• 분석과학
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• 제10권1호
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• pp.60-65
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• 1997

mono-crown ether(benzo-15-crown-5)와 benzo-15-crown-5를 포함한 bis-(crown ether)s(ethylenediamine bis(4'-formylbenzo-15-crown-5))에 의한 알칼리금속과 알칼리토금속 양이온들의 용매추출을 $25^{\circ}C$, 물-클로로포름계에서 조사하였다. mono-crown ether와 bis-(crown ether)s를 사용한 경우 알칼리금속과 알칼리토금속 양이온들에 대한 추출평형상수($K_e$)와 착물형성상수($K_c$)의 크기 순위는 각각 Ca(II)>Na(I)>Sr(II)>K(I)>Mg(II)>Rb(I)와 Sr(II)>Ca(II)>K(I)>Rb(I)>Mg(II)>Na(I) 순으로 증가하였다. 이들 크기 순위는 금속 양이온의 크기 및 전자밀도효과로서 설명할 수 있었다. 또한 mono-crown ether에 비해서 bis-(crown ether)s를 사용한 경우 금속양이온들에 대한 추출효율이 좋게 나타남을 알 수 있었다.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2003년도 제5회 영호남 학술대회 논문집
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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.

• 한국응용과학기술학회지
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• 제32권1호
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• pp.31-39
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• 2015

용매추출법에서 희토류 금속을 효과적으로 분리하기 위해 추출제만 사용하는 것이 아니라 crown ether와 같은 첨가제를 이용하는 연구를 하였다. Host-guest 화합물인 macrocyclic ligand는 금속과 착화물을 형성하는데, 이 때 crown ether의 cavity 크기와 비슷한 크기의 금속 이온들과 안정한 착화물을 형성한다. 이전 연구에서 europium과 yttrium을 분리하기 위해 여러 사슬 길이의 지방산 추출제를 이용한 추출실험을 행하였었다. 이를 토대로 분리효율이 좋지 않았던 hexanoic acid에 크기가 다른 crown ether (18-crown-6 ether, 15-crown-5 ether, 12-crown-4 ether)를 첨가하여 분리효과가 증가하는 것을 연구하였다. hexanoic acid의 농도별로 분리효율을 본 후 가장 분리 효율이 좋은 농도에서 crown ether를 종류와 농도를 다르게 하여 첨가하였다. 그 결과 0.05 M hexanoic acid에서 분리능이 1.72으로 가장 높게 나타났고, crown ether를 첨가하였을 시 분리능이 0.002 M 15-crown-5 ether에서 가장 높게 나왔으며 기존의 분리능보다 2배 이상 더 높았다. 또한 crown ether를 첨가하였을 때 두 금속이 $MLR_3{\cdot}3RH$의 형태로 추출되는 것도 확인 할 수 있었다.

• 한국산업융합학회 논문집
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• 제6권1호
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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.

• 한국산업융합학회 논문집
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• 제6권2호
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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.

• 대한화학회지
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• 제30권4호
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• pp.359-368
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• 1986

Crown ether (DC18C6, DC24C8)과 HDEHP로 알칼리 금속 이온을 용매 추출할 때의 추출평형을 연구하였다. 추출평형상수는 DC18C6계에서 $Na^+순으로 증가하였으며 DC24C8계에서는 $Rb^+순으로 증가하였다. 유기용매상으로 추출되는 추출종은 $M_1(crown ether)_1\;(HDEHP)_1$이며 추출평형상수의 크기는 crown ether의 유기용매상과 수용액상에서의 분배비와 crown ether-알칼리금속 착물의 안정도 상수에 의해서 결정된다.

• 대한화학회지
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• 제32권1호
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• pp.71-78
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• 1988

20,21,24,25-Tetranitrodibenzo-18-crown-6에 알코올성 염기를 가하여 친핵성 치환반응을 유도하면 crown ether 화합물을 이루는 polyether 고리가 끊어져서 주생성물로 2,4,5-trialkoxynitrobenzene 유도체, 4,5-dialkoxy-1,2-dinitrobenzene 유도체 그리고 crown ether 고리가 부분적으로 끊어져 생긴 bis[(alkoxynitrophenoxy)ethyl]ether 유도체가 부생성물로 얻어졌다. 이가 알코올성 염기에서는 polyether 고리가 끊어진 생성물과 분자내 치환반응이 다시 진행되어 고리축소 현상이 일어나 12-crown-4의 유도체를 얻게 되거나 출발물질이 도로 생성되었다. 이상의 실험은 다양한 알코올의 농도에서 염기의 종류를 달리하여 그 선택성을 알아보았다.

• 한국응용과학기술학회지
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• 제22권1호
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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.

• 대한화학회지
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• 제29권3호
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• pp.205-212
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• 1985

2,2'-bipyridyl crown ether에 관한 allosteric 효과를 분자진동연구방법을 사용하여 연구하였는데, 방법으로는 mass-weighted-cartesian 좌표방법을 사용하였다. Crown ether의 pore opening 운동에 관여하는 모드로는 235, 234, 188 그리고 178cm$^{-1}$에 해당되는 파수가 얻어졌고, biphenyl축을 통한 회전운동이 crown ether에 영향을 미치는 rotational vibration 운동은 168, 104 그리고 67cm$^{-1}$에서 파수가 얻어졌다. 특히 178cm$^{-1}$의 모드는 allosteric효과를 가장 많이 포함한 것으로 생각되어 진다.

• 한국응용과학기술학회지
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• 제22권3호
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• pp.219-227
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• 2005

Competitive solvent extraction of the mixure of alkali metal and alkaline earth cation from water into organic solvent containing the crown ether carboxylic acid and anlogous crown ether phosphonic acid was investigated as follows. The lipophilic group is found to strongly influence to the selective extraction in the mixed systems from only alkali metal cation for sym-(n-decyldibenzo)-16-crown-5-oxyacetic acid $\underline{1}$ to mostly alkaline earth metal cation for sym-bis[4(5)-tert-butylbenzo]-16-crown-5-oxyacetic acid $\underline{3}$. Monoethyl sym-(n-decyldibenzo)-16-crown-5-oxymethylphosphonic acid $\underline{2}$. and monoethyl-sym- bis]4(5)-tert-butylbenzo]-16-crown-5-oxymethylphosphonic acid $\underline{4}$ showed good selectivity for $Na^+$ over $Mg^{2+}$, the second extracted ion. Structural variation in the crown ether phosphonic acid somewhat was influenced to the extraction selectivity in the mixed systems. when variation of the ionized group is influenced in the mixed systems, the selectivity of $Na^+$ as the second extracted ion was much better crown ether carboxylic acid $\underline{1}$ than crown ether phosphonic acid $\underline{2}$, while the efficiency of $Na^+$ extraction was better $\underline{2}$ (83% total loading) than $\underline{1}$ (32%).