Ionic liquids halides

The alkylation process possesses the advantages that (a) a wide range of cheap haloalkanes are available, and (b) the substitution reactions generally occur smoothly at reasonable temperatures. Furthermore, the halide salts formed can easily be converted into salts with other anions. Although this section will concentrate on the reactions between simple haloalkanes and the amine, more complex side chains may be added, as discussed later in this chapter. The quaternization of amines and phosphines with haloalkanes has been loiown for many years, but the development of ionic liquids has resulted in several recent developments in the experimental techniques used for the reaction. In general, the reaction may be carried out with chloroalkanes, bromoalkanes, and iodoalkanes, with the reaction conditions required becoming steadily more gentle in the order Cl Br I, as expected for nucleophilic substitution reactions. Fluoride salts cannot be formed in this manner. 

The anion-exchange reactions of ionic liquids can really be divided into two distinct categories direct treatment of halide salts with Lewis acids, and the formation of ionic liquids by anion metathesis. These two approaches are dealt with separately, as quite different experimental methods are required for each. 

All the halide exchange reactions mentioned above proceed more or less quantitatively, causing greater or lesser quantities of halide impurities in the final product. The choice of the best procedure to obtain complete exchange depends mainly on the nature of the ionic liquid that is being produced. Unfortunately, there is no general method to obtain a halide-free ionic liquid that can be used for all types of ionic liquid. This is explained in a little more detail for two defined examples the synthesis of [BMIM][(CF3S02)2N] and the synthesis of [EMIM][BF4]. 

Apart from halide and protic impurities, ionic liquids can also be contaminated with other ionic impurities from the metathesis reaction. This is especially likely if the alkali salt used in the metathesis reaction shows significant solubility in the... 

Without special drying procedures and completely inert handling, water is omnipresent in ionic liquids. Even the apparently hydrophobic ionic liquid [BMIM][(CF3S02)2N] saturates with about 1.4 mass% of water [15], a significant molar amount. For more hydrophilic ionic liquids, water uptake from air can be much greater. Imidazolium halide salts in particular are laiown to be extremely hygroscopic, one of the reasons why it is so difficult to make completely proton-free chloroaluminate ionic liquids. 

For all research carried out with commercial ionic liquids we recommend a serious quality check of the product prior to work. As already mentioned, a good commercial ionic liquid may be colored and may contain some traces of water. However, it should be free of organic volatiles, halides (if not an halide ionic liquid), and all ionic impurities. 

Preparation of ionic liquids by treatment of amines with halide donors in the presence of metal halides [HNR3]C1/A1C13 Akzo Nobel NV, Netherlands 2000 31... 

The second element of general importance in the synthesis of a task-specific ionic liquid is the source of the functional group that is to be incorporated. Key to success here is the identification of a substrate containing two functional groups with different reactivities, one of which allows the attachment of the substrate to the core, and the other of which either is the functional group of interest or is modifiable to the group of interest. Functionalized alkyl halides are commonly used in this capacity, although the triflate esters of functionalized alcohols work as well. 

It must be noted that impurities in the ionic liquids can have a profound impact on the potential limits and the corresponding electrochemical window. During the synthesis of many of the non-haloaluminate ionic liquids, residual halide and water may remain in the final product [13]. Halide ions (Cl , Br , I ) are more easily oxidized than the fluorine-containing anions used in most non-haloaluminate ionic liquids. Consequently, the observed anodic potential limit can be appreciably reduced if significant concentrations of halide ions are present. Contamination of an ionic liquid with significant amounts of water can affect both the anodic and the cathodic potential limits, as water can be both reduced and oxidized in the potential limits of many ionic liquids. Recent work by Schroder et al. demonstrated considerable reduction in both the anodic and cathodic limits of several ionic liquids upon the addition of 3 % water (by weight) [14]. For example, the electrochemical window of dry [BMIM][BF4] was found to be 4.10 V, while that for the ionic liquid with 3 % water by weight was reduced to 1.95 V. In addition to its electrochemistry, water can react with the ionic liquid components (especially anions) to produce products... 

Tables 3.6-1 and 3.6-2 contain electrochemical potential windows for a wide variety of ionic liquids. Only limited information concerning the purity of the ionic liquids listed in Tables 3.6-1 and 3.6-2 was available, so these electrochemical potential windows must be treated with caution, as it is likely that many of the ionic liquids would have had residual halides and water present.

The charged species were in all cases found to concentrate at the surface of the liquid under vacuum conditions. Little surface separation of the anions and cations was observed. For the [PFg] and [BFJ ions, the cation ring was found to prefer a perpendicular orientation to the surface, with the nitrogen atoms closest to the surface. An increase in the alkyl chain length caused the cation to rotate so that the alkyl chain moved into the bulk liquid, away from the surface, forcing the methyl group closer to the surface. For halide ionic liquids, the data were less clear and the cation could be fitted to a number of orientations. 

These reactions occur with similar rates to those carried out in dipolar aprotic solvents such as DMF or DMSO. An advantage of using the room-temperature ionic liquid for this reaction is that the lower reaction temperatures result in higher selec-tivities for substitution on the oxygen or nitrogen atoms. The by-product (sodium or potassium halide) of the reaction can be extracted with water and the ionic liquid recycled. 

Friedel-Crafts acylation reactions usually involve the interaction of an aromatic compound with an acyl halide or anhydride in the presence of a catalyst, to form a carbon-carbon bond [74, 75]. As the product of an acylation reaction is less reactive than its starting material, monoacylation usually occurs. The catalyst in the reaction is not a true catalyst, as it is often (but not always) required in stoichiometric quantities. For Friedel-Crafts acylation reactions in chloroaluminate(III) ionic liquids or molten salts, the ketone product of an acylation reaction forms a strong complex with the ionic liquid, and separation of the product from the ionic liquid can be extremely difficult. The products are usually isolated by quenching the ionic liquid in water. Current research is moving towards finding genuine catalysts for this reaction, some of which are described in this section. 

Ionic liquids formed by treatment of a halide salt with a Lewis acid (such as chloro-aluminate or chlorostannate melts) generally act both as solvent and as co-catalyst in transition metal catalysis. The reason for this is that the Lewis acidity or basicity, which is always present (at least latently), results in strong interactions with the catalyst complex. In many cases, the Lewis acidity of an ionic liquid is used to convert the neutral catalyst precursor into the corresponding cationic active form. The activation of Cp2TiCl2 [26] and (ligand)2NiCl2 [27] in acidic chloroaluminate melts and the activation of (PR3)2PtCl2 in chlorostannate melts [28] are examples of this land of activation (Eqs. 5.2-1, 5.2-2, and 5.2-3). 

As one would expect, in those cases in which the ionic liquid acts as a co-catalyst, the nature of the ionic liquid becomes very important for the reactivity of the transition metal complex. The opportunity to optimize the ionic medium used, by variation of the halide salt, the Lewis acid, and the ratio of the two components forming the ionic liquid, opens up enormous potential for optimization. However, the choice of these parameters may be restricted by some possible incompatibilities with the feedstock used. Undesired side reactions caused by the Lewis acidity of the ionic liquid or by strong interaction between the Lewis acidic ionic liquid and, for example, some oxygen functionalities in the substrate have to be considered. 

Acidic chloroaluminate ionic liquids have already been described as both solvents and catalysts for reactions conventionally catalyzed by AICI3, such as catalytic Friedel-Crafts alkylation [35] or stoichiometric Friedel-Crafts acylation [36], in Section 5.1. In a very similar manner, Lewis-acidic transition metal complexes can form complex anions by reaction with organic halide salts. Seddon and co-workers, for example, patented a Friedel-Crafts acylation process based on an acidic chloro-ferrate ionic liquid catalyst [37]. 

The authors describe a stabilizing effect of the ionic liquid on the palladium catalyst. In almost all reactions no precipitation of elemental palladium was observed, even at complete conversion of the aromatic halide. The reaction products were isolated by distillation from the nonvolatile ionic liquid. 

It is noteworthy that the best results could be obtained only with very pure ionic liquids and by use of an optimized reactor set-up. The contents of halide ions and water in the ionic liquid were found to be crucial parameters, since both impurities poisoned the cationic catalyst. Furthermore, the catalytic results proved to be highly dependent on all modifications influencing mass transfer of ethylene into the ionic catalyst layer. A 150 ml autoclave stirred from the top with a special stirrer... 

A co-solvent that is poorly miscible with ionic liquids but highly miscible with the products can be added in the separation step (after the reaction) to facilitate the product separation. The Pd-mediated FFeck coupling of aryl halides or benzoic anhydride with alkenes, for example, can be performed in [BMIM][PFg], the products being extracted with cyclohexane. In this case, water can also be used as an extraction solvent, to remove the salt by-products formed in the reaction [18]. From a practical point of view, the addition of a co-solvent can result in cross-contamination, and it has to be separated from the products in a supplementary step (distillation). More interestingly, unreacted organic reactants themselves (if they have nonpolar character) can be recycled to the separation step and can be used as the extractant co-solvent. 

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