• 대한화학회지
• /
• 제58권2호
• /
• pp.193-197
• /
• 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.

• KSBB Journal
• /
• 제8권4호
• /
• pp.370-374
• /
• 1993

Crown ether류인 dibenzo-18-crown-건를 carn­e er로 이용하여 액체막을 통해서의 금속이온의 이동 량을 picric acid의 absorbance를 ultraviolet spec trometer로 측정하여 평가하였다. 그 결과 dibenzo 18-crown-6에 의한 금속이온의 이동은 2가 금속이 온이 l가 금속이온 보다도 더 컷다. 이것은 이 계에 서는 이들 금속이온의 크기보다도 이온의 전하와 수 화(hydration)의 영향을 받았다. 이것은 18-crown-6가 $Ca^{2+}$이온과 같은 2가 이온의 수송에 적합하다 는 것을 의미한다. 또한 dibenzo-18-cro뻐-6에 의 한 이온의 수송은 이온의 선택성을 갖지 않고 이온을 포착할 수 있는 능력을 갖는 것이 좋은 것으로 확인되였다.

• Mass Spectrometry Letters
• /
• 제7권4호
• /
• pp.96-101
• /
• 2016

To determine the influence of the cationization agent on the collision activated dissociation (CAD) fragmentation behavior of oligosaccharides, the CAD spectra of the singly protonated, sodiated oligosaccharides and singly sodiated and dibenzo-18-crown-6 ether conjugated oligosaccharides were carefully compared. Each of these three different species showed quite different fragmentation spectra. The comparison of singly protonated and sodiated oligosaccharide CAD spectra revealed that different cationization agents affected the cationization agent adduction sites as well as the fragmentation sites within the oligosaccharides. When the mobility of $Na^+$ was limited by the dibenzo-18-crown-6 ether encapsulation agent, the examined linear oligosaccharides showed fragmentation patterns quite different from the unmodified ones. For the dibenzo-18-crown-6 ether conjugated oligosaccharides, the charge-remote fragmentation pathways were more likely to be activated than the chargedirected pathways. This work demonstrates that dibenzo-18-crown-6 ether conjugation can potentially provide a route to selectively activate the charge-remote fragmentation pathways, albeit to a limited extent, in tandem mass spectrometry studies.

• 약학회지
• /
• 제39권1호
• /
• pp.61-67
• /
• 1995

PVC membrane electrodes based on the lipophilic neutral carrier, dibenzo-18-crown-6, cyclic oligomers of teit-butylphenol-formaidehyde condensates, calix[4]arenes as the active sensors for verapamil have been prepared and tested in a variety of plasticizers. At pH 5.0, the electrode exhibits a Nernstian response in the range of 10$^{-2}$~5$\times$10$^{-5}$ M verapamil with a slope of 49.1$\pm$0.5mV per concentration decade. The electrode constructed in this work can be used continuously for at least 1 month before any damage to the membrane occurs. And the analyses of the local anesthetic amine, which are good to select a specific compound in a mixed solution, were also accomplished by using of another neutral carrier, a DB18C6, for comparing with calix[4]arene.

• 분석과학
• /
• 제11권4호
• /
• pp.248-253
• /
• 1998

수용액에서 poly-dibenzo-18-crown-6를 이용한 알칼리, 알칼리토금속이온 및 전이금속이온들의 흡착 및 분리특성을 조사하였다. 알칼리금속이온들과 알칼리토금속이온들의 흡착정도와 분포비의 순위는 각각 Li(I)

• Bulletin of the Korean Chemical Society
• /
• 제33권8호
• /
• pp.2669-2674
• /
• 2012

Crown ether is one of well-known host molecules and able to selectively sequester metal cation. We employed M06-2X density functional theory with IEFPCM and SMD continuum solvation models to study selectivity of dibenzo-18-crown-6-ether (DB18C6) for alkaline earth dications, $Ba^{2+}$, $Sr^{2+}$, $Ca^{2+}$, and $Mg^{2+}$ in the gas phase and in aqueous solution. $Mg^{2+}$ showed predominantly strong binding affinity in the gas phase because of strong polarization of CO bonds by cation. In aqueous solution, binding free energy differences became smaller among these dications. However, $Mg^{2+}$ had the best binding, being incompatible with experimental observations in aqueous solution. The enthalpies of the dication exchange reaction between DB18C6 and water cluster molecules were computed as another estimation of selectivity in aqueous solution. These results also demonstrated that $Mg^{2+}$ bound to DB18C6 better than $Ba^{2+}$. We speculated that the species determining selectivity in water could be 2:1 complexes of two DB18C6s and one dication.

• 대한화학회지
• /
• 제32권1호
• /
• pp.71-78
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• 제29권10호
• /
• pp.1973-1976
• /
• 2008

Electronic photodepletion spectrum of dibenzo-18-crown-6 with a potassium ion ($K^+$-DB18C6) was obtained in the gas phase using electrospray ionization and quadrupole ion-trap reflectron time-of-flight mass spectrometry. The spectrum exhibited rather a broad absorption band at 36350 $cm^{-1}$, which was tentatively assigned as the origin of the S1 band. The photodepletion spectrum of $Cs^+$-DB18C6 was also obtained to elaborate the effects of metal cations on electronic and geometric structures of metal cation-DB18C6 complexes. We found that the S1 band of $Cs^+$-DB18C6 was red-shifted by 180 $cm^{-1}$ from that of $K^+$-DB18C6. With the results of quantum theoretical calculations using the density functional theory, we suggested that the red-shift arose mainly from weaker binding of $Cs^+$ to DB18C6 than that of K+, which resulted from a larger size of $Cs^+$ than that of the cavity in DB18C6.

• 한국안전학회지
• /
• 제9권1호
• /
• pp.68-75
• /
• 1994

The cetylpyridium ion-selective electrode were developed by dibenzo-18-crown-6 for auto control of the chemical plants. The effect of content of active material and the membrane thickness on the response characteristics of electrode such as the linear reponse range, the detection limit, and Nemstian slope of the electrod, were studied. The electrode characteristics was better with decreasing the content of active material above the optimum content, but became worse below these. DBP was best as a plasticizer, The effect of the membrane thickness on the electrode characteristics was improved with decreasing the membrane thickness, but below the optimum membrane thickness the electrode exhibited an inverse trend.

• 대한화학회지
• /
• 제27권3호
• /
• pp.208-212
• /
• 1983

알칼리토금속이온과 dibenzo-18-crown-6이 디메틸술폭시드, 디메틸포름아미드, 아세토니트릴용매에서 이루는 착물의 안정도상수를 일정한 이온세기에서 $25{\circ}C$와 $35{\circ}C$에서 전기전도도법으로 각각 구하였다. 안정도상수의 순위는 모든 용매에서 $Ca^{2+}이었다. 그 크기는 용매의 염기도에 역으로 비례하였다. 이러한 결과를 이온-공동의 상대적 크기, 용매의 염기도 및 용매화 현상으로 설명하였다.