Catalysis triphasic

Phases. Often there are two Hquid phases (Hquid—Hquid PTC) or one soHd, one Hquid (soHd—Hquid PTC). If the catalyst is bound to a polymeric matrix this may comprise a third phase (triphase catalysis). Examples of gas—Hquid, gas—soHd, and soHd—soHd PTC are stiH relatively rare. In the latter two cases, a small amount of Hquid, eg, water, is probably present as an uimoticed third phase. 

In practice, 1—10 mol % of catalyst are used most of the time. Regeneration of the catalyst is often possible if deemed necessary. Some authors have advocated systems in which the catalyst is bound to a polymer matrix (triphase-catalysis). Here separation and generation of the catalyst is easy, but swelling, mixing, and diffusion problems are not always easy to solve. Furthermore, triphase-catalyst decomposition is a serious problem unless the active groups are crowns or poly(ethylene glycol)s. Commercial anion exchange resins are not useful as PT catalysts in many cases. 

The asymmetric epoxidation of enones with polyleucine as catalyst is called the Julia-Colonna epoxidation [27]. Although the reaction was originally performed in a triphasic solvent system [27], phase-transfer catalysis [28] or nonaqueous conditions [29] were found to increase the reaction rates considerably. The reaction can be applied to dienones, thus affording vinylepoxides with high regio- and enantio-selectivity (Scheme 9.7a) [29]. 

Crown ethers attached to insoluble polymeric substrates (see the following discussion for examples) have been used as phase transfer catalysts for liquid/liquid systems. In using such systems, the catalyst forms a third insoluble phase the procedure being referred to as triphase catalysis (Regen, 1979). This arrangement has the advantage that, on completion of the reaction, the catalyst may be readily separated from the reaction solution and recycled (Montanari, Landini Rolla, 1982). As... 

A particularly ingenious approach is that of triphase catalysis which was developed by Regen (1979). The catalyst is a quaternary ammonium residue which is covalently bound to an insoluble polystyrene resin, and reactions of anionic reagents are carried out in a two-phase water-organic solvent mixture. 

As with classical multiphase catalysis, the organometallic catalyst is retained here in a liquid phase that is immiscible with the second phase containing substrates and/or products. For hydrogenation, the liquid/SCF system is always biphasic, whereas conventional systems are usually triphasic (liquid-1 /liquid-2/ H2). The liquid phase must provide a stable environment for the organometallic catalyst and should be insoluble in the SCF phase. Water, ILs and PEG have been used successfully for this purpose, together with scC02 as the mobile phase. Again, the products must not be too polar in order to be effectively extracted if C02 is used as the SCF. 

Phase transfer catalysis can be conducted under liquid-liquid conditions, liquid-solid conditions, or liquid-liquid-solid triphasic conditions. 

With a view to producing catalysts that can easily be removed from reaction products, typical phase-transfer catalysts such as onium salts, crown ethers, and cryptands have been immobilized on polymer supports. The use of such catalysts in liquid-liquid and liquid-solid two-phase systems has been described as triphase catalysis (Regen, 1975, 1977). Cinquini et al. (1976) have compared the activities of catalysts consisting of ligands bound to chloromethylated polystyrene cross-linked with 2 or 4% divinylbenzene and having different densities of catalytic sites ([126], [127], [ 132]—[ 135]) in the... 

Triphase catalysis is applicable not only to liquid-liquid-solid (L, L, S) systems, but also to liquid-solid-solid (L, S, S) systems. For instance, McKenzie and Sherrington (1978) studied the substitution of phenoxide for bromide in 1-bromobutane using immobilized polyethyleneglycol monoethers such as [131] as triphase catalyst they found (Table 38) that under L, L, S... 

There are numerous types of multiphasic chemical processes. The most common are biphasic although triphasic, tetraphasic and even higher number of phases can also be used to conduct chemical synthesis. All the multiphasic methods aim to overcome the major problem of homogeneous catalysis, which is catalyst recovery and product separation. The simplest systems are biphasic ones that involve immobilizing a catalyst in one solvent, which is immiscible with a second solvent in which the substrates/products are dissolved. If a gas is required as a substrate then the system could be regarded as triphasic (i.e. liquid-liquid-gas), although for the purposes of this book (and as is most commonly defined elsewhere) such as system will be referred to as biphasic. In other words, only the number of different liquid solvent phases will be used to define the phasicity of a system. 

There are various combinations of solvents that lead to the different biphasic and triphasic systems described in Section 2.1 that have found applications in synthesis and catalysis. For practical purposes, it is essential that the catalyst and product... 

The combined catalysis by 18-crown-6 and tetra-n-butylammonium bromide produces higher yields in shorter reaction times than either of the catalysts separately (Table 3.7) [21] and almost quantitative yields have been reported for solid solid liquid triphase catalysed esterification using silica impregnated with tetramethylammonium chloride [22]. 

The simplest C-C bond formation reaction is the nucleophilic displacement of a halide ion from a haloalkane by the cyanide ion. This was one of the first reactions for which the kinetics under phase-transfer catalysed conditions was investigated and patented [l-3] and is widely used [e.g. 4-12], The reaction has been the subject of a large number of patents and it is frequently used as a standard reaction for the assessment of the effectiveness of the catalyst. Although the majority of reactions are conducted under liquiddiquid two-phase conditions, it has also been conducted under solidrliquid two-phase conditions [13] but, as with many other reactions carried out under such conditions, a trace of water is necessary for optimum success. Triphase catalysis [14] and use of the preformed quaternary ammonium cyanide [e.g. 15] have also been applied to the conversion of haloalkanes into the corresponding nitriles. Polymer-bound chloroalkanes react with sodium cyanide and cyanoalkanes under phase-transfer catalytic conditions [16],... 

Catalysts have been bonded to insoluble polymers to allow, in principle, an appreciable simplification of PTC the catalyst represents a third insoluble phase which can be easily recovered at the end of the reaction by filtration, thus avoiding tedious processes of distillation, chromatographic separation and so on. This is of potential interest mainly from the industrial point of view, due to the possibility of carrying on both discontinuous processes with a dispersed catalyst and continuous processes with the catalyst on a fixed bed. This technique was named "triphase catalysis" by Regen (13,33,34). 

Triphase Catalysis by Quaternary Ammonium and Phosphonium Ions. 57... 

The method and speed of mixing affect observed rates in triphase catalysis when the chemical reactions are fast. For the reaction of 1-bromooctane in toluene with aqueous sodium cyanide (Eq. (3))... 

Intraparticle diffusion limits rates in triphase catalysis whenever the reaction is fast enough to prevent attaiment of an equilibrium distribution of reactant throughout the gel catalyst. Numerous experimental parameters affect intraparticle diffusion. If mass transfer is not rate-limiting, particle size effects on observed rates can be attributed entirely to intraparticle diffusion. Polymer % cross-linking (% CL), % ring substitution (% RS), swelling solvent, and the size of reactant molecule all can affect both intrinsic reactivity and intraparticle diffusion. Typical particle size effects on the... 

The most important point about the alkyl halide reactivities in triphase catalysis is that the reactions which have the highest intrinsic rates are the most likely to be limited by intraparticle diffusion. The cyanide ion reactions which showed the greatest particle size and cross-linking dependence with 1-bromooctane had half-lives of 0.5 to 2 h and with benzyl bromide had half-lives of 0.13 to 0.75 h. The reactions of 1-bromooctane and of benzyl chloride which were insensitive to particle size and cross-linking had half-lives of 14 h and 3 h respectively. Practical triphase liquid/ liquid/solid catalysis with polystyrene-bound onium ions has intraparticle diffusional limitations. 

The % ring substitution of the polymer is a critical factor in catalytic activity. Its importance was demonstrated clearly in Regen s first full paper on triphase catalysis 89). Catalysts 2 and 13 (2% CL) were active for cyanide displacement on 1-bromooctane (Eq. (3)) only at 21 % or lower RS (Table 3). Commerical anion exchange resins, polystyrenes highly substituted as benzyltrimethylammonium ions 2 or benzyldimethyl-(2-hydroxyethyl)ammonium ions 14, were inactive. 

Substantial variations of the organic solvent used in triphase catalysis with polystyrene-bound onium ions have been reported only for the reactions of 1-bromo-octane with iodide ion (Eq. (4))74) and with cyanide ion (Eq. (3)) 73). In both cases observed rate constants increased with increasing solvent polarity from decane to toluene to o-dichlorobenzene or chlorobenzene. Since the swelling of the catalysts increased in the same order, and the experiments were performed under conditions of partial intraparticle diffusional control, it is not possible to determine how the solvents affected intrinsic reactivity. 

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