EFFECTS OF STRUCTURAL VARIATION WITHIN PROTON-IONIZABLE CROWN ETHERS UPON THE SELECTIVITY AND EFFICIENCY OF SOLVENT EXTRACTION OF ALKALI METAL AND ALKALINE EARTH CATIONS

Lipophilic crown ethers with pendant proton-ionizable groups are novel complexing agents for use in solvent extraction of alkali metal and alkaline earth cations. A variety of crown carboxylic acids, crown phosphonic acid monoesters, and crown phosphonic acids have been synthesized to probe the effect of structural variation within the complexing agent upon selectivity and efficiency in solvent extraction. Synthetic routes to these novel extractants and results from competitive solvent extractions of alkali metal cations and of alkaline earth cations from aqueous solutions into chloroform are summarized     

冠醚化合物对乳剂晶体外延生长的调变作用

本工作研究了冠醚化合物在外延乳剂生长过程中的调变作用。结果表明，１，４，７，１０，１３，１６－六氧杂环十八烷对ＡｇＢｒ八面体乳剂无侵蚀作用，对非同晶系晶体之间的外延不起调变作用。１，７，１０，１６－四氯－４，１３－二氮代杂环十八烷均使ＡｇＢｒ八面体乳剂的棱角产生了不同程度的侵蚀，可充当不同晶系晶体外延生长的调变剂，对晶体的溶解侵蚀能力依２Ｓ－１８－Ｃ－６，２Ｎ－１８－Ｃ－６，１８－Ｃ－６的次序降低     

Tactic poly(crown ether)s with pendant benzocrown ethers

Summary Tactic and atactic poly(crown ether)s, poly(methacryloyloxymethylbenzo-15-crown-5), were synthesized by polymer reaction of the respective poly(methacrylic acid) with chloromethylbenzo-15-crown-5 and radical polymerization of methacryloyloxymethylbenzo-15-crown-5. By solvent extraction of alkali metal picrates with these poly(crown ether)s, the isotactic poly(crown ether) was found to be a little more selective for K⁺ and Rb⁺ than the syndiotactic and atactic ones.     

Nitrogen containing compounds

Bridge-head nitrogen-containing compounds, (1,4-diaza-bicyclo-[2.2.2]-octane, 1-azabicyclo-[2.2.2]-octane, 1,5-diaza-bicyclo-[5.4.0]-undec-5-ene and l-azabicyclo-[2.2.2]-octane-3-one), successfully catalyze the ethoxylation of dodecyl alcohol. The catalytic activity of any of the first two compounds was four to five times higher than that of an open-chain, symmetrical trialkylamine of similar basicity. The molar mass distribution of the ethoxylated dodecyl alcohol derivatives was of the Weibull-Nycander-Gold type. No Weibull-Törnquist effect could be detected, however, unlike the case realized in ethoxylated systems gained in the presence of trialkylamines. No change in the distribution constant (calculated according to Natta and Mantica) could be observed in the course of these ethoxylation reactions.     

Copper salt–crown ether systems as catalysts for the oxidation of isopropyl arenes with tertiary hydroperoxides to peroxides

Symmetrical and unsymmetrical peroxides can be obtained by the oxidation of isopropyl arenes with tertiary hydroperoxides in the presence of copper salt–crown ether as catalysts. The efficiency of the investigated catalytic system enhances markedly in the presence of some alkali metal salts, with a cation diameter corresponding to the inner diameter of the crown ether. The oxidation of isopropyl arenes with hydroperoxides in the presence of a copper salt–crown ether–alkali metal salt catalytic system proved to be a simple and efficient method for the synthesis of ditertiary peroxides. A possible mechanism of this phenomenon is discussed. The results obtained confirm strongly that phase transfer catalysis operates in the investigated reaction.     

二苯并-18-冠-6及其配合物结构的理论研究

在捕获和输送碱金属离子时,冠醚的分子构型起着重要作用。利用密度泛函理论B3LYP方法,在6-31G(d)水平上对二苯并-18-冠-6及其配合物进行构型优化、频率、相互作用能等计算,得出了最稳定结构。研究表明,直径的匹配,配体的构象变化以及溶剂化效应都影响着二苯并-18-冠-6对离子的选择。     

以苯硫脲基乙酸为端基的开链冠醚的合成及其性质研究

由ＮＨ４ＣＮＳ、ＣｌＣＨ２ＣＯＯＨ和开链冠醚桥联二芳胺在无水ＥｔＯＨ中回流，合成了３个以苯硫脲基乙酸为端基的开链冠醚，并经ＩＲ、＾１ＨＮＭＲ，ＭＳ确证了其结构，。初步试验了其与金属离子 的络合性能。     

复合型碱土金属乙氧基化窄分布催化剂及其性能研究

研制出复合型碱土金属乙氧基化催化剂（简称ＦＨ型）。通过辛基酚和月桂醇的乙氧基化反应考察了其催化活性和产品的分子量分布。结果表明，这种催化剂的催化活性高，合成乙氧基化产物分子量分布窄，色泽好。     

Modifizierung von Faseroberflächen durch permanente Fixierung supramolekularer Komponenten,Teil 3: Azakronenether

The fixation of aza crown ether derivatives onto polymer surfaces by suitable functional groups is described. Ligands with hydrophobic substituents may be applied to fibrous polymers using conventional technologies of textile processing. It is illustrated that the fixed cavities do not lose their complexing power. The modified fibres show resistance against biological attack.     

高加成低PEG含量壬基酚聚氧乙烯醚的合成研究

本文以PEG含量做为主要指标,通过一系列催化剂筛选和条件实验,进一步考察了ZD-Ⅳ催化的壬基酚乙氧基化反应,结果表明ZD—Ⅳ催化剂催化得到的产品成壬基酚聚氧乙烯醚具有PEG含量低、产品色泽洁白和生产工艺简单等优点,是合成高加成壬基酚聚氧乙烯醚的理想催化剂。     

Homogeneous Polymerisation of Methylmethacrylate Initiated by Alkali Metal Salts of Methanol and t-Butyl Alcohol in the Presence of Cryptands and Macrocyclic Crown Ether Compounds

The polymerisation of methylmethacrylate initiated by alkali alkoxides is greatly promoted in the presence of macrocyclic compounds, cryptands and crown ethers. The solubility in toluene and the reactivity of alkoxides is enhanced by these complexing agents. Polymerisations have been carried out in a non-polar solvent in the homogeneous phase.     

桥联双苯硫脲基乙酸的合成

合成了４种烷醚链桥联的双苯硫脲基乙酸，经红外光谱，核磁共振氢谱和质谱表征了结构，初步测试表明它对钴，锑等金属离子具较高的络合灵敏度。     

SURVEYING THE EXTRACTION OF CESIUM NITRATE BY 1,3-ALTERNATECALIX[4]ARENE CROWN-6 ETHERS IN 1,2-DICHLOROETHANE

ABSTRACT

The extraction of cesium nitrate from a mixture of alkali metal nitrates by calix7lsqb;4]arene crown-6 ethers in 1,2-dichloroethane diluent has been surveyed at 25 °C. The results reveal that smaller substituents (but larger than C₂,) at the phenolic positions of the calixarene opposite the crown ether increase both the extraction efficiency and the cesium selectivity. Benzo substituents on the crown ether tend to decrease extraction strength while increasing cesium-to-sodium selectivity. Conversely, a cyclohexano group on the crown ether has a negative impact on both extraction strength and selectivity.     

Alkali Metal tert‐Butoxides,Hydrides and Bis(trimethylsilyl)amides as Efficient Homogeneous Catalysts for Claisen–Tishchenko Reaction

Shelf‐available alkali metal tert‐butoxides, hydrides and bis(trimethylsilyl)amides were shown to be highly efficient homogeneous precatalysts for the disproportionation of aldehydes to the corresponding carboxylic esters. Potassium compounds in combination with 18‐crown‐6 ether could drastically increase the rate of reaction in a few cases. Alternatively, efficient aldol condensations were found for aldehydes possessing an enolizable methylene group at the α‐position to the aldehyde functionality. The active species involved in this esterification using any of these alkali metal catalysts is expected to be the metal alkoxide. Potassium compounds were found to be much more efficient when compared to analogous sodium compounds and kinetic studies revealed the rate‐determining step to be a second order concerted hydride transfer from a potassium hemiacetal species to another molecule of aldehyde.     

Ion-Pair Sorption of Alkali Metal Chlorides by Crown Ether Carboxamide Resins

Abstract

Ten crown ether carboxamide resins are prepared by condensation polymerization of N,N-dialkyl sym-(R)dibenzo-16-crown-5-oxyacetamide monomers with formaldehyde in formic acid. Competitive ion-pair sorption of alkali metal chlorides from aqueous methanol solutions by these novel resins reveals that both sorption selectivity and efficiency are influenced by: 1) the conformational positioning of the pendant carboxamide group with respect to the crown ether cavity; 2) the length of the N,N-dialkyl chains on the pendant carboxamide group; 3) the methanol content of the aqueous methanol solution; 4) the concentration of alkali metal chlorides in the sample solution; and 5) the temperature of the sample solution. The highest sorption efficiency and Na⁺ selectivity are obtained for a resin prepared from N.N-dibutyl sym-(propyl)dibenzo-16-crown-5-oxacetamide monomer in which the geminal propyl group orients the carboxamide-containing side arm over the crown ether cavity. Lengthening the alkyl chains in the carboxamide group is detrimental to both sorption efficiency and selectivity. A very sharp response of alkali metal chloride sorption to the methanol content of the sample solution is noted for the crown ether resins which possess preorganized carboxamide side arms.     

窄分布吐温—80的合成研究

通过对几种碱金属、碱土金属盐催化剂的考察,研究了斯本－８０的乙氧基化反应,筛选出ＤＦ－１型新型催化剂。以该催化剂为重点,对其催化活性、反应影响因素等作了深入的考察。ＤＦ－１型乙氧基化催化剂不但具有催化活性较好,产物分子量分布较窄,色泽较浅等特点,而且在合成工艺上与传统生产工艺相比,具有操作简单的优点,可望在工业生产上获得广泛的应用。     

Extraction of Alkali Metal Cations by Lipophilic Dibenzo-14-crown-4-carboxylic Acids

Abstract

The extraction of alkali metal cations by the lipophilic crown ether, bis-t-octylbenzo-14-crown-4 (BOB14C4), three derivatives of BOB14C4 having pendant carboxylic acid sidearms, and a lipophilic carboxylic acid, 2-methyl-2-heptylnonanoic acid (HMHN) was studied by two-phase potentiometric titration and ion-chromatography. The lipophilic, ionizable crown ethers, BOB14C4-acetic acid (BOB14C4AA), BOB14C4-propanoic acid (BOB14C4PA), and BOB14C4-oxyacetic acid (BOB14C4OAA) extract cations efficiently from aqueous mixed alkali metal chloride solutions into 1-octanol by an ion-exchange mechanism in the range p[H] > 7, as does HMHN. The mode of attachment of the ionizable sidearm, via an ether linkage (BOB14C4OAA) versus a carbon linkage (BOB14C4AA and BOB14C4PA), has a significant effect on the cation selectivity and extraction efficiency of these extractants. BOB14C4 exhibits no p[H] dependent extraction behavior and has no significant effect on the extraction of alkali metal cations by HMHN in a mixture of these two compounds. Although BOB14C4AA and BOB14C4PA extract cations at lower p[H] than HMHN, all three compounds exhibit similar selectivity for Li⁺ over Na⁺, K⁺, Rb⁺ and Cs⁺. A significant reversal in selectivity is observed with BOB14C4OAA, which extracts Na⁺ and K⁺ selectively over Li⁺, Rb⁺, and Cs⁺ and at significanty lower p[H] than BOB14C4AA, BOB14C4PA, or HMHN. The unique behavior of BOB14C4OAA may be attributed to the presence of the ether linkage between the crown ether and the pendant carboxylic acid.     

Über den Einfluß der Hautoberflächenlipide auf Alkalineutralisationsfähigkeit und Alkaliresistenz der Haut

The Influence of Surface Lipids of Skin on Its Ability Towards Alkali Neutralisation and Its Alkali Resistance On 28 experimental persons, the alkali neutralisation time was determined by the method of Tronnier, and the alkali resistance was measured by the method of Burckhardt. Furthermore, the skin surface lipids were extracted with petroleum ether and determined gravimetrically. The composition of skin-surface lipids was determined by thin-layer chromatography. At short alkali neutralisation time, considerably more skin surface lipids were found than for the long periods. Any additional effect of the composition of skin surface lipids on the ability of skin towards alkali neutralisation could not be detected. No evidence on the significance of skin surface lipids towards alkali resistance was found.     

Effect of initiators and ethoxylation degree of non‐ionic emulsifiers on vinyl acetate and butyl acrylate emulsion copolymerization in the loop reactor

Vinyl acetate and butyl acrylate copolymers were synthesized in the presence of ammonium persulfate and potassium persulfate initiators, mixture of non‐ionic and anionic emulsifiers, and polyvinyl alcohol as protective colloid in a loop reactor. The monomer ratio was chosen 85:15. The series of non‐ionic emulsifiers, which have 10–40 moles ethoxylated nonyl phenol, were combined with Nansa 66 (sodium dodecyl benzene sulfonate). The effects of the initiators on the physicochemical properties of copolymers were investigated by measuring conversion, viscosity, molecular weight, molecular weight distribution, and surface tension, respectively by using gravimetric method, Brookfield viscometer, gel permeation chromatograpy (GPC), and ring method. The effects of ethoxylation degrees of the non‐ionic emulsifiers to the same properties of copolymers were also investigated. It was determined that the copolymer viscosities showed different tendency for two initiators. They were increased by the increasing ethoxylation degree of the non‐ionic emulsifier for ammonium persulfate. In contrast, latex viscosity was decreased by increasing the ethoxylation degree in presence of potassium persulfate. Similar changes were also found in number average molecular weights of copolymers. On the other hand, weight average molecular weights of copolymers increased by increasing the ethoxylation degree of the non‐ionic emulsifier for both initiators. In the case of potassium persulfate, the surface tension values of copolymers increased by increasing the ethoxylation degree, but generally increasing the ethoxylation degree did not affect the surface tension of copolymer very seriously for two initiators. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 537–543, 2003     

Environmental Impact of Ether Carboxylic Derivative Surfactants

The ultimate aerobic biodegradability and toxicity of three ether carboxylic derivative surfactants having different alkyl chains and degrees of ethoxylation were investigated. Ultimate aerobic biodegradability was screened by means of dissolved organic carbon determinations at different initial surfactant concentrations. For comparison, the characteristic parameters of the biodegradation process, such as half-life, mean biodegradation rate, and residual surfactant concentration, were determined. Increased surfactant concentrations decreased mineralization and lengthened the estimated half-life. The results demonstrate that the ultimate aerobic biodegradability is higher for the surfactants with the shortest alkyl chain and highest degree of ethoxylation. Toxicity values of the surfactants, and their binary mixtures, were determined using three test organisms, the freshwater crustacea Daphnia magna, the luminescent bacterium Vibrio fischeri and the microalgae Selenastrum capricornutum. The toxicity is lower for the surfactants with the shortest alkyl chain and highest degree of ethoxylation. The toxicity of binary mixtures of the three ether carboxylate surfactants at a 1:1 weight ratio was also measured. The least toxic mixture is formed by the surfactants having lower individual toxicity.