우리나라 海事産業의 지난 20年 : 沿岸海運

金泰麟 한국해사문제연구소 1991 (月刊)海洋韓國 Vol.211 No.-

Synthesis of ${\beta}-({\alpha}$-Benzenesulfonamidobenzal)hydrazine and Its Derivatives

김태린,허태성,한인섭,백연옥,Tae-Rin Kim,Tae-Seong Huh,In-Sup Han,Yun-Ok Baik Korean Chemical Society 1979 대한화학회지 Vol.23 No.5

N-Aryllsufonylbenzimidoyl chloride를 출발물질로 사용하여 다음과 같은 7가지 새로운 히드라진 유도체들을 합성하였다. ${\beta}-({\alpha}-Benzenesulfonamidobenzal)hydrazine\;(II),\;{\beta}-({\alpha}-Benzenesulfonamidobenzal)dimethylmethylenehydrazine\;(III),\;{\beta}-({\alpha}-Benzenesulfonamidobenzal)phenylhydrazine\;(VII),\;{\beta}-({\alpha}-Benzenesulfonamidobenzal)-4-nitrophenylhydrazine\;(VIII),\;{\beta}-({\alpha}-Benzenesulfonamidobenzal)-2,4-dinitrophenylhydrazine\;(IX),\;{\beta}-({\alpha}-Benzenesulfonamidobenzal)dimethylhydrazine\;(X),\;{\beta}-({\alpha}-Benzenesulfonamidobenzal)-p-methylphenylhydrazine\;(XI)$ 이 유도체들의 구조를 원소분석, ir, nmr, mass 스펙트럼 및 기타 화학적인 방법을 통해서 확인하였다. 일반적으로 이 치환반응은 극성인 용매에서, 그리고 친핵체인 페닐히드라진 유도체에 전자를 끄는기가 있을 때 수득율이 높았다. Seven new hydrazine derivatives were prepared from N-Aryllsufonylbenzimidoyl chloride. These were: ${\beta}-({\alpha}-Benzenesulfonamidobenzal)hydrazine\;(II),\;{\beta}-({\alpha}-Benzenesulfonamidobenzal)dimethylmethylenehydrazine\;(III),\;{\beta}-({\alpha}-Benzenesulfonamidobenzal)phenylhydrazine\;(VII),\;{\beta}-({\alpha}-Benzenesulfonamidobenzal)-4-nitrophenylhydrazine\;(VIII),\;{\beta}-({\alpha}-Benzenesulfonamidobenzal)-2,4-dinitrophenylhydrazine\;(IX),\;{\beta}-({\alpha}-Benzenesulfonamidobenzal)dimethylhydrazine\;(X),\;{\beta}-({\alpha}-Benzenesulfonamidobenzal)-p-methylphenylhydrazine\;(XI)$. The structure of these derivatives were identified by elemental analysis, spectral data and other chemical methods. In general, it was found that the yields of these reactions were significantly improved in polar solvent and by the electron attracting substituents in phenylhydrazine.

${\alpha}$-Nitrobenzaldehydephenylhydrazone의 가수분해에 대한 반응속도론적 연구

김태린,최원식,Tae-Rin Kim,Won-Sik Choi 대한화학회 1978 대한화학회지 Vol.22 No.1

25% dioxane 수용액 속에서 ${\alpha}$-nitrobenzaldehydephenylhydrazone의 여러 유도체(p-N$NO_2$,p-Cl, m-$NO_2$, p-$CH_3$)에 대해 pH의 변화에 따르는 가수분해 속도상수를 $25^{\circ}C$에서 자외선 분광광도법으로 측정하여 넓은 pH에서 잘 맞는 반응 속도식을 구하였다. 가수분해 속도에 미치는 치환기효과를 고려하고자 Hammett의 식을 적용한 결과 pH1.0에서는 ${\rho}$=0.18, pH 7.0에서는 ${\rho}$=0.06을 얻었다. pH의 변화에 따르는 반응속도상수의 변화, 용매효과, 치환기효과, 산해리상수 측정 등으로부터 ${\alpha}$-nitrobenzaldehydephenylhydrazone의 가수분해는 pH 3.0 이하에서는 $S_N1$, pH 4.0 이상에서는 1,3-dipole을 거치는 반응이 pH 3.0 과 pH 4.0 사이에서는 이 두 반응이 경쟁적으로 일어남을 알았다. The kinetics of hydrolysis of ${\alpha}$-nitrobenzaldehydephenylhydrazone derivatives (p-$NO_2$, m-$NO_2$, p-Cl, p-$CH_3$) have been investigated by UV spectrometry in 25% dioxane-water at $25^{\circ}C$ and a rate equation which can be applied over wide pH range was obtained. From the rate equation and the effect of solvent, substituent and pKa on the rate equation, the following reaction mechanisms were proposed. Below pH 3.0 the hydrolysis of ${\alpha}$-nitrobenzaldehydephenylhydrazone proceeds by $S_N1$ mechanism, while above pH 4.0 the hydrolysis proceeds through 1,3-dipole ion mechanism. In the range of pH from 3.0 to 4.0 these two reactions occur competitively.

酸性溶煤 속에서의 $\beta$-Nitrostyrene에 대한 親核性 添加反應에 관한 硏究 (II) Ethylmercaptan과 Isopropylmercaptan과 반응

김태린,최영상,Kim, Tae-Rin,Choi, Young-Sang 대한화학회 1968 대한화학회지 Vol.12 No.4

Nucleophile의 親核性添加反應性을 정량적으로 연구하고자 3,4-methylenedioxy-$\beta$ -nitrstyrene에 대해 우선 ethylmercaptan과 isopropylmercaptan을 써서 그외 添加反應速度常數를 측정한 결과 ethylmercaptide와 isopropylmercaptide ion에 대해 각각 $6.82{\times}10^7M^{-2}$,$ sec^{-1}$, and $2.86{\times}10^7M^{-2}$,$sec^{-1}$를 얻었으며 염기성 뿐만 아니라 산성 촉매속에서도 그의 반응메카니즘을 잘 설명할 수 있는 속도식도 구하였다. In order to attempt the quantitative correlation of nucleophilic addition(not nucleopbilic substitution) reactivity of nucleophile, the addition constants of ethyl and isopropyl mercaptan to 3,4-methylenedioxy-$\beta$-nitrostyrene were determined and found to be $6.82{\times}10^7 $ and $2.86{\times}10^7 M^{-2},\;sec^{-1}$ respectively. From the rate equation obtained, the addition mechanism at basic media especially the complex addition mechanism at acidic media which has not been revealed can also be fully explained.

${\beta},\;{\beta}$-Diethoxycarbonylstyrene 유도체에 대한 3-Mercaptopropionic Acid의 친핵성첨가반응에 관한 반응속도론적 연구

김태린,최윤정,정명숙,Tae-Rin Kim,Yun-Chung Choi,Myung-Sook Chung 대한화학회 1989 대한화학회지 Vol.33 No.1

${\beta},\;{\beta}$-diethoxycarbonylstryene 유도체(H, p-OCH$_3$, 3,4,5-(OCH$_3)_3$), 3,4,5-methylenedioxy)에 대한 3-mercaptopropionic acid의 친핵성 첨가반응 속도상수를 자외선 분광법으로 측정하여 넓은 pH 범위에서 적용될수 있는 속도식을 구하였다. pH에 따르는 속도상수의 변화, 일반염기촉매작용등을 바탕으로 이 첨가반응 메카니즘을 제안하였다. 즉 pH 6.0 이하에서는 중성인 3-mercaptopropionic acid 분자의 첨가로 이 반응이 시작되며 pH 6.0∼8.0영역에서는 이 중성분자와 황화음이온의 첨가가 경쟁적으로 일어나며, pH 8.0이상에서는 황화음이온에 의해서만 첨가반응이 진행된다. The rate constants of the nucleophilic addition reaction of 3-mercaptopropionic acid to the ${\beta},\;{\beta}$-diethoxycarbonylstryene derivatives (H, p-OCH$_3$, 3,4,5-(OCH$_3)_3$, 3,4-methylenedioxy) were determined by ultraviolet spectrophotometry, and rate equation which could be applied over a wide pH range was obtained. On the basis of pH-rate profile and the presence of general base catalysis, a plausible mechanism of this addition reaction was propound:Below pH 6.0 the reaction was initiated by the addition of neutral 3-mercaptopropionic acid molecule, and in the range of pH 6.0∼8.0, a neutral 3-mercaptopropionic acid molecule and a sulfide anion competitively attacked to the double bond. Above pH 8.0, the reaction proceeded through the addition of a sulfide anion.

酸性溶媒 속에서의 ${\beta}$-Nitrostyrene에 대한 Mercaptan의 親核性 添加反應에 관한 연구 [IV] n-Amyl-, n-Hexyl-, n-Octyl-, n-Decyl-Mercaptan과의 반응

김태린,최영상,Kim, Tae-Rin,Choi, Young-Sang 대한화학회 1969 대한화학회지 Vol.13 No.3

Nucleophile의 親核性 添加反應性을 정량적으로 연구하고자 전보에 이어 3,4-methylenedioxy-${\beta}$-nitrostyrene에 대한 n-amyl, n-hexyl, n-Octyl, n-decylamercaptanㅓ의 添加反應速度常數를 측정한 결과 n-amylmercaptide, n-hexylmercaptide, n-octylmercaptide, n-decylmercaptide ino에 대해 각각 2.82${\times}10^8$, 100${\times}10^8$, 2.23${\times}10^8$과 1.77${\times}10^8$ $M^{-2} .sec^{-1}$를 얻었고, n-amyl, n-hexyl, n-Octyl, n-decylmercaptan분자에 대해서는 각각 2.82${\times}10^{-2}$, 1.95${\times}10^{-2}$, 7.08${\times}10^{-2}$과 5.63${\times}10^{-2}$$M^{-1} . sec^{-1}$를 얻었으며, 염기성뿐만 아니라 산성용매 속에서도 그의 반응메카니즘을 잘 설명할 수 있는 반응속도 식도 구하였다. The nucleophilic addition rate constants of n-amyl-, n-hexyl-, n-octyl-and n-decyl mercaptide ion to 3,4-methylenedioxy-${\beta}$-nitrostyrene were determined and found to be 2.82 ${\times}10^8$ $M^{-2} .sec^{-1}$, 1.00 ${\times}10^8$ $M^{-2}.sec^{-1}$, 2.23 ${\times}10^8$ $M^{-2} .sec^{-1}$ and 1.77 ${\times}10^8$ $M^{-2}.sec^{-1}$ respectively. At low pH, for n-amyl-, n-hexyl-, n-octyl-and n-decyl mercaptan the values determined are 2.82 ${\times}10^{-2}$ $M^{-1} . sec^{-1}$, 1.95 ${\times}10^{-2}$ $M^{-1} . sec^{-1}$, 7.08 ${\times}10^{-2}$ $M^{-1} . sec^{-1}$ and 5.63 ${\times}10^{-2}$ $M^{-1} . sec^{-1}$ respectively. The rate equations which can fully explain the addition mechanism over wide pH range were also be obtained.

Synthesis of Nucleophilic Adducts of Thiols (VIII). Addition of L-Glutathione to ${\beta},\;{\beta}$-Diethoxycarbonylstyrene Derivatives

김태린,최승용,신준섭,Tae-Rin Kim,Sung-Yong Choi,Joon-Seob Shin Korean Chemical Society 1985 대한화학회지 Vol.29 No.6

물-메탄올(9:1) 용매 속에서 ${\beta},\;{\beta}$-diethoxycarbonylstyrene과 L-glutathione을 반응시켜 좋은 수득율로 다음과 같은 화합물을 합성하였다. 즉 S-(2,2-diethoxycarbonyl-1-phenylethyl)-L-glutathione, S-2,2-diethoxycarbonyl-1-(3',4'-methylenedioxy)phenylethyl-L-glutathione, S-2,2-diethoxycarbonyl-1-(3',4',5'-trimethoxy)phenylethyl-L-glutathione, S-2,2-diethoxycarbonyl-1-(4'-hydroxy)phenylethyl-L-glutathione, S-2,2-diethoxycarbonyl-1-(4'-methoxy)phenylethyl-L-glutathione. 위 화합물들의 구조는 원소분석과 분광학적 방법으로 확인하였고 수득율에 미치는 pH와 용매의 영향을 실험한 결과 pH는 4.0에서 8.0사이가 용매는 물-메탄올이 가장 적합하다는 것을 알았다. 한편 이 화합물의 Gram(+) 박테리아에 대한 항균성을 실험한 결과 약함을 알았다. A series of S-(2,2-diethoxycarbonyl-1-phenylethyl)-L-glutathione derivatives (11a-e) were synthesized from the reaction of ${\beta},\;{\beta}$-diethoxycarbonylstyrene with L-glutathione in 9 : 1 aqueous methanol. Thus, S-(2,2-diethoxycarbonyl-1-phenylethyl)-L-glutathione (11a), S-2,2-diethoxycarbonyl-1-(3',4'-methylenedioxy)phenylethyl-L-glutathione (11b), S-2,2-diethoxycarbonyl-1-(3',4',5'-trimethoxy)phenylethyl-L-glutathione (11c), S-2,2-diethoxycarbonyl-1-(4'-hydroxy)phenylethyl-L-glutathione (11d), S-2,2-diethoxycarbonyl-1-(4'-methoxy)phenylethyl-L-glutathione (11e) were obtained in good yields. The structure of the adducts was characterized by analytical and spectral data. The effects of pH and solvents upon the yields were also briefly examined. In the range of pH from 4.0 to 8.0, the aqueous methanol were found to be the best solvent for the addition reaction and the antibacterial activities of the adducts to Gram(+) bacteria were found to be weak.

4'-[N-(9-Acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide의 가수분해 반응메카니즘에 관한 반응속도론적 연구

김태린,정동인,변상용,Kim, Tae Rin,Chung, Dong In,Pyun, Sang Yong 대한화학회 1996 대한화학회지 Vol.40 No.12

4'-[N-(9-Acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide(AMQD) 의 가수분해속도상수를 25.deg.C의 수용액속에서 자외선 분광법으로 측정하여 넓은 pH에서 잘 맞는 반응속도식을 구하였다. pH에 따르는 속도상수의 변화, Bronsted plot, 가수분해 생성물을 확인, 일반염기 및 치환기 효과 등으로부터 실험 사실에 잘 맞는 반응메카니즘을 제안하였다. 즉 pH 3.00 이하에서는 acridinyl기의 질소에 양성자가 첨가된 다음 quinonoid의 4'-위치에 물의 첨가가 일어나 가수분해가 진행되며, pH 3.00-9.00 사이에서는 물분자와 수산화 음이온의 첨가가 경쟁적으로 일어나 반응이 진행되었고, pH 9.00이상에서는 수산화 음이온의 농도에만 비례함을 알았다. The rate constants for the hydrolysis of 4'-[N-(9-acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide(AMQD) were determined by ultraviolet visible spectrophotometer in water at $25^{\circ}C.$ The rate equation which could be applied over wide pH ranges were obtained. On the basis of pH-rate profile, Bronsted plot, hydrolysis product analysis, general base catalysis and substituent effect, the plausible hydrolysis mechanism was proposed: Below pH 3.00, the hydrolysis reaction was proceeded by the attack of water to 4'-position of quinonoid after protonation at nitrogen of acridinyl and between pH 3.00 and 9.00, the addition of water and hydroxide occurred competitively. However, above pH 9.00, the rate constants were dependent upon only the concentration of hydroxide ion.

${\beta}$-Nitrostyrene 유도체에 대한 Thiourea의 친핵성 첨가반응에 관한 반응속도론적 연구

김태린,정연수,정명숙,Tae-Rin Kim,Yeun-Soo Chung,Myung-Sook Chung 대한화학회 1991 대한화학회지 Vol.35 No.3

${\beta}$-nitrostyrene 유도체(p-H, p-Cl, p-CH$_3$, p-OCH$_3$, p-NO$_2$)에 대한 thiourea의 친핵성 첨가반응속도를 자외선 분광분석법으로 측정하여 pH에 따르는 반응속도 상수의 변화, general base 및 치환기 효과등으로부터 넓은 pH 범위에서 실험치와 잘 일치하는 반응속도식을 구하였고, 실험사실에 잘 맞는 반응 메카니즘을 제안하였다. 즉, pH 9.00 이상에서의 반응속도는 hydroxide ion의 농도에 비례하는 sulfide anion이 첨가되는 전형적인 Michael type의 반응이 일어나며, pH 9.00 ~ 7.00에서는 thiourea의 중성분자와 그의 anion들이 경쟁적으로 첨가되며 pH 7.00 이하에서는 thiourea의 중성분자만이 첨가됨을 알았다. The rate constants for the nucleophilic addition reactions of thiourea to ${\beta}$-nitrostyrene derivatives(p-H, p-Cl, p-CH$_3$, p-OCH$_3$, p-NO$_2$) were determined by UV spectrophotometer and rate equations which can be applied over a wide pH ranges were obtained. On the basis of substituent effect, general base catalysis and rate equations, a reaction mechanism was proposed and revealed quantitively. Above pH 9.00, sulfide anion adds to the double bond(Michael type addition) and between pH 7.00 and 9.00, the neutral molecules and its anions add to the double bond competitively. Below pH 7.00, the addition reaction to double bond is initiated by the addition of neutral thiourea molecule.

${\alpha}$,N-Diphenylnitrone 유도체에 대한 Cysteine 및 Thiophenol의 친핵성 첨가물에 관한 연구

김태린,변상용,한만소,이광일,Tae-Rin Kim,Sang-Yong Pyun,Man-So Han,Kwang-Il Lee 대한화학회 1991 대한화학회지 Vol.35 No.3

${\alpha}$,N-diphenylnitrone에 cysteine과 thiophenol을 반응시켜 4개의 thiazolidine과 다음의 5가지 새로운 화합물을 합성하였다. ${\alpha}$,thiophenoxy-benzylidene aniline : ${\alpha}$, thiophenoxy-p-hydroxybenzylidene aniline : ${\alpha}$,thiophenoxy-p-chlorobenzylidene aniline : ${\alpha}$,thiophenoxy-p-methoxybenzylidene aniline : ${\alpha}$,thiophenoxy-p-nitrobenzylidene aniline. 이 화합물들의 구조는 원소분석, UV-, IR 및 NMR- 스펙트럼에 의해 확인하였다. Four thiazolidines and following five new compounds were prepared by the addition reaction of cysteine and thiophenol to ${\alpha}$,N-diphenylnitrones, respectively ; ${\alpha}$,thiophenoxy-benzylidene aniline ;${\alpha}$,thiophenoxy-p-hydroxybenzylidene aniline ; ${\alpha}$,thiophenoxy-p-chlorobenzylidene aniline ;${\alpha}$,thiophenoxy-p-methoxybenzylidene aniline ; ${\alpha}$,thiophenoxy-p-nitrobenzylidene aniline. The structure of these compounds were confirmed by the elemental analysis, UV-, IR-and NMR-spectra.