Biphasic systems

Hypochlorite readily chlorinates phenols to mono-, di-, and tri-substituted compounds (163). In wastewater treatment chlotophenols ate degraded by excess hypochlorite to eliminate off-flavor (164). Hypochlorite converts btomoben2ene to cb1oroben2ene in a biphasic system at pH 7.5—9 using phase-transfer catalysts (165). 

Saturated hydrocarbons can be chlorinated in moderate yields under mild conditions in a biphasic system consisting of alkaline hypochlorite solution and CH2CI2 containing Ni(Il) bis(saHcyHdene)ethylenediamine as chlorination catalyst and bexadecyltrimetbylammonium bromide as phase-transfer catalyst (166). 

Where Water Hammer Occurs. Water hammer can occur in any water supply line, hot or cold. Its effects can be even more pronounced in heterogeneous or biphase systems. Biphase systems carry water in two states, as a liquid and as a gas. Such a condition exists in a steam system where condensate coexists with live or flash steam in heat exchangers, tracer lines, steam mains, condensate return lines and, in some cases, pump discharge lines. 

Thermal shock In biphase systems, steam bubbles may become trapped in pools of condensate in a flooded main, branch, or tracer line, as well as in heat exchanger tubing and pumped condensate lines. Since condensate temperature is almost always below saturation, the steam will immediately collapse. 

Differential shock Differential shock, like thermal shock, occurs in biphase systems. It can occur whenever steam and condensate flow in the same line, but at different velocities, such as in condensate return lines. 

In biphase systems velocity of the steam is often 10 times the velocity of the liquid. If condensate waves rise and fill a pipe, a seal is formed with the pressure of the steam behind it (Fig. 2). Since the steam cannot flow through the condensate seal, pressure drops on the downstream side. The condensate seal now becomes a piston accelerated downstream by this pressure differential. As it is driven downstream it picks up more liquid, which adds to the existing mass of the slug, and the velocity increases. 

To control differential shock, the condensate seal must be prevented from forming in a biphase system. Steam mains must be properly pitched, condensate lines must be sized and pitched correctly, and long vertical drops to traps must be back-vented. The length of lines to traps should be minimized, and pipes may have to be insulated to prevent water hammer. 

Extractions and separations in two-phase systems require knowledge of the miscibilities and immiscibilities of ILs with other solvents compatible with the process. These are most usually IL/aqueous biphase systems in which the IL is the less polar phase and organic/IL systems in which the IL is used as the polar phase. In these two-phase systems, extraction both to and from the IL phase is important. 

Transition metal catalysis in liquid/liquid biphasic systems principally requires sufficient solubility and immobilization of the catalysts in the IL phase relative to the extraction phase. Solubilization of metal ions in ILs can be separated into processes, involving the dissolution of simple metal salts (often through coordination with anions from the ionic liquid) and the dissolution of metal coordination complexes, in which the metal coordination sphere remains intact. 

Another interesting recent development is the continuous, Rh-catalyzed hydroformylation of 1-octene in the unconventional biphasic system [BMIM][PF6]/scC02, described by Cole-Hamilton et al. [84]. This specific example is described in more detail, together with other recent work in ionic liquid/scC02 systems, in Section 5.4. 

The reaction was carried out in an ionic liquid/toluene biphasic system, which allowed easy product recovery from the catalyst by decantation. However, attempts to recycle the ionic catalyst phase resulted in significant catalyst deactivation after only the third recycle. 

When the products are partially or totally miscible in the ionic phase, separation is much more complicated (Table 5.3-2, cases c-e). One advantageous option can be to perform the reaction in one single phase, thus avoiding diffusional limitation, and to separate the products in a further step by extraction. Such technology has already been demonstrated for aqueous biphasic systems. This is the case for the palladium-catalyzed telomerization of butadiene with water, developed by Kuraray, which uses a sulfolane/water mixture as the solvent [17]. The products are soluble in water, which is also the nucleophile. The high-boiling by-products are extracted with a solvent (such as hexane) that is immiscible in the polar phase. This method... 

Despite all the advantages of this process, one main limitation is the continuous catalyst carry-over by the products, with the need to deactivate it and to dispose of wastes. One way to optimize catalyst consumption and waste disposal was to operate the reaction in a biphasic system. The first difficulty was to choose a good solvent. N,N -Dialkylimidazolium chloroaluminate ionic liquids proved to be the best candidates. These can easily be prepared on an industrial scale, are liquid at the reaction temperature, and are very poorly miscible with the products. They play the roles both of the catalyst solvent and of the co-catalyst, and their Lewis acidities can be adjusted to obtain the best performances. The solubility of butene in these solvents is high enough to stabilize the active nickel species (Table 5.3-3), the nickel... 

In the homogeneous Dimersol process, the olefin conversion is highly dependent on the initial concentration of monomers in the feedstock, which limits the applicability of the process. The biphasic system is able to overcome this limitation and promotes the dimerization of feedstock poorly concentrated in olefinic monomer. 

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]. 

Styrene it was possible to activate, tune, and immobilize the well-loiown Wilke complex by use of this unusual biphasic system (Scheme 5.4-3). Obviously, this reaction benefits from this special solvent combination in a new and highly promising manner. 

When either the organic solvent or the ionic liquid is used as pure solvent, proper control over the water content, or rather the water activity, is of crucial importance, as a minimum amount is necessary to maintain the enzyme s activity. For ionic liquids, a reaction can be operated at constant water activity by use of the same methods as established for organic solvents [17]. [BMIM][PFg] or [BMIM][(CF3S02)2N], for example, may be used as pure solvents and in biphasic systems. Water-miscible ionic liquids, such as [BMIM][BF4] or [MMIM][MeS04], can be used in the second case. 

Thanks to their special properties and potential advantages, ionic liquids may be interesting solvents for biocatalytic reactions to solve some of the problems discussed above. After initial trials more than 15 years ago, in which ethylammonium nitrate was used in salt/water mixtures [29], results from the use of ionic liquids as pure solvent, as co-solvent, or for biphasic systems have recently been reported. The reaction systems are summarized in Tables 8.3-1 and 8.3-2, below. Table 8.3-1 compiles all biocatalytic systems except lipases, which are shown separately in 8.3-2. Some of the entries are discussed in more detail below. 

In contrast to oxoesters, the a-protons of thioesters are sufficiently acidic to permit continuous racemization of the substrate by base-catalyzed deprotonation at the a-carbon. Drueckhammer et al. first demonstrated the feasibility of this approach by performing DKR of a propionate thioester bearing a phenylthiogroup, which also contributes to the acidity of the a-proton (Figure 4.14) [39a]. The enzymatic hydrolysis of the thioester was coupled with a racemization catalyzed by trioctylamine. Owing to the insolubility of the substrate and base in water, they employed a biphasic system (toluene/H2O). Using P. cepacia (Amano PS-30) as the enzyme and a catalytic amount of trioctylamine, they obtained a quantitative yield of the corresponding... 

Jacobs et al. employed an acidic zeolite catalyst for the racemization of sec-alcohols, which occurs through the formation of carbocations [44] (Figure 4.19). The KR is catalyzed by CALB in the presence of vinyl octanoate as acyl donor. DKR takes place successfully in a biphasic system (octane/H2O, 1 1) at 60 °C. 

Other metals can also be used as a catalytic species. For example, Feringa and coworkers <96TET3521> have reported on the epoxidation of unfunctionalized alkenes using dinuclear nickel(II) catalysts (i.e., 16). These slightly distorted square planar complexes show activity in biphasic systems with either sodium hypochlorite or t-butyl hydroperoxide as a terminal oxidant. No enantioselectivity is observed under these conditions, supporting the idea that radical processes are operative. In the case of hypochlorite, Feringa proposed the intermediacy of hypochlorite radical as the active species, which is generated in a catalytic cycle (Scheme 1). 

The application of this biphasic system to the asymmetric oxidation of arylmethylsulfides [9] did not lead to such successful results. Conversions (78-100%) and selectivities to sulfoxide (88-99%) were excellent, much better in general than in homogeneous phase, but enantioselectivities were always very low (up to 17% ee). 

On the other hand, 3-phenylpropionitrile was synthesized from Z-3-phenyl-propionaldoxime (0.75 M) in a quantitative yield (98gP ) by the use of cells of E. coli JM 109/pOxD-9OF, a transformant harboring a gene for a new enzyme, phenylacetaldoxime dehydratase, from Bacillus sp. strain OxB-1. Other arylalkyl- and alkyl-nitriles were also synthesized in high yields from the corresponding aldoximes. Moreover, 3-phenylpropionitrile was successfully synthesized by the recombinant cells in 70 and 100% yields from 0.1 M unpurified P/Z-3-phenylpropionaldoxime, which is spontaneously formed from 3-phenylpropionaldehyde and hydroxylamine in a butyl acetate/water biphasic system and aqueous phase, respectively. 

Recently, the use of ionic liquids instead of organic solvents has been published for the biphasic system. For PaHNL and SbHNL, the reaction rates are increased in comparison to organic solvents without a change of enantioselectivity. ... 

Hori H, A Yamamoto, S Kutsuna (2005b) Efficient photochemical decomposition of long-chain perfluorocarboxylic acids by means of an aqueous/liquid COj biphasic system. Environ Sci Technol 39 7692-7697. 

The efficient hydrogenation of various benzene compounds in biphasic systems has also been described by similar surfactant-protected irid-ium(O) nanoparticles [47]. The solubility of the nanoparticles was assured by 10 equivalents of water-soluble N,N-dimethyl-N-cetyl-Ar-(2-hydroxyethyl)-ammonium chloride salt. TEM observations show that the particles are monodispersed in size with an average diameter of 1.9 0.7 nm (Fig. 7). 

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