Liquefying Flavonoids with Terpenoids through Deep Eutectic Solvent Formation.

The formation of deep eutectic solvents (DES) is tied to negative deviations to ideality caused by the establishment of stronger interactions in the mixture than in the pure DES precursors. This work tested thymol and menthol as hydrogen bond donors when combined with different flavonoids. Negative deviations from ideality were observed upon mixing thymol with either flavone or flavanone, two parent flavonoids that only have hydrogen bond acceptor (HBA) groups, thus forming non-ionic DES (Type V). On the other hand, the menthol systems with the same compounds generally showed positive deviations from ideality. That was also the case with the mixtures containing the more complex hydroxylated flavonoid, hesperetin, which resulted in positive deviations when mixed with either thymol or menthol. COSMO-RS successfully predicted the behavior of the solid-liquid phase diagram of the studied systems, allowing for evaluation of the impact of the different contributions to the intermolecular interactions, and proving to be a good tool for the design of DES.

Experimental and computational study of the thermochemistry of the fluoromethylaniline isomers.

The standard (po = 0.1 MPa) molar enthalpies of formation in the condensed phase of seven isomers of fluoromethylaniline were derived from the standard molar energies of combustion, in oxygen, to yield CO2(g), N2(g) and HF.10H2O(l), at T = 298.15 K, measured by rotating bomb combustion calorimetry. The standard molar enthalpies of vaporization or sublimation of these compounds, also at T = 298.15 K, were determined using Calvet microcalorimetry, while the enthalpies of fusion of the solid compounds were determined by differential scanning calorimetry. The standard molar enthalpies of formation in the gaseous phase, at T = 298.15 K, were derived from the former two experimental quantities. G3MP2//B3LYP calculations were performed for all possible fluoromethylanilines allowing the estimation of data for the isomers that were not studied experimentally. The Cox scheme was applied with two different approaches for the estimation of the standard molar enthalpies of formation of all the isomers studied, and this led to the conclusion that the literature values for the enthalpies of formation of the meta and para isomers of methylaniline seem to be not reliable. Further G3MP2//B3LYPs calculations on the methylaniline isomers yielded new values for the standard molar enthalpies of formation of the isomers of methylaniline, which have been tested under the Cox scheme, resulting in better estimates.

Combined experimental and computational study of the thermochemistry of the fluoroaniline isomers.

The standard (p degrees = 0.1 MPa) molar enthalpies of formation in the condensed phase of all the fluoroanilines, with the exception of the 2,3,5-trifluoroaniline compound, were derived from the standard molar energies of combustion in oxygen at T = 298.15 K, measured by rotating bomb combustion calorimetry. Calvet high-temperature vacuum sublimation experiments were performed to measure their enthalpies of vaporization or sublimation. These experiments allowed the determination of the standard molar enthalpies of formation in the gaseous phase and at T = 298.15 K. These values are also compared with estimates based on G3MP2B3 and BP86/6-31+G(d) computations, which have been extended also to the fluoroaniline that was not studied experimentally. The results are in close agreement with a mean deviation of approximately 3 kJ.mol-1. The largest difference between experimental and G3MP2B3 values is found for the pentafluoroaniline (-7.0 kJ.mol-1). For the three monofluoroanilines, the composite approach has been used also to compute gas-phase acidities, electron and proton affinities, ionization enthalpies and N-H bond dissociation enthalpies. The computed values compare well with available experimental results supporting the new computed data.

Experimental and computational investigation of the energetics of the three isomers of monochloroaniline.

The standard (p degrees = 0.1 MPa) molar enthalpies of formation of 2-, 3-, and 4-chloroaniline were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by rotating bomb combustion calorimetry. The Calvet high-temperature vacuum sublimation technique was used to measure the enthalpies of vaporization or sublimation of the three isomers. These two thermodynamic parameters yielded the standard molar enthalpies of formation of the three isomers of chloroaniline, in the gaseous phase, at T = 298.15 K, as 53.4 +/- 3.1 kJ.mol(-1) for 2-chloroaniline, 53.0 +/- 2.8 kJ.mol(-1) for 3-chloroaniline, and 59.7 +/- 2.3 kJ.mol(-1) for 4-chloroaniline. These values, which correct previously published data, were used to test the computational methodologies used. Therewith, gas-phase acidities, proton affinities, electron donor capacities, and N-H bond dissociation enthalpies were calculated and found to compare well with available experimental data for these parameters.

Energetics of C-F, C-Cl, C-Br, and C-I bonds in 2-haloethanols. enthalpies of formation of XCH(2)CH(2)OH (X = F, Cl, Br, I) compounds and of the 2-hydroxyethyl radical.

The energetics of the C-F, C-Cl, C-Br, and C-I bonds in 2-haloethanols was investigated by using a combination of experimental and theoretical methods. The standard molar enthalpies of formation of 2-chloro-, 2-bromo-, and 2-iodoethanol, at 298.15 K, were determined as Delta(f)H(degree)m(CH2CH2OH, l) = -315.5 +/- 0.7 kJ.mol-1, Delta(f)H(degree)mBrCH2CH2OH, l) = -275.8 +/- 0.6 kJ.mol-1, Delta(f)H(degree)m(ICH2CH2OH, l) = -207.3 +/- 0.7 kJ.mol-1, by rotating-bomb combustion calorimetry. The corresponding standard molar enthalpies of vaporization, Delta(vap)H(degree)m(ClCH2CH2OH) = 48.32 +/- 0.37 kJ.mol-1, Delta(vap)H(degree)m(BrCH2CH2OH) = 54.08 +/- 0.40 kJ.mol-1, and Delta(vap)H(degree)m(ICH2CH2OH) = 57.03 +/- 0.20 kJ.mol-1 were also obtained by Calvet-drop microcalorimetry. The condensed phase and vaporization enthalpy data lead to Delta(f)H(degree)m(ClCH2CH2OH, g) = -267.2 +/- 0.8 kJ.mol-1, Delta(f)H(degree)m(BrCH2CH2OH, g) = -221.7 +/- 0.7 kJ.mol-1, and Delta(f)H(degree)m(ICH2CH2OH, g) = -150.3 +/- 0.7 kJ.mol-1. These values, together with the enthalpy of selected isodesmic and isogyric gas-phase reactions predicted by density functional theory (B3LYP/cc-pVTZ) and CBS-QB3 calculations were used to derive the enthalpies of formation of gaseous 2-fluoroethanol, Delta(f)H(degree)m(FCH2CH2OH, g) = -423.6 +/- 5.0 kJ.mol-1, and of the 2-hydroxyethyl radical, Delta(f)H(degree)m(CH2CH2OH, g) = -28.7 +/- 8.0 kJ.mol-1. The obtained thermochemical data led to the following carbon-halogen bond dissociation enthalpies: DHo(X-CH2CH2OH) = 474.4 +/- 9.4 kJ.mol-1 (X = F), 359.9 +/- 8.0 kJ.mol-1 (X = Cl), 305.0 +/- 8.0 kJ.mol-1 (X = Br), 228.7 +/- 8.1 kJ.mol-1 (X = I). These values were compared with the corresponding C-X bond dissociation enthalpies in XCH2COOH, XCH3, XC2H5, XCH=CH2, and XC6H5. In view of this comparison the computational methods mentioned above were also used to obtain Delta(f)H(degree)m-594.0 +/- 5.0 kJ.mol-1 from which DHo(F-CH2COOH) = 435.4 +/- 5.4 kJ.mol-1. The order DHo(C-F) > DHo(C-Cl) > DHo(C-Br) > DHo(C-I) is observed for the haloalcohols and all other RX compounds. It is finally concluded that the major qualitative trends exhibited by the C-X bond dissociation enthalpies for the series of compounds studied in this work can be predicted by Pauling's electrostatic-covalent model.