Extraction of Strontium and Cesium by Dicarbollides, Crown Ethers and Functionalized Calixarenes

The two main classes of extractantsused for the extraction of cesium and strontium aredicarbollides and crown ethers. Dicarbollides wereused on a large scale for the extraction of these twoelements from high-activity waste. The basicdicarbollides present drawbacks since they need to bediluted in polar solvent such as nitrobenzene and theirefficiency strongly decreases as the acidity of liquidwaste increases. Crown ethers enable cesium andstrontium to be extracted if the concentration ofsodium or the acidity of solutions are not too high.Recently, calixarenes blocked in the 1,3-alternateconformation were used for the selective extractionof cesium, even from high-salt waste matrices.     

Solvent Extraction of Sodium with Crown Ethers

Abstract

The solvent extraction separation of sodium was effected with 15-crown-5 (0.01 M) in methylene chloride in presence of 0.01 M picric acid as a counter ion. It was quantitatively extracted at pH 5.0 and was stripped with 3 M hydrochloric acid and determined by flame emission spectroscopy at 589 nm. Sodium was separated from alkali and alkaline earth metals and common anions. The method was extended to the analysis of sodium from real samples.     

表面高巯基功能化介孔材料的制备及对Hg~(2+)的吸附性能

在酸性条件下,以三嵌段非离子表面活性剂P123为模板剂,四氧基硅烷(TEOS)预水解后与3-巯基丙基三乙基硅(MPTES)共聚,合成了具有不同巯基官能团比例x[n(MPTES)/n(TEOS+MPTES)]的功能化介孔材料(SBA-SH-x),其结构和性能经FT-IR,元素分析,SEM,TEM,小角X-ray和N2吸附-脱附表征。结果表明:x10%,SBA-SH-x为六方p6mm介观结构;10%x15%,SBA-SH-x为立方Ia3d介孔结构;x20%,SBA-SH-x为无序结构。SBA-SH-x在水溶液中吸附Hg2+的研究结果表明:SBA-SH-10和SBA-SH-15对Hg~(2+)吸附性能较好。     

酰胺型开链冠醚稀土配合物的超声化学合成

用声化学方法合成了八种新的酰胺型开链冠醚稀土配合物,经元素分析,IR,NMR,ES－MS表征,确定了配合物的组成,研究了它们的荧光性质。     

The Complexation of Amino Acids by Crown Ethers and Cryptands in Methanol

Complex formation between several crown ethers and the cryptand (222) and -amino acids in methanol was studied by calorimetric titration. The ligand structure and the donor atoms of the ligands play an important role in determining the measured values of the reaction enthalpies and entropies. However, with the exception of the diaza crown ether (22) all stability constants are of the same order of magnitude. The enthalpic and entropic contributions to the stabilities of the complexes formed compensate each other. In methanolic solution the amino acids exist in their zwitterionic form. This equilibrium can be influenced. Under acidic, neutral or basic conditions different values of the reaction enthalpies are measured for the complexation of some amino acids with 18-crown-6. These results demonstrate that the concentration of the zwitterionic form of the -amino acids can be influenced. Thus the reaction between macrocyclic and macrobicyclic ligands and amino acids should be described by at least two different reaction schemes.     

A Convenient and Efficient Method for the Preparation of Unique Fluorophores of Lariat Naphtho‐Aza‐Crown Ethers

New naphtho‐aza‐crown ethers containing different phenolic side‐arms attached through the ortho‐position of the phenol have been prepared under solvent‐free conditions. The starting macrocyclic naphtho‐aza‐crown ether 2 was obtained by treatment of naphthalene dicarboxylic acid diester 1 with diethylenetriamine in EtOH at room temperature for two days without stirring in 77% yield (Scheme 1). Phenolic ligands ( 3 – 14 ) were synthesized by the Mannich reaction of the secondary macrocyclic amine 2 with the substituted phenols using nontoxic and inexpensive CaCl₂. This procedure was applied successfully for the synthesis of Mannich bases from simple secondary amines. The CaCl₂ powder can be reused up to three times after simple washing with dry acetone.     

Complexes of Mercury(II) Cyanide with Crown Ethers in Dimethylsulfoxide

The complexation of mercury(II) cyanide with macrocyclic ligands 15-crown-5,18-crown-6 and dibenzo-24-crown-8 in dimethylsulfoxide was studied using¹⁹⁹Hg NMR measurements. No significant complexation with 15-crown-5was observed. The stability constants K_s for 1 : 1 complexes with two other ligands were determined and found to be similar, in contrary to the results reported in nitrobenzene. Solvent effects on K_s values obtained are discussed in comparison with the literature data. X-ray crystal structure of Hg(CN)₂.A18-crown-6 was also determined.     

Correlation of the Structure and Properties of Alkalides and Electrides That Contain Cryptands or Crown Ethers

Abstract

The structures of several salts that contain alkali metal anions (alkalides) and two that contain trapped electrons (electrides) are correlated with their optical and NMR spectra, and magnetic susceptibilities. The nature of the channels and trapping sites in the two electrides are described.     

Complex Formation Between Crown Ethers and Urea and Some Guanidinium Derivatives in Methanol

The complexation of urea and some guanidinium derivatives by the ligands 15-crown-5, 18-crown-6, benzo-18-crown-6 and diaza-18-crown-6 in methanol has been studied by means of calorimetric titrations. The complex formation is mainly favored by entropic contributions. The number of solvent molecules released during the complex formation is responsible for the stability of the complexes formed.This revised version was published online in November 2005 with corrections to the Cover Date.     

Unusual Regioselectivity in the Reactions of Chlorocyclophosphazene-Containing Crown Ethers with Dinucleophiles

Abstract

New macrocyclic ligands with cyclophosphazene sub-units, representing geminally diamino-bridged derivatives of BINO-crown type (III), and bisansa-cyclosubstituted ones of chiral PNP cryptand type (IV) have been obtained by the regioselective substitution reactions of monoansa(oxytetraethylenoxy) reactive PNP-crown, N₃P3CI₄[O(CH₂CH20)₄] (II) with the dinucleophiles, like alkylenediamines or sodium diarylates. The supramolecular control of these processes is discussed.     

Nitration of Benzo Crown Ethers with Potassium Nitrate in Polyphosphoric Acid

A general method for the nitration of benzo crown ethers with potassium nitrate in polyphosphoric acid has been developed. Mono- and dinitro derivatives of benzo-12-crown-4, benzo-15-crown-5, dibenzo-18-crown-6, and dibenzo-24-crown-8 have been prepared. The role of complex formation in the regioselective tendency for the nitration of dibenzo-18-crown-6 has been demonstrated.     

制备二氮杂冠醚和三氮杂冠醚的新方法

以糖精为原料合成二氮杂冠醚和三氮杂冠醚。使糖精与二甘醇或三甘醇二氯化物和N,N-二(β-氯乙基)丁胺的DMF溶液在少量碘化钾存在下烃化、氨解,再用二甘醇或三甘醇的二对甲苯磺酸酯烃化生成保护的冠醚环。后者与20％盐酸作用除去保护基生成游离的环体。此法合成路线短原料价廉易得。二氮杂18-冠-6总产率37％左右。     

甲基冠醚的合成

将二烯丙基醚(1),乙二醇二烯丙基醚(2)和1,2-丙二醇二烯丙基醚(3)在氯乙醇溶液中汞化-去汞,制得含有甲基侧链的二氯化物(4,5,6),后者与邻苯二酚作用,在KOH存在下,生成相应的甲基冠醚。     

新型套索冠醚-金属离子络合性能的紫外光谱法与质谱法研究

本文合成了3种套索冠醚4、5和6,分别测定了它们与Hg^2^ 、Pb^2^ 、Zn^2^ 、cd^2^ 、Ni^2^ 、Co^2^ 、Cu^2^ 、Ag^ 、Tb^3^ 和Eu^3^ 所形成的络合物的紫外吸收光谱,用电喷雾液相色谱-质谱联用仪分别表征了它们与TB^3^ 形成的络合物,结果显示它们对上述金属离子有很好的络合性。     

N-(2-对甲苯磺酰胺基乙基)单氮杂冠醚的合成及其晶体结构

N-对甲苯磺酰基乙二胺分别与1,11-二碘-3,6,9-三氧杂十一烷和1,14-二碘-3,6,9,12-四氧杂十四烷反应,制得N-(2-对甲苯磺酰胺基乙基)单氮杂-12-冠-4或15-冠-5;当用N-(2-对甲苯磺酰胺基乙基)二乙醇胺与1,11-二对甲苯磺酸酯-3,6,9-三氧杂十一烷反应时,才能获得N-(2-对甲苯磺酰胺基乙基)单氮杂-18-冠-6.从甲醇溶液中培养得N-(2-对甲苯磺酰胺基乙基)单氮杂-12-冠-4单晶,属单斜晶系,P2₁/a空间群;a=1.4229(1)nm,b=0.9595(2)nm,c=1.4564(1)nm,β=102.20(1)°,V=1.9435nm³,Z=4.最终偏离因子R=0.043.     

双臂套索冠醚PVC膜碘离子选择电极

研究了两种新型双臂套索冠醚1，10－二（5－氯－8－羟基喹啉－7－亚甲基）－1，10－二氮杂－4，7，16－三氧杂－13，19－二硫杂环二十一烷（Ⅰ）和1，13－二（5－甲基－8－羟基喹啉－7－亚甲基）－1，13－二氮杂－4，7，10－三氧杂－16，19－二硫杂环二十一烷（Ⅱ）为载体的PVC膜电极的响应行为；实验结果表明，两电极均显示阴离子响 应，其中对碘离子具有优良的能斯特电位响应性能，线性范围为10^－5－10^-1mol/L，斜率分别为－59．1mV/pcI-和－57．6mV/pcI-；电极具有读数稳定，重复性好，PH值范围宽等优点；将该电极用于药品中碘含量的测定，其结果与药典法一致。     

Photochemical Ionic-Conductivity Switching Systems of Photochromic Crown Ethers for Information Technology

Design of two types of ion-conducting systems using photochromic crown ethers as the photocontrol agents is described; one type is based on the phase transition of azobenzene derivatives induced by their photoisomerization and the other based on the molecular control of metal ion complexation by crowned spirobenzopyrans. The photoresponsive ion-conducting systems are applicable to electrostatic imaging and photorefractive materials.     

Synthesis of Highly Functionalized Diaryl Ethers by Copper‐Mediated O‐Arylation of Phenols using Trivalent Arylbismuth Reagents

Highly functionalized diaryl ethers were prepared by copper(II) acetate mediated O‐arylation reaction of phenols using trivalent organobismuthanes. The reaction is performed under simple conditions and tolerates a wide diversity of functional groups on the phenol and on the organobismuth reagent. Substoichiometric amounts of catalyst can be used by performing the reaction under an oxygen atmosphere. The N‐arylation of pyridones is also reported.