• Bulletin of the Korean Chemical Society
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• v.28 no.12
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• pp.2531-2534
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• 2007

• Bulletin of the Korean Chemical Society
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• v.29 no.9
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• pp.1831-1834
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• 2008

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1910-1912
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• 2006

• Bulletin of the Korean Chemical Society
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• v.10 no.6
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• pp.521-524
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• 1989

By cyclocondensation of 1,2-bis(2-hydroxybenzyl)benzene with oligoethylene glycol ditosylate, new crown ethers containing 1,2-dibenzylbenzene subunit were synthesized. By oxidation of the benzylic positions of them, carbonyl-containing crowns having 1,2-dibenzoylbenzene subunit were synthesized.

• Journal of the Korean Chemical Society
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• v.30 no.4
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• pp.359-368
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• 1986

Solvent extraction equilibria of alkali metal cation with crown ether (DC18C6, DC24C8) and HDEHP have been studied. The extraction equilibrium constants increase in the order of, in the DC18C6 system, $Na^+, and in the DC24C8 system, $Rb^+. The species extracted to organic phase are $M_1(crown ether)_1\;(HDEHP)_1$. The magnitude of extraction equilibrium constant is determined by the distribution ratio of crown ether between organic and aqueous phase, and stability constant of crown ether-alkali metal complex.

• Bulletin of the Korean Chemical Society
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• v.35 no.5
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• pp.1506-1510
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• 2014

A kinetic study on nucleophilic substitution reaction of 5-nitro-8-quinolyl picolinate (6) with alkali-metal ethoxides (EtOM; M = K, Na, and Li) in anhydrous ethanol is reported. The plot of $k_{obsd}$ vs. [EtOM] curves upward in the absence of crown ethers but is linear with significantly decreased reactivity in the presence of crown ethers. Dissection of $k_{obsd}$ into $k_{EtO}$- and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is significantly more reactive than the dissociated $EtO^-$ (e.g., $k_{EtOM}/k_{EtO^-}$ = 33.4-141). This indicates that the reaction of 6 is catalyzed by $M^+$ ions in the order $Na^+$ > $Li^+$ > $K^+$ and the catalytic effect disappears in the presence of a proper crown ether. Picolinate ester 6 is much more reactive and is more strongly catalyzed by $M^+$ ions than 5-nitro-8-quinolyl benzoate (5). It has been concluded that $M^+$ ions catalyze the reaction of 6 by increasing electrophilicity of the reaction center through a cyclic transition state, which is structurally not possible for the reaction of 5.

• Journal of the Korean Chemical Society
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• v.31 no.3
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• pp.250-257
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• 1987

The electrical conductances for the thorium (IV) complexes with crown ethers have been measured in DMSO, and water solvents, and the oxidation-reduction reaction mechanisms, electron number and diffusion coefficients in the reversible reduction process have been examined by polarography and cyclic voltammography. The dissociation mole ratio of $Th^{4+}$ and nitrate ion are 1:1 and in aprotic solvent, and 1:4 in protic solvent like as water. The limiting molar conductances of all complexes in aprotic solvent have been found to be in the range of $92.2{\times}159$ $ohm^{-1}cm^2mol^{-1}$. In aprotic solvent, DMSO, the reduction of each complex is reversible by one electron reduction of one step, and the range of diffusion coefficients is obserbed to be $5.83\;10^{-6}{\sim}6.90{\times}10^{-6}$. The complexes which have reduction step were hydrolyzed above at 1.8volt with reference saturated calomel electrode, generating the hydrogen gas. The reaction mechanisms of thorium (IV)-crown ether complexes appear as follows. ${Th_m(IV)L_n(H_2O)_x(NO_3)_{4y}}_=^{DMSO} {\overline{{Th_m(IV)L_n(H_2O)_x(NO_3)_{4y-1}}}^+ + NO_3-$

• Proceedings of the Korea Crystallographic Association Conference
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• 2001.05a
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• pp.14-14
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• 2001

• Proceedings of the Korean Society of Potoscience Conference
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• 2005.06a
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• pp.139-139
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• 2005

• Bulletin of the Korean Chemical Society
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• v.23 no.5
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• pp.688-692
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• 2002

The aminomethylation of phenols with para-substituents by the Mannich reaction has successfully been accomplished to produce the Mannich bases 2-6. The compounds 7-8 have also been synthesized in order to identify the effect of the side arms and t he macrocycle in the complex formation. Protonation constants and stability constants of the double armed diaza-18-crown-6 ethers 2-7 with metal ions have been determined by potentiometric method at 25 $^{\circ}C$ in 95 % methanol solution. Under a basic condition (pH > 8.0), the double-armed crown ethers 2-6 revealed stronger interaction with divalent metal ions than the simple diazacrown ether 1. The stability constants with these metal ions were Co 2+ < Ni2+ < Cu2+ > Zn 2+ in increasing order, which are in accordance with the order of the Williams-Irving series. The stability constants with alkali earth metal ions were Ca 2+ < Sr 2+ < Ba 2+ in increasing order, which may be explained by the concept of size effect. It is noteworthy that the hosts 2-6, which have phenolic side arms and a macrocycle, bind stronger with metal ions than the hosts 1 and 7. On the other hand, the host 8, which has phenolic side arms with a pyperazine ring,provided comparable stability constants to those with the host 3. These facts demonstrate that phenolic side arms play a more important role than the azacrown ether ring in the process of making a complex with metal ions especially in a basic condition. In particular, the log KML values for complexation of divalent metal ions with the hosts 2-6 had the sequence, i.e., 2 (R=OCH3) < 3 (R=CH3) < 4 (R=H) < 5 (R=Cl) < 6 (R=CF3). The stability constants of the hosts 5 and 6 containing an electron-withdrawing group are larger than those of the hosts 2 and 3 containing an electron-donating group. This substituent effect is attributed to the solvent effect in which the aryl oxide with an electron-donating group has a tendency to be tied strongly with protic solvents.