Dielectric constants of acetonitrile, γ-butyrolactone,propylene carbonate,and 1,2-dimethoxyethane as a function of pressure and temperature

The dielectric constants of 1,2-dimethoxyethane, acetonitrile, -butyrolactone, and propylene carbonate were determined from capacitance measurements extrapolated to infinite frequency; ln are reported as a function of pressure up to 80 MPa at 15, 25, 35, 45°C and as a function of temperature in the range 10 to 50°C at 0.10133 MPa. The variation of ln with temperature or pressure can be expressed by a second order polynomial expression. The isothermal compressibilities of the solvents were determined at 25°C from sound velocities, densities, and heat capacities. A simple correlation can be established between ln /P and for most aprotic solvent.     

Reaction of imidazole and its 2-alkyl derivatives with γ-butyrolactone

Reaction of imidazole with -butyrolactone gives N-alkylation and N-acylation products depending upon the reaction conditions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1491–1493, November, 1992.     

Solubilization of naproxen using N-methyl-2-pyrrolidone or ethanol and β-cyclodextrin

Solubility trend of naproxen in the presence of 5 and 10 mM of β-CD was measured at 298.2 K and compared with solubility profiles in the absence of β-CD for water + cosolvent mixtures. The saturated solutions of the given volume fractions were reached using shake-flask method, and then the solubility values were measured by UV spectrophotometric method at 256 nm. Afterwards, the experimental solubility data points of naproxen in water + ethanol (EtOH) and water + N-methyl-2-pyrrolidone with and without β-cyclodextrin (β-CD) were correlated with Jouyban–Acree model. Calculation results revealed that the back-calculated solubilities were in good agreement with the corresponding experimental values. By applying the correlated equations, one can rapidly predict the solubility of naproxen in all solvent compositions.     

Ultrasonic velocities and isentropic compressibilities of N-methyl-2-pyrrolidone with ketones and branched alcohols at 303.15 K

The ultrasonic sound velocities and densities are measured for the binary mixtures of N-methyl-2-pyrrolidone (NMP) with ketones and branched alcohols at 303.15?K. The ketones include methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone and cyclohexanone. The branched alcohols include 2-propanol, 2-methyl-1-propanol, 3-methyl-1-butanol, 2-butanol and 2-methyl-2-propanol. The ultrasonic sound velocity data were used to compute isentropic compressibilities (k _s). The deviations in the value of k _s from ideal value were computed. Except cyclohexanone all the binary mixtures formed by NMP with ketones at 303.15?K exhibit negative deviation from ideal behaviour over the entire range of composition. Cyclohexanone with NMP exhibit positive deviation over the entire range of composition. An inversion in the sign of Δk _s from positive to negative was observed for 2-propanol system and negative deviation was observed in four binary mixtures formed by NMP with other branched alcohols at 303.15?K. The ultrasonic sound velocities of these mixtures have been analysed is terms of Free Length Theory (FLT), Collision Factor Theory (CFT) and Nomoto's relation.     

Natural monocrystalline chalcopyrite and galena as electrochemical sensors in non-aqueous solvents. Part I: potentiometric titrations of weak acids in γ-butyrolactone and propylene carbonate

Natural monocrystalline chalcopyrite and galena as new indicator electrodes for the potentiometric titrations of benzoic, anthranilic, -nitroso--naphthol and salicylic acids in -butyrolactone (GBL) and propylene carbonate have been used. Potassium hydroxide in methanol was employed as the titrating agent. The results are compared with those obtained using a glass electrode. The investigated electrodes showed a linear dynamic response for p-toluensulfonic acid concentrations in the range from 0.1 to 0.001 M, with a Nernstian slope of 63 mV for chalcopyrite, 66 mV per decade for galena in GBL, 77 mV for chalcopyrite and 98 mV per decade for galena in propylene carbonate. Both electrodes showed a relatively fast response time and can be used without any time limit or without considerable divergence in potentials. The standard deviation of the determination of the investigated acids was less than 0.5%.     

Viscosity and surface tension of glycerol + N-methyl-2-pyrrolidone mixtures from 293 to 323 K

The viscosity and surface tension of binary mixtures of glycerol (1) + N-methyl-2-pyrrolidone (2) at T = 293, 298, 303, 308, 313, 318, and 323 K and at atmospheric pressure are reported. The Jouyban–Acree model was used for mathematical correlation of measured data. The average percentage deviation was used as an accuracy criterion. Derived properties from measured thermophysical properties, including deviations in viscosity and surface tension; the enthalpy, entropy and Gibbs energy of flow activation; standard enthalpy and entropy of surface formation data were reported.     

Synthesis of γ-butyrolactone fused cyclooctene

The expeditious route for the synthesis of γ-butyrolactone fused cyclooctene starting from the γ-butyrolactone fused cyclopentane through bicyclo[4.2.1]nonan-9-one is reported. Retro-Dieckmann’s condensation of bicyclo[4.2.1]nonan-9-one in presence of sodium methoxide and methanol furnished γ-butyrolactone fused cyclooctene in good yield. Surprisingly, the stereochemistry of ring-junction of γ-butyrolactone fused cyclooctene is different from the γ-butyrolactone fused cyclopentane, and the position of new ester group, which were confirmed unambiguously by X-ray analysis.     

Reactions of cyclopentanone, γ-butyrolactone,and their derivatives with α-hydroxyethyl radicals

The interaction of cyclopentanone, 2-cyclopentenone, 1,3-cyclopentanedione, 3-methyl-1,2-cyclopentanedione, γ-butyrolactone, 2(5H)-furanone, ascorbic acid, and 5,6-O-isopropylidenyl-2,3-O-dimethylascorbic acid with α-hydroxyethyl radicals (α-HER) generated during the radiolysis of deaerated ethanol has been studied in the continuous irradiation mode. The test compounds, except γ-butyrolactone, oxidize α-HER. 2(5H)-Furanone and 2-cyclopentenone give hydroxyethylation products via the free-radical chain mechanism. In contrast to 2(5H)-furanone and 2-cyclopentenone, ascorbic and 5,6-O-isopropylidenyl-2,3-O-dimethyl-L-ascorbic acids are weaker oxidants for α-HER and attach these radicals at the multiple carbon-carbon bonds.     

Excess thermodynamic properties of the ethylene carbonate–trifluoroethyl methyl carbonate and propylene carbonate–trifluoroethyl methyl carbonate systems at T = (298.15 or 315.15) K

The deviation in excess thermodynamic parameters such as molar volume (V^E ), viscosity ( η^E), dielectric constant (ϵ^E ), Gibbs energy of activation of the viscous flow (G ^* E ) and surface tension ( γ^E) have been determined for propylene carbonate and 2,2,2-trifluoroethyl methyl carbonate (TFMC) mixtures atT =  298.15 K and for ethylene carbonate and TEMC mixtures at T =  313.15 K. All quantities were plotted against mole fraction over the whole concentration range. Polynomial regressions have been fitted with the results. The strength and the nature of the interactions between like and unlike components have been discussed.     

Liquid-liquid equilibria in binary mixtures of N-methyl-α-pyrrolidone and saturated hydrocarbons. Part II

The liquid-liquid equilibria of N-methyl-α-pyrrolidone (NMP) with decane, undecane, dodecane, tridecane and tetradecane were measured by the synthetic method. The data were evaluated by using the NRTL equation and from the smoothed parameters the excess Gibbs energies and the excess enthalpies were calculated. Including the results of the first paper [1], the influence of the parameter α on the value of the excess enthalpy and on the sign of the excess entropy is considered. Different possible correlations of the energy parameters of the NRTL equation are discussed.     

Apparent molar volumes and compressibilities of electrolytes and ions in γ-butyrolactone

The densities of tetraphenylphosphonium bromide, sodium tetraphenylborate, lithium perchlorate, sodium perchlorate and lithium bromide in γ-butyrolactone at (288.15, 293.15, 298.15, 303.15, 308.15 and 313.15) K and speed of sound at 298.15 K have been measured. From these data apparent molar volumes V_Φ at (288.15, 293.15, 298.15, 303.15, 308.15 and 313.15) K and the apparent molar isentropic compressibility K_S,Φ, at T = 298.15 K of the salts have been determined. The apparent molar volumes and the apparent molar isentropic compressibilities were fitted to the Redlich, Rosenfeld and Mayer equation as well as to the Pitzer and Masson equations yielding infinite dilution data. The obtained limiting values have been used to estimate the ionic data of the standard partial molar volume and the standard partial isentropic compressibility in γ-butyrolactone solutions.     

Physicochemical properties of binary solutions of propylene carbonate–acetonitrile in the range of 253.15–313.15 K

The density, dynamic viscosity, and dielectric constant of propylene carbonate solutions with acetonitrile are measured over the composition of a mixed solvent at temperatures of 253.15, 273.15, 293.15, and 313.15 K. The molar volume, molar viscosity, and molar capacity of a mixture of propylene carbonate–acetonitrile and an excess amount of it are calculated. The effect the temperature and composition of the mixture have on the excess molar properties is discussed. A linear correlation is observed between the values of the molar fluidity, capacity, polarization, and molar volume of the studied system.     

Direct synthesis of propylene carbonate from propylene and carbon dioxide catalyzed by quaternary ammonium heteropolyphosphatotungstate–TBAB system

In this paper,we have developed a highly efficient method for the direct preparation of propylene carbonate from propylene and carbon dioxide(CO2) using quaternary ammonium heteropolyphosphatotungstate–quaternary ammonium halide catalytic system with anhydrous hydrogen peroxide as an oxidant through one-pot two-step process.The effects of the amount of tetrabutylammonium bromide(TBAB),the concentration of hydrogen peroxide and other reaction conditions were investigated.The catalyst system gave an optimum propylene oxide yield(91%) at75°C in oxidation step and the highest propylene carbonate yield(99%) at 140°C and 3.0 MPa in cycloaddition step.Based on the results,a reaction mechanism has been proposed.     

Palladium-catalyzed epimerization of γ-alkenyl-γ-butyrolactone derivatives

γ-Alkenyl-α,β,γ-trisubstituted-γ-butyrolactones (12-16) and γ-alkenyl-furofurandione derivatives (21-Z-24-Z; 21-E-24-E; 25-Z-28-Z; and 25-E-28-E) were successfully epimerized in high yield by a palladium catalyst.     

Effect of γ-irradiation and doping with MoO3 and V2O5 on surface and catalytic properties of manganese oxides

The effects of γ-irradiation (0.2–1.6 MGy), thermal treatment and doping with MoO₃ and V₂O₅ (0.25–4 mol%) on the surface and catalytic properties of manganese oxides prepared by thermal decomposition of manganese carbonate at 400°C and 600°C have been investigated. The techniques employed were X-ray diffraction, nitrogen adsorption at −196°C, oxidation of CO by O₂ at 120–220°C and decomposition of H₂O₂ at 20–50°C. The results revealed that γ-irradiation decreased the particle size of manganese oxides, increased their specific surface areas, decreased the amount of surface excess oxygen and decreased their catalytic activities. The doping with MoO₃ and V₂O₅ conducted at 600°C brought about a measurable decrease in the BET-surface area and catalytic activities of the treated solids. These results were discussed in terms of splitting of manganese oxide particles and removal of chemisorbed oxygen by treating with γ-irradiation and formation of manganese molybdate and vanadates by treating with the used dopant oxides.     

Determination and mathematical modelling of budesonide solubility in N-methyl-2-pyrrolidone + water mixtures from T = 293.2 to 313.2 K

The solubilities of budesonide (BDS) in binary aqueous mixtures of N-methyl-2-pyrrolidone at temperatures ranging from 293.2 to 313.2 K were determined and mathematically correlated by three cosolvency models, i.e. Jouyban–Acree model, Jouyban–Acree–van’t Hoff model and modified Wilson model. The solubilities were measured using the shake-flask method and the models wereused to fit the solubility data of BDS in the solvent mixtures. The obtained mean relative deviations (MRDs %) for cosolvency models trained using whole data points varied between 5.0% and 31.0%. Solubilities were also predicted by the generally trained version of the Jouyban–Acree model with the MRD of 37.0%. Furthermore, the apparent thermodynamic properties of dissolution process of BDS in all the mixed solvents were calculated according to van’t Hoff and Gibbs equations. Dissolution of BDS in these mixed solvents is an endothermic process.     

Structural and electronic properties of γ-Tl2Cu(SO4)2

The compound Tl₂Cu(SO₄)₂, belonging to the dehydrated copper Tutton salts [Cat₂Cu(SO₄)₂, where Cat stands for cation], and especially its glassy γ-modification was investigated. The results of X-ray diffraction analysis, electron paramagnetic resonance, differential thermal analysis, electrical conductivity, and thermostimulated depolarization measurements are presented and discussed. An evident correlation among the results of various experimental techniques was found.