• Title/Summary/Keyword: Specific acid ($A_{AC}2$) & base ($B_{AC}2$) catalysis

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Kinetics and hydrolysis mechanism of insecticide O,O-diethyl-O-(1-phenyl-3-trifluoromethylpyrazol-5-yl)phosphorothioate (Flupyrazofos) (살충제 O,O-diethyl-O-(1-phenyl-3-trifluoromethylpyrazol-5-yl)-phosphorothioate(Flupyrazofos)의 가수분해 반응 메커니즘)

  • Sung, Nack-Do
    • The Korean Journal of Pesticide Science
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    • v.6 no.3
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    • pp.218-223
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    • 2002
  • The rate of hydrolysis of insecticide, O,O-diethyl-O-(1-phenyl-3-trifluoromethylpyrazol-5-yl)phosphorothioate (Flupyrazofos) have been investigated in 25% (v/v) aqueous dioxane (${\mu}=0.1M$) at $45^{\circ}C$. The hydrolysis mechanism of flupyrazofos proceeds through the specific acid ($A_{AC}2$) catalysis below pH 4.0, specific base ($B_{AC}2$) catalysis above pH 11.0 and general acid & base ($B_{AC}2$) catalysis between pH 5.0 and pH 10.0 via trigonal-bipyramidal ($d^2sp^3$) intermediate as evidence by solvent effect ($|m|{\ll}|{\ell}|$), rate equation ($kt=ko+k_H+ [H_3O^+]+k_{OH}[OH^-]$) and product analysis. The half-life ($T\frac{1}{2}$) of hydrolytic degradation in neutral media at $45^{\circ}C$ was ca. 3 months.

Understand the Molecular Orbital Theory on the Hydrolytic Reactivity of Herbicide Flumioxazine (제초제 Flumioxazine의 가수분해 반응성에 관한 분자 궤도론적 이해)

  • Sung, Nack-Do;Jung, Hoon-Sung
    • The Korean Journal of Pesticide Science
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    • v.8 no.4
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    • pp.265-271
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    • 2004
  • Hydrolytic reactivities of N-phenylphthalimid herbicide flumioxazine (S) were disccused using molecular orbital (MO) theoretical method. It is revealed that below pH 5.0, the protonation $(SH^+)$ to carbonyl oxygens atom $(O_{21})$ of 1,2-dicarboximino group by general acid catalysis $(k_A)$ with hydronium ion $(H_3O^+)$ proceeds via charge controled reaction. Whereas, the specific base catalysis $(k_{OH})$ with hydroxide anion via orbital controled reaction occurs above pH 8.0. We may concluded that in the range of pH $5.0\sim8.0$, the hydrolysis proceeds through nucleophilic addition elimination $(Ad_{N-E})$ reaction, these two reactions occur competitively.