功能化离子液体的制备及其在合成中的应用

功能化离子液体;手性离子液体;酸性离子液体     

Sugar-Based Ionic Liquids: Multifaceted Challenges and Intriguing Potential

Carbohydrates represent a promising option in transitioning from oil-based chemical resources to renewable ones, with the goal of developing chemistries for a sustainable future. Cellulose, hemicellulose, and largely available monosaccharides already provide useful chemical building blocks, so-called platform chemicals, such as levulinic acid and hydroxymethyl furfural, as well as solvents like cyrene or gamma-valerolactone. Therefore, there is great anticipation for novel applications involving materials and chemicals derived from sugars. In the field of ionic liquids (ILs), sugar-based ILs have been overlooked for a long time, mainly on account of their multistep demanding preparation. However, exploring new strategies for accessing sugar-based ILs, their study, and their exploitation, are attracting increasing interest. This is due to the growing concerns about the negative (eco)toxicity profile of most ILs in conjunction with their non-sustainable nature. In the present review, a literature survey concerning the development of sugar-based ILs since 2011 is presented. Their preparation strategies and thermal behavior analyses, sorted by sugar type, make up the first two sections with the intention to provide the reader with a useful guide. A final overview of the potential applications of sugar-based ILs and their future perspectives complement the present analysis.     

High‐throughput microscale extraction using ionic liquids and derivatives: A review

Ionic liquids and derivatives—mainly polymeric ionic liquids and magnetic ionic liquids—have been extensively used in microscale extraction over the past few years. Current trends in analytical sample preparation gear toward linking microextraction approaches with high‐throughput sample processing to comply with green analytical chemistry requirements. A variety of high sample throughput strategies that are coupled to both ionic‐liquid‐based solid‐phase microextraction and ionic liquid‐based liquid‐phase microextraction are herein reported. The review is focused on microscale extraction methods that use (i) custom‐made and dedicated extraction devices, (ii) parallel extraction, (iii) magnetic‐based separation, and (iv) miniaturized systems employing semi‐automatic or fully automatic flow injection methods, related micro/millifluidic devices, and robotic equipment.     

Liquid Crystals Based on the N-Phenylpyridinium Cation—Mesomorphism and the Effect of the Anion

Families of symmetric, ionic, tetracatenar mesogens are described based on a rigid, N-phenylpyridinium core, prepared as their triflimide, octyl sulfate and dodecyl sulfate salts for a range of terminal chain lengths. The mesomorphism of the individual series is described before a comparison is drawn between the different families and then more broadly with (i) neutral tetracatenar materials and (ii) related bis(3,4-dialkoxystilbazole)silver(I) salts. For the octyl and dodecyl sulfates and the related triflates reported earlier, a SmA phase is seen at shorter chain lengths, giving way to a Col_h phase as the terminal chain lengthens. For the alkyl sulfate salts, an intermediate cubic phase is also seen and the terminal chain length required to cause the change from lamellar to columnar mesophase depends on the anion. Furthermore, there is an unexpected and sometime very large mesophase stabilisation seen on entering the columnar phase. All of the triflimide salts show a rectangular columnar (ribbon) phase.     

Recent developments of task-specific ionic liquids in organic synthesis

Abstract

Task-specific ionic liquids (TSILs) have received increased attention over the past few years as it is possible to form any specific ionic liquid (IL) composition depending upon user's need of the desired physical, chemical, and biological properties. These fascinating materials have shown promising results in various areas such as organic synthesis, catalysis, and specially recent emerging trend of use as functionalized ILs for chiral and nanoparticle synthesis. Present review gives an update of recent developments in the field of TSILs with emphasis on their applications in organic synthesis.     

1-烷基-3-甲基咪唑l-乳酸盐的合成及其物理性质

离子液体;手性离子液体;烷基甲基咪唑l-乳酸盐     

Ionic Transport in Dilute Solid Polymer Electrolytes with Amorphous Structure

The ionic structure and transport properties of amorphous solid polymer electrolytes in the system copolymer of acrylonitrile and butadiene (40 : 60)—lithium hexafluoroarsenate (SPE) is studied in the region of small salt concentrations (up to 0.37 mol dm⁻³) at 298–368 K. In conditions studied, LiAsF₆ is dissociated predominantly to ions. Macroscopic models of ion transport are used to analyze the results of measurements of transport characteristics of SPE. Transport of anions free of the polymer matrix is realized activationlessly and resembles the Stokes drift in viscous media. Transport of cations solvated by electron-donating groups of the polymer turns possible only at temperatures in excess of a critical value (T _crit ≈ 333 K), when the statistical mean of molecules in the first coordination sphere of the lithium cation becomes less than four (which is the coordination number for solvation) and requires the overcoming of an energy barrier of ∼6 kJ mol⁻¹. Below T _crit, the SPE are unipolar anionic conductors.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 537–545.Original Russian Text Copyright © 2005 by Bushkova, Sofronova, Lirova, Zhukovskii.     

一类新型酯类离子液体的合成

以氯乙酸乙酯和氮杂环化合物(1-甲基咪唑、吡啶、N-乙基哌啶、N-甲基吗啉)为原料, 采用两步法合成了一类新型的酯类离子液体, 对合成的12个化合物进行了元素分析, ¹H NMR谱和一些物理性质的测定. 大多数化合物的熔点低于100 ℃, 为室温离子液体. 所合成离子液体的热稳定范围都比较宽, 性质稳定.     

The effect of chiral solvent and various kinds of chiral organic salts on the asymmetric hydrogenation of methyl acetoacetate over an improved tartaric acid modified Raney nickel catalyst

The influence of the chiral ionic liquid (CIL) on the asymmetric hydrogenation of methyl acetoacetate (MAA) over an improved tartaric acid-modified Raney nickel catalyst using it as reaction medium was investigated. At the same time, we also studied the effect of up to eight chiral ionic salts, and ionic liquids on this reaction using these ionic salts as co-catalyst. Although no obviously improved optical yields were gained, the possible cause has been given.     

咪唑基离子液体固定分离CO2的研究进展

以咪唑基离子液体为代表,综述了近期普通咪唑基离子液体、功能咪唑基离子液体、支撑咪唑基离子液体和聚合咪唑基离子液体在分离固定CO2方面的研究进展,说明了各类咪唑基离子液体分离固定CO2的可行性及优缺点,并总结了离子液体固定CO2的影响因素和分离机制.     

New Method for Synthesis of Methacrylate-Type Polymerizable Ionic Liquids

A new method for the synthesis of polymerizable ionic liquids bearing a methacrylate moiety was developed with the aim to avoid premature polymerization of synthesized compounds. Spacer length between the imidazolium cation and the polymerizable functional group varied from 2 to 10 carbon atoms. Different 1-(n-hydroxyalkyl)-3-methylimidazolium bromides and 1-[n-(methacryloyloxy)-alkyl]-3-methylimidazolium bromides were obtained with very good yields (more than 90%).

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource: Full experimental and spectral details.]     

Facile Synthesis of Benzotriazole Derivatives Using Nanoparticles of Organosilane-Based Nitrite Ionic Liquid Immobilized on Silica and Two Room-Temperature Nitrite Ionic Liquids

Nanoparticles of organosilane-based nitrite ionic liquid immobilized on silica, 1-butyl-3-methylimidazolium nitrite, and 1-(3-trimethoxysilylpropyl)-3-methylimidazolium nitrite were used as effective reagents for the preparation of benzotriazole derivatives from 1,2-diaminobenzenes at room temperature under mild solvent-free conditions. These ionic liquids play as nitrosonium sources in this procedure.1,2-Diaminobenzene derivatives have been treated with ionic liquids to give the related diaminobenzenes in very good to excellent yields in short reaction times.

Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the full experimental and spectral details.     

Synthesis of ferrite nanocrystals stabilized by ionic-liquid molecules through a thermal decomposition route

A series of M(x) Fe(3-x) O(4) (M=Fe, Co, Ni, Zn; 0≤x≤1) ferrite nanocrystals stabilized by ionic-liquid molecules have been successfully synthesized through a thermal decomposition route. Instead of the widely used long-chain lipid surfactants and high-boiling solvents, the ionic-liquid molecules not only played the role of surfactants, but also served as reaction and dispersion media simultaneously in the preparation of ferrite nanocrystals. Due to their good fluidity under magnetic fields and high ionic conductivity, the ionic-liquid molecules and M(x) Fe(3-x) O(4) ferrite nanocrystal-based conducting ferrofluids were successfully used as electrolytes in an AC circuit. The open or closed state of the circuit was directly controlled by moving a permanent magnet so as to tune the position of the ferrofluids, and consequently, resulted in the "off" or "on" state of the four indicative yellow-light-emitting diodes. These results demonstrate that the conducting ferrofluids successfully play the role of "magnetic switch".     

Polymerization of the new double‐charged monomer bis‐1,3(N,N,N‐trimethylammonium dicyanamide)‐2‐propylmethacrylate and ionic conductivity of the novel polyelectrolytes

The achievement of high ionic conductivity in single‐ion conducting polymer electrolytes is one of the important aims for various electrochemical devices including modern lithium batteries. One way to enhance the ionic conductivity in polyelectrolyte systems is to increase the quantity of charge carriers in each monomer unit. Highly charged poly(bis‐1,3(N,N,N‐trimethylammonium)‐2‐propylmethacrylate) with one of the most conducting anions, namely dicyanamide, was prepared via free radical bulk polymerization or using ionic liquids as reaction medium. The cationic polymers of the double‐charged monomer have molar masses up to = 1,830,000 g/mol and the ionic conductivity equal to 5.51 × 10^?5 S / cm at 25°C. The film forming ability, crystallinity, thermal stability, and glass transition temperatures of the new polymeric ionic liquids obtained from detailed studies are presented. Copyright © 2009 John Wiley & Sons, Ltd.     

Poly (L-phenylalanine-paired ionic liquid) as halogen-free heterogeneous nanocatalyst toward regiospecific 1,3-dipolar cycloaddition reaction

Although amino acid-paired ionic liquids (IL [AA]) have attracted considerable attention due to their environmental-friendly nature and providing abundant catalytic active sites, polymerized eco-friendly ILs have been rarely reported. Herein, we introduce a novel polymerized L-phenylalanine-paired ionic liquid (PIL [Phe]), synthesized in a new smart manner, as a promising heterogeneous nanocatalyst for regiospecific 1,3-dipolar cycloaddition reaction. For this purpose, new polymerizable ionic liquid (3-(3-aminopropyl)-1-vinylimidazolium (L)-2-amino-3-phenylpropanoate ([AVIm][Phe])) was designed and constructed as a halogen-free multifunctional monomer. The successful fabrication of chiral IL was approved by different techniques including ¹H NMR, FT-IR, and elemental analysis. Next, a green precipitation polymerization approach was applied using a water-soluble initiator under mild conditions. Co₃O₄@PIL [Phe] was synthesized by in situ copolymerization of the [AVIm][Phe] with ethyleneglycoldimethacrylate (EGDMA) (as non-ionic cross-linker) supported on magnetic Co₃O₄@MPS. The obtained data reveal that the supported polymerized form of [AVIm][Phe] is more efficient due to the formation of a porous structure with high-specific surface area (235.5 m²/ g) and a cross-linked network with high thermal stability (35% weight loss around 600 °C). In the following, the proposed Co₃O₄@PIL [Phe] nanostructure was applied as a magnetic catalyst toward the preparation of new and reported pyrrolidinyldispirooxindoles; and it displayed accelerated mass transfer due to its large pore volume (0.85 cm³/ g), and numerous accessible active sites. Consequently, a range of pharmaceutical dispirobisoxindole scaffolds with broad structural diversity were readily obtained in excellent yields (>92%) and high regioselectivity under environmental conditions.     

Measurement and Correlation of the Ionic Conductivity of Ionic Liauid-Molecular Solvent Solutions

The ionic conductivity of the solutions formed from 1-n-butyl-3-methylimidazolium tetrafluoroborate （[Bmim][BF4]） or 1-n-butyl-3-methylimidazolium hexafluorophosphate （[Bmim][PF6]） and different molecular solvents （MSs） were measured at 298.15 K. The molar conductivity of the ionic liquids （ILs） increased dramatically with increasing concentration of the MSs. It was found that the molar conductivity of the IL in the solutions studied in this work could be well correlated by the molar conductivity of the neat ILs and the dielectric constant and molar volume of the MSs.     

Fast and reversible CO2 quartz crystal microbalance response of vinylimidazolium‐based poly(ionic liquid)s

A series of poly(ionic liquid)s (pILs) based on the 1‐vinyl‐3‐hexylimidazolium polymerizable cation and on the bis(trifluoromethylsulfonyl)imide, nonafluoro‐1‐butanesulfonate, dodecylbenzenesulfonate, heptadecafluorooctanesulfonate, and 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11‐heptadecafluoroundecanoate anions have been synthesized and characterized. Their sorption/desorption response towards CO₂ has been tested through quartz crystal microbalance investigations. The obtained results show that all of the pILs here reported are featured by peculiar CO₂ sorption properties as they display fast and linear response, reversibility without any memory effect, and reproducibility, suggesting that anion plays a key role in determining sensitivity. Copyright © 2011 John Wiley & Sons, Ltd.     

工科无机化学中“分子结构和分子间力”的教学思考与探索

“分子结构和分子间力”在人们认识物质世界的过程中起着承上启下的重要作用。然而,在“新工科”建设背景下,化学教学内容要少而精,以强化专业的应用特色建设。对工科学生历年来对于共价键理论、分子间力和离子极化中易错或不易理解的相关内容进行了分析和讨论,旨在帮助学习者在认识物质世界的过程中能更好地在微观世界和宏观世界之间切换,并学会预测或解释物质的性质及其递变规律,同时落实化学核心素质及德育素质的培养。     

离子液体型表面活性剂研究

以1-甲基咪唑为原料, 制备了6个常规离子液体: 1-正丁基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[bmim][BF₄]及[bmim][PF₆])、1-正己基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[hmim][BF₄]及[hmim][PF₆])、1-正十六烷基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[C₁₆mim][BF₄]及[C₁₆mim][PF₆])和4个功能化离子液体: 1-(2-羟乙基)-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[2-hemim][BF₄]及[2-hemim][PF₆])、1-乙氧羰基甲基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[eocmmim][BF₄]及[eocmmim][PF₆]). 研究了这两类离子液体的一些物理性能, 旨在挖掘离子液体在香料香精化妆品工业中的应用价值. 分别检测了它们与一般溶剂的互溶性, 并测定了它们的表面张力和发泡性能, 实验结果表明, 仅[C₁₆mim][BF₄]和[C₁₆mim][PF₆]具有发泡性能, 发泡力分别为68和120 mm.