• Title/Summary/Keyword: Co(salen)

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Asymmetric Ring Opening Reaction of Racemic Epoxides by Polymeric Chiral Salen Catalyst containing Metal Salts (금속염 함유 고분자형 키랄 살렌촉매에 의한 라세믹 에폭사이드의 광학선택적 비대칭 고리열림반응)

  • Lee, Kwang Yeon;Rahul, B. Kawthekar;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.18 no.6
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    • pp.562-567
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    • 2007
  • The stereoselective synthesis of chiral terminal epoxide is of immense academic and industrial interest due to their use as versatile starting materials as well as chiral intermediates. In this study, new polymeric chiral Co(salen) complexes bearing tallium (III)chloride and iron (III)chloride (ferric chloride) have been synthesized and characterized. Their catalytic activity and selectivity have been demonstrated for the asymmetric ring opening of various terminal epoxides using water and phenol derivatives as nucleophiles. The easily prepared polymeric complexes exhibited very high enantioselectivity for the asymmetric ring opening of epoxides with $H_2O$ and phenol nucleophiles, providing enantiomerically enriched terminal epoxides (> 98% ee). The system described in this work is very efficient for the synthesis of chiral epoxide, 1,2-diol and ${\alpha}$-aryloxy alcohol intermediates.

Dependence of Electronic Spectra on the Degree of Conjugation in Organocobalt(Ⅲ) Complexes (공액도에 따른 유기코발트 착화합물의 전자스펙트럼에 관한 연구)

  • Hye Kyung Seo;Chan Ah Bong;Young Ae Hwang Park
    • Journal of the Korean Chemical Society
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    • v.37 no.12
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    • pp.1047-1052
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    • 1993
  • The electronic spectra of enzyme-model organocobalt(Ⅲ) complexes containing completely or partially conjugated macrocyclic ligands were measured in various solvents to investigate the solvent effect on the charge transfer band for the axial cobalt-carbon bond by the extent of conjugation in the equatorial macrocyclic ring; completely conjugated, $CH_3CoL,\;C_6H_5CoL,\;CNCoL,\;CH_3CoL',\;CNCoL'$, partially conjugated $CH_3(py)Co(DH)_2, CH_3CoL"$, unconjugated dienes, $[CH_3Co(1,4-CT)](ClO_4)_2$, and open ring, $CH_3Co(salen)$. The position of the charge transfer band which corresponds to the cobalt-carbon bond was shifted to a shorter wavelength as the polarity of solvent increased and the transition energy $(E_T)$ had a linear relationship with solvent polarity parameter, Z-value, only in the case of completely conjugated system. However, the linear correlation between $E_T$and Z was not observed for partially conjugated and open ring systems.

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Mesoporous Silica-Carbon Composite Membranes for Simultaneous Hydrolysis and Separation of Chiral Epoxide (카본/메조세공 실리카 복합 막을 응용한 키랄 에폭사이드의 가수분해반응과 동시 분리)

  • Choi, Seong Dae;Jeon, Sang Kwon;Park, Geun Woo;Yang, Jin Young;Kim, Geon-Joong
    • Applied Chemistry for Engineering
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    • v.25 no.5
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    • pp.503-509
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    • 2014
  • The carbon/porous silica composite membrane was fabricated in a simple manner, which could be successfully for the simultaneous separation and production of chiral epoxides and 1,2-diols, based on their differences in hydrophilic/hydrophobic natures. The chiral Co(III)-$BF_3$ salen catalyst adopted in the membrane reactor system has given the very high enantioselectivity and recyclability in hydrolysis of terminal epoxides such as ECH, 1,2-EB, and SO. The optically pure epoxide and the chiral catalyst were collected in the organic phase after hydrolysis reaction. The hydrophilic water-soluble 1,2-diol product hydrolyzed by chiral salen diffused into the aqueous phase through the SBA-16 or NaY/SBA-16 silica composite layer during the reaction. The water acted simultaneously as a reactant and a solvent in the membrane system. One optical isomer was obtained with high purity and yield, and furthermore the catalysts could be recycled without observable loss in their activity in the continuous flow-type membrane reactor.

The Extraction of Metal Contaminants using Supercritical CO2 (초임계이산화탄소를 이용한 방사성 금속이온 추출)

  • Ju, Minsu;Kim, Jung-Hoon;Kang, Se-Sik
    • The Journal of the Korea Contents Association
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    • v.16 no.5
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    • pp.660-667
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    • 2016
  • Conventional decontamination methods utilize water-based systems, which generate high amounts of secondary wastes. Herein, we describe an environmentally benign decontamination method using liquid and supercritical $CO_2$. The use of $CO_2$ as a solvent affords effective waste reduction by its ability to be recycled, thereby leaving be hind only the contaminants upon its evaporation. In this study, a $CO_2$ solution process was assessed using t-salen(t-butylsalen), DC18C6 (dicyclohexano-18Crown6), 8-HQN(8-hydroxyquinoline), NEt4PFOSA(perfluoro-1-octanesulfonic acid tetra-ethyl ammonium salt), and NEt4PFOA(pentadecafluorooctanoic acid ammonium salt) to extract spiked radioactive contaminants(Nb,Zr,Co,Sr) from an inert sample matrix, namely filter paper. With the static extraction method, Sr was extracted with a maximum extraction rate of 97%, and Nb was extracted with a maximum extraction rate of 75%. Additionally, we were also able to extract Co and Zr with maximum extract ion ratesof 73% and 64%, respectively.

[살렌-크롬(III)]·Cl 착물을 단일 촉매로 한 고리형 카보네이트와 폴리카보네이트가 생성되는 반응 경로 제시

  • Park, Hyeon-U;Kim, Yeon-Jun;Baek, Gyeong-Yeop;Kim, U-Yeon
    • Proceeding of EDISON Challenge
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    • 2016.03a
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    • pp.113-115
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    • 2016
  • 온실가스의 주범을 친환경적으로 활용한다는 측면과 carbon source를 영구적으로 저렴한 비용으로 공급할 수 있다는 경제적 측면에서 CO2를 활용한 고부가가치 화학물질의 합성이 최근에 주목 받고 있다. 본 연구에서는 살렌(salen)-전이금속 착물을 단일 촉매로 사용한 모델 시스템을 통해 고부가가치 소비재의 주된 원료인 고리형 카보네이트 (cyclic carbonate)와 폴리카보네이트 (polycarbonate)가 생성되는 반응경로를 규명하였으며, 이들의 활성화 에너지를 조절함으로써 생성물을 선택적으로 합성할 수 있다는 이론적 근거를 제시하였다.

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