• Title/Summary/Keyword: Nucleophilic addition

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

  • Kim, Tae-Rin;Choi, Young-Sang
    • Journal of the Korean Chemical Society
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    • v.10 no.4
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    • pp.158-160
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    • 1966
  • The nucleophilic addition constants 3,4-methylenedioxy-${\beta}$-nitrostyrene were determined for various nucleophiles. Considerably more data would be desirable, but it appears at present that there is no proportionality between the nucleophilic addition and substitution constant.

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

  • Lee, Ki-Chang;Mok, Gap-Young;Oh, Se-Young;Ryu, Jung-Wok
    • Journal of the Korean Applied Science and Technology
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    • v.14 no.1
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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.

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

  • Lee, Ki-Chang;Lee, Kwang-Il;Hwang, Yong-Hyun;Ryu, Jung-Wook;Yoon, Cheol-Hun
    • Journal of the Korean Applied Science and Technology
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    • v.13 no.1
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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.

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

  • Lee, Ki-Chang;Yoon, Chul-Hun;Hwang, Sung-Kwy;Ryu, Jung-Uk
    • Journal of the Korean Applied Science and Technology
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    • v.12 no.2
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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.

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

  • Park, Ok-Hyun
    • Journal of the Korean Chemical Society
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    • v.12 no.3
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    • pp.106-113
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    • 1968
  • The rate-constants of the nucleophilic addition reaction of n-butylmercaptan to 3,4-methylenedioxy-${\beta}$-nitrostyrene were determined at various acidic pH and a rate equation which can be applied over wide pH range was obtained. From this equation, one may conclude that this reaction is started by addition of mercaptan molecule below pH 3, while above pH 6, the overall rate of addition is almost only depend upon the concentration of nitrostyrene and the mercaptide ion. At pH 3∼6, the complex mechanism of this addition reaction can also be fully explained by the rate equation.

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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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    • v.18 no.4
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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.

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

  • OK-HYUN PARK;TAE-SUP UHN
    • Journal of the Korean Chemical Society
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    • v.13 no.4
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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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    • v.30 no.1
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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.