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IONIC LIQUIDS – CLASSES AND PROPERTIES Edited by Scott T. Handy Ionic Liquids – Classes and Properties Edited by Scott T. Handy Published by InTech Janeza Trdine 9, 51000 Rijeka, Croatia Copyright © 2011 InTech All chapters are Open Access articles distributed under the Creative Commons Non Commercial Share Alike Attribution 3.0 license, which permits to copy, distribute, transmit, and adapt the work in any medium, so long as the original work is properly cited. After this work has been published by InTech, authors have the right to republish it, in whole or part, in any publication of which they are the author, and to make other personal use of the work. Any republication, referencing or personal use of the work must explicitly identify the original source. Statements and opinions expressed in the chapters are these of the individual contributors and not necessarily those of the editors or publisher. No responsibility is accepted for the accuracy of information contained in the published articles. The publisher assumes no responsibility for any damage or injury to persons or property arising out of the use of any materials, instructions, methods or ideas contained in the book. Publishing Process Manager Alenka Urbancic Technical Editor Teodora Smiljanic Cover Designer Jan Hyrat Image Copyright Pedro Salaverría, 2011. Used under license from Shutterstock.com First published September, 2011 Printed in Croatia A free online edition of this book is available at www.intechopen.com Additional hard copies can be obtained from orders@intechweb.org Ionic Liquids – Classes and Properties, Edited by Scott T. Handy p. cm. ISBN 978-953-307-634-8 free online editions of InTech Books and Journals can be found at www.intechopen.com Contents Preface IX Part 1 Classes of Ionic Liquids 1 Chapter 1 1,2,3-Triazolium Salts as a Versatile New Class of Ionic Liquids 3 Zekarias Yacob and Jürgen Liebscher Chapter 2 Thiazolium and Benzothiazolium Ionic Liquids 23 Munawar Ali Munawar and Sohail Nadeem Chapter 3 Glycoside-Based Ionic Liquids 65 Robert Engel Chapter 4 Ionic Liquids from (Meth) Acrylic Compounds 81 Sindt M., Mieloszynski J.L. and Harmand J. Part 2 Theoretical Studies 105 Chapter 5 Theoretical Description of Ionic Liquids 107 Enrico Bodo and Valentina Migliorati Chapter 6 Classical Density Functional Theory of Ionic Liquids 127 Jan Forsman, Ryan Szparaga, Sture Nordholm, Clifford E.Woodward and Robert Penfold Part 3 Physical Properties 151 Chapter 7 Interactions and Transitions in Imidazolium Cation Based Ionic Liquids 153 Madhulata Shukla, Nitin Srivastava and Satyen Saha Chapter 8 High Pressure Phase Behavior of Two Imidazolium-Based Ionic Liquids, [bmim][BF 4 ] and [bmim][PF 6 ] 171 Yukihiro Yoshimura, Takekiyo Takekiyo, Yusuke Imai and Hiroshi Abe VI Contents Chapter 9 Dielectric Properties of Ionic Liquids Proposed to Be Used in Batteries 187 Cserjési Petra, Göllei Attila, Bélafi-Bakó Katalin and Gubicza László Chapter 10 Translational and Rotational Motions for TFSA-Based Ionic Liquids Studied by NMR Spectroscopy 209 Kikuko Hayamizu Part 4 Applications in Synthesis 237 Chapter 11 Ionic Liquids Recycling for Reuse 239 Samir I. Abu-Eishah Chapter 12 Ionic Liquids in Green Carbonate Synthesis 273 Jianmin Sun, Ruixia Liu, Shin-ichiro Fujita and Masahiko Arai Chapter 13 Ionic Liquids in Polar Diels-Alder Reactions Using Carbocycles and Heterocycles as Dienophiles 311 Mancini Pedro M.E., Kneeteman María, Della Rosa Claudia, Bravo Virginia and Adam Claudia Preface Ionic liquids (more specifically, room temperature ionic liquids (RTIL)) have attracted considerable interest over the last few years. Although the specific definition of what an RTIL is varies from person to person, the prevailing definition would be that it is a salt with a melting point below 100 °C. Such a broad definition leaves considerable room for flexibility, which contributed to labeling RTILs as “designer solvents.” 1 The history of ionic liquids (and the closely related molten salts) has a rather ill- defined beginning, although it is most commonly dated back to 1914 and the work of Walden on the use of alkylammonium nitrates. 2,3 The next burst of interest occurred with the discovery of chloroaluminates formed by combining quaternary heterocyclic cations with aluminum chloride. These materials exhibited a great deal of potential for use in a variety of areas, but all suffered from extreme sensitivity to moisture. A major step forward was made by Wilkes in the early 1990’s, with the report of moisture stable ionic liquids created by replacing the aluminum chloride with other anions, such as tetrafluoroborate or hexafluorophosphate. 4 Since that seminal report by Wilkes and co-workers, the family of RTILs has seen explosive growth. Starting with imidazolium cations, the cationic component has been varied to include pyridinium, ammonium, phosphonium, thiazolium, and triazolium species. 5 In general, these cations have been combined with weakly coordinating anions, although not all weakly coordinating anions result in RTILs (for example, the very weakly coordinating polyhedral borane anions of Reed afford salts with melting points between 45 and 156 °C for a series of imidazolium cations). 6 Common examples include tetrafluoroborate, hexafluorophosphate, triflate, triflimide, and dicyanimide. The first two have been explored the most, and must be treated with the greatest caution as they are fairly readily hydrolyzed to boric acid and phosphate respectively. 7 Indeed, various phosphate and phosphinate anions have been employed to some advantage in RTILs. 8 The list of possible anionic components continues to grow at a rapid rate. X Preface Several chapters in this volume display the increasing variability found in the family of components used to prepare RTILs, notably those of Sindt, Mieloszynki, and Harmand; Yacob and Liebscher; Engel; and Munawar and Nadeem. Fig. 1. Representative Ionic Liquid Components The remaining focus of interest in RTIL research are methods for determining and predicting their physical properties, especially since their unusual and tunable properties are often mentioned as one of the key advantages of RTILs over conventional solvents. Several chapters in this volume focus on this area as well, including those by Shukla, Srivastava, and Saha; Bodo and Migliorati; Forsman, Szparaga, Nordholm, Woodward, and Penfold; Hayamizu; Yoshimura, Takekiyo, Imai and Abe; and Petra, Attila, Katalin, and Laszlo. However, even with this impressive effort, there is still a lot of work to be done before the true power of RTILs as designer solvents (i.e. predictable selection of a particular RTIL for any given application) is effectively harnessed. Cation Anion N N N R R R 4 N R 4 P BF 4 PF 6 N(CN) 2 NTf 2 [...]... “Room-Temperature Ionic Liquids: Solvents for Synthesis and Catalysis 2 ” Chem Rev 2011, 111, 3508-3576 [18] Parvulescu, V.I.; Hardacre, C “Catalysis in Ionic Liquids. ” Chem Rev 2007, 107, 2615-2665 Part 1 Classes of Ionic Liquids 1 1,2,3-Triazolium Salts as a Versatile New Class of Ionic Liquids Zekarias Yacob and Jürgen Liebscher Humboldt-University Berlin Germany 1 Introduction Among the various classes of ionic. .. ionic liquids counter-ions (Jeong and Ryu 2010; Khan, Hanelt et al 2009) These reports indicated good thermal stability up to 355 °C, which is strongly dependent on several variables such as the kind of counter-ion and the nature of substituents on the triazolium ring One can tune the stability of 1,2,3- 8 Ionic Liquids – Classes and Properties triazolium ionic liquids by the choice of substituents and. .. triazolium ionic liquids 18, 19 3 Properties of 1,2,3-triazolium ionic liquids Most of the 1,2,3-triazolium based ionic liquids are room temperature ionic liquids (RTILs) (Fletcher, Keeney et al 2010; Khan, Hanelt et al 2009) So far, not so many physical constants have been reported Viscosity measurements and differential thermogravimetry (TGA) measurements of some 1,3,4-trisubstituted 1,2,3-triazolium ionic. .. 2 (Yacob, Shah et al 2008) 3 (Jeong and Ryu 2010) 4 (Fletcher, Keeney et al 2010) Table 1 Some examples of 1,2,3-triazolium ionic liquids 9 6 Ionic Liquids – Classes and Properties cycloaddition reaction Remarkably, even iodoarenes which normally are unsuitable substrates for a nucleophilic substitution by azides can be transformed to the corresponding arylazides and further converted to 1-aryl-1,2,3-triazoles... 1,3dialkylimidazolium tetrafluoroborate ionic liquids using microwaves.” Tetrahedron Lett 2002, 43, 5381-5383 [12] Estager, J.; Leveque, J-M.; Cravotto, G.; Boffa, L.; Bonrath, W.; Draye, M “One -pot and Solventless Synthesis of Ionic Liquids under Ultrasonic Irradiation.” Synlett 2007, 2065-2068 [13] Narodai, N.; Guise, S.; Newlands, C.; Andersen, J-A “Clean catalysis with ionic solvents – phosphonium tosylates for... excellent review regarding the early history of ionic liquids, see Wilkes, J.S Green Chem 2002, 4, 73 [4] Wilkes, J.S.; Zaworotko, M.J J Chem Soc Chem Commun 1992, 965 [5] Handy, S.T.; “Room Temperature Ionic Liquids: Different Classes and Physical Properties. ” Curr Org Chem 2005, 9, 959-989 [6] Larsen, A.; Holbrey, J.D.; Tham, F.S.; Reed, C.A “Designing Ionic Liquids: Imidazolium Melts with Inert Carborane... used to synthesize 1,3-dialkyl-1,2,3-triazolium salts as ionic liquid solvents useful for Baylis-Hillman reactions (Jeong and Ryu 2010) Catalyst 38, which 12 Ionic Liquids – Classes and Properties lack a substituent in position 4 of the 1,2,3-triazole ring and thus is less lipophilic performed poorer as compared to catalyst 30, resulting in 78% ee and 82% yield (Khan, Shah et al 2011) R N N N R= C6H11... properties of the ionic liquid such as viscosity and melting points but also to facilitate the deprotection reaction 16 Ionic Liquids – Classes and Properties The -aminoxylations of carbonyl compounds with nitrosobenzene was also investigated using catalyst 30 and analogous 4-hydroxy-(S)-proline derived catalyst (where the counteranion is triflate) resulting from alkylation with MeOTf and lysine derived... stable and recyclable solvents for the Baylis-Hillman reaction The Baylis-Hillman reaction between p-chlorobenzaldehyde and methyl acrylate was conducted in 1,2,3-triazolium ionic liquids at room temperature in the prescence of DABCO Interestingly the reaction furnished improved yields within shorter reaction time in the triazolium ionic liquids as compared to analogous imidazolium ionic liquids (Jeong and. .. and contain oxygen-rich anions 3 (Figure 1) and thus can be utilized as highly energetic fuels (Drake, Kaplan et al 2007) Here, a review is provided on the state of the art in the area of 1,2,3-triazolium salts as ionic liquids and ionic liquid tags for organocatalysts Fig 1 General structure of common ionic liquids 2 Synthesis of 1,2,3-triazolium ionic liquids The syntheses of 1,2,3-triazolium salts . IONIC LIQUIDS – CLASSES AND PROPERTIES Edited by Scott T. Handy Ionic Liquids – Classes and Properties Edited by Scott T. Handy Published. orders@intechweb.org Ionic Liquids – Classes and Properties, Edited by Scott T. Handy p. cm. ISBN 978-953-307-634-8 free online editions of InTech Books and Journals can be found. Part 1 Classes of Ionic Liquids 1 Chapter 1 1,2,3-Triazolium Salts as a Versatile New Class of Ionic Liquids 3 Zekarias Yacob and Jürgen Liebscher Chapter 2 Thiazolium and Benzothiazolium Ionic