In two-phase systems

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. 

Since industrial nitration occurs, in most cases, in two-phase systems a number of workers have investigated the kinetics in both organic and acid phases (Refs 18b, 46 81). The consensus is that nitration occurs mainly in the acid phase. In what follows we will examine reaction rate effects in industrial-type nitrations for producing TNT, NG and EGDN... 

The stress acting on particles is of high importance for many technical processes. As well as dispersion processes in two-phase systems (liquid/liquid or gas/Hquid), where the disintegration of particles is desirable, there are also a number of processes that may be adversely affected by particle disintegration. These include precipitation, agglomeration, crystalHsation processes, and also bio conversion with immobilised enzymes and the fermentation of sensitive microorganisms and animal and plant cells. 

An unusual enhancement of catalytic activity in a two-phase system has been reported by Fremy et al. (1998) for the hydroformylation of acrylic esters using Rh complex of TPTS as catalyst. Even though acrylic esters have reasonable solubility in water, rate enhancements in two-phase systems by a factor of 2 to 14 have been reported. It seems that water is not an inert solvent but also acts as a reactant or a co-ordinating solvent which can modify elementary steps of the catalytic cycle (Cornilis, 1997). 

The role of biocatalysis in two-phase systems has many parallels with the subject we have covered under extractive reactions. It appears that a two-phase system was originally considered for transformations of water insoluble substances like steroids. Now, a series of treatises are available which teach us that the maximum value of the apparent equilibrium constant for a second-order reaction in a two-phase system can exceed the equilibrium... 

For instance, we study here the influence of the surrounding media on the behavior of two enzymatic reactions in two-phase systems ... 

Several micro-organism- or enzyme-catalyzed reactions are performed in two-phase systems (Table 1 and 4). The examples given illustrate the advantages of the procedure which may be of practical interest in technological applications of biocatalysts. 

For long chain olefins, the hydroformylation generally proceeds slowly and with low selectivity in two-phase systems due to their poor solubility in water. Monflier et al. recently reported a conversion of up to 100% and a regioselectivity of up to 95% for the Rh-catalyzed hydroformylation of dec-l-ene in water, free of organic solvent, in the presence of partially methylated 6-cyclodextrins (Eq. 3.42).173... 

Johansson, P.-A. Gustavii, K., Potentiometric titration of ionizable compounds in two phase systems. 2. Determination of partition coefficients of organic acids and bases, Acta Pharm. Suecica 13, 407 -20 (1976). 

Saha, P., M. Ishii, and N. Zuber, 1976, An Experimental Investigation of the Thermally Induced Flow Oscillations in Two-Phase Systems, Trans. ASME, J. Heat Transfer 95 616-622. (6)... 

The principles of conservation of mass and momentum must be applied to each phase to determine the pressure drop and holdup in two phase systems. The differential equations used to model these principles have been solved only for laminar flows of incompressible, Newtonian fluids, with constant holdups. For this case, the momentum equations become... 

HCN is the most preferred cyanide source in cyanohydrin synthesis. Besides HCN, several different cyanide sources, like potassium cyanide, are being used in biotransformation. Alternative methods for the safe handling of cyanides on a laboratory scale are, for instance, to use cyanide salts in solution. These solutions can be acidified and used as the aqueous layer in two-phase systems or the HCN can be extracted into the organic layer with the desired solvent for reactions in an organic phase. After the reaction, excess cyanide can readily be destroyed with iron(II) sulfate, or iron(III) chloride or bleach. Cyanide can also be presented in the form of organic cyano, such as acetone cyanohydrin [46] or cyanoformates. However, as claimed by Effenberger, some results could not be reproduced [47]. 

Acids that are used in addition to trifluoroacetic acid include trifluoroacetic acid with added sulfuric acid203 or boron trifluoride etherate,210,211 perfluorobu-tyric acid,212 hydrogen chloride/aluminum chloride,136,146,213 perchloric acid in chloroform,214 p-loluenesull onic acid alone134 or with aluminum bromide or aluminum chloride,192 concentrated sulfuric acid in two-phase systems with dichloromethane, alcohol, or ether solvents,209,215 trifluoromethanesulfonic acid,216 chlorodifluoroacetic acid,134 and the monohydrate of boron trifluoride... 

Landini et al. (1974, 1975) have studied nucleophilic substitutions in n-octyl derivatives in two-phase systems (substrate-water) catalysed by a mixture of dicyclohexyl-18-crown-6 isomers ([20] + [21]). They observed the following order of nucleophilicity I- > CN-, Br > Cl- > F (Table 32), which is... 

Most of these chiral recognition experiments with amino-acid ester salts were carried out in two-phase systems in which the organic solvents were... 

The preparation of phosphoramidates from dialkyl phosphites, using the Todd-Atherton procedure, has been carried out in two-phase systems containing a phase-transfer agent, for example benzyltriethylammonium chloride, at 5 mole % concentration.84... 

Quaternary ammonium salts are also known to promote nucleophilic substitution reactions in two-phase systems through the formation of micelles [15], but there is no evidence for micellar formation by bulky ammonium salts, such as tetra-n-buty-lammonium bromide, under liquidrliquid two-phase conditions [16]. 

Quaternary ammonium periodates, prepared either from periodic acid and the quaternary ammonium hydroxide [21, 22] or by metathesis from sodium periodate and a quaternary ammonium salt [e.g. 23-25], have been used for a range of oxidations at stoichiometric levels in two-phase systems [21-33], The tetra-n-butyl-ammonium and hexadecyltrimethylammonium salts are both highly soluble in organic solvents (considerably less so in water), whereas benzyltriethylammonium periodate has a lower solubility and stability than either salt. 

Rasmussen and co-workers. Chapter 10, have shown that many free-radical polymerizations can be conducted in two-phase systems using potassium persulfate and either crown ethers or quaternary ammonium salts as initiators. When transferred to the organic phase persulfate performs far more efficiently as an initiator than conventional materials such as azobisisobutyronitrile or benzoyl peroxide. In vinyl polymerizations using PTC-persulfate initiation one can exercise precise control over reaction rates, even at low temperatures. Mechanistic aspects of these complicated systems have been worked out for this highly useful and economical method of initiation of free-radical polymerizations. 

Quaternary onium salts were the first phase-transfer catalysts used subsequently, a number of compounds (linear polyethers, polypodands, crown-ethers, cryptands, cage-compounds, etc.) were found effective for the anion activation in two-phase systems. These structurally different systems must satisfy at least two fundamental conditions in order to behave as phase-transfer catalysts i) solubility in the organic phase ii) steric hindrance around the cationic center leading to a good cation-anion separation within the ion-pair. 

Both quaternary onium salts and cation complexes of lipophilic multidentate ligands (crown-ethers and cryptands) have been used as catalysts in two-phase systems in the presence of base (OH, F, etc.). However, under these conditions, the lack of chemical stability of quaternary salts and the very low complexation constants of multidentate ligands (especially crown-ethers) make all these systems barely effective in the activation of such anions. 

In this Chapter we shall look at hydrogenations both in one-phase and in two-phase systems organized according to the various reducible functional groups. However, early work, described adequately in [3] will be mentioned only briefly. 

Dehydropeptides were reduced (Scheme 3.9) on a preparative scale in two-phase systems with catalysts prepared in situ from [ RhCl(COD) 2] and chiral water-soluble ligands 35, 36, and 37 (Ch.2). The highest (87%) diastereoselectivity was obtained with [ RhCl(COD) 2] + tetrasuhbnated 2,4-bis(diphenylphosphino)pentane, BDPPTS, 36 [121]. 

In the preceeding paragraphs we described the effect of surfactants in reactions proceeding in a single liquid phase. A logical extension of this concept is in the use of surfactants in two-phase systems where their... 

A collection of cutting-edge methods intended to provide practical guidelines for those who are new to the area of separations in two-phase systems has been published by Hatti-Kaul [29]. 

Some insights can be obtained from the mechanisms of extraction in two-phase systems. As in conventional solvent extraction, the mechanism of transfer of the solute is either physical or chemical. In conventional solvent extraction, physical transfer is used for species that prefer the organic phase, i.e., their distribution coefficient D allows the use of conventional solvent extraction. In some cases of low solubility in the organic phase, microemulsions have proved to enhance extraction. An important example in this... 

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