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5,6-Dihydro-1,4-thiazine 유도체의 가수분해 메카니즘과 반응속도론적 연구
이광일,이석우,곽천근,장병만,김영주,이기창,Lee, Gwang Il,Lee, Seok U,Gwak, Cheon Geun,Jang, Byeong Man,Kim, Yeong Ju,Lee, Gi Chang 대한화학회 1994 대한화학회지 Vol.38 No.5
5,6-dihydro-1,4-thiazine 유도체의 가수분해 반응속도를 25$^{\circ}C$의 수용액중에서 자외선 분광기를 사용하여 측정하고 넓은 pH범위에서 적용될 수 있는 반응속도식을 유도하였다. 가수분해 반응속도에 미치는 치환기 효과를 검토하기 위하여 Hammett plot한 결과 전자 주는기에 위하여 반응속도가 촉진됨을 확인할 수 있었다. 가수분해 최종생성물은 2-(N-acetylaminoethylthio)-acetoacetanilide enol형 이었으며 가수분해 반응속도상수 측정실험과 반응속도식의 유도과정, general base 효과, 활성화 파라미터 및 최종생성물의 결과로부터 5,6-dihydro-1,4-thiazine 유도체의 가수분해 반응은 pH 1.0∼10.0 에서는 중성의 물분자에 의해서 시작되며, pH 10.0∼11.0에서는 물분자와 히드록시 이온의 경쟁적인 반응이 pH11.0 이상에서는 히드록시이온에 의하여 진행됨을 알 수 있었다. 이러한 실험결과을 토대로 하여 5,6-dihydro-1,4-thiazine 유도체의 가수분해 반응메카니즘을 규명하였다. The kinetics of the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives was investigated by ultraviolet spectrophotometry in $H_2O$ at 25$^{\circ}C$. A rate equation which can be applied over a wide pH range was obtained. The substituent effects on the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives were studied and the rate of hydrolysis was shown to be accelerated by electron donating groups. Final product of the hydrolysis was 2-(N-acetylaminoethylthio)-acetoacetanilide enol from Judging from the results of the rate equation, general base effect, activation parameters and final products, the hydrolysis of 5,6-dihydro-1,4-thiazine derivatives seemed to be initiated by the neutral $H_2O$ molecule which does not dissociate at pH below 10.0, but proceeded by the hydroxide ion at pH above 11.0, and those two reactions occurred competively at pH 10.0∼11.0 range. On the basis of these findings a plausible mechanism for the hydrolysis of 5,6-dihydro-1,4-thiazine derivative was proposed.
$\alpha$-(n-Butyl)-N-Phenylnitrone 유도체에 대한 Sodium Thiophenoxide의 친핵성 첨가반응 메카니즘과 그의 반응 속도론적 연구
이광일,이석우,곽천근,김영주,노승일,이기창,Lee, Gwang Il,Lee, Seok U,Gwak, Cheon Geun,Kim, Yeong Ju,No, Seung Il,Lee, Gi Chang 대한화학회 1994 대한화학회지 Vol.38 No.6
The rate constants of the nucleophilic reaction of ${\alpha}$-(n-butyl)-N-phenylnitrone and its derivatives have been determined by ultraviolet spectrophotometry at $25^{\circ}C$ and a rate equation which can be applied over a wide pH range was obtained. Final product of the addition reaction was $\alpha$-phenylthiobutylidene-aniline. Base on the rate equation, genernal base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Below pH 3.0 the reaction was inititated by the addition of thiophenol, and in the range of pH 3.0∼10.0, proceeded by the competitive addition of thiophenol and thiophenoxide anion. Above the pH 10.0, the reaction proceeded through the addition of a thiophenoxide anion. ${\alpha}$-(n-Butyl)-N-Phenylnitrone 유도체의 첨가 반응속도상수를 25^{\circ}C$의 수용액에서 자외선 분광광도법으로 측정하여 넓은 pH범위에서 잘 맞는 반응속도식을 유도하였다. 첨가반응생성물은 ${\alpha}$-phenylthiobutylidene-aniline이었으며, 첨가반응속도상수 측정과 반응속도식의 유도, 일반기염 효과, 치환기 효과 및 최종생성물의 결과로부터 반응 메카니즘을 제안하였다. 즉, pH 3.0 이하에서는 티오페놀의 첨가로 반응이 시작되며, pH 3.0∼10.0에서는 티오페놀과 티오페녹시드 음이온이 경쟁적으로 첨가되어 진행되며, pH10.0이상에서는 티오페녹시드 음이온의 첨가에 의해서 반응이 진행된다.
Chitosan 및 Chitosan 유도체를 이용한 중금속 이온 흡착에 관한 연구
이광일,곽천근,장병만,김영주,박태홍,노승일,이기창 ( Kwang Ill Lee,Chun Geun Kwak,Young Ju Kim,Tae Hong Park,Seung IlI Roh,Ki Chang Lee ) 한국유화학회 1996 한국응용과학기술학회지 Vol.13 No.3
We have synthesized the water-insoluble chitosan derivative, N-dithiocarboxy chitosan sodium salt, through the reaction of chitosan with carbon disulfide in the presence of alkali metal hydroxide, Chitosan itselt has been prepared using chitin, one of the most abundant compounds in nature, as a starting material. To elucidate this natural polymer the capacity of adsorbing heavy metal ions, we have performed adsorption experiments using chitosan derivatives of various average molecular weights with different contents of sulfur. The effect of pH, adsorption time and temperature on adsorption efficiency was also studied. The adsorbent derived from chitosan of average molecular weight ranging 5,700~20,000 was shown to have the highest capacity of adsorbing heavy metal ions. Adsorbing efficiency was increased as the reaction time was increased and as the reaction temperature range of 25~45℃. The adsorption capacity at various pH, however, appeared to vary depending on the heavy metal ions studied,
이광일,박준희,Lee, Gwang-Il,Park, Jun-Hui 한국통신학회 2013 정보와 통신 Vol.30 No.10
최근 기술 발전과 더불어 해양에서의 안전과 환경보호를 위해 선박에서의IT기술 특히 정보통신 기술과의 융합에 대한 중요성이 증가되고 있다. 특히, 국제해사기구에서 추진하고 있는 e-navigation은 조선 및 선박에 IT 융합의 새로운 패러다임을 제공하고 있다. 이를 위해, 선박에 디지털 및 전자장비들이 도입되고 있으며, 통신의 형태도 폐쇄적인 선박 통신 구조에서 개방형, 통합형 형태로 변화되어가고 있다. 본 고에서는 해양 안전을 위해 국제해사기구에서 추진하고 있는 e-navigation과 이를 실현하기 위한 조선-IT 융합 특히 선박에서의 통신과 관련된 기술동향에 대해서 살펴보았다. 특히, IEC와 ISO와 같은 국제 표준화 기구들의 역할과 최근 동향 및 향후 국제표준화 방향에 대해 정리하였다.
수용성 Chitosam 유도체를 이용한 중금속 이온 흡착에 관한 연구
이광일,곽천근,김영주,장병만,김상호,이기창 ( Kwang Il Lee,Chun Geun Kwak,Young Ju Kim,Buyng Man Jang,Sang ho Kim,Ki Chang Lee ) 한국유화학회 1996 한국응용과학기술학회지 Vol.13 No.2
Chitosan itself has been prepared using chitin, one of the most abundant compounds in nature, as a starting material. We have synthesized the water-soluble chitosan derivative, N-dithiocarboxy chitosan sodium salt, through the reaction of water-soluble chiotsan with carbon disulfide in the presence of alkali metal hydroxide. To elucidate this natural polymer capacity of adsorbing heavy metal ions, we have performed adsorption experiments using the water-soluble chitosan derivative various average molecular weight and of different percent contents of sulfur. The effect of pH, adsorption time and temperature on adsorption efficiency was also studied, The adsorbent derived from water-soluble chitosan of average molecular weight ranging 9,000~120,000 was shown to have the highest capacity of adsorbing heavy metal ions. On the whole, adsorbing efficiency was increased as the reaction time goes longer and also increased as the reaction temperature goes higer in temperature range of 15℃~45℃. The adsorption capacity at various pH, however, was appeared to vary depending on the heavy metal ions studied Judging from these finding, water-soluble N-dithiocarboxy chitosan sodium salt, a derivative of a biodegradable nature polymer, is believed to be a potential adsorbent for heavy metal ions since it not only is shown to lower the concentration of heavy metal ions to below the drainage quality standard, but also it would not cause acidification and hardening of soil which is one of the detrimental effects of synthetic macromolecular adsorbents present.
Dihydro-1,4-oxathiin 유도체의 가수분해 Mechanism과 반응속도론적 연구
이광일,곽천근,장병만,김영주,한호규,남기달,이기창,Lee, Kwang Il,Kwak, Chun Geun,Jang, Byung Man,Kim, Young Ju,Hahn, Hoh Gyu,Nam, Kee Dal,Lee, Ki Chang 대한화학회 1996 대한화학회지 Vol.40 No.2
Dihydro-1, 4-oxathiin 유도체의 가수분해 반응속도를 25.deg.C의 수용액에서 자외선 분광기를 사용하여 측정하고 넓은 pH범위에서 적용될 수 있는 반응속도식을 유도하였다. 가수분해 반응속에에 미치는 치환기 효과를 검토하기 위하여 Hammett plot한 결과 전자 끄는기에 의하여 반응속도가 촉진됨을 확인할 수 있었다. 가수분해 최종 생성물은 2-(2-hydroxyethylthio)acetoacetanilide enol형이었다. 가수분해 반응속도상수 측정실험과 반응식 유도과장, 일반염기 효과, 치환기 효과 및 최종 생성물의 결과로부터 dihydro-1, 4-oxathiin 유도체의 기수분해 반응 메카니즘을 제안하였다. pH3.5이하에서는 양서자가 첨가된 dihydro-1, 4-oxathiin의 2번 탄소에 물분자의 공격에 의해 진행되며, pH3.5 이상에서는 2번 탄소에 히드록시이온의 첨가에 의하여 진행됨을 알 수 있었다. pH4.0-9.0사이에서는 dihydro-1, 4-oxathiin에 중성의 물분자가 첨가되는 것이 속도결정단계임을 알았다. The kinetics of the hydrolysis of dihydro-1, 4-oxathiin derivatives were investigated by ultraviolet spectrophotometry in H2O at $25^{\circ}C.$ A rate equation which can be applied over a wide pH range was obtained. The substituent effects on the hydrolysis of dihydro-1, 4-oxathiin derivatives were studied and the rate of hydrolysis was shown to be accelerated by electron accepting groups. Final product of the hydrolysis was 2-(2-hydroxyethylthio)acetoacet-anilide enol form. On the basis of rate equations derived and judging from hydrolysis products obtained and from general base effect and substituent effects, plausible mechanism of the hydrolysis in various pH range have been proposed. Below pH 3.5, the hydrolysis was initiated by the protonation and followed by the addition of water to 2-carbon. Above pH 10.0, the hydrolysis was proceeded by the addition of hydroxide to 2-carbon. In the range of pH 4.0∼10.0, the addition of water to dihydro-1,4-oxathiin is rate controlling step.