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21.
Chromatographic and spectroscopic methods for the determination of solvent properties of room temperature ionic liquids 总被引:5,自引:0,他引:5
Poole CF 《Journal of chromatography. A》2004,1037(1-2):49-82
Room temperature ionic liquids are novel solvents with favorable environmental and technical features. Synthetic routes to over 200 room temperature ionic liquids are known but for most ionic liquids physicochemical data are generally lacking or incomplete. Chromatographic and spectroscopic methods afford suitable tools for the study of solvation properties under conditions that approximate infinite dilution. Gas-liquid chromatography is suitable for the determination of gas-liquid partition coefficients and activity coefficients as well as thermodynamic constants derived from either of these parameters and their variation with temperature. The solvation parameter model can be used to define the contribution from individual intermolecular interactions to the gas-liquid partition coefficient. Application of chemometric procedures to a large database of system constants for ionic liquids indicates their unique solvent properties: low cohesion for ionic liquids with weakly associated ions compared with non-ionic liquids of similar polarity; greater hydrogen-bond basicity than typical polar non-ionic solvents; and a range of dipolarity/polarizability that encompasses the same range as occupied by the most polar non-ionic liquids. These properties can be crudely related to ion structures but further work is required to develop a comprehensive approach for the design of ionic liquids for specific applications. Data for liquid-liquid partition coefficients is scarce by comparison with gas-liquid partition coefficients. Preliminary studies indicate the possibility of using the solvation parameter model for interpretation of liquid-liquid partition coefficients determined by shake-flask procedures as well as the feasibility of using liquid-liquid chromatography for the convenient and rapid determination of liquid-liquid partition coefficients. Spectroscopic measurements of solvatochromic and fluorescent probe molecules in room temperature ionic liquids provide insights into solvent intermolecular interactions although interpretation of the different and generally uncorrelated "polarity" scales is sometimes ambiguous. All evidence points to the ionic liquids as a unique class of polar solvents suitable for technical development. In terms of designer solvents, however, further work is needed to fill the gaps in our knowledge of the relationship between ion structures and physicochemical properties. 相似文献
22.
Andrew J. Smith Daniela Dimitrova Jude N. Arokianathar Kenneth F. Clark Darren L. Poole Stuart G. Leach John A. Murphy 《Chemical science》2020,11(45):12364
The combination of potassium tert-butoxide and triethylsilane is unusual because it generates multiple different types of reactive intermediates simultaneously that provide access to (i) silyl radical reactions, (ii) hydrogen atom transfer reactions to closed shell molecules and to radicals, (iii) electron transfer reductions and (iv) hydride ion chemistry, giving scope for unprecedented outcomes. Until now, reactions with this reagent pair have generally been explained by reference to one of the intermediates, but we now highlight the interplay and competition between them.The combination of potassium tert-butoxide and triethylsilane provides simultaneous access to multiple reactive intermediates, radicals, H-atom donors, hydride donors and electron donors, giving scope for unprecedented reaction outcomes. 相似文献
23.
Back Cover: Rhodium‐Catalyzed Ketone Methylation Using Methanol Under Mild Conditions: Formation of α‐Branched Products (Angew. Chem. Int. Ed. 3/2014) 下载免费PDF全文
24.
Electrochemical Vicinal Difluorination of Alkenes: Scalable and Amenable to Electron-Rich Substrates
Sayad Doobary Alexi T. Sedikides Henry P. Caldora Dr. Darren L. Poole Dr. Alastair J. J. Lennox 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(3):1171-1176
Fluorinated alkyl groups are important motifs in bioactive compounds, positively influencing pharmacokinetics, potency and conformation. The oxidative difluorination of alkenes represents an important strategy for their preparation, yet current methods are limited in their alkene-types and tolerance of electron-rich, readily oxidized functionalities, as well as in their safety and scalability. Herein, we report a method for the difluorination of a number of unactivated alkene-types that is tolerant of electron-rich functionality, giving products that are otherwise unattainable. Key to success is the electrochemical generation of a hypervalent iodine mediator using an “ex-cell” approach, which avoids oxidative substrate decomposition. The more sustainable conditions give good to excellent yields in up to decagram scales. 相似文献
25.
26.
B. R. Sheridan G. Poole E. Dowdall C. Chiu 《International journal of environmental analytical chemistry》2013,93(2-4):195-202
Abstract The analysis of PCBs often involves lengthy and expensive cleanup procedures to remove interferences associated with environmental sample matrices. Gel permeation chromatography (GPC) has proven to be a useful tool in removing many of these interferences from environmental samples, especially from difficult matrices such as oils, lipids and sediments. This paper describes the effect of temperature upon the GPC column in separating PCBs from transformer oil and its implication on GC-MS analysis. 相似文献
27.
Rhodium‐Catalyzed Ketone Methylation Using Methanol Under Mild Conditions: Formation of α‐Branched Products 下载免费PDF全文
Dr. Louis K. M. Chan Darren L. Poole Di Shen Dr. Mark P. Healy Prof. Timothy J. Donohoe 《Angewandte Chemie (International ed. in English)》2014,53(3):761-765
The rhodium‐catalyzed methylation of ketones has been accomplished using methanol as the methylating agent and the hydrogen‐borrowing method. The sequence is notable for the relatively low temperatures that are required and for the ability of the reaction system to form α‐branched products with ease. Doubly alkylated ketones can be prepared from methyl ketones and two different alcohols by using a sequential one‐pot iridium‐ and rhodium‐catalyzed process. 相似文献
28.
Electrochemical Vicinal Difluorination of Alkenes: Scalable and Amenable to Electron‐Rich Substrates
Sayad Doobary Alexi T. Sedikides Henry P. Caldora Darren L. Poole Alastair J. J. Lennox 《Angewandte Chemie (International ed. in English)》2020,59(3):1155-1160
Fluorinated alkyl groups are important motifs in bioactive compounds, positively influencing pharmacokinetics, potency and conformation. The oxidative difluorination of alkenes represents an important strategy for their preparation, yet current methods are limited in their alkene‐types and tolerance of electron‐rich, readily oxidized functionalities, as well as in their safety and scalability. Herein, we report a method for the difluorination of a number of unactivated alkene‐types that is tolerant of electron‐rich functionality, giving products that are otherwise unattainable. Key to success is the electrochemical generation of a hypervalent iodine mediator using an “ex‐cell” approach, which avoids oxidative substrate decomposition. The more sustainable conditions give good to excellent yields in up to decagram scales. 相似文献
29.
The solvation parameter model is used to determine the system constants for two sol-gel coated open-tubular columns at five equally spaced temperatures in the range 60-140 degrees C. Differences in the system constants as a function of temperature are used to determine the affect of sol-gel structure on the selectivity of SolGel-l and SolGel-Wax columns compared with conventionally coated and immobilized poly(dimethylsiloxane) and poly(ethylene glycol) stationary phases. The sol-gel columns should be suitable for similar separations to those presently performed on conventional immobilized liquid film columns of the same type but selectivity differences for polar compounds, which depend on temperature, should be anticipated. 相似文献
30.
Donati C Glotzer SC Poole PH Kob W Plimpton SJ 《Physical review. E, Statistical physics, plasmas, fluids, and related interdisciplinary topics》1999,60(3):3107-3119
Using extensive molecular dynamics simulations of an equilibrium, glass-forming Lennard-Jones mixture, we characterize in detail the local atomic motions. We show that spatial correlations exist among particles undergoing extremely large ("mobile") or extremely small ("immobile") displacements over a suitably chosen time interval. The immobile particles form the cores of relatively compact clusters, while the mobile particles move cooperatively and form quasi-one-dimensional, stringlike clusters. The strength and length scale of the correlations between mobile particles are found to grow strongly with decreasing temperature, and the mean cluster size appears to diverge near the mode-coupling critical temperature. We show that these correlations in the particle displacements are related to equilibrium fluctuations in the local potential energy and local composition. 相似文献