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Phase Transfer and Related Methods

R. C. F. Jones, Phase Transfer and Related Methods , This Report. [Pg.428]

From time to time, we plan to devote space in the Reports to special topics which are undergoing rapid development or growth. In this first volume, for example, an additional chapter (Chapter 10) reports on the important growth area of Phase Transfer and Related Methods . Because of the enormous volume of review literature dealing with general and synthetic methods, we have sought to provide a service to readers and have compiled a comprehensive list of Reviews on General Synthetic Methods at the end of the Report. [Pg.453]

Applications to Phase-transfer and Related Methods.— The synthesis of vinyli-dene crowns, such as methylene-16-crown-5 (74), opens a new avenue to funtionalized crown moleculesfor example, after hydration (74) can lead to the new immobilized crown (75) that acts as a phase-transfer (PT) catalyst in the halogen exchange of 1-bromo-octane with KI. [Pg.159]

SECM-Induced Transfer and Related Methods in Two-Phase Systems.428... [Pg.417]

SECM-INDUCED TRANSFER AND RELATED METHODS IN TWO-PHASE SYSTEMS... [Pg.428]

The efficiencies which may be obtained can consequently be calculated by simple stoichiometry from the equilibrium data. In the ease of countercurrent-packed columns, the solute can theoretically be completely extracted, but equilibrium is not always reached because of the poorer contact between the phases. The rate of solute transfer between phases governs the operation, and the analytical treatment of the performance of such equipment follows closely the methods employed for gas absorption. In the ease of two immiscible liquids, the equilibrium concentrations of a third component in each of the two phases are ordinarily related as follows ... [Pg.326]

Tomoi and coworkers adopted a somewhat more direct approach in their synthesis of 16-crown-5 derivatives bearing a single alkenyl residue. They hoped to obtain precursors to polymers which could be used as phase transfer catalysts. In this approach I,I-bis-chloromethylethylene (a-chloromethallyl chloride) was allowed to react with the dianion of tetraethylene glycol (NaH/THF). By this method, methylene-16-crown-5 could be isolated in 66% yield after vacuum distillation. Ozonolysis led, in almost quantitative yield, to the formation of oxo-16-crown-5 as shown in Eq. (3.38). These authors prepared a number of other, closely related species by similar methods. [Pg.40]

Amides are very weak nucleophiles, far too weak to attack alkyl halides, so they must first be converted to their conjugate bases. By this method, unsubstituted amides can be converted to N-substituted, or N-substituted to N,N-disubstituted, amides. Esters of sulfuric or sulfonic acids can also be substrates. Tertiary substrates give elimination. O-Alkylation is at times a side reaction. Both amides and sulfonamides have been alkylated under phase-transfer conditions. Lactams can be alkylated using similar procedures. Ethyl pyroglutamate (5-carboethoxy 2-pyrrolidinone) and related lactams were converted to N-alkyl derivatives via treatment with NaH (short contact time) followed by addition of the halide. 2-Pyrrolidinone derivatives can be alkylated using a similar procedure. Lactams can be reductively alkylated using aldehydes under catalytic hydrogenation... [Pg.513]

Preparing isotopically enriched carbonyls and related species is not always a trivial problem. We have recently developed (20) a method which looks particularly promising in some cases. CW CO2 laser irradiation of a gas phase mixture containing SF5 as an energy transfer agent can promote thermal chemistry without complications due to wall reactions, e.g. [Pg.38]

In one of the earliest studies of phase-transfer catalysed reactions, Makosza and his research group generated dichlorocarbene using a catalytic amount of benzyltriethyl-ammonium chloride in an aqueous sodium hydroxiderchloroform two-phase system [2, 3] and it has become the standard method for the phase-transfer catalytic production of dichlorocarbene and related dihalocarbenes. [Pg.303]

Keller, W. E. Ed., "Compendium of Phase-Transfer Reactions and Related Synthetic Methods," Fluka AG, CH-9470 Buchs, Switzerland, 1979. [Pg.183]

Electrodeposition is by its nature a condensed phase process, whereas most studies of ALE have been performed using gas phase or vacuum methodologies, CVD or MBE. A solution phase deposition methodology related to ALE has been developed in France by Nicolau et al. [27-32] (Fig. 2), in which adsorbed layers of elements are formed by rinsing a substrate in aqueous solutions containing ionic precursor for the desired elements, sequentially, in a cycle. After exposure to each precursor, the substrate is copiously rinsed and then transferred to a solution containing the precursor for the next element. The method is referred to as successive ionic layer adsorption and reaction (SILAR). Reactivity in SILAR appears to be controlled by the rinsing procedure, solution composition, pH, and specifically... [Pg.78]

Kinetic Acidities in the Condensed Phase. For very weak acids, it is not always possible to establish proton-transfer equilibria in solution because the carbanions are too basic to be stable in the solvent system or the rate of establishing the equilibrium is too slow. In these cases, workers have turned to kinetic methods that rely on the assumption of a Brpnsted correlation between the rate of proton transfer and the acidity of the hydrocarbon. In other words, log k for isotope exchange is linearly related to the pK of the hydrocarbon (Eq. 13). The a value takes into account the fact that factors that stabilize a carbanion generally are only partially realized at the transition state for proton transfer (there is only partial charge development at that point) so the rate is less sensitive to structural effects than the pAT. As a result, a values are expected to be between zero and one. Once the correlation in Eq. 13 is established for species of known pK, the relationship can be used with kinetic data to extrapolate to values for species of unknown pAT. [Pg.94]


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And phase transfer

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Method transfer

Phase relations

Phase transfer method

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