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首次合成一系列杯[10]冠醚。通过将对叔丁基杯[10]芳烃和乙二醇双对甲苯磺酸酯或多甘醇双对甲苯磺酸酯在K2CO3/甲苯或Cs2CO3/丙酮体系中反应,得到一系列杯[10]冠醚:1,2-杯[10]冠-4、1,3-杯[10]冠-2、1,2-,1,3-杯[10]冠-3、1,4-杯[10]冠-4、和1,6-杯[10]冠-4。 相似文献
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新一代大环化合物杯芳烃(calixarcne)的研究已引起广泛的兴趣,它是由酚环和亚甲基组成的环多聚体,其结构呈杯状.杯底OH及杯盖R基可被各种基团取代,在其环形结构中具有适当体积的洞穴,在此空穴中能容纳客体而形成主客体配合物,可模拟酶催化的初始过程,在催化及分析分离等方面也有广泛的应用.但杯芳烃的配位化学研究很少,本文首先合成了对叔丁基杯[4]芳烃、对叔丁基杯[6]芳烃及对叔了基杯[8]芳烃(分别简称杯[4]、杯[6]及杯[8]),研究它们对铜的萃取,并探讨了萃取机理. 相似文献
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硫杂杯[4]芳烃衍生物的合成及萃取性能研究 总被引:1,自引:1,他引:0
通过两个不同的平台合成了一系列结构新颖的硫杂杯[4]芳烃衍生物,阳离子萃取试验表明该硫杂杯[4]芳烃衍生物比含有相似官能团的杯[4]芳烃衍生物具有更好的软金属离子萃取性能,新化合物的结构经IR, 1H NMR,MS和元素分析等证实. 相似文献
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新一代大环化合物杯芳烃(calixarcne)的研究已引起广泛的兴趣,它是由酚环和亚甲基组成的环多聚体,其结构呈杯状.杯底OH及杯盖R基可被各种基团取代,在其环形结构中具有适当体积的洞穴,在此空穴中能容纳客体而形成主客体配合物,可模拟酶催化的初始过程,在催化及分析分离等方面也有广泛的应用.但杯芳烃的配位化学研究很少,本文首先合成了对叔丁基杯[4]芳烃、对叔丁基杯[6]芳烃及对叔了基杯[8]芳烃(分别简称杯[4]、杯[6]及杯[8]),研究它们对铜的萃取,并探讨了萃取机理. 相似文献
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设计并合成了下沿含柠檬醛片段的新型杯[4]芳烃衍生物,经1H NMR、MS和元素分析等表征确证其结构,测定了新型杯[4]芳烃衍生物对金属阳离子和氨基酸分子的两相萃取性能,结果表明主体分子通过多官能团的协同作用具有较好的配位性能。 相似文献
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A series of calixarene derivatives 2―5 containing heteroatom at the lower rim have been synthesized. 1H NMR studies and crystallographic structures demonstrated that the calix[4]arene derivatives adopted cone conformations. Their cationic binding abilities and selectivities towards heavy and tran- sition metal ions have been evaluated by solvent extraction of aqueous metal picrates. The obtained results indicated that the introduction of nitrogen, sulfur, and/or phosphor atoms to the calix[4]arene framework could effectively enhance their binding ability and selectivity for heavy and transition metal ions, such as Pb2 or Ag . 相似文献
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O. Klimchuk L. Atamas S. Miroshnichenko V. Kalchenko I. Smirnov V. Babain A. Varnek G. Wipff 《Journal of inclusion phenomena and macrocyclic chemistry》2004,49(1-2):47-56
A new series of the cone-shaped tetraalkoxycalix[4]arenes substituted at the wide rim with four phosphomethyl groups have been synthesized by the Arbuzov, Michaelis–Becker and Aterthon–Todd reactions of the chloromethyl or phenylhydrophosphinylmethylcalix[4]arenes. Their binding properties towards Eu3+ and Am3+ cations were investigated by the liquid–liquid extraction method. Due to the ‘calixarene effect’ the tetraphosphorylated calixarenes are more effective extractants for the metal cations than their acyclic analogs or some industrial extractants such as trialkylphosphinoxides, carbamoylphosphinoxide, bis-2-diethylhexyl phosphoric acid. 相似文献
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Aytan Yilmaz Shahabuddin Memon Mustafa Yilmaz 《Journal of polymer science. Part A, Polymer chemistry》1999,37(23):4351-4355
Two calix[4]arene derivatives (5 and 8) and their telomers are synthesized to estimate selective extraction of alkali and transition metal cations from the aqueous to the organic phase (chloroform). Compound 5 shows selectivity toward Hg2+. Compound 8 and telomers 6 and 9 are not selective but are good extractants for all used transition metal ions. The observations suggest that ethylene glycol bridges are efficient for carrying transition metal cations in a two-phase solvent system. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4351–4355, 1999 相似文献
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Sergey N. Podyachev Svetlana N. Sudakova Victor V. Syakaev Azat K. Galiev Roald R. Shagidullin Alexander I. Konovalov 《Supramolecular chemistry》2013,25(5):479-486
The binding properties of the cone conformer of O,O,O,O-tetrakis[hydrazinocarbonylmethyl]-4-tert-butylcalix[4]arene, the cone and the 1,3-alternate conformers of the corresponding thia analogue have been evaluated by means of liquid–liquid extraction for a large variety of metal ions. The extraction constants and the stoichiometries of the complexes formed have been determined. Comparison of the extraction properties of calix[4]arenes with their acyclic monomeric analogue clearly demonstrated, that the preorganization of acetylhydrazide groups on the calix[4]arene platform is the cause for a significant improvement of its binding properties. The presence of additional “soft” nitrogen binding sites in acetylhydrazide derivatives of calix[4]arenes compared to their amide derivatives leads to a shift from their classical selectivity for alkali and alkaline earth cations to transition metals. The cone conformer of tetrathiacalix[4]arene shows higher selectivity in a series of d-metal ions compared with its “classical” analogue. The 1,3-alternate conformer exhibits an excellent extraction selectivity for Cu2+ and Hg2+. 相似文献
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Fumio Hamada Takenori Fukugaki Koichi Murai G. William Orr Jerry L. Atwood 《Journal of inclusion phenomena and macrocyclic chemistry》1991,10(1):57-61
The liquid-liquid extraction of various metal ions by a diphenylphosphino calix[4]arene (1) using picrate counter ion has been studied and compared with those ofp-tert-butyl-calix[4]arene methyl ether (2) and triphenylphosphine (3). The calixarene 1 shows strong binding ability to almost all metal cations examined, but calixarene 2 shows little ability to extract any of them. Based on the continuous variation method, calixarene 1 formed 1: 2 complexes with copper(II) ion. 相似文献
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Saliha Bouhroum Francoise Arnaud-Neu Zouhair Asfari Jacques Vicens 《Supramolecular chemistry》2013,25(8):629-635
Tetra(diethyl)amide-p-tert-butylthiacalix[4]arene 1a in the cone conformation was synthesized and its binding properties towards a large variety of metal ions were established on the basis of liquid–liquid and solid–liquid extraction as well as complexation experiments. This compound is a less efficient and selective compound than the “classical” tetra(diethyl)amide-p-tert-butylcalix[4]arene 3 in the cone conformation for alkali and alkaline earth metal ions. However, Pb2+ is selectively extracted and complexed within heavy and transition metal ions. 相似文献
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Five novel Schiff's bases p‐tert‐butylcalix[4]arenes have been synthesized in high yields by the reaction of 1,3‐distally disubstituted p‐tert‐butylcalix[4]arene amine (1) with the corresponding aromatic aldehydes, and their cation binding abilities and selectivities with alkali and heavy metal ions have been evaluated by solvent extraction of aqueous metal picrates to show the highest Ag+ extractability for Schiff's base p‐tert‐butylcalix[4]arene (6) and the best Na+/Li+ and Ag+/Ti+ selectivities for Schiff's base p‐tert‐butylcalix[4]arene (4 and 2) over any other calix[4]arene derivatives, respectively. 相似文献
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Xiaoming He Wai Han Lam Nianyong Zhu Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(35):8842-8851
Two calixarene‐based bis‐alkynyl‐bridged AuI isonitrile complexes with two different crown ether pendants, [{calix[4]arene‐(OCH2CONH‐C6H4C≡C)2}{Au(CNR)}2] (R=benzo[15]crown‐5 ( 1 ); R=benzo[18]crown‐6 ( 2 )), together with their related crown‐free analogue 3 (R=C6H3(OMe)2‐3,4) and a mononuclear gold(I) complex 4 with benzo[15]crown‐5 pendant, have been designed and synthesized, and their photophysical properties have been studied. The X‐ray structure of the ligand, calix[4]arene‐(OCH2CONH‐C6H4C?CH)2 has been determined. The cation‐binding properties of these complexes with various metal ions have been studied using UV/Vis, emission, 1H NMR, and ESI‐MS techniques, and DFT calculations. A new low‐energy emission band associated with Au???Au interaction could be switched on upon formation of the metal ion‐bound adduct in a sandwich fashion. 相似文献
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Polymer Supported Calix[4]arene Schiff Bases: A Novel Chelating Resin for Hg2+ and Dichromate Anions
《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6):691-704
This article describes the synthesis and characterization of two new calix[4]arene Schiff bases and their polymeric resins. The extraction properties of these “proton switchable extractants” with alkali, transition, post transition metal cations and for dichromate anions are reported. The two new calix[4]arene based Schiff bases (5 and 6) have been synthesized from 5,17‐diformyl‐25,27‐dipropoxy‐26,28‐dihydroxycalix[4]arene (4) by treatment with 3‐amino‐methylpyridine and 1,8‐diaminooctane in two separate reaction flasks following the same procedure. Compounds 5 and 6 have been appended to a polymeric resin by treatment with Merrifield resin through a nucleophilic substitution reaction. The receptor compounds (3 and 5–8) do not extract alkali metal cations, but show some selectivity toward transition metal cations, and a particularly high selectivity to Hg2+ and Pb2+. The protonated forms of all of the calixarene‐based receptors are good extractants for transferring Cr2O7 2?/HCr2O7 ? anions from an aqueous into a dichloromethane layer. 相似文献
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《International journal of mass spectrometry》1999,182(2-3):197-204
Matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) and electrospray ionization mass spectrometry (ESI-MS) are used to evaluate the alkali metal ion binding selectivities of a series of calixarenes. Each calixarene of interest is mixed with one or more alkali metal salts (1:100 ratio of calixarene to metal), either in the ESI solution or on the MALDI probe surface, and the relative binding selectivities are directly determined from the intensities of the calixarene/metal complexes in the mass spectra. For t-butylcalix[4]arene-tetraacetic acid tetraethyl ester (calixarene 1), complexation of Na+ is favored over complexation of K+, in agreement with prior solution results obtained by conventional methods. For the three calixarenes that do not have t-butyl groups on the upper rims, the calixarenes preferentially bind K+ over Na+, thus demonstrating that size selective complexation can be probed with both the ESI and MALDI methods. Collision-activated dissociation results indicate that the phenyl oxygens, but not necessarily the ethoxy ethyl oxygens of the lower rims, are the primary binding sites for the alkali metal ions. 相似文献