Distillable ionic liquids for a new multicomponent reaction

2007 ◽  
Vol 79 (11) ◽  
pp. 1869-1877 ◽  
Author(s):  
Anthony E. Rosamilia ◽  
Christopher R. Strauss ◽  
Janet L. Scott
Keyword(s):  
Carbon Dioxide ◽  
Ionic Liquid ◽  
Ionic Liquids ◽  
Multicomponent Reaction ◽  
Reaction Medium ◽  
Building Blocks ◽  
Substituted Anilines ◽  
Reaction Sequence ◽  
Unsaturated Ketones ◽  
Direct Preparation

Adducts of dimethylamine and carbon dioxide form a "distillable ionic liquid" (DIMCARB) that may used as both a reaction medium and catalyst in the direct, atom-economical synthesis of useful synthetic building blocks, such as mono-condensed α,β-unsaturated ketones. The utilization of such building blocks in the synthesis of two new classes of versatile macrocycles, by a sequence of condensation reactions (H2O by-product), is described. Investigation into the mechanism of action of DIMCARB catalysis and observation of an aniline impurity arising from a competing reaction sequence led to development of a new multicomponent reaction for the direct preparation of 2- or 4-substituted anilines. Some of the macrocycles and anilines are, respectively, supramolecular host compounds and ligands for the preparation of metal complexes.

Acceleration of Baylis-Hillman reaction using ionic liquid supported organocatalyst

2021 ◽  
Vol 08 ◽  
Author(s):  
Vivek Srivastava
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Reaction Rate ◽  
Reaction Medium ◽  
Catalyst Loading ◽  
Catalyst Recycling ◽  
Catalytic Systems ◽  
Heterogeneous Catalytic ◽  
Highly Active ◽  
Low Catalyst Loading

Background: Baylis-Hillman reaction suffers from the requirement of cheap starting materials, easy reaction protocol, possibility to create the chiral center in the reaction product has increased the synthetic efficacy of this reaction, and high catalyst loading, low reaction rate, and poor yield. Objective: The extensive use of various functional or non-functional ionic liquids (ILs) with organocatalyst increases the reaction rate of various organic transformations as a reaction medium and as a support to anchor the catalysts. Methods: In this manuscript, we have demonstrated the synthesis of quinuclidine-supported trimethylamine-based functionalized ionic liquid as a catalyst for the Baylis-Hillman reaction. Results: We obtained the Baylis-Hillman adducts in good, isolated yield, low catalyst loading, short reaction time, broad substrate scope, accessible product, and catalyst recycling. N-((E,3S,4R)-5-benzylidene-tetrahydro-4-hydroxy-6-oxo-2H-pyran-3-yl) palmitamide was also successfully synthesized using CATALYST-3 promoted Baylis-Hillman reaction. Conclusion: We successfully isolated the 25 types of Baylis-Hillman adducts using three different quinuclidine-supported ammonium-based ionic liquids such as Et3AmQ][BF4] (CATALYST-1), [Et3AmQ][PF6] (CATALYST-2), and [TMAAmEQ][NTf2](CATALYST-3) as new and efficient catalysts. Tedious and highly active N-((E,3S,4R)-5-benzylidene-tetrahydro-4-hydroxy-6-oxo-2H-pyran-3-yl) palmitamide derivative was also synthesized using CATALYST-3 followed by Baylis-Hillman reaction. Generally, all the responses demonstrated higher activity and yielded high competition with various previously reported homogenous and heterogeneous Catalytic systems. Easy catalyst and product recovery followed by six catalysts recycling were the added advantages of the prosed catalytic system.

Ionic Liquid [Bmim]OH Grafted Catalyst for Cycloaddition of Carbon Dioxide

2014 ◽  
Vol 989-994 ◽  
pp. 676-679 ◽  
Author(s):  
Xue Lan Zhang ◽  
Deng Feng Wang
Keyword(s):  
Carbon Dioxide ◽  
Ionic Liquid ◽  
Ionic Liquids ◽  
Silica Gel ◽  
Propylene Carbonate ◽  
Propylene Oxide ◽  
Heterogeneous Catalysts ◽  
Element Analysis ◽  
Mild Conditions ◽  
Adsorption Desorption

An ionic liquid 1-butyl-3-methylimidazolium hydroxide ([Bmim]OH) was grafted on silica gel by post-grafting method. Such grafted ionic liquids (GILs) which were verified by means of FTIR, element analysis N2adsorption-desorption and TG could be used as highly effective heterogeneous catalysts toward propylene carbonate synthesis through cycloaddition of carbon dioxide with propylene oxide under solventless and mild conditions.

Ionophilic phosphonium-appended carbopalladacycle catalyst for Suzuki–Miyaura and Heck cross-coupling catalysis

2010 ◽  
Vol 88 (1) ◽  
pp. 27-34 ◽  
Author(s):  
Jocelyn J. Tindale ◽  
Paul J. Ragogna
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Catalyst Activity ◽  
Reaction Medium ◽  
Cross Coupling ◽  
Metal Catalyst ◽  
Phosphonium Salts ◽  
Transition Metal Catalyst ◽  
Imidazolium Ionic Liquids ◽  
Liquid Reaction

An ionic liquid, covalently tethered to an efficient transition-metal catalyst in the presence of an ionic liquid reaction medium, can utilize ionophilic interactions to improve catalyst activity, recyclability, and product isolation while decreasing catalyst leaching. Given the greater stability of phosphonium salts in comparison to imidazolium ionic liquids under basic conditions, phosphonium-tagged oxime carbopalladacycle salts were prepared and employed in both Heck and Suzuki–Miyaura reactions. The desired product was obtained in good yields for up to four catalyst cycles in the case of the Suzuki–Miyaura reaction. While taking advantage of the non-volatile nature of ionic liquids, the product was isolated through simple sublimation from the reaction mixture, eliminating issues associated with catalyst leaching, and the remaining ionic liquid solvent–catalyst mixture was ready for further catalysis.

Preparation and Activity of Ionic Liquid Catalysts Grafted on Hydrophobic Silica Gel

2012 ◽  
Vol 476-478 ◽  
pp. 2621-2624
Author(s):  
Xue Lan Zhang ◽  
Deng Feng Wang
Keyword(s):  
Carbon Dioxide ◽  
Ionic Liquid ◽  
Ionic Liquids ◽  
Silica Gel ◽  
Propylene Oxide ◽  
Heterogeneous Catalysts ◽  
N2 Adsorption ◽  
Mild Conditions ◽  
Hydrophobic Silica ◽  
Adsorption Desorption

An ionic liquid 1- (triethoxysilyl) propyl-3-methylimidazolium hydroxide ([Smim]OH) was grafted on three kinds of mesoporous hydrophobic silica gel by means of post-grafting under mild conditions. The catalysts were [Smim]OH/SiO2-MTES (methyltriethoxysilane), [Smim]OH/SiO2-TMCS (trimethylchlorosilane), [Smim]OH/SiO2-CPTEO (triethoxysilyl propyl chloride). Such grafted ionic liquids (GILs), which were characterized by means of FTIR and N2 adsorption-desorption could be used as effective heterogeneous catalysts toward propylene carbonate synthesis through cycloaddition of carbon dioxide with propylene oxide under solventless and mild conditions.

A Robust Ionic Liquid as Reaction Medium and Efficient Organocatalyst for Carbon Dioxide Fixation

ChemSusChem ◽  
2008 ◽  
Vol 1 (1-2) ◽  
pp. 67-70 ◽  
Author(s):  
Wing-Leung Wong ◽  
Pak-Ho Chan ◽  
Zhong-Yuan Zhou ◽  
Kam-Han Lee ◽  
Kwong-Chak Cheung ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Ionic Liquid ◽  
Reaction Medium ◽  
Carbon Dioxide Fixation

Electrochemical reduction of aromatic ketones in 1-butyl-3-methylimidazolium-based ionic liquids in the presence of carbon dioxide: the influence of the ketone substituent and the ionic liquid anion on bulk electrolysis product distribution

2015 ◽  
Vol 17 (29) ◽  
pp. 19247-19254 ◽  
Author(s):  
Shu-Feng Zhao ◽  
Mike Horne ◽  
Alan M. Bond ◽  
Jie Zhang
Keyword(s):  
Carbon Dioxide ◽  
Ionic Liquid ◽  
Ionic Liquids ◽  
Electrochemical Reduction ◽  
Product Distribution ◽  
Aromatic Ketone ◽  
Aromatic Ketones ◽  
Bulk Electrolysis ◽  
Electrolysis Product

The yield of electrocarboxylation of aromatic ketone depends on the imidazolium-based ionic liquid anion and the ketone substituent.

A Phosphine-mediated Synthesis of 2,3,4,5-tetra-substituted Nhydroxypyrroles from α-oximino Ketones and Dialkyl Acetylenedicarboxylates Under Ionic Liquid Green-media

2018 ◽  
Vol 21 (1) ◽  
pp. 14-18
Author(s):  
Ashraf S. Shahvelayati ◽  
Maryam Ghazvini ◽  
Khadijeh Yadollahzadeh ◽  
Akram S. Delbari
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Organic Solvents ◽  
Condensation Reaction ◽  
Reaction Medium ◽  
Sustainable Chemistry ◽  
Polyfunctional Compounds ◽  
High Yields ◽  
Work Up ◽  
Reaction Media

Background: The development of multicomponent reactions (MCRs) in the presence of task-specific ionic liquids (ILs), used not only as environmentally benign reaction media, but also as catalysts, is a new approach that meet with the requirements of sustainable chemistry. In recent years, the use of ionic liquids as a green media for organic synthesis has become a chief study area. This is due to their unique properties such as non-volatility, non-flammability, chemical and thermal stability, immiscibility with both organic compounds and water and recyclability. Ionic liquids are used as environmentally friendly solvents instead of hazardous organic solvents. Objective: We report the condensation reaction between α-oximinoketone and dialkyl acetylene dicarboxylate in the presence of triphenylphosphine to afford substituted pyrroles under ionic liquid conditions in good yields. Result: Densely functionalized pyrroles was easily prepared from reaction of α-oximinoketones, dialkyl acetylene dicarboxylate in the presence of triphenylphosphine in a quantitative yield under ionic liquid conditions at room temperature. Conclusion: In conclusion, ionic liquids are indicated as a useful and novel reaction medium for the selective synthesis of functionalized pyrroles. This reaction medium can replace the use of hazardous organic solvents. Easy work-up, synthesis of polyfunctional compounds, decreased reaction time, having easily available-recyclable ionic liquids, and good to high yields are advantages of present method.

Fluorous Phases and Compressed Carbon Dioxide as Alternative Solvents for Chemical Synthesis: A Comparison

2004 ◽  
Author(s):  
Walter Leitner
Keyword(s):  
Carbon Dioxide ◽  
Chemical Synthesis ◽  
High Throughput Screening ◽  
Large Scale ◽  
Ecological Impact ◽  
Reaction Medium ◽  
Building Blocks ◽  
Liquid Phases ◽  
Synthetic Procedure ◽  
Reaction Media

The principal goal of basic research in chemical synthesis is the development of efficient tools for functional group transformations and for the assembly of building blocks during the construction of molecules with increasing complexity. Traditionally, new approaches in this area have focused on the quest for new reaction pathways, reagents, or catalysts. Comparably less effort has been devoted to utilize the reaction medium as a strategic parameter, although the use of solvents is often crucial in synthetically useful transformations. The first choice for a solvent during the development of a synthetic procedure is usually an organic liquid, which is selected on the basis of its protic or aprotic nature, its polarity, and the temperature range in which the reaction is expected to proceed. Once the desired transformation is achieved, yield and selectivity are further optimized in the given medium by variation of temperature, concentration, and related process parameters. At the end of the reaction, the solvent must be removed quantitatively from the product using conventional workup techniques like aqueous extraction, distillation, or chromatography. If the synthetic procedure becomes part of a large-scale application, the solvent can sometimes be recycled, but at least parts of it will ultimately end up in the waste stream of the process. Increasing efforts to develop chemical processes with minimized ecological impact and to reduce the emission of potentially hazardous or toxic organic chemicals have stimulated a rapidly growing interest to provide alternatives to this classical approach of synthesis in solution. At the same time, researchers have started to realize that the design and utilization of multifunctional reaction media can add a new dimension to the development of synthetic chemistry. In particular, efficient protocols for phase separations and recovery of reagents and catalysts are urgently required to provide innovative flow schemes for environmentally benign processes or for high-throughput screening procedures. Fluorous liquid phases and supercritical carbon dioxide (sc CO2) have received particular attention among the various reaction media that are discussed as alternatives to classical organic solvents. The aim of this chapter is to compare these two media directly and to critically evaluate their potential for synthetic organic chemistry.

scholarly journals Selective monoalkylation of p-tert-butylcalix-[4]-arene in a methyl carbonate ionic liquid

2018 ◽  
Vol 54 (85) ◽  
pp. 12037-12040
Author(s):  
R. E. Whiteside ◽  
H. Q. Nimal Gunaratne ◽  
A. F. V. Muzio ◽  
P. Nockemann
Keyword(s):  
Carbon Dioxide ◽  
Ionic Liquid ◽  
Ionic Liquids ◽  
Methyl Carbonate

Methyl carbonate ionic liquids are shown to readily mono-deprotonate p-tert-butylcalix-[4]-arenes initiating the formation of an organic mono-anionic p-tert-butylcalix-[4]-arate salt, methanol and carbon dioxide.

scholarly journals Metal-Catalyzed Degradation of Cellulose in Ionic Liquid Media

Inorganics ◽  
2018 ◽  
Vol 6 (3) ◽  
pp. 78 ◽  
Author(s):  
Tiina Aid ◽  
Mihkel Koel ◽  
Margus Lopp ◽  
Merike Vaher
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Molybdenum Oxide ◽  
Cellulose Degradation ◽  
Biomass Conversion ◽  
Reaction Medium ◽  
Good Activity ◽  
Industrial Chemicals ◽  
Liquid Media ◽  
Metal Catalyzed

Biomass conversion to 5-hydroxymethylfurfural (HMF) has been widely investigated as a sustainable alternative to petroleum-based feedstock, since it can be efficiently converted to fuel, plastic, polyester, and other industrial chemicals. In this report, the degradation of commercial cellulose, the isomerization of glucose to fructose, and the conversion of glucose to HMF in 1-butyl-3-methylimidazolium chloride ([BMIM]Cl]) using metal catalysts (CrCl3, ZnCl2, MgCl2) as well as tungsten and molybdenum oxide-based polyoxometalates (POM) were investigated. Tungsten and molybdenum oxide-based POMs in ionic liquids (IL) were able to degrade cellulose to majority glucose and epimerize glucose to mannose (in the case of the molybdenum oxide-based POM). A certain amount of glucose was also converted to HMF. The tungsten oxide-based POM in IL showed good activity for cellulose degradation but the overall products yield remained 28.6% lower than those obtained using CrCl3 as a catalyst. Lowering the cellulose loading did not significantly influence the results and the addition of water to the reaction medium decreased the product yields remarkably.

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