Correlating ionic liquid solvent effects with solvent parameters for a reaction that proceeds through a xanthylium intermediate

2019 ◽  
Vol 17 (42) ◽  
pp. 9336-9342 ◽  
Author(s):  
Alyssa Gilbert ◽  
Götz Bucher ◽  
Ronald S. Haines ◽  
Jason B. Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Rate Constant ◽  
Solvent Effects ◽  
Solvent Parameters

The effects of ionic liquids on the rate constant of an SN1 process with a xanthylium intermediate differ from those observed for other SN1 reactions. These effects can be correlated to solvent parameters of the ionic liquids allowing predictability.

Understanding the effects of ionic liquids on a unimolecular substitution process: correlating solvent parameters with reaction outcome

2019 ◽  
Vol 17 (3) ◽  
pp. 675-682 ◽  
Author(s):  
Alyssa Gilbert ◽  
Ronald S. Haines ◽  
Jason B. Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Rate Constant ◽  
Solvent Parameters ◽  
Substitution Process

The polarisability of an ionic liquid is key in determining the rate constant of a unimolecular substitution process.

Controlling the reactions of 1-bromogalactose acetate in methanol using ionic liquids as co-solvents

2020 ◽  
Vol 18 (28) ◽  
pp. 5442-5452 ◽  
Author(s):  
Alyssa Gilbert ◽  
Ronald S. Haines ◽  
Jason B. Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Rate Constant ◽  
Solvent Mixture ◽  
Solvent Composition ◽  
Composition Changes

Using an ionic liquid in the solvent mixture for the reaction of a galactose substrate leads to changes in both the rate constant and the products as the solvent composition changes.

Ionic liquid solvents: the importance of microscopic interactions in predicting organic reaction outcomes

2017 ◽  
Vol 89 (6) ◽  
pp. 745-757 ◽  
Author(s):  
Sinead T. Keaveney ◽  
Ronald S. Haines ◽  
Jason B. Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Transition State ◽  
Physical Properties ◽  
Solvent Effects ◽  
Recent Progress ◽  
Comprehensive Understanding ◽  
Organic Reaction ◽  
Microscopic Interactions ◽  
Molecular Solvents

AbstractIonic liquids are attractive alternatives to molecular solvents as they have many favourable physical properties and can produce different organic reaction outcomes compared to molecular solvents. Thus far, interactions between the ionic liquid components and specific sites (such as charged centres, lone pairs and π systems) on the reagents and transition state have been identified as affecting reaction outcome; a comprehensive understanding of these interactions is necessary to allow prediction of ionic liquid solvent effects. This manuscript summarises our recent progress in the development of a framework for predicting the effect of an ionic liquid solvent on the outcome of organic processes. There will be a particular focus on the importance of the different interactions between the ionic liquid components and the species along the reaction coordinate that are responsible for the changes in reaction outcome observed in the cases described.

Effect of Modifying the Anion of an Ionic Liquid on the Outcome of an SN2 Process

2015 ◽  
Vol 68 (1) ◽  
pp. 31 ◽  
Author(s):  
Sinead T. Keaveney ◽  
Dominic V. Francis ◽  
Winnie Cao ◽  
Ronald S. Haines ◽  
Jason B. Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Rate Constant ◽  
Kinetic Data ◽  
Activation Parameters ◽  
Temperature Dependent ◽  
Substitution Process

The effect of a series of ionic liquids containing different anions (bis(trifluoromethanesulfonyl)imide, dicyanimide, hexafluorophosphate, tetrafluoroborate, and bromide) on the rate constant of a bimolecular substitution process was investigated. A general ionic liquid effect was noted, with increases in the rate constant observed in all ionic liquids used when compared with that in acetonitrile. Temperature-dependent kinetic data allowed calculation of activation parameters in each of the reaction mixtures considered; these parameters showed that the microscopic origins of the rate enhancements observed were not the same for all of the ionic liquids used, demonstrating the importance of the nature of the anion.

The effect of varying the anion of an ionic liquid on the solvent effects on a nucleophilic aromatic substitution reaction

2018 ◽  
Vol 16 (18) ◽  
pp. 3453-3463 ◽  
Author(s):  
Rebecca R. Hawker ◽  
Ronald S. Haines ◽  
Jason B. Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Solvent Effects ◽  
Substitution Reaction ◽  
Nucleophilic Aromatic Substitution ◽  
Aromatic Substitution

Variety of ionic liquids with different anions used as solvents for a nucleophilic aromatic substitution reaction.

Rational selection of the cation of an ionic liquid to control the reaction outcome of a substitution reaction

2018 ◽  
Vol 54 (18) ◽  
pp. 2296-2299 ◽  
Author(s):  
Rebecca R. Hawker ◽  
Ronald S. Haines ◽  
Jason B. Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Rate Constant ◽  
Substitution Reaction ◽  
Rational Selection ◽  
Substitution Process ◽  
Selection Of

Rational selection of ionic liquids to get the rate constant you want in a substitution process.

Mapping the “Extra Solvent Power, ESP” of Ionic Liquids for Monomers, Polymers and Globular Nanoparticles

2017 ◽  
Author(s):  
Jose A. Pomposo
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Linear Polymers ◽  
Green Solvents ◽  
Ionic Polymers ◽  
First Time ◽  
Solvent Power

Understanding the miscibility behavior of ionic liquid (IL) / monomer, IL / polymer and IL / nanoparticle mixtures is critical for the use of ILs as green solvents in polymerization processes, and to rationalize recent observations concerning the superior solubility of some proteins in ILs when compared to standard solvents. In this work, the most relevant results obtained in terms of a three-component Flory-Huggins theory concerning the “Extra Solvent Power, ESP” of ILs when compared to traditional non-ionic solvents for monomeric solutes (case I), linear polymers (case II) and globular nanoparticles (case III) are presented. Moreover, useful ESP maps are drawn for the first time for IL mixtures corresponding to case I, II and III. Finally, a potential pathway to improve the miscibility of non-ionic polymers in ILs is also proposed.

Dynamics of Ion Locking in Doubly Polymerized Ionic Liquids

2020 ◽  
Author(s):  
Swati Arora ◽  
Julisa Rozon ◽  
Jennifer Laaser
Keyword(s):  
Dielectric Constant ◽  
Ionic Liquid ◽  
Ionic Liquids ◽  
Ion Pairs ◽  
Polymer Chains ◽  
Ion Motion ◽  
Charged Species ◽  
Broadband Dielectric Spectroscopy ◽  
Covalently Linked ◽  
Insight Into

<div>In this work, we investigate the dynamics of ion motion in “doubly-polymerized” ionic liquids (DPILs) in which both charged species of an ionic liquid are covalently linked to the same polymer chains. Broadband dielectric spectroscopy is used to characterize these materials over a broad frequency and temperature range, and their behavior is compared to that of conventional “singly-polymerized” ionic liquids (SPILs) in which only one of the charged species is attached to the polymer chains. Polymerization of the DPIL decreases the bulk ionic conductivity by four orders of magnitude relative to both SPILs. The timescales for local ionic rearrangement are similarly found to be approximately four orders of magnitude slower in the DPILs than in the SPILs, and the DPILs also have a lower static dielectric constant. These results suggest that copolymerization of the ionic monomers affects ion motion on both the bulk and the local scales, with ion pairs serving to form strong physical crosslinks between the polymer chains. This study provides quantitative insight into the energetics and timescales of ion motion that drive the phenomenon of “ion locking” currently under investigation for new classes of organic electronics.</div>

Ionic Liquid Assisted Synthesis of Some 2-Aminobenzenethiols

2019 ◽  
Vol 16 (7) ◽  
pp. 550-555
Author(s):  
Dinesh K. Jangid ◽  
Keshav L. Ameta ◽  
Surbhi Dhadda ◽  
Anjali Guleria ◽  
Prakash G. Goswami ◽  
...  
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Comparative Study ◽  
Maximum Yield ◽  
Efficient Synthesis ◽  
Target Molecules ◽  
Presence And Absence

Ionic Liquid assisted efficient synthesis of some 2-aminobenzenethiols has been reported using three different Ionic Liquids (ILs) namely methylimidazolium tetrafluoroborate [MIM]+[BF4]−, methylimidazolium chloride [MIM]+[Cl]− and methylimidazolium nitrate [MIM]+[NO3]−. A comparative study has been carried out for the synthesis of target molecules in the presence and absence of IL, leading to conclusion that maximum yield has been observed with [MIM]+[BF4]−.

Dispersive Liquid-Liquid Microextraction Based on Ionic Liquid and Spectrophotometric Determination of Bilirubin in Biological Samples

2020 ◽  
Vol 16 (5) ◽  
pp. 652-659
Author(s):  
Asiye A. Avan ◽  
Hayati Filik
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Biological Samples ◽  
Urine Samples ◽  
Spectrophotometric Detection ◽  
Full Color ◽  
Dispersive Liquid Liquid Microextraction ◽  
Urine And Serum ◽  
Liquid Microextraction

Background: An Ionic Liquid-based based Dispersive Liquid-Liquid Microextraction (IL-DLLME) method was not applied to preconcentration and determination of bilirubin. Ionic Liquids (ILs) are new chemical compounds. In recent years, Ionic Liquids (ILs) have been employed as alternative solvents to toxic organic solvents. Due to these perfect properties, ILs have already been applied in many analytical extraction processes, presenting high extraction yield and selectivity for analytes. Methods: In this study, IL-DLLME was applied to biological samples (urine and serum) for the spectrophotometric detection of bilirubin. For bilirubin analysis, the full-color development was based on the reaction with periodate in the presence of hydrochloric acid. The high affinity of bilirubin for the ionic liquid phase gave extraction percentages above 98% in 0.3 M HCl solution. Results: Several IL-extraction parameters were optimized and room temperature ionic liquid 1-butyl- 1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and ethanol were used as extraction and disperser solution. The linear range was found in the range of 0.5-6.0 μM (0.3-3.5 μg mL-1) and the limits of detection of the proposed method was 0.5 μM (0.3 μg mL-1). The proposed method was applied for the preconcentration and separation of trace bilirubin in real urine samples. Also, the recoveries for bilirubin in spiked biological samples (urine and serum) were found to be acceptable, between 95-102%. Conclusion: The proposed IL-DLLMEapproach was employed for the enrichment and determination of trace levels of bilirubin in urine samples using NaIO4 as an oxidizing agent and Uv-vis spectrophotometric detection. The periodate oxidation of bilirubin is rapid, effective, selective, and simple to perform. The method contains only HCl, NaOI4, and an anionic surfactant. The method may be useful for economizing in the consumption of reagents in bilirubin determining. The IL-DLLMEmethod ensures a high yield and has a low toxicity no skin sensitization, no mutagenicity and no ecotoxicity in an aquatic environment since only very low quantities of an IL is required. For full-color formation, no any extra auxiliary reagents are required. Besides, the IL-DLLME technique uses a low-cost instrument such as Uv-vis which is present in most of the medical laboratories.

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