, and Butanone + Hexane Solvent Mixtures Using Polythermal Method

Experimental and Modeling Studies on the Solubility of 2-Chloro-N-(4-methylphenyl)propanamide (S1) in Binary Ethyl Acetate + Hexane, Toluene + Hexane, Acetone + Hexane, and Butanone + Hexane Solvent Mixtures Using Polythermal Method

Solubility Measurement and Thermodynamic Modeling of N-(4-Methylphenyl-Z-3-chloro-2-(phenylthio)propenamide in 12 Pure Solvents at Temperatures Ranging from 278.15 to 318.15 K

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