Diels-Alder reactions in pyridinium based ionic liquids

Diels-Alder reactions have been investigated in pyridinium based ionic liquids. These solvents are found to be more effective compared to the organic solvent studied, in enhancing the reaction rate and product yields. Recycled ionic liquids also gave excellent results.     

Friedel-Crafts acylation reactions in pyridinium based ionic liquids

The Friedel-Crafts acylations of representative aromatic compounds with acetic anhydride in pyridinium based ionic liquids (ILs) were investigated. The effect of factors such as reactant composition, catalyst-IL composition, catalyst dosage and reaction temperature were studied. The reactions were found to proceed under relatively mild conditions with excellent conversions; and a simple product isolation procedure was achieved. ILs could also be recycled and reused effectively, thus rendering green characteristic to this reaction.     

Ultrafast dynamics of pyrrolidinium cation ionic liquids

We have investigated the ultrafast molecular dynamics of five pyrrolidinium cation room temperature ionic liquids using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids studied are N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P14+/NTf2-), N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bromide P1EOE+, and N-ethoxyethyl-N-methylpyrrolidinium dicyanoamide P1EOE+/DCA-). For comparing dynamics among the five ionic liquids, we categorize the ionic liquids into two groups. One group of liquids comprises the three pyrrolidinium cations P14+, P1EOM+, and P1EOE+ paired with the NTf2- anion. The other group of liquids consists of the P1EOE+ cation paired with each of the three anions NTf2-, Br-, and DCA-. The overdamped relaxation for time scales longer than 2 ps has been fit by a triexponential function for each of the five pyrrolidinium ionic liquids. The fast ( approximately 2 ps) and intermediate (approximately 20 ps) relaxation time constants vary little among these five ionic liquids. However, the slow relaxation time constant correlates with the viscosity. Thus, the Kerr spectra in the range from 0 to 750 cm(-1) are quite similar for the group of three pyrrolidinium ionic liquids paired with the NTf2- anion. The intermolecular vibrational line shapes between 0 and 150 cm(-1) are fit to a multimode Brownian oscillator model; adequate fits required at least three modes to be included in the line shape.     

Ion-exchange as a mode of cation transfer into room-temperature ionic liquids containing crown ethers: implications for the 'greenness' of ionic liquids as diluents in liquid-liquid extraction

The transfer of strontium ion from acidic nitrate media into a series of 1-alkyl-3-methylimidazolium-based room-temperature ionic liquids containing dicyclohexano-18-crown-6 is shown to proceed via cation-exchange, in contrast to conventional solvents such as alkan-1-ols, in which extraction of a strontium nitrato-crown ether complex is observed.     

Design and synthesis of pyridinium chiral ionic liquids tethered to a urea functionality

Nine chiral room-temperature ionic liquids (RTILs), which contain a chiral moiety and a urea functionality bonded to a pyridinium ring, have been designed and synthesized. The synthesis of these ionic liquids is concise and practical due to the commercial availability of the starting materials. These novel RTILs were readily prepared from 2-(aminomethyl)pyridine and amino acid ester derived isocyanates. We envision that these new chiral RTILs can serve as effective reaction media as well as chiral catalysts for asymmetric reactions, which are presently being investigated in our laboratory.     

Selectivity of stationary phases based on pyridinium ionic liquids for capillary gas chromatography

A number of capillary columns with stationary liquid phases based on mono- and dication pyridinium ionic liquids (ILs) were prepared. Their polarity was evaluated using McReynolds system and the selectivity was estimated from intermolecular interactions. The parameters of intermolecular interactions were obtained from retention data using the (Abraham) model of the linear free energy relationship. The dependences of intermolecular interactions on the structure of the cation in the ILs under study were revealed. The results were compared with the data for the traditional phases (HP-5, ZB-WAX). Examples of separation of mixtures of oxygen-containing compounds on the phases under study are given.     

Palladate salts from chiral pyridinium ionic liquids: synthesis and crystal structures

This paper reports the preparation, characterization and the crystal X-ray structures of metal-containing ionic liquid complexes based on chiral pyridinium cations and tetrachloropalladate (II) [PdCl4]2-.     

Protic pyridinium ionic liquids: Synthesis, acidity determination and their performances for acid catalysis

Three new protic ionic liquids based on 2-methylpyridinium were prepared and characterized. Their catalytic activities for the tert-butylation of phenol and the esterification of cyclic olefins with acetic acid were examined and satisfactory results were obtained over 2-methylpyridinium trifluoromethanesulfonate ([2-MPyH]OTf). Hammett method was used to determine the acidity order of these ionic liquids and the results are consistent with the catalytic activities observed in the acid-catalyzed probe reactions.     

Optimization of cation structure of imidazolium-based ionic liquids as ionic solvents for rechargeable magnesium batteries

A series of imidazolium cation-based ionic liquids (ILs) have been synthesized and examined as ionic solvents for rechargeable magnesium batteries. The electrolyte solutions consist of these ILs dissolving methylmagnesium bromide with tetrahydrofuran (MeMgBr/THF). The chemical structure of imidazolium cation much influenced the ionic conductivity and the electrochemical window of the system. A reversible process of cathodic deposition and anodic dissolution of magnesium has been successfully achieved at room temperature. The highest value of anodic peak current for magnesium dissolution was obtained in an optimized-structure IL with allyl and methoxyethyl groups as the substituents.     

Determination of the polarities of some ionic liquids using 2-nitrocyclohexanone as the probe

Solute-solvent interactions on the keto-enol tautomerism of 2-nitrocyclohexanone in several organic solvents and room-temperature ionic liquids (RTILs) have been analyzed in terms of multiparameter equations. Permittivity and cohesive pressure values of the RTILs, unavailable by direct measurements, have been derived.     

Anisotropic ionic liquids built from nonmesogenic cation surfactants and Keggin-type polyoxoanions

Non-mesogenic unit bearing Keggin-type polyoxoanions with tetra-n-octylammonium counterions exhibit an ionic liquid crystalline structure via ionic self-assembly in a certain temperature range.     

Self-aggregation and antimicrobial activity of imidazolium and pyridinium based ionic liquids in aqueous solution

Adsorbed cetyldimethylbenzylammonium chloride (CDBACl) or cetyltrimethylammonium bromide (CTAB) on mercury is used as template for the adsorption of CTAB, CDBACl, or their equimolar mixture at 20 °C. Adsorptive stripping voltammetry with the two step procedure is used. The results are compared with previously published results on the adsorption of CTAB and CDBACl on mercury and then transferred in base electrolyte. A surfactant is preadsorbed. The adsorption of the second does not remove away from the mercury the first one, as evidenced by the capacitance measurements and the repeated scans. The surfactants were maintained close to each other and in the vicinity of the electrode by the applied electric field. In all cases studied, there was a decrease in the capacitance in the potential range -0.8 to -1 V to very low capacitance values forming condensed film. Mixed films and synergy effects were observed. The already adsorbed CTAB on mercury did not permit the desorption-reorientation peaks of CDBACl. Shifts of the capacitance peaks were observed to more positive potentials and were attributed to the occurrence of a slow change in the organization of the monolayer. The electrical state of the preadsorbed surfactant would be of critical importance in the formation of the various structures. The results suggested that the ordering and arrangement of molecules could be controlled by appropriate selection of templates.     

Solvent effects in ionic liquids: empirical linear energy-density relationships

Multiparameter linear energy-density relationships to model solvent effects in room temperature ionic liquids (RTILs) are introduced and tested. The model incorporates two solvent dependent and two specific solute-solvent parameters represented by a set of electronic indexes derived from the conceptual density functional theory. The specific solute-solvent interactions are described in terms of the electronic chemical potential for proton migration between the anion or cation and the transition state structure of a specific reaction. These indexes provide a quantitative estimation of the hydrogen bond (HB) acceptor basicity and the hydrogen bond donor acidity of the ionic solvent, respectively. A sound quantitative scale of HB strength is thereby obtained. The solvent dependent contributions are described by the global electrophilicity of the cation and nucleophilicity of the anion forming the ionic liquid. The model is illustrated for the kinetics of cycloaddition of cyclopentadiene towards acrolein. In general, cation HB acidity outweighs the remaining parameters for this reaction.     

Study on the phase behaviour and thermodynamic properties of ionic liquids containing imidazolium cation with ethanol at several temperatures

Experimental densities, speeds of sound and refractive indices of the binary mixtures of ethanol with MMIM MeSO₄ (1,3-dimethylimidazolium methyl sulfate), BMIM MeSO₄ (1-butyl-3-methylimidazolium methyl sulfate), BMIM PF₆ (1-butyl-3-methylimidazolium hexafluorophosphate), HMIM PF₆ (1-hexyl-3-methylimidazolium hexafluorophosphate) and OMIM PF₆ (1-methyl-3-octylimidazolium hexafluorophosphate) were determined from T = (293.15 to 303.15) K. Excess molar volumes, changes of refractive index on mixing and deviations in isentropic compressibility for the above systems were calculated. The (liquid + liquid) equilibrium (LLE) data of (IL + ethanol) were carried out experimentally and the NRTL and UNIQUAC correlative equation was applied to these mixtures.     

Sodium carbonate as phase promoter in aqueous solutions of imidazolium and pyridinium ionic liquids

Several methylsulfate and chloride anion-based ionic liquids, such as 1-alkyl-3-methyl imidazolium methyl sulfate, C_nMIM CH₃SO₄ (n = 1, 2, and 4), 1-benzyl-3-methyl imidazolium methyl sulfate, BzMIM CH₃SO₄, 1-benzyl, or hexyl-3-methyl imidazolium chloride, XMIM Cl (X = Bz and Hx), and methylpyridinium methylsulfate, Mpy CH₃SO₄, with sodium carbonate, Na₂CO₃, as phase forming salt, have been investigated and discussed for their potential use in separations based on aqueous two-phase systems (ATPS). Phase diagrams have been experimentally ascertained at T = 298.15 K, and Merchuck equation and a variation of this model have been used for correlating the binodal data. The alkyl chain length in the cation and the type of anion and cation have been explored and discussed due to their decisive influence in the ATPS behavior. The consistence of tie-line data was ascertained by applying the Othmer–Tobias and Bancroft equations.     

Catalytically active palladium pyridylidene complexes: pyridinium ionic liquids as N-heterocyclic carbene precursors

Pyridinium salts similar to those used as ionic liquid solvents readily undergo palladation in the presence of a base, thus giving palladium-pyridylidene N-heterocyclic carbene complexes that are active catalysts for Suzuki-type cross-coupling reactions.     

Using spectroscopic data on imidazolium cation conformations to test a molecular force field for ionic liquids

A molecular force field for the computer simulation of ionic liquids is evaluated a posteriori by confrontation against Raman spectroscopic data, published after the force field had been formulated. Specifically, the terms in the force field describing the conformational aspects of dialkylimidazolium cations, which were specifically developed for these compounds using high level ab initio calculations, are those affecting the distribution of conformers in simulated ionic liquids. Those distributions are compared with analyses of the liquid-phase Raman spectra, and the features of a series of dihedral torsions along the alkyl side chains in 1-alkyl-3-methylimidazolium cations in several ionic liquids are discussed.     

Thermophysical properties of two ionic liquids based on benzyl imidazolium cation

Density, refractive index, and dynamic viscosity of two new ionic liquids involving the 1-benzyl-3-methyl imidazolium cation and the common anions chloride and methylsulfate have been determined and correlated as a function of temperature. Volumetric properties for the ionic liquids are calculated from the density and the results are also enclosed. The Lorentz–Lorenz, Dale–Gladstone, Eykman, Oster, Arago–Biot, and Newton equations, as well as a modified Eykman were used to correlate satisfactorily the relation between the densities and refractive indices of the selected ionic liquids. The influence of the benzyl group on the density was compared with other alkyl imidazolium cations and the same anions.     

Supported ionic liquids: ordered mesoporous silicas containing covalently linked ionic species

Ordered mesoporous silicas with hexagonal or lamellar architectures incorporating covalently bound ionic species were synthesized via a template directed hydrolysis-polycondensation of tetraethoxysilane (TEOS) with triethoxysilylated imidazole [(EtO)(3)Si(CH(2))(3)-Im] or alkylimidazolium halides [(EtO)(3)Si(CH(2))(3)-Im(+)-R Hal(-)].