Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of Hydrolysis of Insecticidal 2-chloro-1-(2,4,5-trichlorophenyl) vinyldimethylphosphate (Gardona)$^{\(R)}$

살충성 2-Chloro-1-(2,4,5-trichlorophenyl)vinyldimethylphosphate (Gardona)$^{\(R)}$의 가수분해 반응메카니즘

  • Sung, Nack-Do (Department of Agricultural Chemistry, Chungnam National University) ;
  • Yun, Tae-Yong (Department of Agricultural Chemistry, Chungnam National University) ;
  • Kwon, Ki-Sung (Department of Chemistry, Chungnam Natinal University) ;
  • Kim, Tae-Rin (Department of Chemistry, Korea University)
  • 성락도 (충남대학교 농과대학 농화학과) ;
  • 윤태용 (충남대학교 농과대학 농화학과) ;
  • 권기성 (충남대학교 자연과학대학 화학과) ;
  • 김태린 (고려대학교 이과대학 화학과)
  • Published : 19900900
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Abstract

The rate of hydrolysis of insecticidal 2-chloro-l-(2,4,5-trichlorophenyl)-vinyldimethylphosphate(Gardona) have been investigated in 25${\%}$ aqueous methanol. Studies at varying pH suggest that the hydrolysis of Gardona proceeds through the bimolecular (Ad$_{N-E}$) mechanism involving the transition state and carbanion intermediate as evidenced by solvent effect (m < 0.4, n < 0.7, [m] ${\ll}$ [l](associative SN$_2$ type)), thermodynamic parameters (${\{Delta}S^{\neq}$ = -27∼-32 e.u. & ${\{Delta}H^{\neq}$ = 13∼18 Kcal/mole), hydrolysis rate equation (k = k$_A+_B$ [OH-]), general base catalysis and hydrolysis product analysis, respectively.

25${\%}$ methanol-수용액 속에서 살충성 2-chloro-l-(2,4,5-trichlorophenyl)-vinyldimethylphosphate(Gardona)의 가수분해 반응을 관찰하였다. 다양한 pH에서의 연구결과는 용매효과(m < 0.4, n < 0.7, |m| ${\ll}$ |l|(화합 S$_N$2 형)), 열역학적 파라미터 (${\{Delta}S^{\neq}$ = -27∼-32 e.u. ${\{Delta}H^{\neq}$ = 13∼18 Kcal/mole), 반응속도(k = k$_A$＋k$_B$ [OH$^-$]), 일반염기 촉매 효과 및 가수분해 생성물 분석에 의하여 Gardona의 가수분해 반응이 전이상태와 carbanion 중간체를 포함하는 2분자적(Ad$_{N-E}$) 메카니즘으로 일어남을 암시하고 있다.

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