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1.
Zhi Bin Huang 《Tetrahedron letters》2005,46(20):3461-3464
Unique structures of tetra-crown ethers were successfully synthesized by the reaction of tetramethylolmethane tetraacrylate (TMMT) reacted with crown ethers containing primary amine functional group such as 2-aminomethyl crown ethers and 4-aminobenzo crown ethers; containing secondary amine group like 1-aza crown ethers through Michael reaction. The newly synthesized tetra-crown ethers were characterized by 1H NMR, 13C NMR, FAB mass spectrum, elemental analyses, IR, respectively. 相似文献
2.
Unique structures of novel ionophores of double-armed penta-crown ethers were successfully synthesized. Diaza 18-crown-6 was designed as the parent crown ring. The penta-crown ethers were prepared by the reaction of trimethylolpropane triacrylate (TMPTA) with diaza 18-crown-6 and further with 1-aza crown ethers through the Michael reaction. The newly synthesized penta-crown ethers were characterized by 1H NMR, 13C NMR, FAB mass spectrum, IR and elemental analyses, respectively. 相似文献
3.
V. I. Kalchenko N. A. Parhomenko L. I. Atamas O. A. Alek-syuk D. M. Rudkevich L. N. Markovsky 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract The crown ethers 1,2, containing exocyclic phosphorus groups, were obtained1 by the interaction of, bromo-, iodo-, and sulpamidoderivatives of mono- and dibenzocrown ethers with esters of trivalent phosphoric acids, alkenylphos-phonates and phosphorus pentachloride in presence of metal catalysts. On the basis of these compounds the crown ethers with various substitutes at phosphorus atom (including the polymeric ones) were synthesized. Further reaction of the crown ether 1 (X = “-” R = Ph, R′ = H) with glycol dichlo-rides gave first phosphorus-containing bis-crown ethers 3. 相似文献
4.
o-Dihydroxy-4-(3,4-dimethoxyphenyl)-chromenones (coumarins; 3a,b) were synthesised from 1,2,3-trihydroxy- or 1,2,4-triacetoxybenzenes through a reaction with ethyl 3-(3,4-dimethoxyphenyl)-3-oxopropanoate in H2SO4 or CF3COOH. The chromenone-crown ethers (4a–f) were prepared from the cyclic condensation of o-dihydroxy-4-(3,4-dimethoxyphenyl)chromenones (3a,b) with poly(ethylene glycol) ditosylates, in the presence of CH3CN/alkali carbonates. The chromatographically purified original chromenone-crown ethers were identified by 1H NMR, 13C NMR, MALDI-TOF mass spectrometry and elemental analysis. The 1:1 binding constants of Li+, Na+ and K+ with the chromenone-crown ethers were estimated in acetonitrile using fluorescence emission spectroscopy. The complexing-enhanced fluorescence spectra and complexing-enhanced quenching fluorescence spectra, along with the cationic recognition rules of the crown ethers allowed the ion binding powers to be determined. 相似文献
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7.
用两类结构不同的Schiff碱型、仲胺型双-(苯并-18-冠-6)在氯仿-水体系中对碱金属苦味酸盐进行萃取,测量了配合物组成比和萃取平衡常数。 相似文献
8.
Mutsuo Tanaka Yoshihiro Higuchi Yasuhiko Shibutani Shinpei Kado Keiichi Kimura 《Tetrahedron》2005,61(34):8159-8166
Polybenzyl ether type dendrons bearing the crown ether moieties at the periphery, namely, crowned dendrons were synthesized, and the effect of complex formation on their flexibility with metal-ion binding properties was examined. Upon addition of Na+, 1H NMR spectra of the crowned dendrons in CD3CN were significantly broadened, reflecting the flexibility restriction of the crowned dendrons by the complex formation with Na+. Such a significant flexibility restriction was observed only with Na+, although ESI-MS studies revealed that the crowned dendrons formed 1:2 complexes (a metal ion:the crown ether moiety) regardless of the kind of metal ions. The flexibility restriction became significant with increasing dendron generation on the basis of 1H NMR spectra and spin-lattice relaxation time (T1) measurements. Binding constants of the crowned dendrons with metal ions in CD3CN decreased with the increase of the dendron generation, reflecting an influence of the charge repulsion as well as a dendrimer effect to cause the steric hindrance. The examination of UV-vis absorption spectra for complexes of the crowned dendron with metal picrates in THF displayed the formation of a loose ion-pair complex with Na+, namely, a typical sandwich type complex. However, in CH3CN, all metal picrates were solvated to be in a loose ion-pair even without complex formation. These results suggested that the control of macromolecular flexibility with metal ions is feasible by the integration of crown ether moieties with a dendritic structure. 相似文献
9.
Synthesis of Double-Armed Benzo-15-crown-5 and Their Complexation Thermodynamics with Alkali Cations
A series of double-armed benzo-15-crown-5 lariats (3–8) have been synthesized by the reaction of 4′, 5′-bis(bromomethyl)-benzo-15-crown-5 (2) with 4-hydroxybenzaldehyde, phenol, 4-chlorophenol, 4-methoxyphenol, 2-hydroxybenzaldehyde, and 4-acetamidophenol in 43 ~ 82% yields, respectively. The complex stability constants (K
S) and thermodynamic parameters for the stoichiometric 1:1 and/or 1:2 complexes of benzo-15-crown-5 1 and double-armed crown ethers 3–8 with alkali cations (Na+, K+, Rb+) have been determined in methanol–water (V/V=8:2) at 25 °C by means of microcalorimetric titrations. As compared with the parent benzo-15-crown-5 1, double-armed crown ethers 3–8 show unremarkable changes in the complex stability constants upon complexation with Na+, but present significantly enhanced binding ability toward cations larger than the crown cavity by the secondly sandwich complexation. Thermodynamically, the sandwich complexations of crown ethers 3-8 with cations are mostly enthalpy-driven processes accompanied with a moderate entropy loss. The binding ability and selectivity of cations by the double-armed crown ethers are discussed from the viewpoints of the electron density, additional binding site, softness, spatial arrangement, and especially the cooperative binding of two crown ether molecules toward one metal ion.Graphical Abstract Synthesis of Double-Armed Benzo-15-crown-5 and Their Complexation Thermodynamics with Alkali CationsYU LIU*, JIAN-RONG HAN, ZHONG-YU DUAN and HENG-YI ZHANG
This revised version was published online in July 2005 with a corrected issue number. 相似文献
10.
Jeng-Shong Shih 《中国化学会会志》1994,41(3):309-314
Artificial macrocyclic polyethers were synthesized and applied as neutral carriers for ion-selective PVC membrane electrodes, ion-chromatographic packing materials, extractants and adsorbents for ion separation, coating materials for piezoeletrical membrane sensors for organic species, and ion-transport carriers through liquid membranes. Ion-selective electrodes such as those for K+ Na+, UO22+, Cs+, Pb2+, Fe3+, Hg2+ and Ag+ ions based on crown ether-phosphotungstic acid (PW) precipitates and dithio crown ethers respectively were prepared and showed good sensitivity and selectivity. Crown ether-PW precipitates were applied as adsorbents of rare-earth ions and some common heavy-metal ions. Some rare-earth ions were easily extracted with crown ethers, especially 15-crown-5. Poly(stytene/divinyl benzene) cryptand-22 resin was synthesized and applied as a bifunctional stationary phase of ion chromatography to separate bom cations and anions, even some organic carboxylate geometric isomers. Crown ethers such as mono-benzo-15-crown-5 was successfully applied as a coating material on piezoelectric quartz membrane sensors for some organic species. The oscillation frequency of the crown-ether quartz-membrane sensor was sensitive to organic vapours such as amines and alcohols. Upon adsorption of organic species on the crown-ether quartz membrane, the oscillation frequency of the sensor decreased obviously. Special crown ether such as dibenzo-16-crown-5-oxyacetic acid, decyl-cryptand-22 and 1, 4-dihydro-pyridine-18-crown-5 were synthesized and successfully applied as ion-transport carriers (ionophores) for transport of Na+ K+ and Mg2+ ions through liquid membranes. 相似文献
11.
以2-苯氧乙基为氮支链的[18]和[15]环系氮支套索冠醚的合成及其络合性能 总被引:1,自引:0,他引:1
以2-苯氧乙醇为起始剂, 合成了两种新型氮支套索冠醚: N-(2-苯氧乙基)单氮杂-18-冠-6 (18CE)与N-(2-苯氧乙基)单氮杂-15-冠-5 (15CE). 通过红外光谱、核磁共振氢谱和紫外光谱表征了新冠醚及其中间体的结构. 用电导滴定法研究了两冠醚与Na+, K+, Ag+, NH4+, Ni2+, Cu2+, Pb2+和Co2+在25 ℃的配位作用, 计算了1∶1配合物的稳定常数. 实验结果表明, 由于N-(2-苯氧乙基)引入氮杂冠醚环和参与配位, 18CE和15CE配合物的稳定常数分别比单氮杂-18-冠-6, N-(2-羟基乙基)单氮杂-18-冠-6, N-(2-甲氧基乙基)单氮杂-18-冠-6和单氮杂-15-冠-5, N-(2-甲氧乙基)单氮杂-15-冠-5, N-(2-甲氧乙基)单氮杂-15-冠-5的对应配合物明显提高. 配合物的稳定常数和紫外光谱皆提供了支链的苯氧基参与配位的信息. 相似文献
12.
Jong Seung Kim Won Ku Lee Wonbo Sim Jong Won Ko Moon Hwan Cho Do Young Ra Jong Wan Kim 《Journal of inclusion phenomena and macrocyclic chemistry》2000,37(1-4):359-370
A series of calix[4]arene-bis-crownethers were synthesized in a fixed 1,3-alternateconformation with good yields by the reaction of amonocyclic calixcrown ether with multi-ethyleneglycoldi-p-toluenesulfonate in the presence of cesiumcarbonate. In the preparation of the monocycliccalixcrown ethers (1 and 2), the use ofpotassium carbonate as a base provided the best yieldregardless of the template concept. In two phaseextraction and competitive transport experiments forligand-metal complexation, calix[4]arene biscrown(5) provided the best selectivity for potassiumion. When a calixbiscrown ether (4) bearingdifferent sized crown ether loops coordinates to K+and Cs+, respectively, the changes of peak splittingpatterns and chemical shift on 1H NMR spectra aredependent on the complexed metal ion species. 相似文献
13.
Chien-Chung Liou Jennifer S. Brodbelt 《Journal of the American Society for Mass Spectrometry》1992,3(5):543-548
Ladders of relative alkali ion affinities of crown ethers and acyclic analogs were constructed by using the kinetic method. The adducts consisting of two different ethers bound by an alkali metal ion, (M1 + Cat + M2)+, were formed by using fast atom bombardment ionization to desorb the crown ethers and alkali metal ions, then collisionally activated to induce dissociation to (M1 + Cat)+ and (M2 + Cat)+ ions. Based on the relative abundances of the cationized ethers formed, orders of relative alkali ion affinities were assigned. The crown ethers showed higher affinities for specific sizes of metal ions, and this was attributed in part to the optimal spatial fit concept. Size selectivities were more pronounced for the smaller alkali metal ions such as Li+, Na+, and K+ than the larger ions such as Cs+ and Rb+. In general, the cyclic ethers exhibited greater alkali metal ion affinities than the corresponding acyclic analogs, although these effects were less dramatic as the size of the alkali metal ion increased. 相似文献
14.
A simple and efficient synthetic protocol for an easy access of carbohydrate-linked crown ethers from cheap and readily available D-glucose in good yields has been devised. The base-mediated cyclization of sugar-linked bis-iodo podands in CH3CN with amines, including ethylamine and furfurylamine afforded the novel chiral monoaza-15-crown-5-type macrocyclic crown ethers anellated to 3-O-benzyl-1,2-O-isopropylidene-α-D-glucofuranose and 3-O-benzyl-1,2-O-isopropylidene-α-D-allofuranose. The glucose-based crown ethers have been characterized by spectroscopy techniques including IR, 1H NMR, and 13C NMR. 相似文献
15.
Júlia KertészBalázs Bognár Attila KormosIldikó Móczár Péter BaranyaiMiklós Kubinyi Tamás KálaiKálmán Hideg Péter Huszthy 《Tetrahedron》2011,67(46):8860-8864
Double (spin and fluorescence) labeled pyrroline derivatives of crown ethers containing an acridone or an acridine fluorophore unit (1 and 2) and their diamagnetic analogues (3 and 4) were synthesized. Their fluorescent behavior as well as their complexation properties toward selected metal ions (Na+, K+, Mg2+, Ca2+, Zn2+) were examined. 相似文献
16.
3‐Phenyl‐ and 3‐(p‐methoxyphenyl)‐7,8‐dihydroxy and ‐6,7‐dihydroxychromenones were prepared from ethyl 3‐oxo‐2‐phenylpropanoate, ethyl 3‐oxo‐2‐(4‐methoxyphenyl)‐propanoate and the trihydroxy benzenes in H2SO4. 3‐Aryl‐7,8‐ and 3‐aryl‐6,7‐dihydroxy‐2H‐chromenones reacted with the bis‐dihalides of poly‐glycols in DMF/MeCO3 to afford 12‐Crown‐4, 15‐Crown‐4 and 18‐Crown‐6‐chromenones. The products were identified with IR, 1H NMR, low and high resolution mass spectroscopy and elemental analysis. Some 1:1 cation association constants, Kb, of the 3‐phenyl chromenone crown ethers with Li+, Na+, K+ and Rb+ cations were studied by steady state emission fluorescence spectroscopy; Kb chromenone‐crown complexes displayed crown ether‐cation binding selectivity rules properly in acetonitrile. 相似文献
17.
Bis-crown ethers in which the benzo-15-crown-5 units were linked to 1,1′-positions of metallocene (M = Fe or Ru) with amide, ester, or ? C? C? bonds were synthesized. Complexing ability of the compounds with alkali, alkali earth, and transition metal cations were measured by the solvent extraction method. The results showed that these crown ethers had high affinity toward alkali metal cations (Li+, Na+, K+, and Rb+) and heavy-metal cations (Ag+ and Tl+). The difference of complexing ability for metal cations between ferrocene and ruthenocene derivatives could not be detected significantly. The extractability of metallocene-bis-crown ethers for metal cations was more larger than that of the corresponding mono-crown ethers, and irregular increments of extractability were explained by assuming the existence of a mixture of 1:1 and 2:1 complexes. 相似文献
18.
S. N. Dmitrieva M. V. Churakova N. A. Kurchavov A. I. Vedernikov L. G. Kuz’mina A. Ya. Freidzon A. A. Bagatur’yants Yu. A. Strelenko J. A. K. Howard S. P. Gromov 《Russian Chemical Bulletin》2010,59(6):1192-1206
A number of N-alkylnitrobenzoaza-15-crown-5 with the macrocycle N atom conjugated with the benzene ring were obtained. The structural and
complexing properties of these compounds were compared with those of model nitrobenzo- and N-(4-nitrophenyl)aza-15-crown-5 using X-ray diffraction, 1H NMR spectroscopy, and DFT calculations. The macrocyclic N atom of benzoazacrown ethers are characterized by a considerable
contribution of the sp3-hybridized state and a pronounced pyramidal geometry; the crownlike conformation of the macrocycle
is preorganized for cation binding, which facilitates complexation. The stability constants of the complexes of crown ethers
with the NH4
+, EtNH3
+, Na+, K+, Ca2+, and Ba2+ ions were determined by 1H NMR titration in MeCN-d3. The most stable complexes were obtained with alkaline-earth metal cations, which is due to the higher charge density at
these cations. The characteristics of the complexing ability of N-alkylnitrobenzoaza-15-crown-5 toward alkaline earth metal cations are comparable with analogous characteristics of nitrobenzo-15-crown-5
and are much better than those of N-(4-nitrophenyl)aza-15-crown-5. 相似文献
19.
Density Functional Theory Study of Selectivity of Crown Ethers to Li+ in Spent Lithium-Ion Batteries Leaching Solutions
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Yong-lin Yao Mei-ying Zhu Zhuo Zhao Wen-gang Liu Bi-hai Tong Ming-yang Li 《化学物理学报(中文版)》2019,32(3):343-348
It is a challenge to recover lithium from the leaching solution of spent lithium-ion batteries, and crown ethers are potential extractants due to their selectivity to alkali metal ions. The theoretical calculations for the selectivity of crown ethers with different structures to Li ions in aqueous solutions were carried out based on the density functional theory. The calculated results of geometries, binding energies, and thermodynamic parameters show that 15C5 has the strongest selectivity to Li ions in the three crown ethers of 12C4, 15C5, and 18C6. B15C5 has a smaller binding energy but more negative free energy than 15C5 when combined with Li+, leading to that the lithium ions in aqueous solutions will combine with B15C5 rather than 15C5. The exchange reactions between B15C5 and hydrated Li+, Co2+, and Ni2+ were analyzed and the results show that B15C5 is more likely to capture Li+ from the hydrated ions in an aqueous solution containing Li+, Co2+, and Ni2+. This study indicates that it is feasible to extract Li ions selectively using B15C5 as an extractant from the leaching solution of spent lithium-ion batteries. 相似文献
20.
The coordinative properties of perfluoro-15-crown-5 with monocations were investigated using 19F NMR spectroscopy and ion-selective electrodes with perfluoro-15-crown-5 as the matrix of their sensor membranes and the fluorophilic tetrakis[3,5-bis(perfluorohexyl)phenyl]borate as ion exchanger site. The results show that perfluoro-15-crown-5 interacts weakly but significantly with Na+ and K+. Assuming 1:1 stoichiometry, the formal complexation constants were determined to be 5.5 and 1.7 M−1, respectively. This weak binding is consistent with the strong electron withdrawing nature of the many fluorine atoms in the perfluorocrown ether. While perfluorinated crown ethers have been known to form host-guest complexes with the anions O2− and F− in the gas-phase, this is the first study that quantitatively confirms cation binding to a perfluorocrown ether. 相似文献