• 제목/요약/키워드: nucleophilic addition

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${\beta}$-Nitrostyrene에 대한 Nucleophilic Addition Constant의 측정 (I) (Determination of Nucleophilic Addition Constant to ${\beta}$-Nitrostyrene (I))

  • 김태인;최영상
    • 대한화학회지
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    • 제10권4호
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    • pp.158-160
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    • 1966
  • 여러가지 nucleophile을 써서 3,4-methylene-dioxy-${\beta}$-nitrostyrene에 대한 nucleophilic addition constant를 측정하여 이미 알려진 nucleophilic substitution constant와 비교해 보았더니, 이 둘 사이에는 비례관계가 성립되지 않으리라 생각된다. 이것을 정량적으로 취급하려면 앞으로 많은 nucleophile에 대해서 더욱 정확한 실험치를 얻을 수 있어야 하겠다.

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Furfurylidene acetophenone유도체에 대한 Thiourea의 친핵성 첨가반응 메카니즘과 그 반응속도론적 연구 (The Kinetics and Mechanism of the Nucleophilic Addition of Thiourea for Furfurylidene Acetophenone derivatives)

  • 이기창;목갑영;오세영;류정욱
    • 한국응용과학기술학회지
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    • 제14권1호
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    • pp.27-32
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    • 1997
  • Furfurylidene acetophenone derivatives were synthesis, it was measured that nucleophilic addition made use of UV at a wide pH 1.0${\sim}$13.0 range in 30% dioxane-$H_2O$ solution, 25$^{\circ}C$. On the basis of general base catalysis, substitutent effect, confirmation of nucleophilic addition products, it was measured the reaction rate of furfurylidene acetophenone derivatives for the pH change. It may be concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion: Above pH 10.0. sulfide anion adds to the double bond (Michael type addition), a part having no concern with pH, addition reaction to double bond is initiated by addition of neutral thiourea molecule. From the result of measurement the reaction rate, nucleophilic addition of furfurylidene acetophenone derivatives confirmed to the irreversible first order. Through measurement the substituent effect. It found that reaction rate was accelerated by electron attracting group. On the basis of these findings, nucleophilic addition of thiourea for the furfurylidene acetophenone derivative was proposed a fitting mechanisms.

2-Fluorenylidene chalcone유도체에 대한 Thioglycolic acid의 친핵성 첨가 반응에 관한 연구 (Nucleophilic Addition Reaction of Thioglycolic acid to 2-Fluorenylidene chalcone Derivatives)

  • 이기창;이광일;황용현;류정욱;윤철훈
    • 한국응용과학기술학회지
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    • 제13권1호
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    • pp.107-113
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    • 1996
  • Fluorenylidene chalcone derivatives were synthesized by condensation. The structure of these compounds were ascertained by means of UV, melting point, IR and $^1H-NMR$ spectra. The nucleophilic addition reaction kinetics of Thioglycolic acid to fluorenylidene chalcone was investigate by UV in 20% $dioxane-H_2O$ at $25^{\circ}C$. The rate equation which were applied over a wide $pH1.0{\sim}13.0$ range. On the basis of general base catalysis and confirmation of addition reaction product, the nucleophilic addtion reaction kinetics of thioglycolic acid to fluorenylidene chalcone were measured by the pH change. From the result of the above caption, a plausible nucleophilic addition reaction mechanism of thioglycolic acid to fluorenylidene chalcone was proposed. These compounds may be used as the starting materials for the preparation of the engineering plastics or the germicide.

Benzoyl styrene유도체에 대한 Thiourea의 친핵성 첨가반응 메카니즘과 그 반응속도론적 연구 (The Kinetics and Mechanism of the Nucleophilic Addition of Thiourea for Benzoyl Styrene Derivatives)

  • 이기창;윤철훈;황성규;류정욱
    • 한국응용과학기술학회지
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    • 제12권2호
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    • pp.107-113
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    • 1995
  • Benzoyl styrene derivatives were synthesized by Claisen-Schmidt condensation. It was measured that nucleophilic addition of thiourea for benzoyl styrene made use of ultraviolet spectrophotometery at a wide pH $1.0{\sim}13.0$ range in 5% $dioxane-H_2O$ at $40^{\circ}C$. On the basis of general base catalysis, substitutent effect, and confirmation of addtion reaction product, the nucleophilic addtion kinetics of thiourea for benzoylstyrene derivatives were measured by pH change. It maybe concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion : Above pH 10.0. It was in propotion to concentration of hydroxide ion, a part having no concern with pH was added to the neutral thiourea molecule. From the results of measurement the reaction rate and there findings, nucleophilic addition of thiourea to benzoylstyrene derivative was proposed a fitting mechanism.

${\beta}$-Nitrostyrene에 대한 Mercaptan의 親核性 添加反應에 關한 硏究 (I) (The Kinetics and Mechanism of Nucleophilic Addition of Mercaptan to a ${\beta}$-Nitrostyrene in Acidic Media (I))

  • 박옥현
    • 대한화학회지
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    • 제12권3호
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    • pp.106-113
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    • 1968
  • 여러 酸性溶媒 속에서 3,4-methylenedioxy-${\beta}$-nitrostyrene에 대한 n-butylmercaptan의 親核性 添加反應速度常數를 측정하여 넓은 pH범위에서 잘 맞는 反應速度式을 구하였다. 이 식에 의하면 pH3이하에서는 mercaptan분자가 첨가하며 pH6이상에서는 mercaptide ion이 첨가함을 알 수 있고 이 중간 pH범위에서 일어나는 복잡한 반응 메카니즘도 이 식에 의해 정량적으로 잘 설명할 수 있음을 알았다.

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Kinetic Studies on the Nucleophilic Addition of Thiophenol Derivatives to 4'-[N- (9-Acridinyl) ]-1'-( N- methanesulfonyl) -3'-methoxyquinonediimide

  • 김태린;정동인;변상용
    • Bulletin of the Korean Chemical Society
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    • 제18권4호
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    • pp.374-379
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    • 1997
  • The rate constants for the nucleophilic addition of thiophenol derivatives (p-OCH3, H, p-CH3, m-CH3, p-Br and p-NO2) to 4'-[N-(9-acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide (AMQD) were determined by ultraviolet spectrophotometer in water at 5 ℃, and rate equations which can be applied over a wide pH range were obtained. On the basis of pH-rate profile, Bronsted plot, adduct analysis, general base catalysis and substituent effect, a plausible mechanism of this addition reaction was proposed: Below pH 2.5, the reaction proceeded by the addition of thiophenol molecule to 6'-position of quinonoid after protonation at the acridinyl nitrogen. Above pH 6.2, the addition of sulfide anion to 6'-position of quinonoid was rate controlling. However, in the range of pH 3.0-6.0, these two reactions occured competively.

炭素二重結合에 대한 Mercaptan의 친핵성 첨가 반응의 Extrathermodynamic Relationship에 관한 연구 (Extrathermodynamic Relationships for the Nucleophilic Addition Reaction of Mercaptan to a Carbon Double Bond)

  • 박옥현;엄태섭
    • 대한화학회지
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    • 제13권4호
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    • pp.297-302
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    • 1969
  • The activation parameters for the nucleophilic addition reactions of n-propyl-, n-butyl-, n-amyl-and n-hexyl-mercaptan to 3, 4-methylene-dioxy-${\beta}$-nitrostyrene were determined at pH 5.8 and pH 2.0, and also the isokinetic temperature of the reactions at pH 5.8 was obtained numerically 262${\circ}$K, and at pH 2.0, 17.1${\circ}$K. From the values obtained above, the fact that the mercaptan having the longer carbon chain has the greater nucleophilicity of it in the addition reactions has been discussed by the extrathermodynamic analysis of ${\Delta}H^{\neq}$and ${\Delta}S^{\neq}$.

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Stereoselective Synthesis of Diverse α-Hydroxy-β-amino Acids and It's Application for Synthesis of Dipeptide Expecting as a Protease Inhibitor

  • Jang, Sang-Hun;Kim, Ju-Young;Kim, Min-Kyu;Han, Jeong-Woo;Park, Ki-Hun;Yoon, Yong-Jin;Lee, Sang-Gyeong
    • Bulletin of the Korean Chemical Society
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    • 제30권1호
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    • pp.163-171
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    • 2009
  • Few $\alpha$-Hydroxy-$\beta$-amino acids were synthesized via various nucleophilic addition of the epoxide and followed by stereoselective nucleophilic substitution reaction and eliminative cleavage of the acetal selectively in diacetal compound. One of the synthesized $\alpha$-Hydroxy-$\beta$-amino acid reacted with L-leucine methylester to give corresponding dipeptide in good yields.