• Journal of the Korean Chemical Society
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• v.58 no.2
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• pp.193-197
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• 2014

Dibenzo-18-crown-6, dibenzo-21-crown-7 and dihydroxy dibenzo-18-crown-6 were synthesized by Bayer-Villiger oxidation strategy. Dibenzo-18-crown-6 and dibenzo-21-crown-7 could be synthesized through a three-step protocol starting from salicylaldehyde. Salicylaldehyde was reacted with bis-(2-chloroethyl)ether using $K_2CO_3$ in acetonitrile to link the two phenolic groups with the oxyethylene bridge followed by conversion of the formyl group to the hydroxy group via a Baeyer-Villiger reaction and finally linking the two phenolic group with appropriate oxyethylene bridge. The two target crown ethers were obtained in overall yield, 24% and 30%, respectively. This method has a great potential for synthesis of symmetrical as well as unsymmetrical dibenzo crowns with varying oxyethylene bridges. Baeyer-Villiger oxidation could be used to prepare dihydroxy derivative of dibenzo-18-crown-6 through acetylation of dibenzo-18-crown-6 followed by Baeyer-Villiger oxidation. The Baeyer-Villiger oxidation could be substantially accelerated using trifluoroacetic acid.

• 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.

• Analytical Science and Technology
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• v.6 no.1
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• pp.83-92
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• 1993

The electrochemical behaviors of lanthanide ion(La and Nd) and lanthanide complexes with 2, 2, 6, 6-tetramethyl-3, 5-heptanedione(THD), sym-hydroxydibenzo-16-crown-5(HD16C5) and sym-dibenzo-16-crown-5-oxyacetic acid(D16C5A) ligands in acton solution have been investigated by the use of cyclic voltammetry and direct current polarography. The peak potential and peak current, their dependency on the concentration, temperature, the reversibility of the eleotrode reactions are described. The reduction of the lanthanide ions and complexes in 0.05 M TEAP proceeded one-electron step in first step and one two-electron step in second step. These reduction step was irreversible and the reduction current was diffusion controlled. Macrovcyclic crown ethers, sym-hydroxydibenzo-16-crown-5(HD16C5) and sym-dibenzo-16-crown-5-oxyacetic acid(D16C5A), were prepared from 1, 5-bis-(2-hydroxyphenoxy)-3-oxapentane with epichlorohydrin. The voltammetric behaviors of Ln(III)-HD16C5 and Ln-D16C5A complexes in aceton solution have been investigated by the voltammetric method. The composition and stability constants of lanthanide complexes were determined.