• Analytical Science and Technology
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• v.10 no.1
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• pp.60-65
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• 1997

Solvent extraction of alkali metal and alkaline earth metal cations by mono-crown ether(benzo-15-crown-5) and bis-(crown ether)s(ethylenediamine bis(4'-formyl benzo-15-crown-5)) containing benzo-15-crown-5 moieties were investigated with water-chloroform system at $25^{\circ}C$. The order of the extraction equilibrium constants($K_e$) and the complexation constants($K_c$) for the alkali metal and alkaline earth metal cations with mono-crown ether and bis-(crown ether)s were Ca(II)>Na(I)>Sr(II)>K(I)>Mg(II)>Rb(I) and Sr(II)>Ca(II)>K(I)>Rb(I)>Mg(II)>Na(I) respectively. These results were explained in terms of the size effect of metal cation and electron density effect. Also, the bis-(crown ether)s was found to extract metal cations more effectively than the corresponding mono-crown ether.

• Journal of the Korean Chemical Society
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• v.39 no.9
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• pp.698-704
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• 1995

The ion-selective membrane fabricated with 33 wt% PVC, 66 wt% o-NPOE and 1 wt% 4'-benzothiazolylbenzo-15-crown-5 (TB15C5) as a neutral carrier exhibited an enhanced selectivity to potassium ion over sodium ion compared to those prepared with other 15-crown-5 or 18-crown-6 derivatives. The potentiometric properties (response slope, selectivity, detection limits and lifetime) of TB15C5-based ISE membranes along with those based on valinomycin, benzo-15-crown-5 (B15C5), 4'-aminobenzo-15-crouwn-5 (AB15C5), benzo-18-crown-6 (B18C6), dibenzo-18-crown-6 (DB18C6) and bis[(benzo-15-crown-5)-4'-ylmethyl]pimelate (PI-Ⅱ) ionophores were carefully examined under the same experimental conditions. The enhanced selectivity of TB15C5-based membrane to potassium is explained in terms of the effect of the benzothiazol functional group and the distribution coefficients of metal ions.

• Journal of the Korean Society of Industry Convergence
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• v.6 no.1
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• pp.73-80
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• 2003

We report herein synthetic results obtained six new types of bis-benzocrown ethers containing imine group. Bis crown ethers1~3 are aminobenzo-15-crown-5-ether linked with terephthalaldehyde, isophthalaldehyde, phthaldehyde respectively by imine reaction. Bis crown ethers1~3 are different distances in each crown ether rings. Bis crown ether 4 has large cavity in crown ethers. Functionalized crown ether 5 is synthesized amonobenzo-15-crown-5-ether and terephthaladehyde same ratio at one to one. Bis crown ether 6 has photosensitive linkage between crown ethers. Bis crown ether 7 is prepared by amonobenzo-15-crown-5-ether and triethyl ortho formate. 4'-Nitrobenzo-crown ethers and 3',4'-dinitrobenzo-crown ethers were prepared by nitration of benzo crown ethers, obtained from the reaction of catechol and oligoethylene glycol ditosylate. Crown ethers containing aldehyde group were synthesized from the reaction of 3,4-dihydroxybenzaldehyde and corresponding ditosylate respectively. The synthesized crown ethers were characterized respectively by IR, NMR, GC-Mass.

• Journal of the Korean Chemical Society
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• v.40 no.2
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• pp.117-121
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• 1996

Two new crown ethers containing nitrogen and sulfur atoms adjacent to the crown rings were prepared. 4'-Benzothiazolylbenzo-12-crown-4 (1) or 4'-benzothiazolylbenzo-15-crown-5 (2) were synthesized by reaction of 2-aminothiophenol with 4'-formylbenzo-12-crown-4 (3) or 4'-formylbenzo-15-crown-5 (4) respectively. (3) and (4) were obtained by reaction of 3, 4-dihydroxybenzaldehyde with tri- or tetraethyleneglycol ditosylate. Triethyleneglycol ditosylate or tetraethyleneglycol ditosylate were synthesized by reaction of p-toluenesulfonylchloride with triethyleneglycol or tetraethyleneglycol in the presence of sodium hydroxide.

• Journal of the Korean Chemical Society
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• v.39 no.4
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• pp.266-274
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• 1995

The extractions of aqueous Eu3+ and Tb3+ ions into ethylacetate or dichloromethane were conducted by using 12-crown-4, 15-crown-5 and 18-crown-6 ethers as ligand. Benzoate ion was selected as counter anion for the complexes formed between the lanthanide ions and crown ethers. Fluorescence spectra of the lanthanide ions induced by the energy transfer from benzoate anion to the cations were also measured. The quantitative analysis of the lanthanide ions extracted into organic phase were made on the basis of the results of fluorescence. The measured extractivity is interpreted in terms of the ion-dipole interaction.

• Journal of the Korean Society of Industry Convergence
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• v.6 no.2
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• pp.109-113
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• 2003

We report herein synthetic results obtained new types of crown ethers containing coumarin group. Crown ethers containing coumarin group 1~3 are hydroxymethyl-15-crown-5-ether linked with 4-hydroxy coumarin-4-acetic acid by esterification reaction. Crown ethers containing coumarin group 1~3 have different cavity in each crown ether rings. The 12-crown-4 ether with coumarin 1 has the smallest cavity size. The 15-crown-5 ether with coumarine 2 has the medium cavity size. The 18-crown-6 ether with coumarin 3 has the largest cavity size. Therefore each crown ether with coumarin group will recognize different ionic radius meta. Because of different hole size in crown ethers, these crown ethers seem to be had different selectivity in luminescent sensors. The crown ethers with coumarine 1~3 synthesized hydroxymethyl-15-crown-5-ether and 4-hydroxy coumarin-4-acetic acid same ratio at one to one. The synthesized crown ethers were characterized respectively by IR, NMR. GC-Mass.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2003.08a
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• pp.110-113
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• 2003

We report herein synthetic results obtained six new types of bis-benzocrown ethers containing imine group. Bis crown ethers l~3 are aminobenzo-15-crown-5-ether linked with terephthalaldehyde, isophthalaldehyde, phthaldehyde respectively by imine reaction. Bis crown ethers l~3 are different distances in each crown ether rings. Bis crown ether 4 has large cavity in crown ethers. Functionalized crown ether 5 is synthesized amonobenzo-l5-crown-5-ether and terephthaladehyde same ratio at one to one. Bis crown ether 6 has phothosensitive linkage between crown ethers. Bis crown ether 7 is prepared by amonobenzo-l5-crown-5-ether and triethyl ortho formate. 4'-Nitrobenzo-crown ethers and 3',4'-dinitrobenzo-crown ethers were prepared by nitration of benzo crown ethers, obtained from the reaction of catechol and oligoethylene glycol ditosylate. Crown ethers containing aldehyde group were synthesized from the reaction of 3,4-dihydroxybenzaldehyde and corresponding ditosylate respectively. The synthesized crown ethers were characterized respectively by IR, NMR. GC-Mass.

• Journal of the Korean Chemical Society
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• v.41 no.7
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• pp.337-342
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• 1997

Acryloylmethylbenzo-15-crown-5 was prepared from the reaction of 4'-hydroxymethylbenzo-15-crown-5 with acryloyl chloride. And, poly(acryloylmethylbenzo-15-crown-5) [poly(AMB15C5)] was synthesized by radical polymerization using AIBN as initiator in benzene. Coated wire lead(II) ion-selective electrodes ($Pb^{2+}$-CWISEs) using either poly(AMB15C5) or B15C5 as neutral carrier were prepared, respectively. $Pb^{2+}$-CWISEs gave linear responses with slopes of 28$\pm$ 1mV per decade within the concentration range of $10^{-5} M{\sim}10^{-1}$ M, respectively. Also, the detection limits were $10^{-6}$ M and response times were either 3 or 5 min. for B15C5 and poly(AMB15C5), respectively. $Pb^{2+}$-CWISE base on B15C5 was rather unstable than poly(AMB15C5)'s due to solubility of the B15C5 in water. The selectivity coefficients of a variety of interfering ions such as $Mg^{2+},\; Ca^{2+},\; Co^{2+},\; Ni^{2+},\; Cu^{2+},\; Zn^{2+}$ and $Cd^{2+}$ were small ($10^{-4}{\sim}10^{-5}$), while those of $Na^+$ and $K^+$ were large (0.1∼0.01). In addition, the electrode responses depended upon the pH of test solution and the composition of the membrane. In the range pH 3∼6 of test solution, potentials of Pb2+-CWISEs were hardly changed. The optimal contents of B15C5 and poly(AMB15C5) were 7.7 wt% and 13.1 wt%, respectively.

• Fibers and Polymers
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• v.3 no.2
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• pp.49-54
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• 2002

Radical copolymerization behavior of 4'-vinylbenzo-15-crown-5, a vinyl monomer having a pendant 15-membared crown ether unit (VCE) with di(ethylene glycol) ethyl ether acrylate (DEGEEA) was carried out in toluene solution using 2,2-azobisisobutyronitrile (AIBN) as an initiator. The copolymers were characterized by means of FT-IR, $^1{H-NMR}$, and $^{13}{C-NMR}$ . The reactivity ratio of VCE and DEGEEA, determined by Fineman-Ross and Kelen-Tudos method, gave values 0.55 for VCE, and 0.11 for DEGEEA respectively.

• Journal of the Korean Applied Science and Technology
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• v.32 no.1
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• pp.31-39
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• 2015

The synergistic solvent extraction of rare earth elements such as europium and yttrium has been investigated by the extractant with crown ether as an additive. Macrocyclic ligand as host-guest compounds form more stable complexes with metal ions which have the similar size of the cavity of crown ether. In our previous study[14] founded that the extraction used fatty acid of the various alkyl chain length. Based on the results of the previous experiment, the synergistic separation effect of two metals investigated that the hexanoic acid had was the worst extraction effect which added a crown ether such as 18-crown-6 ether, 15-crown-5 ether, and 12-crown-4 ether. In this study, the concentrations of hexanoic acid have showed the separation effect, and then the concentrations and kind of crown ether are performed for synergistic extraction at the hexanoic acid concentration of the highest separation effect. As a results, the separation rate is the highest value of 1.72 at 0.05 M hexanoic acid, and 0.002M 15-crown-5 ether is the best value in other concentrations and kind of crown ether, it is about twice of using only hexanoic acid. Moreover, the extraction species of two metals has been founded $MLR_3{\cdot}3RH$ form when added the crown ether.