Glass transition behaviour of ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate–H2O mixed solutions

Here, we have measured the glass transition temperature (T_g) of the ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate–H₂O mixed solutions as a function of H₂O concentration (x mol% H₂O). The glass-forming composition region was also determined. Contrary to the results of the quaternary ammonium type of ionic liquid, N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate–H₂O mixed solutions, we did not observed the multiple glass transition behaviour. We also measured the glassy Raman spectra of the solutions at T = 77 K. We find that the “nearly free” hydrogen bonded Raman band of water molecules in the aqueous [bmim][BF₄] solution exists up to around x = 60 mol% H₂O, even at T = 77 K.     

Electrochemical properties of the system of Ag—1-butyl-3-methylimidazolium bromide low-temperature ionic liquid—silver bromide

The methods of potentiometry, electrochemical impedance spectroscopy, cyclic voltammetry, and gravimetry were used to study the electrochemical behavior of a silver electrode in low-temperature ionic liquids of BMImBr and BMImBr—AgBr, and also the process of cathodic reduction of Ag(I) compounds out of a BMImBr—AgBr melt. It is shown that an AgBr film is formed on the silver surface and its properties are determined by the ionic liquid composition. It is found that the process of silver electrodeposition from a BMImBr—AgBr binary alloy occurs irreversibly, at a high current efficiency (up to 100%) and a good quality of the deposit at low current densities. At 70°C, the transfer coefficients of the cathodic process (α = 0.56 and 0.16) and diffusion coefficients (D _Ag(I) = 0.48 × 10⁻⁷ cm²/s and 3.3 × 10⁻⁷ cm²/s) of silver-containing ions are determined in ionic liquids with the AgBr concentration of 0.81 and 1.53 mol/kg BMImBr, accordingly.     

Efficient Friedel–Crafts benzoylation of aniline derivatives with 4-fluorobenzoyl chloride using copper triflate in the synthesis of aminobenzophenones

An efficient pathway for the synthesis of the aminobenzophenone derivatives via Friedel–Crafts benzoylation using copper triflate as catalyst is proposed. New derivatives are synthesized. The copper triflate could be easily recovered and reused without loss of catalytic activity. Both the use of ionic liquids and microwave heating turned out to be fruitful.     

Friedel–Crafts acylation using bismuth triflate in [BMI][PF6]

Bismuth trifluoromethanesulfonate was found to be a good catalyst for the Friedel–Crafts acylation. Bismuth triflate immobilized in an ionic liquid was the most efficient catalytic system. Bismuth triflate in [BMI][PF₆] catalyzes this reaction under microwave irradiation allowing the rapid synthesis of aryl ketones in excellent yields. The catalyst system was easily recovered and reused several times.     

Friedel–Crafts alkylation of 4-hydroxycoumarin catalyzed by sulfonic-acid-functionalized pyridinium chloride as a new ionic liquid

A green, simple and efficient synthesis of bis-coumarin derivatives via the condensation of 4-hydroxycoumarin with arylaldehydes using sulfonic-acid-functionalized pyridinium chloride {[Pyridine–SO₃H]Cl} as a new, homogeneous and reusable catalyst and ionic liquid is reported.     

The study of industrializable ionic liquid catalysts for long-chain alkenes Friedel–Crafts alkylation

Catalysts based on different halo-alkanes structures with durable catalytic performance were synthesized and applied to the Friedel–Crafts alkylation of long-chain alkenes (mixed C_16–24 olefins) with toluene. Surprisingly, compared with the usual industrial catalysts (~10 runs), the cyclic times of the ionic liquid (IL) catalysts reached up to 24 runs, which greatly promotes the industrialization process. Then, Lewis acids of catalysts with different precursor/AlCl₃ molar ratios were investigated and a close relation was discovered between the Lewis acid and catalytic activity. In addition, a comparison of the different halo-alkanes structures about those catalysts was made. The results showed that the [C₆Et₃N]Cl–AlCl₃ had the strongest Lewis acid, corresponding to the highest catalytic performance. Also, the structures of precursors and the specific gravity and active site species of catalysts were investigated by Fourier transform infrared and Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR). Meanwhile, the various parameters (catalyst dosage, toluene/olefin molar ratio, reaction temperature and reaction time) of long-chain alkenes alkylation with toluene were studied. Finally, under the optimized reaction conditions, the conversion and selectivity of long-chain alkenes alkylation reached 99.92 and 32.99%, respectively.     

Solid–liquid equilibria for systems containing 1-butyl-3-methylimidazolium chloride

The solubility of 1-butyl-3-methylimidazolium chloride [C₄mim][Cl] in alcohols {ethanol, 1-butanol, 1-hexanol, 1-octanol, 1-decanol, 1-dodecanol, 2-butanol, 2-methyl-2-propanol (tert-butanol)} has been measured by a dynamic method from 270 K to the melting point of the ionic liquid or to the boiling point of the solvent. The melting point, enthalpy of fusion, and the temperature of the glass phase transition were determined by differential scanning calorimetry.The solubility data were correlated by means of the Wilson, UNIQUAC ASM and modified NRTL1 equations utilizing parameters derived from the solid–liquid equilibrium data. The root-mean-square deviations of the solubility temperatures for all calculated data were higher than 0.9 K and depended on the particular equation used.     

Magnetically recoverable γ-Fe2O3 nanoparticles as a highly active catalyst for Friedel–Crafts benzoylation reaction under ultrasound irradiation

A simple, facile and efficient method has been developed for the Friedel–Crafts benzoylation of arenes using magnetic γ-Fe₂O₃ nanoparticles under solvent-free sonication. The γ-Fe₂O₃ nanoparticles were used as an efficient and magnetically recoverable catalyst for the synthesis of aromatic ketones in good to excellent yields at room temperature under solvent-free. The reaction occurred with high regioselectivity under mild condition. The magnetic γ-Fe₂O₃ nanoparticles are economically synthesized in large-scale, easily separated from the reaction mixture by an external magnet and able to be reused several times without significant loss of the catalytic performance, which make them easy application to industrial processes.     

Nanostructuring of 1-butyl-4-methylpyridinium chloride in ionic liquid–iron oxide nanofluids

Journal of Thermal Analysis and Calorimetry - Understanding the behavior of ionic liquids (ILs) in ionic liquid-based nanofluids has great significance for its proper application. The phase changes...     

Dissolution of zinc oxide in a protic ionic liquid with the 1-methylimidazolium cation and electrodeposition of zinc from ZnO/ionic liquid and ZnO/ionic liquid–water mixtures

We show that zinc oxide can be dissolved in the protic ionic liquid 1-methylimidazolium trifluoromethylsulfonate, [MIm]TfO at quite a high concentration (~ 2.5 mol/L). FTIR and Raman spectra revealed the association of zinc ions with 1-methylimidazole. The ZnO/[MIm]TfO solutions and their mixtures with water were employed as electrolytes for the electrodeposition of zinc. High current density electrodeposition of zinc can be achieved in the employed electrolytes. Spongy-like zinc structures with a high porosity were obtained in ZnO/[MIm]TfO and the formation of Au_1.2Zn_8.8 alloy was observed. Compact and hexagonal zinc deposits were found in the presence of water. The present results show the potential of ionic liquids as electrolytes for rechargeable zinc–air batteries.     

Activity coefficients at infinite dilution of organic solutes in the ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate using gas–liquid chromatography at T = (313.15, 323.15, and 333.15) K

Activity coefficients at infinite dilution were determined for 24 solutes (n-alkanes, alk-1-enes, alk-1-ynes, cycloalkanes, alkylbenzenes, and alcohols) in the ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate by gas-liquid chromatography at three different temperatures T = (313.15, 323.15, 333.15) K. The partial molar excess enthalpy values at infinite dilution were calculated from the experimental results over the same temperature range. Selectivities and capacities at infinite dilution for the hexane/benzene and methanol/benzene separation problems were calculated from experimental infinite dilution activity coefficient values. The activity coefficients, enthalpies, selectivities, and capacities are discussed and compared to literature values for other ionic liquids, as well as industrial molecular solvents.     

A Bloembergen–Purcell–Pound <Superscript>13</Superscript>C NMR relaxation study of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

The molecular structure and rotational motion of the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) were studied over a wide temperature range using the Bloembergen–Purcell–Pound ¹³C NMR spin–lattice relaxation method and NOE factors. Examination of the spin–lattice relaxation times (T ₁) and the rates (R ₁=1/T ₁) of the 1-butyl-3-methylimidazolium cation reveals the relative motions of each carbon in the imidazolium cation. The rotational characteristics of the [BMIM] cation are supported by ab-initio molecular structures of [BMIM][PF6] using density functional theory (DFT) and Hartree–Fock (HF) methods. The ab-initio gas phase structures of [BMIM][PF6] indicate that the 1-butyl-3-methylimidazolium C2 hydrogen, the ring methyl group, and the butyl side-chain hydrogen atoms form hydrogen bonds with the hexafluorophosphate anion.     

Viscosity reduction of cellulose + 1-butyl-3-methylimidazolium acetate in the presence of CO2

Viscosities of microcrystalline cellulose + 1-butyl-3-methylimidazolium acetate ([bmIm][Ac]) solutions (0.6–1.2 wt%) in contact with CO₂ were measured at 312 K with a resonant vibrational viscometer. At 4 MPa and 312 K, the CO₂ could reduce the viscosity of 1.2 wt% cellulose + [bmIm][Ac] solution by about 80 %, whereas N₂ at the same conditions gave less than a 10 % reduction in viscosity. The viscosity-averaged degree of polymerization and IR spectrum showed that cellulose did not decompose during experiments and that [bmIm][Ac] acted as a non-derivatizing solvent during the dissolution and viscosity reduction process. Further, although CO₂ does react with [bmIm][Ac] to form 1-butyl-3-methylimidazolium-2-carboxylate, the reaction seems to be reversible and it does not affect the cellulose. Thus, [bmIm][Ac] with CO₂ provides an effective solvent for cellulose and the solvent system can probably be recycled or reused.     

Activity coefficients at infinite dilution of organic solutes in the ionic liquid 1-butyl-3-methylimidazolium hexafluoroantimonate using gas–liquid chromatography at T = (313.15, 323.15, and 333.15) K

Activity coefficients at infinite dilution were determined for 27 solutes: n-alkanes, alk-1-enes, alk-1-ynes, cycloalkanes, alkylbenzenes, alcohols, and ketones in the ionic liquid 1-butyl-3-methylimidazolium hexafluoroantimonate, [BMIM][SbF₆], by gas–liquid chromatography at three different temperatures, T = (313.15, 323.15, and 333.15) K. The results are compared to published data on related compounds. The partial molar excess enthalpy values at infinite dilution were calculated from the experimental data over the same temperature range. Selectivities and capacities at infinite dilution were calculated for the hexane/benzene and methanol/benzene systems from experimental infinite dilution activity coefficients and compared to the literature values for related ionic liquids, as well as to data on industrial molecular solvents.     

Activity coefficients at infinite dilution of hydrocarbons,alkylbenzenes, and alcohols in the paramagnetic ionic liquid 1-butyl-3-methyl-imidazolium tetrachloridoferrate(III) using gas–liquid chromatography

Activity coefficients at infinite dilution ${\gamma }_i^{\infty }$ of alkanes, alkenes, and alkylbenzenes as well as of the linear C₁–C₆ alcohols in the paramagnetic ionic liquid 1-butyl-3-methyl-imidazolium tetrachloridoferrate(III) have been determined by gas chromatography using the ionic liquids as stationary phase. The measurements were carried out at different temperatures between (305 and 403) K. From the temperature dependence of the limiting activity coefficients partial molar excess enthalpies at infinite dilution $H_i^{E\text{,}\infty }$ of the solutes in the ionic liquids have been derived. Activity coefficients at infinite dilution ${\gamma }_i^{\infty }$ of ionic liquid with the ionic liquids containing 1-butyl-3-methyl-imidazolium cation and different non-magnetic anions have been compared at 298 K with results for 1-butyl-3-methyl-imidazolium tetrachloridoferrate(III). No significant effects caused by the paramagnetic anion anion have been observed.     

GC–MS study of thermochemical conversion of guaifenesin in the presence of 1-butyl-3-methylimidazolium-based ionic liquids

Research on Chemical Intermediates - Thermochemical conversion of guaifenesin was performed in the presence of 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4] ionic liquid at...     

1-Butyl-3-methylimidazolium hexafluorophosphate ionic liquid-based liquid–liquid microextraction for the determination of 4-nonylphenol and 4- tert -octylphenol in environmental waters

In the present study, room-temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium hexafluorophosphate was used as extraction solvent in a liquid–liquid microextraction (LLME) procedure followed by liquid chromatography for determining 4-nonylphenol (4-NP) and 4-tert-octylphenol (4-t-OP) in environmental water samples. RTIL-based LLME was a simple, inexpensive, and fast sample preparation method, and its parameters such as extraction time, addition of salt, selection of phase ratio, and pH value were optimized. The optimized method had acceptable limits of detection (LOD) and a precision of 2?µg?L^?1 and 8.1% for 4-NP and 0.6?µg?L^?1 and 3.7% for 4-t-OP, respectively. The proposed method was successfully applied in river water and effluent from a sewage-treatment plant, and the recoveries spiked at 6?µg?L^?1 and 25?µg?L^?1 levels were in the range of 82–113%.     

Alkylsulfate-based ionic liquids in the liquid–liquid extraction of aromatic hydrocarbons

The (liquid + liquid) equilibrium data (LLE) for the extraction of toluene from heptane with different ionic liquids (ILs) based on the alkylsulfate anion (R-SO₄) was determined at T = 313.2 K and atmospheric pressure. The effect of more complex R-SO₄ anions on capacity of extraction and selectivity in the liquid–liquid extraction of toluene from heptane was studied. The ternary systems were formed by {heptane + toluene + 1,3-dimethylimidazolium methylsulfate ([mmim][CH₃SO₄]), 1-ethyl-3-methylimidazolium hydrogensulfate ([emim][HSO₄]), 1-ethyl-3-methylimidazolium methylsulfate ([emim][CH₃SO₄]), or 1-ethyl-3-methylimidazolium ethylsulfate ([emim][C₂H₅SO₄])}. The degree of quality of the experimental LLE data was ascertained by applying the Othmer–Tobias correlation. The phase diagrams for the ternary systems were plotted, and the tie lines correlated with the NRTL model compare satisfactorily with the experimental data.     

Regioselective Friedel–Crafts deacylations of polycyclic aromatic ketones in the pyrene series

1,3,6,8-tetrabenzoylpyrene (1,3,6,8-Bz ₄ PY) and 1,3,6-tribenzoylpyrene (1,3,6-Bz ₃ PY) were synthesized and their crystal structures were determined. The Friedel–Crafts deacylations in PPA of 1,3,6,8-Bz ₄ PY (at 120–200 °C) and of 1,3,6-Bz ₃ PY (at 80–160 °C) have been studied. The mono-deacylation of 1,3,6-Bz ₃ PY was regioselective and led to three dibenzoylpyrenes in the following order of relative amounts: 1,8-Bz ₂ PY > 1,6-Bz ₂ PY > 1,3-Bz ₂ PY. 1,3,6,8-Bz ₄ PY was resistant to deacylation at 120–160 °C. The deacylations of 1,3,6,8-Bz ₄ PY at 200 °C gave the polycyclic aromatic ketone (PAK) 8H-dibenzo[def,qr]chrysen-8-one (DBCO) via an intramolecular Scholl reaction. Two plausible pathways of the Friedel–Crafts deacylation of 1,3,6,8-Bz ₄ PY to give DBCO are proposed. A density functional theory (DFT) B3LYP/6-311(d,p) computational study of the conformational spaces of 1,3,6-Bz ₃ PY and 1,3,6,8-Bz ₄ PY was performed. The estimated energy barriers of formation of dibenzoylpyrenes by deacylation of 1,3,6-Bz ₃ PY increase in the following order: 1,8-Bz ₂ PY < 1,3-Bz ₂ PY < 1,6-Bz ₂ PY. A mechanism of the Friedel–Crafts deacylation of 1,3,6-Bz ₃ PY in PPA via the respective O-protonated ketone and σ-complexes is presented.