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Kinetics and Reaction Mechanism for Alkaline Hydrolysis of Y-Substituted-Phenyl Diphenylphosphinates
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  • Kinetics and Reaction Mechanism for Alkaline Hydrolysis of Y-Substituted-Phenyl Diphenylphosphinates
  • Kinetics and Reaction Mechanism for Alkaline Hydrolysis of Y-Substituted-Phenyl Diphenylphosphinates
저자명
Hong. Hyo-Jeong,Lee. Jieun,Bae. Ae Ri,Um. Ik-Hwan
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2013년|34권 7호|pp.2001-2005 (5 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 ($k_{OH^-}$) for the reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with $OH^-$ in $H_2O$ at $25.0{pm}0.1^{circ}C$ have been measured spectrophotometrically. Comparison of $k_{OH^-}$ with $k_{EtO^-}$ (the second-order rate constants for the corresponding reactions with $EtO^-$ in ethanol) has revealed that $EtO^-$ is less reactive than $OH^-$ although the former is ca. 3.4 $pK_a$ units more basic than the latter, indicating that the reactivity of these nucleophiles is not governed by their basicity alone. The Br${o}$nsted-type plot for the reactions of 4a-4i with $OH^-$ is linear with ${eta}_{lg}$ = -0.36. The Hammett plot correlated with ${sigma}^-$ constants results in a slightly better correlation than that correlated with ${sigma}^{circ}$ constants but exhibits many scattered points. In contrast, the Yukawa-Tsuno plot for the same reactions exhibits an excellent linear correlation with ${ ho}$ = 0.95 and r = 0.55. The r value of 0.55 implies that a negative charge develops partially on the O atom of the leaving group. Thus, the reactions of 4a-4i with $OH^-$ have been concluded to proceed through a concerted mechanism.