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Decomposition of Paraoxon and Parathion by Amines, HOO- and OH- Ions: Reaction Mechanism and Origin of the α-Effect
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  • Decomposition of Paraoxon and Parathion by Amines, HOO- and OH- Ions: Reaction Mechanism and Origin of the α-Effect
  • Decomposition of Paraoxon and Parathion by Amines, HOO- and OH- Ions: Reaction Mechanism and Origin of the α-Effect
저자명
Bae. Ae-Ri,Lee. Jieun,Um. Ik-Hwan
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2013년|34권 1호|pp.201-206 (6 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

The second-order rate constants have been measured spectrophotometrically for the reactions of paraoxon 1 and parathion 2 with a series of alicyclic secondary amines, $OH^-$ and $HOO^-$ ions in $H_2O$ at $25.0{pm}0.1^{circ}C$. A linear Br${o}$nsted-type plot with ${eta}_{nuc}$ = 0.40 was obtained for the reactions of 1 with amines and $OH^-$. The reaction has been concluded to proceed through a concerted mechanism. $HOO^-$ deviates positively from the linear Br${o}$nsted-type plot, implying that the ${alpha}$-effect is operative. The magnitude of the ${alpha}$-effect ($k_{HOO^-}/k_{OH^-}$) was found to be ca. 55 for the reaction of 1 and 290 for that of parathion 2, indicating that $HOO^-$ is highly effective in decomposition of the toxic phosphorus compounds although it is over 4 $pK_a$ units less basic than $OH^-$. Among the theories suggested as origins of the ${alpha}$-effect (e.g., TS stabilization through an intramolecular Hbonding interaction, solvent effect, and polarizability effect), polarizability effect appears to be the most important factor for the ${alpha}$-effect in this study, since the polarizable $HOO^-$ exhibits a larger ${alpha}$-effect for the reaction of the more polarizable substrate 2.