Organic-Phase Method

A Polar Organic Phase Method Development Protocol for CYCLOBOND 1 2000... 

In 2000, Sun et al researchers at IBM reported an elegant organic-phase method to prepare Fe-Pt magnetic nanoparticles with a diameter of 4-5 nm [129,180]. 

Figure 4.7 (a) Schematic illustration of the organic-phase method. Examples of catalysts prepared through this method, (b) PtFe nanoparticles [129]. (c) PtCr/C (28wt%, D = 23 nm... 

Memfield s concept of a solid phase method for peptide synthesis and his devel opment of methods for carrying it out set the stage for an entirely new way to do chem ical reactions Solid phase synthesis has been extended to include numerous other classes of compounds and has helped spawn a whole new field called combinatorial chemistry Combinatorial synthesis allows a chemist using solid phase techniques to prepare hun dreds of related compounds (called libraries) at a time It is one of the most active areas of organic synthesis especially m the pharmaceutical industry... 

A variety of methods have been devised to stabilize shales. The most successful method uses an oil or synthetic mud that avoids direct contact between the shale and the emulsified water. However, preventing direct contact does not prevent water uptake by the shale, because the organic phase forms a semipermeable membrane on the surface of the wellbore between the emulsified water in the mud and the water in the shale. Depending on the activity of the water, it can be drawn into the shale (activity lower in the shale) or into the mud (activity higher in the shale) (95—97). This osmotic effect is favorable when water is drawn out of the shale thus the aqueous phase of the oil or synthetic mud is maintained at a low water activity by a dding a salt, either sodium chloride or more commonly, calcium chloride. The salt concentration is carried somewhat above the concentration required to balance the water activity in the shale to ensure water movement into the mud. 

Many techniques have been developed to accomplish this, for example, the use of a cooled recirculating system in which the chlorine is dissolved in one part and the allyl chloride is dissolved and suspended in another (61). The streams are brought together in the main reaction zone and thence to a separator to remove water-insoluble products. Another method involves maintaining any organic phase present in the reaction zone in a highly dispersed condition (62). A continuous reactor consists of a recycle system in which make-up water and allyl chloride in a volume ratio of 10—50 1 are added... 

One patent (64) describes an extraction method to remove both trichloropropane and tetrachloropropyl ether from the dichi orohydrin solution by the use of carbon tetrachloride as a solvent. In this way the by-products are removed from the aqueous phase iato an organic phase from which they can be separated by distillation and disposed of ia a safe and proper manner. 

Product recoveiy from reversed micellar solutions can often be attained by simple back extrac tion, by contacting with an aqueous solution having salt concentration and pH that disfavors protein solu-bihzation, but this is not always a reliable method. Addition of cosolvents such as ethyl acetate or alcohols can lead to a disruption of the micelles and expulsion of the protein species, but this may also lead to protein denaturation. These additives must be removed by distillation, for example, to enable reconstitution of the micellar phase. Temperature increases can similarly lead to product release as a concentrated aqueous solution. Removal of the water from the reversed micelles by molecular sieves or sihca gel has also been found to cause a precipitation of the protein from the organic phase. 

The influence of temperature, solution s pH and other parameters in formation of ionic associate is investigated. As a result, optimal conditions of determination are established pH 4,0 volume of acetate buffer - 0,5 ml volume of 0,1% aqueous solution of CV - 0,3 ml extraction time - 3 minutes. The ratio of aqueous and organic phases is 1 1. Photometric measurement of toluene layer is carried out at = 606,0 nm. The accuracy of procedures checked by the method of additives. 

There are a number of the optimal conditions for sorption pointed below volume of extract - 4 ml ratio of aqueous and organic phases is 1 1 cyllindric foampolyurethan (marc - T 25-3,8) with diameter 8 mm, height - 4,5 mm, mass - 0.007 g. Time of full soi ption is 20 min. Completeness of soi ption is determined by spectrophotometric method. 

Relationships connecting stmcture and properties of primary alkylamines of normal stmcture C, -C gin chloroform and other solvents with their ability to extract Rh(III) and Ru(III) HCA from chloride solutions have been studied. The out-sphere mechanism of extraction and composition of extracted associates has been ascertained by UV-VIS-, IR-, and H-NMR spectroscopy, saturation method, and analysis of organic phase. Tertiary alkylamines i.e. tri-n-octylamine, tribenzylamine do not extract Ru(III) and Rh(III) HCA. The decrease of radical volume of tertiary alkylamines by changing of two alkyl radicals to methyl make it possible to diminish steric effects and to use tertiary alkylamines with different radicals such as dimethyl-n-dodecylamine which has not been used previously for the extraction of Rh(III), Ru(III) HCA with localized charge. 

High tendency of ZnfSCN) ion to extraction into organic phase is widely used for zinc determination by extraction photometry method. Recently it was shown that when single-chai ged anions ai e exchanged for double-chai ged ones, the selectivity of this process depends on the number of methyl substitutients in quaternary ammonium salt (QAS) cation. 

In most situations the eluent composition is chosen to minimize the effects of hydrophobic interaction, but these secondary effects can be used to advantage. By careful selection of a salt and its concentration, specific selectivities for analytes can be achieved without the use of organic solvents. Therefore, many separations usually run by solvent gradient reversed-phase methods can be completed with a purely aqueous isocratic eluent (13,14). 

Phase-transfer catalysis (Section 22.5) Method for increasing the rate of a chemical reaction by transporting an ionic reactant from an aqueous phase where it is solvated and less reactive to an organic phase where it is not solvated and is more reactive. Typically, the reactant is an anion that is carried to the organic phase as its quaternary ammonium salt. 

Soapless seeded emulsion copolymerization has been proposed as an alternative method for the preparation of uniform copolymer microspheres in the submicron-size range [115-117]. In this process, a small part of the total monomer-comonomer mixture is added into the water phase to start the copolymerization with a lower monomer phase-water ratio relative to the conventional direct process to prevent the coagulation and monodispersity defects. The functional comonomer concentration in the monomer-comonomer mixture is also kept below 10% (by mole). The water phase including the initiator is kept at the polymerization temperature during and after the addition of initial monomer mixture. The nucleation takes place by the precipitation of copolymer macromolecules, and initially formed copolymer nuclei collide and form larger particles. After particle formation with the initial lower organic phase-water ratio, an oligomer initiated in the continuous phase is... 

The oxidation methods described previously are heterogeneous in nature since they involve chemical reactions between substances located partly in an organic phase and partly in an aqueous phase. Such reactions are usually slow, suffer from mixing problems, and often result in inhomogeneous reaction mixtures. On the other hand, using polar, aprotic solvents to achieve homogeneous solutions increases both cost and procedural difficulties. Recently, a technique that is commonly referred to as phase-transfer catalysis has come into prominence. This technique provides a powerful alternative to the usual methods for conducting these kinds of reactions. 

The second method is based on selective extraction that consists of extraction into two different organic solutions. In the first step, tantalum is extracted into an organic phase. In the second step of the procedure, niobium is extracted into a separate portion of the extractant. Fig. 126 presents a flow chart of the process based on the selective extraction scheme. 

Method A MsOH (0.96 g, 10 mmol) was added to a suspension of salicylohydrazide (1 1.52 g, 10 mmol) in toluene (50 mL) and the mixture was stirred for 10 min. An acid chloride or anhydride (10 mmol) was added and the mixture was heated under reflux for a specified time. The mixture was cooled, neutralized with sat. aq NaHCO, and the layers were separated. The aqueous layer was extracted with CH2C12 (2 x 20 mL) and the combined organic phases were dried (MgS04) and evaporated in vacuo. Chromatography (silica gel, CH2C12) gave the product, which separated from EtOH as colorless crystals. 

Phase-transfer catalysed oxidation of sulphoxides to sulphones using copper(II) permanganate or a mixture of potassium permanganate and copper(II) sulphate is also possible156. In this case hexane is used as the solvent for the organic phase and the reaction is carried out under reflux for 24 hours. Sulphones are prepared by this method in quantitative yields and the mechanism proposed is given in equation (51). 

This latter situation affords a good method for separating uranium from plutonium. Hydroxylammonium formate (HAF) and hydrazium formate (NHF) were added to the formic acid to reduce Pu(IV) to Pu(III) to aid in plutonium recovery, although formic acid alone will strip tetravalent actinides, e.g., Th(IV) from 0D[IB]CMP0, once excess HNO3 present in the organic phase is removed. Thus, formic acid with HAF and NHF affords an excellent method for stripping all the actinides from these very powerful CMP extractants. Under the above conditions Am(III) and Cm(III) present in... 

One-phase titration methods have also been developed. These methods are not truly one-phase titrations but the term is used to indicate the absence of a second organic phase. One of these methods, applied to the analysis of sodium and triethanolamine lauryl sulfates and lauryl ether sulfates, use a quaternary amine as a titrant and cobalt(II) thiocyanate as indicator. Centrimide was found to avoid the use of chloroform which was not possible with other titrants examined, such as domiphen bromide and oxyphenonium bromide. The pink color of the indicator changes to violet as an excess of titrant forms a complex with the indicator [238]. 

Methode 1 lm Reaktionskolben legt man 40 ml Diathylather und 5 mMol Sulfoxid vor und kiihlt mit einem Wasserbad. Unter Riihren gibt man rasch das Titan(IV)-chlorid und anschlieBend in kleinen Portionen den Zink-staub zu. Nach 1 Min. gibt man 50 ml Wasser zu, trennt die organ. Phase ab, wascht sie mit Wasser, trocknet, engt ein und chromatographiert den Riickstand mit Hexan oder Pentan an Kieselgel. 

In this method, a catalyst is used to carry the nucleophile from the aqueous into the organic phase. As an example, simply heating and stirring a two-phase mixture of 1-chlorooctane for several days with aqueous NaCN gives essentially no yield of 1-cyanooctane. But if a small amount of an appropriate quaternary ammonium salt is added, the product is quantitatively formed in about 2 h." There are two principal types of phase-transfer catalyst. Though the action of the two types is somewhat different, the effects are the same. Both get the anion into the organic phase and allow it to be relatively free to react with the substrate. 

The theory and development of a solvent-extraction scheme for polynuclear aromatic hydrocarbons (PAHs) is described. The use of y-cyclodextrin (CDx) as an aqueous phase modifier makes this scheme unique since it allows for the extraction of PAHs from ether to the aqueous phase. Generally, the extraction of PAHS into water is not feasible due to the low solubility of these compounds in aqueous media. Water-soluble cyclodextrins, which act as hosts in the formation of inclusion complexes, promote this type of extraction by partitioning PAHs into the aqueous phase through the formation of complexes. The stereoselective nature of CDx inclusion-complex formation enhances the separation of different sized PAH molecules present in a mixture. For example, perylene is extracted into the aqueous phase from an organic phase anthracene-perylene mixture in the presence of CDx modifier. Extraction results for a variety of PAHs are presented, and the potential of this method for separation of more complex mixtures is discussed. 

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