• Title/Summary/Keyword: Nucleophilic addition reaction

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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 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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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.

A Study on the Nucleophilic Addition Reaction of L-cysteine for PVS (PVS 유도체에 대한 L-Cysteine의 친핵성 첨가반응에 관한 연구)

  • Lee, Ki-Chang;Lee, Kwang-Iil;Yoon, Chul-Hun;Hwang, Sung-Kwy;Kong, Seung-Dae
    • Journal of the Korean Applied Science and Technology
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    • v.12 no.2
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    • pp.99-105
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    • 1995
  • Phenylvinylsulfone derivatives were synthesized by Kirners condition. The structure of these compounds were ascertained by means of ultraviolet, melting point, IR and $^1H-NMR$ spectra. The nucleophilic addtion reaction kinetics of L-cysteiene for phenylvinylsulfone was investigated by ultraviolet spectrophotometery in 40% $EtOH-H_2O$ at $25^{\circ}C$. The rate equations which were applied over a wide pH $1.0{\sim}13.0$ range. On the basis of general base catalysis and confirmation of addtion reaction product, the nucleophilic addtion reaction kinetics of L-cysteiene for phenylvinylsulfone were measured by the pH change. From the result of the above caption, a plausible nucleophilic addtion reaction mechanism of L-cysteiene for phenylvinylsulfone was proposed. These compounds may by used ad the starting materials for the preparation of the engineering plastics or the germicide.

Solvent Effects on the Nucleophilc Addition (I) Effect of Solvent Polarity on the Nucleophilic Addition of Amine to Phenylvinylketone (친핵성 첨가반응에 대한 용매효과 (I) Phenylvinylketone에 대한 아민의 첨가반응속도에 미치는 용매의 극성효과)

  • Gap-Cheol Shin;Tae-Rin Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.287-292
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    • 1992
  • The rate constants of the nucleophilic addition reaction of amines (piperidine and diethylamine) to phenylvinylketone in various solvents have been determined by UV spectrophotometry at $25^{\circ}C$. On the basis of the high sensitivity of the rate to the polarity of the medium, it may be concluded that the reaction intermediate has zwitterionic character. The effect of the solvents on the rate of the bimolecular nucleophilic addition reaction is described well by the Kirkwood equation: The transition state of the reaction has a cyclic structure formed through an intramolecular hydrogen bond. The addition reaction of primary and secondary amines to phenylvinylketone in all solvents take place considerably faster than that of tertiary amine and this results also can be explained by the intermediate products in the reaction have a cyclic structure formed through an intramolecular hydrogen bond for the primary and secondary amines but not for the tertiary amine.

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A Study on the Kinetics and Mechanism of Nucleophilic Addition of 1-Propanethiol to ${\alpha}-Phenyl-N-iso-propylnitrone$ Derivatives. ((${\alpha}-Phenyl-N-iso-propylnitrone$유도체에 대한 1-Propanethiol의 친핵성 첨가반응에 관한 연구)

  • Lee, Kwang-Il;Kwak, Chun-Geun;Jang, Byung-Man;Kim, Young-Ju;Ji, Yun-Seup;Lee, Ki-Chang
    • Journal of the Korean Applied Science and Technology
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    • v.12 no.2
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    • pp.85-92
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    • 1995
  • The rate constant of the nucleophilic addition of 1-propanethiol to ${\alpha}-phenyl-N-iso-propylnitrone$ derivatives were determined at various pH and a rate equation which can be applied over wide pH range is obtained. Final product of the addition reaction was ${\alpha}-thiopropyl-p-phenylbenzylideneamine$. Base on the rate equation, general base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Below pH 3.0, the reaction was initiated by the addition of 1-propanthiol, and in the range of pH 3.0-10.0, proceeded by the competitive addition of 1-propanethiol and propanethiolate. Above the pH 10.0, the reaction proceeded through the addition of propanethiolate.

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.

Kinetics and Mechanism of Nucleophilic Addition of Sodium Thiophenoxide to ${\alpha}-Phenyl-N-iso-Propylnitrone$ derivatives ((${\alpha}-Phenyl-N-iso-propylnitrone$유도체에 대한 Sodium Thiophenoxide의 친핵성 첨가반응 메카니즘과 그의 반응 속도론적 연구)

  • Lee, Kwang-Il;Kim, Young-Ju;Kqak, Chun-Geun;Jang, Buyng-Man;Lee, Ki-Chang
    • Journal of the Korean Applied Science and Technology
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    • v.12 no.2
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    • pp.93-98
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    • 1995
  • The rate constant of Nucleophilic addition of sodium thiophenoxide to nitrone were determined by UV Spectrophotometry and a rate equation which can be applied over wide pH range was obtained. Base on the rate equation, general base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Blow pH 3.0, the reaction was initiated of thiophenol, and in the range of pH $3.0{\sim}10.0$, 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.