Carbonylation of Benzyl Halides Over Two-Phase Catalyst of Iron Pentacarbonyl

Carbonylation of benzyl halides to phenylacetic acid was studied in a two-phase system with iron pentacarbonyl as the catalyst precursor. The solutions consisted of a benzyl halide and iron pentacarbonyl in benzene and tetrabutylammonium hydrogen sulfate in aqueous sodium hydroxide. Stirring under carbon monoxide readily produced phenylacetic salts in aqueous phase which were then acidified and extracted with ether. The yields of phenylacetic acid from benzyl iodide and from benzyl bromide were similar at a evel of about 50percnt;, that of the latter being higher by 1%. The yield from benzyl chloride was far less, at a level of only 21%. The rate as studied with gas chromatography was found to decrease in the order benzyl iodide>benzyl bromide>benzyl chloride.     

PREPARATION OF MICROGEL-EPOXY RESIN TWO-PHASE POLYMERS BY IN SITU POLYMERIZATION~*

Microgel-epoxy resin two-phase polymers were prepared by in situ copolymerization of ethylenic monomers with unsaturated polyesters. The choice of monomers and the effect of monomer concentration on microgel particle size were discussed. Agglomeration of particles played a significant role in the early stage of polymerization. The microgel dispersion in epoxy resin was stable after the finish of polymerization. Upon curing the particles remained well dispersed.     

阴阳离子型表面活性剂双水相萃取色氨酸衍生物和牛血清白蛋白

溴化十二烷基三乙胺（Ｃ１２ＮＥ）和十二烷基硫酸钠（ＳＤＳ）在一定条件下混合可以形成具有清晰界面的两个水相，称为阴阳离子型表面活性剂双水相。作者研究了利用该双水相萃取３种色氨酸衍生物和牛血清白蛋白的可能性．文中采用工作曲线校正扣除表面活性剂背景的影响，萃取结果准确可信。     

On the mechanism of growth of cells (Bacillus amyloliquefaciens) in the mixed aqueous two-phase system

The growth ofBacillus amyloliquefaciens in the aqueous two-phase system, made up of polyethylene glycol, dextran, and water, was investigated. Generally,Bacillus partitions in the dextran phase, but the magnitude of the separation depends largely on the overall composition of polymers in the phase system. The kinetics of growth ofBacillus amyloliquefaciens was studied in the polyethylene glycol-rich continuous phase, dextran-rich dispersed phase, and in the mixed phase. From the kinetic data it appears that increasing the overall polymer composition causes the cells to adsorp at the interface. On the other hand, partition measurements indicate that increasing polymer concentrations make the cell partitioning more one-sided. This anomaly is explained by studying the interfacial adsorption of cells via dynamic surface tension measurements.     

Selective two-phase hydrogenation of sorbic acid using [Cp*Ru(sorbic acid)]+ catalyst?

Summary Unsaturated hexenoic acids are important compounds due to their utilization for specific aromatic alcohol (leaf alcohols) preparation. The influences of the reaction conditions on the sorbic acid hydrogenation to cis-hex-3-enoic acid are given. [Cp*Ru(sorbic acid)]CF₃SO₃ was used as a catalyst in two-phase hydrogenation.     

Distribution behavior of some drug enantiomers in an aqueous two-phase system using counter-current extraction with protein

Summary The partial resolution of some drug enantiomers by counter-current extraction in an aqueous two-phase system using bovine serum albumin (BSA) or ovomucoid (OVM) as chiral discriminator is described. The phase system was prepared with dextran 40, polyethylene glycol and a protein. Ofloxacin (OFLX) enantiomer was well recognized by the BSA system, whereas the enantiomers of carvedilol (-blocker) and DG-5128 (a new oral hypoglycaemic drug) were hardly recognized by the OVM system. The distribution coefficients of (S)-, (R)- and rac-OFLX varied with pH. Good enantioselectivity for OFLX was obtained at relatively high pH ( pH 9). The crude optically enriched OFLX enantiomers were extracted from the aqueous fractions and finally purified by thin-layer chromatography.     

Small-angle x-ray scattering studies on epoxidized butadiene-styrene block copolymers

Small-angle x-ray scattering (SAXS) and scanning electron microscopy (SEM) investigations for epoxidized butadiene-styrene (BS) block copolymers were performed. For unepoxidized copolymers, the SAXS curve exhibits a maximum which indicates that the copolymer has heterogeneity domain morphology. Using the standard theory for a two-phase system, mean distances between domains, the correlation length l _p , and the thickness of the phase boundary were calculated from the SAXS data. It was found that the epoxidation of BS copolymers decreases the ability of the copolymer to separate the individual components. As the content of the epoxide groups increases, the dimensions of the domains decrease until they disappear, the boundary between domains and the matrix becomes less and less definite, and the copolymer composes a homogeneous system. The disappearance of the two-phase structure of the BS copolymers indicates an increase in the compatibility of polystyrene and epoxidized polybutadiene. According to the method of Van Krevelen, the solubility parameters of polystyrene and epoxypolybutadiene were calculated. Small differences between these parameters support the conclusions drawn from the SAXS investigations     

Purification of plasmid DNA vectors by aqueous two-phase extraction and hydrophobic interaction chromatography

The current study explores the possibility of using a polyethyleneglycol(PEG)-ammonium sulphate aqueous two-phase system (ATPS) as an early step in a process for the purification of a model 6.1 kbp plasmid DNA (pDNA) vector. Neutralised alkaline lysates were fed directly to ATPS. Conditions were selected to direct pDNA towards the salt-rich bottom phase, so that this stream could be subsequently processed by hydrophobic interaction chromatography (HIC). Screening of the best conditions for ATPS extraction was performed using three PEG molecular weights (300, 400 and 600) and varying the tie-line length, phase volume ratio and lysate load. For a 20% (w/w) lysate load, the best results were obtained with PEG 600 using the shortest tie-line (38.16%, w/w). By further manipulating the system composition along this tie-line in order to obtain a top/bottom phase volume ratio of 9.3 (35%, w/w PEG 600, 6%, w/w NH4)2 SO4), it was possible to recover 100% of pDNA in the bottom phase with a three-fold increase in concentration. Further increase in the lysate load up to 40% (w/w) with this system resulted in a eight-fold increase in pDNA concentration, but with a yield loss of 15%. The ATPS extraction was integrated with HIC and the overall process compared with a previously defined process that uses sequential precipitations with iso-propanol and ammonium sulphate prior to HIC. Although the final yield is lower in the ATPS-based process the purity grade of the final pDNA product is higher. This shows that it is possible to substitute the time-consuming two-step precipitation procedure by a simple ATPS extraction.     

A facile access to ureido sugars. Synthesis of urea-bridged β-cyclodextrins

The preparation of a urea-bridged β-cyclodextrin dimer and of a 6-monodeoxy-6-mono[3-(β-d-glucopyranos-2-yl)ureido]-β-cyclodextrin has been developed, using triphosgene as the isocyanation agent in an aqueous two-phase system. Per-O-acetylated β-d-gluco and mannopyranosylamines and 2-amino-2-deoxy-α- and β-d-glucose were also transformed into the corresponding isocyanates and converted in situ into ureas by coupling with aromatic and aliphatic amines.     

Influence of quaternary onium salts,crown ethers and cryptands on olefin epoxidations promoted by HOCl/ClO− in the Presence of Mn(III)-tetrakis(2,6-dichlorophenyl)porphyrin chloride

Reaction rates of alkene epoxidations, promoted by aqueous NaOCl and catalyzed by Mn(III)-tetrakis(2,6-dichlorophenyl)porphyrin chloride1 (P) in the presence of a lipophilic axial ligand (L) (e.g.N-hexylimidazole) and carried out under H₂O/CH₂Cl₂ two phase conditions at 0°C, are strongly enhanced by lowering the pH of the aqueous phase from 12.7 to 9.5. Under these conditions, a further relevant increase in the reaction rates can be achieved by adding phase-transfer catalysts (PT), e.g. quaternary ammonium salt 3, lipophilic crown ether4 or cryptand5, provided that the amount of L is very small (L/P=1 for very reactive alkenes, e.g. cyclooctene, and 10 for poorly reactive ones, e.g. 1-dodecene). In the case of cyclooctene epoxidation, the use of 0.006–0.03 mol. equiv. of PT completes the reaction in 1–10 min., the initial rates being up to 600 turnovers/min. with (2.2.2,C₁₀) cryptand. In the absence of the axial ligand, the quaternary ammonium salt3 and cryptand5 show an inhibitory effect. Such an effect is due to the formation of the poorly reactive Mn(P)CI species, by Cl– extraction to the organic phase. However, dibenzo crown ether 4 does not show this effect. In the presence of 4, and with L/P =1, the 1-dodecene epoxidation reaches 94% in 1 min. The unique behavior of crown ethers can be explained by their ineffectiveness in extracting alkali chlorides, providing a very low concentration of Cl– in the organic phase and thus avoiding the Mn(III)-porphyrin deactivation.This paper is dedicated to the memory of the late Dr C. J. Pedersen.