N-Cyclopropanecarbonylimidazole과 N-Propionylimidazole의 가수분해반응

이종팔,Lee, Jong-Pal 대한화학회 2009 대한화학회지 Vol.53 No.2

아미드 가수분해반응에서 2가 금속이온의 촉매작용

이종팔,박유미,엄태섭 東亞大學校附設基礎科學硏究所 1992 基礎科學硏究論文集 Vol.9 No.1

N-Thenoyl imidazole과 N-furoyl imidazole의 가수분해반응속도를 40℃ 물속에서 분광광도법으로 조사하였다. 산촉매반응과 염기촉매반응에 의해 가수분해반응이 진행되었다. 산촉매반응의 2차 반응속도상수는 두 기질이 비슷한 크기를 가졌으나, 염기촉매반응에서는 N-furoyl imidazole이 N-thenoyl imidazole보다 우세하였다. ??, ??, 그리고 ?? 이온에 의해 가수분해반응의 속도는 산촉매반응만을 증가시켰으며, 이때 금속이온의 포화효과도 나타났다. 이와 같은 현상은 아마 헤테로고리를 포함하는 아실기의 특성이 가수분해반응에 중요한 영향을 주는 것 같다. Rate constants have been determined for hydrolysis of N-thenoyl imidazole and N-furoyl imidazole in water at 40℃ by spectrometry. Hydronium ion and hydroxide ion catalyzed reaction were observed. Though the second order rate constants for hydronium ion catalysis of substrates is likely same, but for hydroxide ion catalysis of N-furoyl imidazole is faster than those of the N-thenoyl imidazole. Pronounced metal ion catalysis occurs in hydrolysis of this compound in the presence of ??, ??, or ??. Saturation effect was observed at high metal ion concentration in the hydrolysis of N-thenoyl imidazole and N-furoyl imidazole. Nevertheless, metal ion promoted hydronium ion catalyzed reactions occur with a little bit rate enhancements in ??, ranging from 10-20 fold with ??, ?? and ??. This results are expected that sulfur atom of thenoyl group and oxygen atom of furoyl group may be a important factor in which effects on the rate constant of hydrolysis.

헤테로고리 산염화물의 가용매분해반응에서 전이상태의 구조변화

李鍾八,金忠植,成大東 東亞大學校 1983 東亞論叢 Vol.20 No.3

2-염화휴로일, 5-브로모-2-염화휴로일, 2-염화테노일을 가용매분해반응시켯을 때, 전이상태에서 반응물의 구조변화를 예견하여 More O` Ferrall plot에 나타내었다. 각 혼합 용매간의 반응속도상수의 크기는 대체로 EtOH-H₂o>TFE-H₂O>TFE-EtOH순이었다. 가용매분해 반응에서 용매의 친핵성도를 고려하여 Extended Grunwald-Winstein식에 의하여 m값을 구하였고, 결과적으로 반응은 ??메카니즘으로 진행함을 알았다. The prediction of the effects of reactant of variation on transition atate structure in solvolysis of 2-furoyl chloride, 5-bromo-2furoyl chloride and 2-thenoyl chloride has applied to More O` Ferrall plot. The sequence of magnitude for the rate constant of each solvent is EtOH-H₂O>TFE-H₂O>TFF-EtOH. The m values obtained from extended Grunwald-Winstein equation, after due consideration of the nucleophilicity of solvent in solvolytic reaction. As a result of the reactions proceed by a associative ?? mechanism.

아연광산 인근 토양중의 중금속함량이 옥수수 생육에 미치는 영향

이종팔,박노권,김복진 한국응용생명화학회 1994 한국응용생명화학회 학술발표회 Vol.1994 No.1

This research was carried out to investigate how the growth of corn was affected by the heavy metal contents in soils near the old zinc-mining sites, by analyzing correlation between the growth of corn and heavy metal contents in soils collected from Yonghari Ilwoulmyun YongyangGun in Kyeongpook province in 1993. The results obtained were summarized as follows. 1. The contents of heavy metals such as Zn, Cu, Pb, Cd, and as in the Youngyang area were very high compared with those in a normal area. Heavy metal contents in soils collected from 2.0∼2.5Km distance from the mining area were the highest, and those from 3.0Km than those from 1.5Km were even higher. 2. For heavy metal contents in leaves of all surveyed crops, Zn, Pb, Cu and As were the highest in soybean, followed by corn and rice. 3. Growth parameters of corn in polluted fields were comparatively poor and heavy metal contents in soils of the respective sites were higher than those in fields where rice was cultivated 8 years ago and irrigation was not done previously. 4. Heavy metal contents in the leaf part of corn plant showed a similar tendency to those in soils, being the highest among the different parts of corn plant, and they were in the decreasing order of Zn > Cu > As > Cd > Pb in each part. But the differences of metal contents in each part varied. 5. Generally, a negative relationship existed between the growth of corn and heavy metal contents in soil, of which Cu and Pb were significantly correlated with plant height, ear height, diameter of stem, ear length and yield of corn. 6. There existed a positive correlation between the contents of Pb, Cd and As in soils and those in the different parts of corn plant. The higher contents of Pb, Cd, and As in soil, the more those in corn plant increased. The contents of Pb and As in corn grains showed a highly significant positive correlation with Cd and As contents in soils.

N-테노일 이미다졸 유도체의 가수분해반응

이종팔,성대동,엄태섭 東亞大學校 大學院 1994 大學院論文集 Vol.19 No.-

The oseudo first order rates for hydrolses of N-thenoylimidazole(N-TI), N-thenoylbenzimidazole and N-thenoyl-2-phenylimidazole(N-TPI) have been determined at over all pH range with the ionic strength of 0.5M KCl at 40℃ by spectrometry. Hydronium ion and hydroxide in catalyzed reaction observed. The reaction of the diprotonated species occured at pH=3.5 in N-TI and at less than pH=6 in N-TPI. Metal ion catalyses were observed very weakly in hydrolyses of these compounds in the presence of divalent metal ions Cu², Ni², or Zn². We have observed that metal ion promoted hydronium ion catalyzed reaction. Saturation effects were observed only in the metal ion catalyzed hydrolysis of N-TI.

술핀아미드의 가수분해반응에 미치는 산 및 친핵체의 촉매작용

李鍾八,嚴泰燮 東亞大學校附設基礎科學硏究所 1997 基礎科學硏究論文集 Vol.14 No.1

술핀아미드류의 가수분해반응에 미치는 산 및 친핵체의 촉매작용을 25℃, 이온세기 0.1 M(NaClO₄)로 조절된 수용액에서 UV/VIS 분광광도법으로 조사하였다. 산 촉매반응은 벤젠술핀아미드의 이탈기 아닐린에 전자주게 치환기를 가진 반응기질과 벤젠술피닐기의 치환기가 전자주게인 반응기질 모두 pH 3 부근에서 가수분해반응속도상수의 대수값이 현저한 차이를 보였다. 이와 같은 현상은 위와 같은 반응기질이 산 촉매가 수분해될 때 초원자가중간체를 거쳐 진행된다는 사실의 속도론적 증거가 됨을 알았다. 반면, 벤젠술핀아미드의 치환기가 전자받게기인 경우는 pH 3 부근에서 변곡점이 생기지 않음을 보였다. 할로겐화이온에 의한 촉매반응은 Br?이 Cl?보다 크게 나타났으며 이때 반응속도는 반응용액의 산의 농도에 영향을 받음을 보였다. 술핀아미드의 치환기효과로부터 얻은 Hammett의 반응상수 ρ값으로부터 예상되는 할로겐화이온에 의한 촉매반응메카니즘은 술포늄 양이온을 거쳐 진행될 것으로 예상할 수 있었다. We have been kinetically studied on acid and nucleophile catalysis for hydrolysis of sulfinamides at 25℃ in aqueous solution at the ionic strength of 0.1M with NaClO₄by spectrophotometrically. The substrates which the leaving group aniline has electron donating group were shown a breakdown of pH-rate profile at near pH 3 as well as the substrate having electron donating group at benzenesulfinyl group. The break is ascribed to a change in the rate determining step of the reaction involving a hypervalent intermediate. However, the substrates which have the leaving group with electron withdrawing group were not observed a breakdown of pH- rate profile at pH3. Catalysis of halide ion was observed in the hydrolysis of sulfinamides. The nucleophile reactivity observed was in the order of Br?>Cl?, but also found to depend upon the acid concentration of solution. From the Hammett's reaction constant ρ values which were obtained by effect of substituent of sulfinamides, we expect that the reaction mechanism may proceed via sulfonium cation.

자연과학대학, 화학과

이종팔,엄태섭,성대동 東亞大學校 大學院 1988 大學院論文集 Vol.13 No.-

The nucleophilic substitution reaction of p-substituted anilines and solvolyses of various substrates in tetrahydrofuran and methanol binary solvent mixtures have been investigated by means of conduct metrically. In order to investigate solvent effect on the rate of reaction, the solvatochromic parameters of tetrahyd rofuran and methanol bianry solvent mixtures have been determined by mean of UV-vis. sepctrophotometer. From the results of rate constants the following conlution have been obtatined. The values of solvatochromic parameters, α,βand π?? values increased with the methanol content, the increase in the αvalues being the greatest. And hence the solvent effect is controlled mainly by αvalues, i.e., hydrogen bond donor ability, of the transition state and the reactants. As the substituent of benzenesulfonyl chloride is varied from one of electorn donating to that of withdrowing, ???? values increase, while the variation of the substituent in aniline to one of electron donating caused ?? values to increase. The reaction center, sulfer atom has shown to develope negative charge and nitogen atom on the nucleophile has shown to develope positie charge in the transition state. From application of potential energy surface model, teh reacton are shown to proceed by an associative S??2 reaction which is in between the S??N and S??2 mechanism.

이성분 혼합용매계에서 염화 안트라퀴논-2-카르보닐의 가용매 분해반응$^{1,2}$

이종팔,성대동,엄태섭,이익춘,손세철,Jong Pal Lee,Dae Dong Sung,Tae Sup Uhm,Ikchoon Lee,Se Chul Sohn 대한화학회 1985 대한화학회지 Vol.29 No.5

메탄올-아세토니트릴, 메탄올-아세톤, 에탄올-아세토니트릴 및 에탄올-아세톤의 이성분 혼합용매에서 2-염화 안트라퀴논 카르보닐의 가용매분해반응 속도상수를 전기전도도법으로 측정하였다. 메탄올-아세토니트릴 이성분 혼합용매계에서는 메탄올의 몰분율 $X_{MeOH}$ = 0.73∼0.81에서, 메탄올-아세톤 이성분 혼합용매계에서는 메탄올의 몰분율 $X_{MeOH}$ = 0.83에서 각각 최대 반응속도 현상이 나타났다. Kivinen 관계식과 Grunwald-Winstein 관계식등의 적용으로 부터 본 반응이 $S_N2$형태의 반응메카니즘으로 진행함을 알 수 있었다. Taft의 분광용매화 관계식의 적용으로 부터 메탄올-아세토니트릴 및 메탄올-아세톤 혼합용매계에서는 용매의 수소결합주게효과(${\alpha}$)와 극성-편극성 효과가 중요하게 작용함을 알 수 있었으며, 에탄올의 이성분 혼합용매계에서는 용매의 수소결합주게 효과만 이 반응에 크게 기여함을 알 수 있었다. The rate constants for the solvolysis of anthraquinone-2-carbonyl chloride in binary solvent mixtures, methanol-acetonitrile, methanol-acetone, ethanol-acetonitrile and ethanol-acetone, have been studied by means of conductometry. Maximum rate phenomena were observed at the methanol mole fraction, $X_{MeOH}$ = 0.73~0.81 for methanol-acetonitrile and at $X_{MeOH}$ = 0.83 for methanol-acetone mixtures. The Kivinen and Grunwald-Winstein plots indicated that the reaction proceeds via $S_N2$ type mechanism. Application of Taft's solvatochromic correlation on the solvolysis rate revealed that both $\alpha$ and ${\pi}^*$ are important for reactions in methanol-acetonitrile and methanol-acetone mixtures, while only ${\alpha}$ influences significantly on the rate in ethanol-acetonitrile and ethanol-acetone mixtures.

아실이동반응의 전이상태구조

이종팔,박현석,성대동 東亞大學校附設基礎科學硏究所 1992 基礎科學硏究論文集 Vol.9 No.1

30℃ 물속에서 N-acetylimidazole유도체의 가수분해반응을 속도론적으로 조사하였다. 분광광도법에 의해 얻은 속도자료는 물 촉매반응 경우 N-acetyl-(2,4,5-triphenyl)-imidazole (N-ATPI)이 N-acetyl-(4,5-diphenyl)-imidazole(N-ADPI)보다 빨랐으며 ?? 촉매반응은 N-ATPI의 경우 pH=9 가까이에서 나타났고, N-ADPI의 경우 pH=7.3 근처에서 일어남을 알았다. N-ATPI의 물 촉매반응에 대한 전이상태의 구조를 알아보기위한 H₂O 와 D₂O 에서의 속도자료비가 ?/?됨을 보였다. 또한 염기의 농도변화에 대한 물의 촉매방응속도를 조사한 결과 Bronsted의 β값이 0.31로 보임에 따라 전이상태(TS)에서 물분자의 결합이 느슨함을 암시하였다. pH=6.05에서 N-ATPI의 반응에서 구한 △??와 △??는 각각 7.29 ㎉/㏖, -35.5 e.u 가 됨을 알았다. 구한 자료에 의해 본 반응의 전이상태구조는 early TS에서 약간 loose한 구조가 예상되었다. The hydrolysis of N-acetylimidazoles have been studied kinetically in water at 30℃. The kinetic data by spectrometry was shown that rate constants of N-acetyl- (2,4,5-triphenyl)-imidazole(N-ATPI) are a little bit faster than those of N-acetyl-(4,5-diphenyl)-imidazole(N-ADPI) in the regions of reaction. In the case of N-ATPI, general base catalysis has been observed in near pH=9, while in the case of N-ADPI has been observed in pH=7. In order to investigate transition state structure for hydrolysis of N-ATPI in pH independent reaction region, we obtained solvent isotope effect, ??/??. △?? =7.29 ㎉/㏖, △?? = -35.5 e.u. From these results, the transition state structure of pH independent reaction is expected loose structure which is located in early TS.

N-Propionylbenzimidazole과 N-Propionyl-5-nitrobenzimidazole의 가수분해반응

이종팔,이용희,Lee, Jong-Pal,Lee, Yong-Hee 대한화학회 2008 대한화학회지 Vol.52 No.4