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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,
담지된 Pb 촉매에 의한 Ethylene Glycol 로부터 Oxalic Acid 의 합성
이광일,곽천근,장병만 ( Kwang Il Lee,Chun Geun Kwak,Byung Man Chang ) 한국공업화학회 1995 공업화학 Vol.6 No.6
Pd 금속을 활성탄에 담지 시킨 촉매를 제조하여 주 촉매로 사용하였고, 아울러 Pd와 Ni, Cu 및 Co와 같은 함금 촉매를 제조하여 ethylene glycol로부터 oxalic acid의 합성에 관하여 연구하였다. 본 연구에서 사용된 촉매는 함침법 중 흡착법과 초기 함침법으로 제조하였으며, 초기 함침법에서는 함침 과정이 끝난 촉매를 120℃에서 12시간 건조 시킨 후 430℃에서 수소 가스를 통과 시키면서 8시간 소성하여 환원 시킬 때 수율이 좋은 결과를 나타냈다. 값비싼 귀금속 촉매의 양을 줄이고 Ni, Cu 및 Co 등을 조촉매로 사용하여 활성도를 조사한 결과, Co를 사용한 촉매에서 활성이 우수하였다. 촉매의 특성을 조사하기 위하여 SEM-EDAX, X-ray diffraction 및 BET장치를 이용하였으며 촉매의 제조방법에 따라 촉매의 활성도가 다르게 나타남을 알 수 있었다. To investigate the optimum catalytic condition in the synthesis of oxalic acid from ethylene glycol, we empolyed palladium catalyst supported on activated carbon or bimetallic catalysts such as palladium-cobalt, palladium-nickel and palladium-copper supported on activated carbon. In this way, catalysts were prepared either by adsortion method or by incipient wetness method. The most effective catalyst was obtained when the catalyst was dried at 120℃ for 12hrs, followed by the reduction at 430℃ under the stream of hydrogen gas for 8hrs. In an attempt to reduce the amount of expensive noble metals to be used as a catalyst, we studied the effect of metallic promoters such as cobalt, nickel and copper as a co-catalyst. Cobalt was the only effective one when used along with palladium catalyst. In order to characterize the catalyst, we utilized scanning electron microscopy-energy dispersive X-ray spectrometer, X-ray diffraction and BET surface area. The activity of catalyst was shown to be changed depending upon how it was prepared.
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.