• Journal of the Korean Applied Science and Technology
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• v.22 no.1
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• pp.9-14
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• 2005

Competitive solvent extraction of alkaline earth metal cations from water into organic solvent containing the carboxylic acid crown ether and analogous crown ether phosphonic acid monoethyl esters were investigated. sym-(n-Decyldibenzo)-16-crown-5xyacetic acid $\underline{1}$ and monoethyl sym-(n-decyldibenzo)-16-crown-5-oxymethylphosphonic acid $\underline{3}$ are structurally identical except for the ionizable groups. Both of them provide similar extraction behavior in terms of efficiency and selectivity, but monoethyl sym-(n-decyldibenzo)-16-crown-5-oxymethylphosphonic acid $\underline{3}$ showed higher alkaline earth metals loadings at acidic or neutral media. Monoethylsym-(n-octyldibenzo)-16-rown-5-oxymethylphosphonic acid $\underline{2}$ showed better selectivity and alkaline earth metals loading than did the analogous sym-(n-octyldibenzo)-16-crown-5-oxymethyldiphosphonic acid $\underline{6}$.

• 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.53 no.5
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• pp.521-529
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• 2009

Molecular structures of the various conformers for the 1,3-dimethoxy-p-tert-butylthiacalix[4] crown-5-ether (3) were optimized by using DFT B3LYP/6 - 31 + G(d,p) and mPW1PW91/6 - 31 + G(d,p) (hybrid HF-DF) calculation methods. We have analyzed the energy differences and structures of eight in/out orientations (cone_oo, cone_oi, pc_oo, pc_io, pc_oi, pc_ii, 13a_oo, 13a_io) of two methoxy groups in three major conformations (cone, partial-cone and 1,3-alternate). The 13a_oo (out-out orientation of the 1,3-alternate conformer) is calculated to be the most stable among eight different conformations of 3, and in accord with the experimental result. The ordering of relative stability resulted from the mPW1PW91/6 - 31 + G(d,p) calculation method is following: 13a_oo > 13a_io$\sim$pc_io$\sim$cone_oo > cone_oi$\sim$pc_oo$\sim$pc_oi > pc_ii.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.37-45
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• 1989

Voltammetric behavior of alkylammonium ion was studied in the absence and in the presence of crown ether in propylene carbonate as solvent. The peak potentials and the peak currents, their dependency on the concentrations, the reversibility of the electrode reactions are described. In the presence of crown ether chemical reaction might be preceeded before the electron-transfer process, the peak potential for the reduction shifts at the negative direction as the concentration of crown ether to the electrolyte solution increases. The addition of crown ether(20mM 18CR6)to the electrolyte solution made it possible to determine voltammetrically the dialkylammonium ions($Me_2NH^{+}_{2};O.6{\sim}0.8mM$) in the presence of the monoalkylammonium ions ($EtNH^{+}_{3} ;1.6mM$) and the monoalkylammonium ions ($EtNH^{+}_{3} ; 0.5{\sim}2.5mM$) in the presence of the dialkylammonium ions($Me_2NH^{+}_{2};0.5mM$)

• Journal of the Korean Graphic Arts Communication Society
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• v.19 no.1
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• pp.17-27
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• 2001

플라티늄포르피린 핵과 주위에 8, 16, 32 그리고 64 개의 벤질 단위를 갖는 새로운 덴드리머를 압력 감지형 페인트에 사용할 발광체로 합성하였다. 플라티늄포르피린 핵을 갖는 제 1 세대의 덴드리머는 Lindsey형 합성법을 이용하여 제조하였으며, 제 2 세대에서 제 4 세대까지의 플라티늄포르피린 핵을 갖는 덴드리머는 플라티늄 테트라키스(3,5-디히드록시페닐)포르피린을 적합한 덴드론 브로마이드와 Williamson 에테르 합성법에 따라 알킬화반응시켜 제조하였다. 이러한 에테르 연결의 생성 반응들은 $K_2$CO$_3$와 18-크라운-6를 사용하여 아세톤 용매에서 질소 기류 하에서 6$0^{\circ}C$에서 수행하였을 때 가장 좋은 결과를 주었다. 그리고 이렇게 합성한 덴드리머들을 $^1$H-NMR, $^{13}$C-NMR, Mass spectrum 이용하여 구조를 확인하고, 그리고 UV-VIS spectroscopy를 이용하여 분광학적인 특성을 조사하였다.

• 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.

• KSBB Journal
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• v.25 no.5
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• pp.449-452
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• 2010

L-Thyroxine possessing a chiral center, the naturally occurring thyroid hormone has been used for the treatment of thyroid dysfunctions and marketed as levothyroxine (L-thyroxine) sodium salt. In this study, after extraction of levothyroxine tablet as a pre-treatment process, direct enantiomer separation of thyroxine on crown ether derived chiral columns for determination of optical purity was performed using reversed mobile phase with acid additive. The chromatographic method developed in this study was applied in the determination of optical purity of several current domestic and foreign commercialized levothyroxine tablets. Optical purity values of these commercialized L-thyroxine sodium tablets except one were higher than 99 percents.

• Journal of the Korean Chemical Society
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• v.38 no.7
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• pp.509-515
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• 1994

The interactions of 11 kinds of primary and secondary alkylammonium ions with cyclic (12C4, 15C5, 18C6, DT18C6 and DA18C6) and acyclic$(Q_2O_5)$ polyethers were investigated by NMR titration and conductometry. All of the alkylammonium ions under investigation form the relatively stable 1 : 1 complexes with crown ethers and acyclic polyether by H-bond. The interactions of alkylammonium ions with analogeous hosts having different size were in the order of 18C6 > 15C5 > 12C4, and the strengthes of donor atoms toward the alkylammonium ions were in the order of N > O > S. 18C6 forms more favorable interactions with primary alkylammonium ions than secondary alkylammonium ions, otherwise DA18C6 shows the opposite behaviors. The stability constants for complexations of 18C6 with the alkylammonium ions were determined conductometrically in methanol at 25$^{\circ}C$. The major factors affecting the stability of complexes were the type of alkylammonium ions, the length of alkyl-chain and the steric hindrance due to the structure of alkyl groups on complexation.

• Journal of the Korean Applied Science and Technology
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• v.22 no.1
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• pp.50-55
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• 2005

A comparison of alkali metal cation and alkaline earth cation solvent extraction was made for three additional monoionizable crown ethers and one diionizable crown ether. sym-(n-Octyldibenzo)-16-crown-5-oxyacetic acid $\underline{1}$ exhibited high efficiency and selecvity in solvent extraction of alkali metal cations with respect to that observed with alkaline earth cations. Sizes of $Na^+$ and $Ca^{2+}$ appropriately match with the cavity size of monoethyl sym-bis[4(5)-tert-butylbenzo]-16-crown-5-oxymethylphosphonic acid $\underline{3}$. As the result, $Na^+$ and $Ca^{2+}$ are the best extracted. sym-(n-Octyldibenzo)-16-crown-5-oxymethyldiphosphonic acid $\underline{4}$was found to be somewhat selective for $Na^+$ over $Li^+$ and other alkaline earth metal cations. In the complexation of alklaine earth cations by crown ether diphosphonic acid $\underline{4}$, $Ca^{2+}$ and $Sr^{2+}$ are the appropriate sizes, but lager $Ba^{2+}$ may be due to favorable formation of a sandwich type complex between the crown ether cavity and the dianion of the deprotonated crown ether phoaphonic acid moiety.

• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.34-43
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• 1980

The reaction of thianthrene cation radical perchlorate with thioxanthene in acetonitrile gave thianthrene and dark reddish thioxanthylium ion instead of thioxanthene cation radical. Addition of aromatic nucleophiles such as anisole, aniline, N,N-diethylaniline, catechol, ethylbenzene, to the above mixture yielded the corresponding thioxanthenes with substituent at 9 position. Reactions with dibenzo-18-crown-6-ether, diphenylmercury, and triphenylphosphine gave similar products. However, reactions with aromatics with electron-withdrawing group were either too slow or inert to such a reaction.