Theoretical study of the Michael addition of acetylacetone to methyl vinyl ketone catalyzed by the ionic liquid 1‐butyl‐3‐methylimidazolium hydroxide

By performing density functional theory calculations, we have investigated the Michael addition of acetylacetone to methyl vinyl ketone in the absence and presence of the ionic liquid 1‐butyl‐3‐methylimidazolium hydroxide ([bmIm]OH). In the absence of ionic liquids, acetylacetone is firstly tautomerized to enol form and then takes place Michael addition to methyl vinyl ketone. As in the catalyzed Michael addition reaction, a bmIm⁺‐OH^? ion pair is introduced into the reaction system to model the effect of the ionic liquid environment on the reactivity. The calculated results show that the anion enhances nucleophilic ability of acetylacetone since the OH^? anion captures a proton to form an acetylacetone anion‐H₂O complex, and the cation improves the electrophilic ability of methyl vinyl ketone by forming intermolecular hydrogen‐bonds. Both the remarkable effects of the cation and anion on the reactivity of reactants promote this reaction, which take place more easily compared with uncatalyzed reaction. The calculated results show that the main product of the Michael addition is in its ketone form. Our study provides a detailed reaction mechanism of Michael addition catalyzed by basic ionic liquid [bmIm]OH and clearly reveal the catalytic role of ionic liquid in important chemical reaction. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

1‐Octanol/Water Partition Coefficients of 1Alkyl‐3‐methylimidazolium Chloride

The solubilities of 1alkyl‐3‐methylimidazolium chloride, [C_nmim][Cl], where n=4, 8, 10, and 12, in 1octanol and water have been measured by a dynamic method in the temperature range from 270 to 370 K. The solubility data was used to calculate the 1octanol/water partition coefficients as a function of temperature and alkyl substituent. The melting point, enthalpies of fusion, and enthalpies of solid–solid phase transitions were determined by differential scanning calorimetry, DSC. The solubility of [C_nmim][Cl], where n=10 or 12 in 1octanol is comparable and higher than that of [C₄mim][Cl] in 1octanol. Liquid 1n‐octyl‐3‐methylimidazolium chloride, [C₈mim][Cl], is not miscible with 1octanol and water, consequently, the liquid–liquid equilibrium, LLE was measured in this system. The differences between the solubilities in water for n=4 and 12 are shown only in α₁ and γ₁ solid crystalline phases. Additionally, the immiscibility region was observed for the higher concentration of [C₁₀mim][Cl] in water. The intermolecular solute–solvent interaction of 1butyl‐3‐methylimidazolium chloride with water is higher than for other 1alkyl‐3‐methylimidazolium chlorides. The data was correlated by means of the UNIQUAC ASM and two modified NRTL equations utilizing parameters derived from the solid–liquid equilibrium, SLE. The root‐mean‐square deviations of the solubility temperatures for all calculated data are from 1.8 to 7 K and depend on the particular equation used. In the calculations, the existence of two solid–solid first‐order phase transitions in [C₁₂mim][Cl] has also been taken into consideration. Experimental partition coefficients (log P) are negative at three temperatures; this is evidence for the possible use of these ionic liquids as green solvents.     

Interactions of Ionic Liquids with Polysaccharides 1. Unexpected Acetylation of Cellulose with 1‐Ethyl‐3‐methylimidazolium Acetate

The homogeneous conversion of cellulose in the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate with 2‐furoyl chloride, p‐toluenesulfonyl chloride, and triphenylmethyl chloride yields surprisingly pure cellulose acetate samples in any case. From NMR spectroscopic studies, it may be concluded that during the homogeneous functionalization reactive intermediates including furane‐2‐carboxylic acid/acetic acid anhydride and acetic acid triphenylmethyl ester are formed leading to the cellulose acetates with DS values in the range from 0.55 to 1.86.

     

Living/controlled radical copolymerization of N‐substituted maleimides with styrene in 1‐butyl‐3‐methylimidazolium hexafluorophosphate and anisole

The atom transfer radical copolymerization of N‐substituted maleimides such as N‐phenylmaleimide (PhMI), N‐cyclohexylmaleimide (ChMI), and N‐butylmaleimide (NBMI) with styrene initiated with dendritic polyarylether 2‐bromoisobutyrates in an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim][PF₆]), at room temperature and anisole at 110 °C was investigated. The dendritic‐linear block copolymers obtained in ionic liquid possessed well‐defined molecular weight and low polydispersity (1.05 < M_w/M_n < 1.32) and could be used as a macroinitiator for chain‐extension polymerization, suggesting the living nature of the reaction system. The ionic liquids containing catalyst could be recycled in the atom transfer radical polymerization systems without further treatment. Compared with polymerization conducted in anisole, the polymerization in ionic liquid had a stronger tendency for alternation. The tendency for alternation decreased in the order PhMI > NBMI > ChMI in [bmim][PF₆] and PhMI > ChMI > NBMI in anisole. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2156–2165, 2003     

Aggregation of phosphate and 1‐tetradecyl‐3‐methylimidazolium chloride background electrolytes during micellar electrokinetic chromatography

We report the possible aggregation of phosphate and ionic liquid (1‐tetradecyl‐3‐methylimidazolium chloride) based BGEs during MEKC. After a certain transit period, the aggregates appear as a random sequence of spikes on a UV detector signal. Root mean square values of the spikes and aggregation time (T_a) were plotted against BGE concentrations. The observation suggests that MEKC is a simple and easy technique for micelle aggregation studies.     

Raman Spectroscopic Study on Alkyl Chain Conformation in 1‐Butyl‐3‐methylimidazolium Ionic Liquids and their Aqueous Mixtures

Ionic liquids of 1‐butyl‐3‐methylimidazolium ([BMIM]) cation with different anions (Cl^?, Br^?, I^?, and BF₄^?), and their aqueous mixtures were investigated by using Raman spectroscopy and dispersion‐included density functional theory (DFT). The characteristic Raman bands at 600 and 624 cm^?1 for two isomers of the butyl chain in the imidazolium cation showed significant changes in intensity for different anions as well as in aqueous solutions. The area ratio of these two bands followed the order I^?>Br^?>Cl^?>BF₄^? (in terms of the anion X in [BMIM]X), indicating that the butyl chain of [BMIM]I tends to adopt the trans conformation. The butyl chain was found to adopt the gauche conformation upon dilution, irrespective of the anion type. The Raman bands in the butyl C?H stretch region for [BMIM]X (X=Cl^?, Br^?, and I^?) blueshifted significantly with the increase in the water concentration, whereas that for [BMIM]BF₄ changed very little upon dilution. The blueshift in the C?H stretch region upon dilution also followed the order: [BMIM]I>[BMIM]Br>[BMIM]Cl>[BMIM]BF₄, the same order as the above trans conformation preference of the butyl chain in pure imidazolium ionic liquids, which suggested that the cation‐anion interaction plays a role in determining the conformation of the chain.     

Synthesis,structural characterization and luminescence properties of 1‐carboxymethyl‐3‐ethylimidazolium chloride

A microcrystalline carboxyl‐functionalized imidazolium chloride, namely 1‐carboxymethyl‐3‐ethylimidazolium chloride, C₇H₁₁N₂O₂⁺·Cl⁻, has been synthesized and characterized by elemental analysis, attenuated total reflectance Fourier transform IR spectroscopy (ATR‐FT‐IR), single‐crystal X‐ray diffraction, thermal analysis (TGA/DSC), and photoluminescence spectroscopy. In the crystal structure, cations and anions are linked by C—H…Cl and C—H…O hydrogen bonds to create a helix along the [010] direction. Adjacent helical chains are further interconnected through O—H…Cl and C—H…O hydrogen bonds to form a (10) layer. Finally, neighboring layers are joined together via C—H…Cl contacts to generate a three‐dimensional supramolecular architecture. Thermal analyses reveal that the compound melts at 449.7 K and is stable up to 560.0 K under a dynamic air atmosphere. Photoluminescence measurements show that the compound exhibits a blue fluorescence and a green phosphorescence associated with spin‐allowed (¹π←¹π*) and spin‐forbidden (¹π←³π*) transitions, respectively. The average luminescence lifetime was determined to be 1.40 ns for the short‐lived (¹π←¹π*) transition and 105 ms for the long‐lived (¹π←³π*) transition.     

Uses of ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate as a good separation electrolyte for direct electrophoretic separation of quaternary ammonium herbicides

This paper describes a new method for the direct separation of paraquat and diquat by CZE with ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate employed as reliable electrolyte. Several factors that affect the separation efficiency were investigated in detail. The experimental results indicated that the optimal running buffer consisted of 50 mM 1‐butyl‐3‐methylimidazolium hexafluorophosphate and 10% ethanol (pH 5.0), applied voltage was 15 kV, and temperature was kept at 30°C and baseline‐separation was achieved within 18 min for the analytes. The proposed method would be very useful and have wide use to monitor the residual level of such pollutants when combined with high‐sensitive detector and an excellent sample preconcentration technique with high enrichment factor in the future.     

Raman and FTIR Spectroscopic Studies of 1‐Ethyl‐3‐methylimidazolium Trifluoromethylsulfonate,its Mixtures with Water and the Solvation of Zinc Ions

In this paper we report on the interactions of the ionic liquid 1‐ethyl‐3‐methylimidazolium trifluoromethylsulfonate ([EMIm]TfO) with water and the solvation of zinc ions in neat [EMIm]TfO and [EMIm]TfO–water mixtures investigated by FTIR and Raman spectroscopy. The structures and physicochemical properties of the [EMIm]TfO–water mixtures are strongly dependent on the interaction between cations, anions, and water. The structure was changed from ionic‐liquid‐like to water‐like solutions upon addition of water. In addition, zinc salts can precipitate in 0.2 M Zn(TfO)₂/[EMIm]TfO upon addition of 10 % (v/v) water, presumably as a result of polarity change of the solution. The average coordination number of TfO^? per zinc ion calculated from Raman spectra is 3.8 in neat [EMIm]TfO, indicating that [Zn(TfO)₄]^2?, and [Zn(TfO)₃]^? complexes are present in the solution. However, in the presence of water, water interacts preferentially with the zinc ions, leading to aqueous zinc species. The solvation of zinc ions in 1‐butyl‐1‐methylpyrrolidinium trifluoromethylsulfonate ([Py_1,4]TfO) was also investigated. In [Py_1,4]TfO, there are, on average, 4.5 TfO^? anions coordinating each zinc ion, corresponding to the weak interaction between [Py_1,4]⁺ cations and TfO^? anions. The species present in [Py_1,4]TfO are likely a mixture of [Zn(TfO)₄]^2? and [Zn(TfO)₅]^3?.     

1‐Carboxymethyl‐3‐methyl‐1H‐imidazol‐3‐ium chloride 2‐(3‐methyl‐1H‐imidazol‐3‐ium‐1‐yl)acetate monohydrate: a crystal stabilized by imidazolium zwitterions

The title compound, C₆H₉N₂O₂⁺·Cl⁻·C₆H₈N₂O₂·H₂O, contains one 2‐(3‐methyl‐1H‐imidazol‐3‐ium‐1‐yl)acetate inner salt molecule, one 1‐carboxymethyl‐3‐methyl‐1H‐imidazol‐3‐ium cation, one chloride ion and one water molecule. In the extended structure, chloride anions and water molecules are linked via O—H...Cl hydrogen bonds, forming an infinite one‐dimensional chain. The chloride anions are also linked by two weak C—H...Cl interactions to neighbouring methylene groups and imidazole rings. Two imidazolium moieties form a homoconjugated cation through a strong and asymmetric O—H...O hydrogen bond of 2.472 (2) Å. The IR spectrum shows a continuous D‐type absorption in the region below 1300 cm⁻¹ and is different to that of 1‐carboxymethyl‐3‐methylimidazolium chloride [Xuan, Wang & Xue (2012). Spectrochim. Acta Part A, 96 , 436–443].     

Mass Distribution and Diffusion of [1‐Butyl‐3‐methylimidazolium][Y] Ionic Liquids Adsorbed on the Graphite Surface at 300–800 K

The structure and diffusion behavior of 1‐butyl‐3‐methylimidazolium ([bmim]⁺) ionic liquids with [Cl]^?, [PF₆]^?, and [Tf₂N]^? counterions near a hydrophobic graphite surface are investigated by molecular dynamics simulation over the temperature range of 300–800 K. Near the graphite surface the structure of the ionic liquid differs from that in the bulk and it forms a well‐ordered region extending over 30 Å from the surface. The bottom layer of the ionic liquid is stable over the investigated temperature range due to the inherent slow dynamics of the ionic liquid and the strong Coulombic interactions between cation and anion. In the bottom layer, diffusion is strongly anisotropic and predominantly occurs along the graphite surface. Diffusion perpendicular to the interface (interfacial mass transfer rate k_t) is very slow due to strong ion–substrate interaction. The diffusion behaviors of the three ionic liquids in the two directions all follow an Arrhenius relation, and the activation barrier increases with decreasing anion size. Such an Arrhenius relation is applied to surface‐adsorbed ionic liquids for the first time. The ion size and the surface electrical charge density of the anions are the major factors determining the diffusion behavior of the ionic liquid adjacent to the graphite surface.     

Molecular Reorientational Dynamics of the Neat Ionic Liquid 1‐Butyl‐3‐methylimidazolium Hexafluorophosphate by Measurement of 13C Nuclear Magnetic Relaxation Data

The reorientational dynamics of the ionic liquid 1butyl‐3‐methylimidazolium hexafluorophosphate ([BMIM]PF₆) were studied over a wide range of temperatures by measurement of ¹³C spin–lattice relaxation rates and NOE factors. The reorientational dynamics were evaluated by performing fits to the experimental relaxation data. Thus, the overall reorientational motion was described by a Cole–Davidson spectral density with a Vogel–Fulcher–Tammann temperature dependence of the correlation times. The reorientational motion of the butyl chain was modelled by a combination of the latter model for the overall motion with a Bloembergen–Purcell–Pound spectral density and an Arrhenius temperature dependence for the internal motion. Except for C2 in the aromatic ring, an additional reduction of the spectral density by the Lipari–Szabo model had to be employed. This reduction is a consequence of fast molecular motions before the rotational diffusion process becomes effective. The C2 atom did not exhibit this reduction, because the librational motion of the corresponding C2? H vector is severely hindered due to hydrogen bonding with the hexafluorophosphate anion. The observed dynamic features of the [BMIM]⁺ cation confirm quantum‐chemical structures obtained in a former study.     

1‐Butyl‐3‐methylimidazolium Hydrogen Sulfate [Bmim]HSO4: An Efficient Reusable Acidic Ionic Liquid for the Synthesis of 1,8‐Dioxo‐Octahydroxanthenes

1‐Butyl‐3‐methylimidazolium hydrogen sulfate [bmim]HSO₄ as an acidic ionic liquid was prepared and used as a catalyst for the synthesis of 1,8‐dioxo‐octahydroxanthenes in excellent yields and short reaction times at 80 °C. The ionic liquid was easily separated from the reaction mixture by water extraction and was recycled four times without any loss in activity.     

Understanding the Effect Models of Ionic Liquids in the Synthesis of NH4‐Dw and γ‐AlOOH Nanostructures and Their Conversion into Porous γ‐Al2O3

Well‐dispersed ammonium aluminum carbonate hydroxide (NH₄‐Dw) and γ‐AlOOH nanostructures with controlled morphologies have been synthesized by employing an ionic‐liquid‐assisted hydrothermal process. The basic strategies that were used in this work were: 1) A controllable phase transition from NH₄‐Dw to γ‐AlOOH could be realized by increasing the reaction temperature and 2) the morphological evolution of NH₄‐Dw and γ‐AlOOH nanostructures could be influenced by the concentration of the ionic liquid. Based on these experimental results, the main objective of this work was to clarify the effect models of the ionic liquids on the synthesis of NH₄‐Dw and γ‐AlOOH nanostructures, which could be divided into cationic‐ or anionic‐dominant effect models, as determined by the different surface structures of the targets. Specifically, under the cationic‐dominant regime, the ionic liquids mainly showed dispersion effects for the NH₄‐Dw nanostructures, whereas the anionic‐dominant model could induce the self‐assembly of the γ‐AlOOH particles to form hierarchical structures. Under the guidance of the proposed models, the effect of the ionic liquids would be optimized by an appropriate choice of cations or anions, as well as by considering the different effect models with the substrate surface. We expect that such effect models between ionic liquids and the target products will be helpful for understanding and designing rational ionic liquids that contain specific functional groups, thus open up new opportunities for the synthesis of inorganic nanomaterials with new morphologies and improved properties. In addition, these as‐prepared NH₄‐Dw and γ‐AlOOH nanostructures were converted into porous γ‐Al₂O₃ nanostructures by thermal decomposition, whilst preserving the same morphology. By using HRTEM and nitrogen‐adsorption analysis, the obtained γ‐Al₂O₃ samples were found to have excellent porous properties and, hence, may have applications in catalysis and adsorption.     

Glass slides functionalized by 1‐carboxyethyl‐3‐methylimidazolium chloride for the determination of triazine herbicides in rice using high‐performance liquid chromatography

A novel and simple supported ionic‐liquid‐based solid‐phase extraction method for the determination of triazine herbicides in rice was developed. Glass slides were functionalized by an ionic liquid, 1‐carboxyethyl‐3‐methylimidazolium chloride, and were used for the simultaneous extraction of seven triazine herbicides in rice samples. The effects of the type of extraction solvent, the extraction time, the type and volume of loading solvent, and the type of eluting solvent on the extraction efficiency were investigated and optimized. Under the optimum operation conditions, the limits of detection for seven triazine herbicides in rice samples obtained by high‐performance liquid chromatography were 3.16–5.42 ng/g, which were lower than the maximum residue levels established by various organizations. The linear correlation coefficients were higher than 0.9975 in the concentration range of 0.015–1.08 μg/g for the seven triazine herbicides. The recoveries of the seven triazine herbicides at the two concentration levels of 0.15 and 0.45 μg/g are between 82.47 and 104.21%, with relative standard deviations of 0.69–9.19%. The intra‐ and inter‐day (n = 5) precisions for all triazine herbicides at the spiked level of 0.30 μg/g were 1.72–11.71%.     

The Effect of C4H and C5H on the Microstructure of Aqueous Solutions of 1‐Alkyl‐3‐methylimidazolium Tetrafluoroborate Ionic Liquids

As is well‐known, the C2?H proton of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate ([Emim]BF₄) and 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([Bmim]BF₄) has a strong ability to form hydrogen bonds. The purpose of this work is to evaluate the effect of the interactions of the C4?H and C5?H protons on the microstructure of [Emim]BF₄ and [Bmim]BF₄ with water by using ¹H NMR spectroscopy. The differences between the relative ¹H NMR chemical shifts of C2?H, C4?H, and C5?H and between the interaction‐energy parameters obtained from these chemical shifts are minor, thus suggesting that the interactions of C4?H and C5?H may have a considerable effect on the microstructure. To confirm this, the viscosities of the systems are estimated by using the interaction‐energy parameters obtained from the ¹H NMR chemical shifts of the three studied aromatic protons and water, showing that the interactions of C4?H and C5?H also play an important role in the microstructure.     

Aluminium Speciation in 1‐Butyl‐1‐Methylpyrrolidinium Bis(trifluoromethylsulfonyl)amide/AlCl3 Mixtures

Aluminium speciation : Aluminium speciation in NTf₂ ionic liquids has a strong influence on its electrodeposition from the liquid mixture. This work probed the nature of these species and proposes that the electroactive species involved are either [AlCl₃(NTf₂)]^? or [AlCl₂(NTf₂)₂]^? (e.g., see figure).