Ionic liquids sensitivity

The DPM rearrangement of 16a in the presence of a soluble ionic liquid sensitizer in the ionic liquid [bmin]BF4 gives 17a in 87% yield (upper part in Scheme 4.8) [10]. Chiral ionic liquids have been evaluated as chiral induction solvents for the DPM rearrangement of 16b (bottom part in Scheme 4.8) [11]. 

Erotic impurities have to be taken into account for two groups of ionic liquids those that have been produced by an exchange reaction involving a strong acid (often the case, for example, for [BMIM][PEg]), and those that are sensitive to hydrolysis. In the latter case, the protons may originate from the hydrolysis of the anion, forming an acid that may be dissolved in the ionic liquid. 

Eor ionic liquids that do not mix completely with water (and which display sufficient hydrolysis stability), there is an easy test for acidic impurities. The ionic liquid is added to water and a pEf test of the aqueous phase is carried out. If the aqueous phase is acidic, the ionic liquid should be washed with water to the point where the washing water becomes neutral. Eor ionic liquids that mix completely with water we recommend a standardized, highly proton-sensitive test reaction to check for protic impurities. 

The reported densities of ionic liquids vary between 1.12 g cm for [(n-QHi7)(C4H9)3N][(CF3S02)2N] and 2.4 g cm for a 34-66 mol% [(CH3)3S]Br/AlBr3 ionic liquid [21, 23]. The densities of ionic liquid appear to be the physical property least sensitive to variations in temperature. For example, a 5 degree change in temperature from 298 to 303 K results in only a 0.3 % decrease in the density for a 50.0 50.0 mol % [EMIM]C1/A1C13 [17]. In addition, the impact of impurities appears to be far less dramatic than in the case of viscosity. Recent work indicates that the densities of ionic liquids vary linearly with wt. % of impurities. For example, 20 wt. % water (75 mol %) in [BMIM][BF4] results in only a 4 % decrease in density [33]. 

Reactions in chloroaluminate(III) salts and other related binary salts often proceed smoothly to give products. However, it should be noted that these salts are water-sensitive and must be handled under dry conditions. They react with water to give hydrated aluminium(III) ionic species and HCl. When a reactant or product contains a heteroatomic functional group, such as a ketone, a strong ketone/alumini-um(III) chloride adduct is formed. In these cases, this adduct can be difficult to separate from the ionic liquid at the end of a reaction. The isolation of the product often... 

Eee has used chloroaluminate(III) ionic liquids in the Diels-Alder reaction [36]. The endo. exo ratio rose from 5.25 to 19 on changing the composition of the ionic liquid from X(A1C13) = 0.48 to X(A1C13) = 0.51 (Scheme 5.1-16). The reaction works well, giving up to 95 % yield, but the moisture-sensitivity of these systems is a major disadvantage, the products being recovered by quenching the ionic liquid in water. 

However, a number of limitations are still evident when tetrafluorohorate and hexafluorophosphate ionic liquids are used in homogeneous catalysis. The major aspect is that these anions are still relatively sensitive to hydrolysis. The tendency to anion hydrolysis is of course much less pronounced than that of the chloroalu-minate melts, hut it still occurs and this has major consequences for their use in transition metal catalysis. For example, the [PF ] anion of l-hutyl-3-methylimida-2olium ([BMIM]) hexafluorophosphate was found (in the author s laboratories) to hydrolyze completely after addition of excess water when the sample was kept for 8 h at 100 °C. Gaseous HF and phosphoric acid were formed. Under the same conditions, only small amounts of the tetrafluorohorate ion of [BMlMjjBFJ was converted into HF and boric acid [10]. The hydrolytic formation of HF from the anion of the ionic liquid under the reaction conditions causes the following problems with... 

In the light of these results, it becomes important to question whether a particular catalytic result obtained in a transition metal-catalyzed reaction in an imidazolium ionic liquid is caused by a metal carbene complex formed in situ. The following simple experiments can help to verify this in more detail a) variation of ligands in the catalytic system, b) application of independently prepared, defined metal carbene complexes, and c) investigation of the reaction in pyridinium-based ionic liquids. If the reaction shows significant sensitivity to the use of different ligands, if the application of the independently prepared, defined metal-carbene complex... 

One of the key factors controlling the reaction rate in multiphasic processes (for reactions talcing place in the bulk catalyst phase) is the reactant solubility in the catalyst phase. Thanks to their tunable solubility characteristics, the use of ionic liquids as catalyst solvents can be a solution to the extension of aqueous two-phase catalysis to organic substrates presenting a lack of solubility in water, and also to moisture-sensitive reactants and catalysts. With the different examples presented below, we show how ionic liquids can have advantageous effects on reaction rate and on the selectivity of homogeneous catalyzed reactions. 

In comparison with classical processes involving thermal separation, biphasic techniques offer simplified process schemes and no thermal stress for the organometal-lic catalyst. The concept requires that the catalyst and the product phases separate rapidly, to achieve a practical approach to the recovery and recycling of the catalyst. Thanks to their tunable solubility characteristics, ionic liquids have proven to be good candidates for multiphasic techniques. They extend the applications of aqueous biphasic systems to a broader range of organic hydrophobic substrates and water-sensitive catalysts [48-50]. 

For example, Novasina S.A. (www.novasina.com), a Swiss company specializing in the manufacture of devices to measure humidity in air, has developed a new sensor based on the non-synthetic application of an ionic liquid. The new concept makes simple use of the close correlation between the water uptake of an ionic liquid and its conductivity increase. In comparison with existing sensors based on polymer membranes, the new type of ionic liquid sensor shows significantly faster response times (up to a factor of 2.5) and less sensitivity to cross contamination (with alcohols, for example). Each sensor device contains about 50 pi of ionic liquid, and the new sensor system became available as a commercial product in 2002. Figure 9-1 shows a picture of the sensor device containing the ionic liquid, and Figure 9-2 displays the whole humidity analyzer as commercialized by Novasina S.A.. 

Room temperature ionic liquids are air stable, non-flammable, nonexplosive, immiscible with many Diels-Alder components and adducts, do not evaporate easily and act as support for the catalyst. They are useful solvents, especially for moisture and oxygen-sensitive reactants and products. In addition they are easy to handle, can be used in a large thermal range (typically —40 °C to 200 °C) and can be recovered and reused. This last point is particularly important when ionic liquids are used for catalytic reactions. The reactions are carried out under biphasic conditions and the products can be isolated by decanting the organic layer. 

Based on the properties of ionic hquids in high-temperature microwave-enhanced reactions, the authors chose l-butyl-3-methylimidazolium tetraflu-orophosphate ([bmimjPFe) as the suitable ionic liquid (Scheme 23). The addition of 0.15 mmol of [bmimjPFe to a reaction in 2.0 mL of DCF was found to increase the reaction rate dramatically and a set-temperature of 190 °C was reached in a mere 1 min, while the reactions programmed at 190 °C, in the absence of the ionic liquid, reached only 170 °C in 10 min. The reactions were finished in a mere 18-25 min of irradiation time, including the hydrolysis of the sensitive imidoyl chloride moiety with water. The formed bis-lactams were isolated in good yield and purity. 

Recently, room temperature ionic liquids (RT-ILs) have attracted much attention for their excellent properties, e.g., wide temperature range of liquid phase, ultra-low vapor pressure, chemical stability, potential as green solvents, and high heat capacities [64,65]. These properties make them good candidates for the use in many fields, such as thermal storage [66], electrochemical applications, homogeneous catalysis [67], dye sensitized solar cells [68], and lubricants [69,70]. 

The types of ionic liquids shown in Figure 5.4 have been most extensively studied, especially ones based on chloroaluminate. Whilst these chloroaluminate materials also display useful Lewis acid properties they are highly air and moisture sensitive, which renders them relatively commercially unattractive. Newer ionic liquids containing C104 and NOa anions, for example, which are less air and moisture sensitive, are now being more widely studied, but these are less catalytically active. Other than lack of vapour pressure and catalytic properties there are several other features common to most ionic liquids that make them attractive reaction solvents. These include ... 

Recently, there has been considerable interest in developing molten salts that are less air and moisture sensitive. Melts such as l-methyl-3-butylimidazolium hexa-fluorophosphate [211], l-ethyl-3-methylimidazolium trifluoromethanesulfonate [212], and l-ethyl-3-methylimidazolium tetrafluoroborate [213] are reported to be hydro-phobic and stable under environmental conditions. In some cases, metal deposition from these electrolytes has been explored [214]. They possess a wide potential window and sufficient ionic conductivity to be considered for many electrochemical applications. Of course if one wishes to take advantage of their potential air stability, one loses the opportunity to work with the alkali and reactive metals. Further, since these ionic liquids are neutral and lack the adjustable Lewis acidity common to the chloroaluminates, the solubility of transition metal salts into these electrolytes may be limited. On a positive note, these electrolytes are significantly different from the chloroaluminates in that the supporting electrolyte is not intended to be electroactive. 

In 1992, the ionic liquid methodology received a substantial boost when Wilkes and Zaworotko described the synthesis of non-chloroaluminate, room temperature liquid melts (e. g. low melting tetrafluoroborate melts) which may be regarded as second generation ionic liquids [6]. Nowadays, tetrafluoroborate and (the slightly later published [7]) hexafluorophosphate ionic liquids are still widely used in ionic liquid research. However, their use in many technical applications will be clearly limited by their relatively high sensitivity towards hydrolysis. Of course, the tendency of their anions to hydrolyse is much less pronounced than for the chloroaluminate melts but it still clearly exists. Consequently, the technical application of tetrafluoroborate and hexafluorophosphate ionic liquids will be effectively restricted to those applications where water-free conditions can be realised at acceptable costs. 

Another type of chiral rhodium complex [Rh-MeDuPHOS] was also immobilized in [BMIM][PF6] and used in the enantiomeric hydrogenation of related enamides [95] (Fig. 41.5). Geresh et al. focused their research on the stabilization of the air-sensitive catalyst in the air-stable ionic liquid, so that the complex was protected from attack by atmospheric oxygen and recycling was possible. 

Some ionic liquids (e.g. chloroaluminates) are highly sensitive to oxygen and water, which means they can only be used in an inert environment and that all substrates must be dried and degassed before use. 

Lei, B.-X. Fang, W.-J. Hou, Y.-F. Liao, J.-Y. Kuang, D.-B. Su, C.-Y., All-solid-state electrolytes consisting of ionic liquid and carbon black for efficient dye-sensitized solar cells. 

Halogen content If halogens in the anion are not crucial for specific reactions performed in the ionic liquid, they should be avoided. Moisture sensitivity, halogenide transfers, alcoholysis and toxic effects are often connected with halogen atoms in the molecule [27]. In addition, the hydrolysis products HCl or HF act corrosively. Within the project reported by Wasserscheid and coworkers they successfully developed ionic liquids with alkylsulfate groups as anions to overcome the halogen content. These new solvents show very favorable properties. 

It has been shown that metal-free Lewis acids have been applied as catalysts in a broad variety of reactions. However, in several cases the asymmetric induction in the reactions has to be improved. While many of the highly active salts are moisture sensitive, ionic liquids with the right choice of cation and anion, are quite stable. Therefore their catalytic Lewis acidic activity is weak. The research field presented still has much room for improvanent and further investigations and results are continuously reported in the literature in an uiCTeasing number due to the large potential of metal-free Lewis acids. 

In contrast to most of the high energy-density alkali and silver (NO- and NO2-substituted) methanides, the ionic liquids of these methanides with a bulky organic cation are neither heat nor shock sensitive, and hence can be prepared and stored in large scale. Nevertheless, this type of methanide-based ionic liquids can also be considered energetic ionic liquids since the thermodynamically unstable methanide anion is only kinetically... 

It has recently been demonstrated that solutes can be extracted from ionic liquids by perevaporation. This technique is based on the preferential partitioning of the solute from a liquid feed into a dense, non-porous membrane. The ionic liquids do not permeate the membrane. This technique can be applied to the recovery of volatile solutes from temperature-sensitive reactions such as bioconversions carried out in ionic liquids (34). 

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