One-pot Synthesis of Lewis Acidic Ionic Liquids for Friedel-Crafts Alkylation

Novel Lewis acidic ionic liquids containing thionyl cations and chloroaluminate anions were obtained by one-pot synthesis for the first time. Their acidities were determined by acetonitrile probe on IR spectrography. The ionic liquids were used as catalyst for Friedel-Crafts alkylation of benzene and 1-dodecene. The turnovers of l-dodecene were higher than 99%. Monoalkylbenzene selectivity was 98%, while the 2-substituent product selectivity was 45%.

Solvent Free One-Pot Synthesis of 1,2,4,5-Tetrasubstituted Imidazoles Catalyzed by Secondary Amine Based Ionic Liquid and Defective Keggin Heteropoly Acid

Secondary amine based ionic liquid and defective Keggin type heteropoly acid (HPA) are separately used for efficient one-pot four-component synthesis of 1,2,4,5-tetrasubstituted imidazoles assisted by microwave (MW). Eco-friendly solvent free procedure, short reaction time, high yield of products and reusability of catalysts are important features of the synthesis. A comparative study on the efficiency of the two catalysts is reported. This work further demonstrates the alternate use of urea, instead of often used ammonium acetate, as source of nitrogen.

Novel manganese(Ⅱ)-based deep eutectic solvents: Synthesis and physical properties analysis

Type IV deep eutectic solvent（DES） involves the formation of metal-based eutectics from metal salts or metal salt hydrate in combination with various hydrogen-bond donors（HBDs） such as urea, ethylene glycol or acetamide. In current study, two distinguished approaches were used to synthesize potential DESs, given as the direct heating and the evaporating methods. Successful synthesized DESs were subjected for physical properties characterization by Fourier Transform Infrared（FTIR） Spectroscopy, thermal stability, viscosity,and conductivity analyses. Five novel manganese（II）-based DESs were successfully synthesized as reported in this study. Data obtained indicated that the Mn Cl2á4H2Oáacetamide DES exhibits the lowest freezing point（27.5℃）, highest thermal stability（193℃ point of dehydration）, lowest viscosity（E = 112.8cP） and the highest conductivity（0.12723 mS/cm）. The findings obtained reveal the characteristics, nature or features of synthesized DESs as potential industrial solvents.

Ionic Liquids: Progress and Prospective

Ionic liquids （ILs） are green solvents that have attracted great attention in recent years due to their unique properties. In this paper the latest progresses in both the fundamental studies and applications of ILs have been summarized, with the emphasis on the topics of physical properties, catalytic reactions, and biochemical engineering. The critical problems in the applications of the ILs have been addresses, and the prospective of the ILs were finally predicted.

Novel N-methylimidazolium Chiral Ionic Liquids with Esterfunction Functionality in Cation

Using （S）-（-）-2-chloropropionie acid ethyl ester and N-methylimidazole as raw materials, we designed and synthesized three N-methylimidazolium chiral ionic liquids by the nucleophilic substitution reaction or anion exchange reaction. These chiral ionic liquids structures were analyzed with structure optimization calculation, IR, and HNMR. Their reaction mechanism and physical chemistry properties were explored. As a result, these chiral ionic liquids possess optical activity, low melting point, high conductivity, and weak acidity, etc. They can serve as effective reaction media as well as chiral catalysts. They are presently being investigated as dispersion agent in molecular imDrinting, nlover in our laboratory.

Revisiting greenness of ionic liquids and deep eutectic solvents

Green solvents are one of the hot topics of green chemistry.Ionic liquids(ILs)and deep eutectic solvents(DESs)are deemed as green solvents to a certain extent,and they have been applied in many areas,such as dissolution,separation,catalysis,electrochemistry and material synthesis.However,the greenness of ILs and DESs should be revisited because more and more evidences have shown that they are not always green.In this perspective,besides the reported merits,the disadvantages and problems of some ILs and DESs,such as instability,volatility,hygroscopicity,toxicity,flammability,regenerability,cost,energy consumption and impurities are discussed.Moreover,13 strategies to avoid the disadvantages of ILs and DESs and to increase the greenness are proposed.Comparison of the greenness of ILs and DESs is further conducted.This perspective provides some new viewpoints on the greenness of ILs and DESs.

A QUICK AND GREEN IONIC LIQUID-MEDIATED APPROACH FOR THE SYNTHESIS OF HIGH-PERFORMANCE, ORGANOSOLUBLE AND THERMALLY STABLE POLYIMIDES

Three diamine monomers with different derivatives of imidazole heterocyclic ring and meta-linked aryl ethers were synthesized and used in polycodensation reaction with various commercial dianhydrides for preparation of a series of novel poly（ether-imide） （PEI）s. The polycodensation reactions were carried out by using conventional method and in a green medium of ionic liquid （IL） without using NMP-pyridine-acetic anhydride. The PEIs were obtained in good yields （80%-96%） with moderate viscosity （0.48-0.66 dL/g） in a shorter reaction time （10 h） in IL as compared with the conventional method （36 h）. All of the polymers were amorphous in nature, showed excellent solubility in amide-type polar aprotic solvents with ability to form tough and flexible films, and excellent thermal stability with Tgs in the range of 212-340℃ and 10% weight loss temperature （T10） up to 570℃ in N2 and 528 ℃ in air.

A new green approach for the synthesis of 12-aryl-8,9,10,12-tetrahydrobenzo[a]xanthene-11-one derivatives using task specific acidic ionic liquid[NMP]H_2PO_4

12-Aryl-8,9,10,12-tetrahydrobenzo[a]xanthene-11-one derivatives were synthesized by a convenient and environmentally benign procedure involving multicomponent condensation reactions of substituted aromatic aldehydes with 2,7-dihydroxynaphthalene/2-naphthols/2,6-dihydroxynaphthlene and cyclic 1,3-dicarbonyl compounds in task specific acidic ionic liquid[NMP]HPOat 80 ℃.This protocol has proved to be efficient in terms of good yields,operational simplicity,easy workup,recyclability of reaction medium/catalyst,and short reaction time.

Green solvent-based approaches for synthesis of nanomaterials

The use of green solvents (including supercritical fluids and ionic liquids) in the synthesis of nanomaterials is highlighted. The methods described can not only reduce or eliminate the use or generation of substances hazardous to health and the environment, but can also be used to efficiently prepare nanomaterials with high performances. The unique characteristics of green solvents are responsible for the green features and unusual advantages of these approaches.

Synthesis of fused pyran and arylbis(4-hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)methane in ionic liquid

Promoted and mediated by an ionic liquid-[bmim][BF4], fused pyrans or arylbis（4-hydroxy-6-methyl-2-oxo-2H-pyran-3- yl）methanes were efficiently and selectively prepared from the reaction of aldehyde and 4-hydroxy-6-methyl-2-oxo-pyran with or without acetic anhydride. By using these novel procedures, pyrimidine nucleoside-fused pyran and arylbis（pyranon-3-yl）methane hybrids with potential biological activities were constructed.

Synthesis and kinetics of 2,5-dicyanofuran in the presence of hydroxylamine ionic liquid salts

2,5-Dicyanofuran(DCF)is an important biomass-derived platform compound primarily used to prepare bio-based adiponitrile,which is the key precursor for the synthesis of nylon 66 and 1,6-hexanediisocyanate(HDI).In this study,one-pot,green and safe synthesis of DCF from 2,5-diformylfuran(DFF)and hydroxylamine ionic liquid salts was proposed.Eco-friendly hydroxylamine ionic liquid salts were used as the nitrogen source.Ionic liquid exhibited three-fold function of cosolvent,catalysis and phase separation.The conversion of DFF and yield of DCF reached 100%under the following optimum reaction conditions:temperature of 120℃ for 70 min,volume ratio of paraxylene:[HSO_(3)-b-Py]
HSO4 of 2:1,and molar ratio of DFF:(NH_(2)OH)_(2)
[HSO_(3)-b-Py]
HSO4 of 1:1.5.The reaction mechanism for the synthesis of DCF was proposed,and the kinetic model was established.The reaction order with respect to DFF and intermediate product 2,5-diformylfuran dioxime(DFFD)was 1.06 and 0.16,and the reaction activation energy was 64.07 kJ·mol^(-1) and 59.37 kJ·mol^(-1) respectively.After the reaction,the ionic liquid was easy to separate,recover and recycle.

Ionic Liquid [bmim][BF_4] as a Green Medium for Passerini Reaction

The Passerini three-component reaction of carboxylic acid, aromatic aldehyde and isocyanide was carried out smoothly and efficiently in ionic liquid [bmim]BF4. Through this reaction, a series of α-acyloxycarboxamides were obtained in high yields. Advantages of this proccedure include a green nature, high efficiency and operational simplicity

Molar volume of eutectic solvents as a function of molar composition and temperature

The conventional Rackett model for predicting liquid molar volume has been modified to cater for the effect of molar composition of the Deep Eutectic Solvents(DES). The experimental molar volume data for a group of commonly used DES has been used for optimizing the improved model. The data involved different molar compositions of each DES. The validation of the new model was performed on another set of DESs. The average relative deviation of the model on the training and validation datasets was approximately 0.1% while the Rackett model gave a relative deviation of more than 1.6%. The modified model deals with variations in DES molar composition and temperature in a more consistent way than the original Rackett model which exhibits monotonic performance degradation as temperature moves away from reference conditions. Having the composition of the DES as a model variable enhances the practical utilization of the predicting model in diverse design and process simulation applications.

New process development and process evaluation for capturing CO2 in flue gas from power plants using ionic liquid[emim][Tf2N]

Using the ionic liquid[emim][Tf2N]as a physical solvent,it was found by Aspen Plus simulation that it was possible to attempt to capture CO2 from the flue gas discharged from the coal-fired unit of the power plant.Using the combination of model calculation and experimental determination,the density,isostatic heat capacity,viscosity,vapor pressure,thermal conductivity,surface tension and solubility of[emim][Tf2N]were obtained.Based on the NRTL model,the Henry coefficient and NRTL binary interaction parameters of CO2 dissolved in[emim][Tf2N]were obtained by correlating[emim][Tf2N]with the gas–liquid equilibrium data of CO2.Firstly,the calculated relevant data is imported into Aspen Plus,and the whole process model of the ionic liquid absorption process is established.Then the absorption process is optimized according to the temperature distribution in the absorption tower to obtain a new absorption process.Finally,the density,constant pressure heat capacity,surface tension,thermal conductivity,and viscosity of[emim][Tf2N]were changed to investigate the effect of ionic liquid properties on process energy consumption,solvent circulation and heat exchanger design.The results showed that based on the composition of the inlet gas stream to the absorbers,CO2 with a capture rate of 90%and a mass purity higher than 99.5%was captured.These results indicate that the[emim][Tf2N]could be used as a physical solvent for CO2 capture from coal-fired units.In addition,the results will provide a theoretical basis for the design of new ionic liquids for CO2 capture.

[bmim]OH： An efficient catalyst for the synthesis of mono and bis spirooxindole derivatives in ethanol at room temperature

A rapid and efficient, one pot synthesis of spirooxindole derivatives has been attempted by three- component reaction of isatin, malononitrile and carbonyl compound possessing a reactive c^-methylene group by using task specific ionic liquid, 1-butyl-3-methyl imidazolium hydroxide [bmim]OH as a catalyst. The important features of this methodology are straight forward route in short reaction time at room temperature and avoid any hazardous organic solvent, toxic catalyst, tedious purification step. Interestingly, this protocol is not only limited to mono-systems but also to the synthesis of newer bis- spirooxindole system. The separation of the product and reusability of the catalyst are easy with excellent yield. The [bmim]OH catalyst system could be reused up to five recycles without appreciable loss of activity.

新型吸收式制冷体系工质对溶液研究进展

吸收式制冷系统是一种低碳/零碳制冷技术,利用低品位热源(如工业余/废热、太阳能热源等)作为其驱动能源,能有效提高能源系统综合利用效率。当前商业吸收式制冷剂体系主要基于水-溴化锂和氨-水体系,水-溴化锂溶液存在腐蚀性强、易结晶和制冷效果差等问题,氨体系有毒性较强、爆炸性以及氨-水制冷设备无法小型化等缺点。新型制冷剂-吸收剂工质对的研发是设计更环保高效的新型吸收式制冷系统的核心。总结了近年来备受关注的新型工质对体系,从吸收剂角度出发,探讨了离子液体、低共熔溶剂、大分子有机溶剂以及其它吸收剂与制冷剂组成的工质对溶液热力学性质的计算和实验研究方法。特别讨论了吸收剂-制冷剂相互作用类型和机制,及其对工质对溶液热力学性质和制冷性能的影响规律。总结研究发现对于新型工质对体系,普遍存在的问题是工质对溶液对制冷剂蒸汽的吸收性能欠佳。通过调控吸收剂化学结构和工质对组成,增强吸收剂-制冷剂相互作用是进一步优化工质对体系的关键途径。该综述为优化、设计工质对溶液体系提供了参考。

锂离子电池绿色回收在物理化学教学中的应用

随着锂离子电池的日益普及,废旧锂离子电池的数量越来越多;锂离子电池绿色回收对固体废物治理和资源的可持续利用具有重要意义。物理化学是化学、化工相关专业的一门重要基础课程。物理化学中的热力学第一定律、热力学第二定律、多组分热力学、相平衡、化学平衡、电解质溶液、可逆电池的电动势、电解池与极化、动力学、胶体界面等章节融入锂离子电池绿色回收对物理化学课程的建设、环境治理和绿色高质量发展提供科学依据和理论指导。

离子液体的发展及其在有机合成中的应用

绿色发展是化学化工领域的新思想和新追求,离子液体是一种绿色的催化剂和反应溶剂,其具有不易挥发,不易燃烧,热稳定高,绿色环保,并且可回收等特点,因此,日益受到化学家的青睐,对其进一步的研究也日趋成熟。本文就离子液体的发展历程,分类和特性,及其在有机合成化学中的应用进行了阐述,离子液体目前已经被应用到了氧化反应,还原反应,傅-克反应,偶联反应,缩合反应和加成反应中,在这些不同类型的反应中,均取得了不错的结果。本文综述了以上内容,通过分析,总结和归纳,希望提出创新性的思想,使得离子液体的研究和应用在未来具有更加巨大的进步。

Development of sequential type iron salt-catalyzed Nazarov/Michael reaction in an ionic liquid solvent system

Sequential type one pot Nazarov/Michael reaction of pyrrole derivatives has been demonstrated using 5 tool% Fe（C104）3· A120 as catalyst in an ionic liquid as solvent. We succeeded in obtaining 4,5-dihydrocyclopenta[b]pyrrol-6（1H）-one derivative in good yield for five repetitions of the reactions without any addition of the catalyst using an ionic liquid, [bmim][NTf2], as sol- vent system.