Dataset Information

Microwave-Assisted Ionic Liquid-Catalyzed Selective Monoesterification of Alkylphosphonic Acids-An Experimental and a Theoretical Study.

ABSTRACT: It is well-known that the P-acids including phosphonic acids resist undergoing direct esterification. However, it was found that a series of alkylphoshonic acids could be involved in monoesterification with C2-C4 alcohols under microwave (MW) irradiation in the presence of [bmim][BF4] as an additive. The selectivity amounted to 80-98%, while the isolated yields fell in the range of 61-79%. The method developed is a green method for P-acid esterification. DFT calculations at the M062X/6-311+G (d,p) level of theory (performed considering the solvent effect of the corresponding alcohol) explored the three-step mechanism, and justified a higher enthalpy of activation (160.6-194.1 kJ·mol-1) that may be overcome only by MW irradiation. The major role of the [bmim][BF4] additive is to increase the absorption of MW energy. The specific chemical role of the [BF4] anion of the ionic liquid in an alternative mechanism was also raised by the computations.

SUBMITTER: Harsagi N

PROVIDER: S-EPMC8434145 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature

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Publications

Microwave-Assisted Ionic Liquid-Catalyzed Selective Monoesterification of Alkylphosphonic Acids-An Experimental and a Theoretical Study.

Harsági Nikoletta N Henyecz Réka R Ábrányi-Balogh Péter P Drahos László L Keglevich György G

Molecules (Basel, Switzerland) 20210831 17

It is well-known that the P-acids including phosphonic acids resist undergoing direct esterification. However, it was found that a series of alkylphoshonic acids could be involved in monoesterification with C2-C4 alcohols under microwave (MW) irradiation in the presence of [bmim][BF4] as an additive. The selectivity amounted to 80-98%, while the isolated yields fell in the range of 61-79%. The method developed is a green method for P-acid esterification. DFT calc ...[more]

PMID: 34500735

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Project description:Here, we have investigated some physicochemical parameters to understand the molecular interactions by means of density (ρ) measurement, measurement of viscosity (η), refractive index(n D) measurement, and conductance and surface tension measurements between two significant aqueous ionic liquid solutions: benzyl trimethyl ammonium chloride (BTMAC) and benzyl triethyl ammonium chloride (BTEAC) in an aqueous l-methionine (amino acid) solution. The apparent molar volume (Φv), coefficient of viscosity (B), and molar refraction (R M) have been used to analyze the molecular interaction behavior associated in the solution at various concentrations and various temperatures. With the help of some important equations such as the Masson equation, the Jones-Doles equation, and the Lorentz-Lorenz equation, very significant parameters, namely, limiting apparent molar volumes (Φv 0 ), coefficient of viscosity (B), and limiting molar refraction (R M 0), respectively, are obtained. These parameters along with specific conductance (κ) and surface tension (σ) are very much helpful to reveal the solute-solvent interactions by varying the concentration of solute molecules and temperature in the solution. Analyses of Δμ1 0#, Δμ2 0#, TΔS 2 0#, ΔH 2 0#, and thermodynamic data provide us valuable information about the interactions. We note that l-Met in 0.005 molality BTEAC ionic liquid at 308.15 K shows maximum solute-solvent interaction, while l-Met in 0.001 molality BTMAC aqueous solution of ionic liquid at 298.15 K shows the minimum one. Spectroscopic techniques such as Fourier transform infrared (FTIR), 1H-NMR, and UV-vis also provide supportive information about the interactions between the ionic liquid and l-methionine in aqueous medium. Furthermore, adsorption energy, reduced density gradient (RDG), and molecular electrostatic potential (MESP) maps obtained by the application of density functional theory (DFT) have been used to determine the type of interactions, which are concordant with the experimental observations.

Dataset Information

Microwave-Assisted Ionic Liquid-Catalyzed Selective Monoesterification of Alkylphosphonic Acids-An Experimental and a Theoretical Study.

Publications

Microwave-Assisted Ionic Liquid-Catalyzed Selective Monoesterification of Alkylphosphonic Acids-An Experimental and a Theoretical Study.

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