Polymer-Supported Azide and Copper(I): Green Reusable Reagent and Catalyst for Click Cyclization

In this work, polymer-supported copper(I) iodide catalyst and macroporous polymer-supported azide reagent were used to simplify the synthesis of 1,4-disubstituted-1H-1,2,3-triazoles from α-bromo ketones/amides/esters following green chemistry principles. This new one-pot protocol facilitates the workup of the reaction and provides the products in short times and excellent yields. Heterogeneous catalyst and reagent can be reused at least for five runs without significant yield decreases.     

A Reusable Efficient Green Catalyst of 2D Cu-MOF for the Click and Knoevenagel Reaction

[Cu(CPA)(BDC)]_n (CPA = 4-(Chloro-phenyl)-pyridin-4-ylmethylene-amine; BDC = 1,4-benzenedicarboxylate) has been synthesized and structurally characterized by single crystal X-Ray diffraction measurement. The structural studies establish the copper (II) containing 2D sheet with (4,4) square grid structure. The square grid lengths are 10.775 and 10.769 Å. Thermal stability is assessed by TGA, and subsequent PXRD data establish the crystallinity. The surface morphology is evaluated by FE-SEM. The N₂ adsorption−desorption analysis demonstrates the mesoporous feature (∼6.95 nm) of the Cu-MOF. This porous grid serves as heterogeneous green catalyst with superficial recyclability and thermal stability and facilitates organic transformations efficiently such as, Click and Knoevenagel reactions in the aqueous methanolic medium.     

Imidazolium-Based Phosphinite Ionic Liquid (IL-OPPh2) as Reusable Catalyst and Solvent for the Knoevenagel Condensation Reaction

A task-specific ionic liquid (IL, OPPh₂) that bears a phosphinite weak Lewis base group in an imidazolium cation was found to efficiently catalyze the Knoevenagel condensation of arylaldehydes with malononitrile, dimethyl(diethyl)malonate, and ethyl cyanoacetate. This IL plays a dual role as both the reaction media and also catalyst, and it can be easily recovered and reused in several runs. Satisfactory results were obtained with good yields, short reaction time, and simplicity in the experimental procedure. A variety of coumarin derivatives were synthesized in this procedure.     

Multicomponent Reaction in Ionic Liquid： A Novel and Green Synthesis of 1, 4-Dihydropyridine Derivatives

1, 4-Dihydropyridine (DHP) heterocyclic ring is a common feature of various bioactivecompounds such as vasodilator, bronchodilator and antiatherosclerotic, antitumor, andantidiabetic agents1. Due to their important pharmacological activities, many methods…     

Basic Ionic Liquid： A Reusable Catalyst for Knoevenagel Condensation in Aqueous Media

IntroductionThe Knoevenagel condensation of aldehydes/ketones and activated methylene compounds is one ofthe most common synthetic methods to produce func-tionalized alkenes. Theα,β-unsaturated productsobtained by this method have been widely used as th…     

Green Synthesis of Spiro Compounds with Potential Anticancer Activity through Knoevenagel/Michael/Cyclization Multicomponent Domino Reactions Organocatalyzed by Ionic Liquid and Microwave-Assisted

In this work a microwave-assisted Knoevenagel/Michael/cyclization multicomponent domino methodology, using ethanol as solvent and the ionic liquid 1-methylimidazolium chloride as catalyst was developed for the synthesis of spiro compounds. The reaction conditions considered ideal were determined from a methodological study varying solvent, catalyst, amount of catalyst, temperature, and heating mode. Finally, the generality of the methodology was evaluated by exploring the scope of the reaction, varying the starting materials (isatin, malononitrile, and barbituric acid). Overall, the twelve spiro compounds were synthesized in good yields (43–98%) and the X-ray structure of compound 1b was obtained. In addition, the in vitro antiproliferative activities of the spirocycles against four types of human cancer cell lines including HCT116 (human colon carcinoma), PC3 (prostate carcinoma), HL60 (promyelocytic leukemia), and SNB19 (astrocytoma) were screened by MTT-based assay. It is noteworthy that spiro compound 1c inhibited the four cell lines tested with the lowest IC₅₀ values: 52.81 µM for HCT116, 74.40 µM for PC3, 101 µM for SNB19, and 49.72 µM for HL60.     

Task-Specific Ionic Liquid as the Recyclable Catalyst for the Rapid and Green Synthesis of Dihydropyrano[3,2-c]chromene Derivatives

Abstract

A task-specific ionic liquid, [H₃N⁺–CH₂–CH₂–OH][CH₃COO^?], was successfully applied as an efficient and reusable catalyst for the one-pot domino to approach to dihydropyrano[3,2-c]chromene derivatives with atom economy in a condensation reaction of 4-hydroxycoumarin, aldehydes, and malononitrile in a combinatorial fashion. The reaction gave excellent yields within short reaction times at room temperature under solvent-free grinding conditions. The products and ionic liquid could be conveniently separated from the reaction mixture, indicating that the whole process was performed as a green chemical transformation.      

离子液体介质中有机合成及不对称催化反应研究新进展

总结了近年离子液体中有机合成反应及不对称催化反应研究新进展，包括还原 反应、氧化反应、Friedel-Crafts反应、Diels-Alder反应、交叉偶联反应、加成 反应、环缩合反应、自由基反应、Witting反应、重排反应、不对称催化反应及其 它合成反应。     

离子液体对PMMA绿色增塑性能

离子液体对PMMA绿色增塑性能;离子液体;环境友好;增塑剂;绿色增塑     

Biochar-Based Graphitic Carbon Nitride Adorned with Ionic Liquid Containing Acidic Polymer: A Versatile,Non-Metallic Catalyst for Acid Catalyzed Reaction

A novel biochar-based graphitic carbon nitride was prepared through calcination of Zinnia grandiflora petals and urea. To provide acidic and ionic-liquid functionalities on the prepared carbon, the resultant biochar-based graphitic carbon nitride was vinyl functionalized and polymerized with 2-acrylamido-2-methyl-1-propanesulfonic acid, acrylic acid and the as-prepared 1-vinyl-3-butylimidazolium chloride. The final catalytic system that benefits from both acidic (–COOH and –SO₃H) and ionic-liquid functionalities was applied as a versatile, metal-free catalyst for promoting some model acid catalyzed reactions such as Knoevenagel condensation and Biginelli reaction in aqueous media under a very mild reaction condition. The results confirmed high activity of the catalyst. Broad substrate scope and recyclability and stability of the catalyst were other merits of the developed protocols. Comparative experiments also indicated that both acidic and ionic-liquid functionalities on the catalyst participated in the catalysis.     

Molecular Iodine in Ionic Liquid: A Green Catalytic System for Esterification and Transesterification

Esterification of carboxylic acids and transesterification of β-ketoesters with alcohols have been developed using a catalytic amount of iodine in polyethylene glycol (PEG) ionic liquid (IL 1000) to afford the corresponding esters in good yields. By simple separation of the ionic-liquid phase containing the iodine, the system of I₂/IL 1000 can be reused several times.     

利用离子液体负载反应底物的有机合成

综述了固相、液相组合化学中以可溶性离子液体为载体的有机合成新概念及最新研究进展,并主要介绍了离子液体作为载体负载反应底物在有机合成中的一些应用,如有关的重要有机反应、组合化学、小分子库合成等。该方法具有上载率高、适用反应范围宽、分离纯化简便、结构检测容易和可回收重复使用等诸多优越性,这对于传统的固相、液相合成方法是一个重大的进步。     

SO3H-Functionalized Ionic Liquids: Green, Efficient and Reusable Catalysts for the Facile Dehydration of Aldoximes into Nitriles

Easily synthesized aldoximes have been converted to the corresponding nitriles under very mild conditions by a simple reaction using two halogen‐free SO₃H‐functionalized ionic liquids, 3‐methyl‐1‐(4‐sulfonic acid)butylimi‐ dazolium hydrogen sulfate [MIM(CH₂)₄SO₃H][HSO₄] and 1‐(4‐sulfonic acid)butylpyridinium hydrogen sulfate [PY(CH₂)₄SO₃H][HSO₄], as catalyst and reaction medium without any additional organic solvent. The method was equally effective for aromatic aldoximes bearing electron‐donating and electron‐withdrawing substituents. Taking into account environmental and economical consideration, the protocol presented here has the merits of environmentally friendly, simple operation, easy work‐up and very good yields. The catalysts could be recycled and reused for several times without noticeably decreasing in their catalytic activities.     

新型Br(o)nsted-Lewis酸性离子液体的合成及其在松香二聚反应中的应用

合成、表征了新型Bronsted-Lewis酸性离子液体1-(3-磺酸)-丙基-3-甲基咪唑氯锌酸盐([HO3S-(CH2)3-mim]Cl-ZnCl2),并将其用于催化松香二聚反应.结果表明,[HO3S-(CH2)3-mim]Cl-ZnCl2(ZnCl2摩尔分数x＞0.5)为Bronsted和Lewis双酸性,且以[HO3S-(CH2)3-mim]Cl-ZnCl2 (x=0.64)的催化性能较佳.在松香5.0 g,甲苯15 g,离子液体质量分数5%,反应温度110℃和反应时间4 h的较佳实验条件下,所得产物聚合松香的软化点为118 ℃.此外,该催化剂的使用有利于产物的分离且分离的离子液体催化剂具有良好的重复使用性能.     

Basic Ionic Liquid as Catalyst for the Efficient and Green Synthesis of 2-Amino-3-nitrobenzonitriles in Ethanol

A basic ionic liquid, [BmIm]OH was used as catalyst in the cyclocondensation of various kinds of vinylmalononitriles with nitroolefins in ethanol at reflux. A series of 2-amino-3-nitrobenzonitriles were obtained in reasonable yields. The straightforward and green protocol was found to be fairly efficient, and the catalyst could be recycled and reused in subsequent reactions with consistent activity. The mechanism of the reaction was discussed.

Acidic Ionic Liquid [(CH2)4SO3HMIM][HSO4]: A Green Media for the Simple and Straightforward Synthesis of 2,4,5-Trisubstituted Imidazoles

2,4,5-Trisubstituted imidazoles have been synthesized in excellent yields (85–95%) in the presence of 5 mol% of [(CH₂)₄SO₃HMIM][HSO₄] as a Brønsted acidic ionic liquid.     

Immobilization of Pd(II) Catalysts for Cyclopropanation in Ionic Liquid

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Immobilization of Pd（Ⅱ）Catalysts for Cyclopropanation in Ionic Liquid

Cyclopropanation of styrene with ethyl diazoacetate catalyzed by Pd(Ⅱ） in ionic liquid [omim][BF4] was investigated.Palladium catalysts can be effectively immobilized in ionic liquid.The catalysts PdCl2 and cyclopalladated complex 2 contained in ionic liquid could be recycled for 6 and 7 times,respectively,without losing the efficiency.     

Guanidinium Lactate Ionic Liquid： An Efficient and Recycling Catalyst for Michael Addition Reaction

A facile and efficient 1, 4-conjungate addition(Michael addition) reaction of active methylene compounds to α,β-unsaturated compounds, catalyzed by guanidinium lactate ionic liquid(IL9), has been developed. A range of chalcones and nitroalkenes together with active methylene compounds have been converted smoothly to the corresponding products in high yields.     

Oxime‐derived palladacycle Immobilized in an Ionic Liquid Brush as an Efficient and Reusable Catalyst for Mozoroki‐Heck Reaction in Neat Water

An efficient and reusable heterogeneous catalyst with oxime‐derived palladacycle immobilized in an ionic liquid brush has been synthesized and an environmentally‐friendly procedure have been developed for coupling aryl iodides and bromides with acrylic acid. These reactions were conducted in neat water under aerobic conditions with water‐insoluble or even solid aryl halides and they proceeded smoothly and cleanly without any organic co‐solvent or other additives. The ionic liquid brush could be easily recovered and reused at least five times without significant loss of activity. The protocol has the advantages of excellent yields, environmental friendliness, and catalyst recyclability.