Bulletin of the Korean Chemical Society

  • 제29권9호
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  • Pages.1747-1751
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  • 2008
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Application of the Extended Grunwald-Winstein Equation to Solvolyses of n-Propyl Fluoroformate and a Consideration of Leaving Group Effects

  • Seong, Mi-Hye (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Kyong, Jin-Burm (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Kim, Dong-Kook (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Kevill, Dennis N. (Department of Chemistry and Biochemistry, Northern Illinois University)
  • 발행 : 2008.09.30
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초록

Reactions of n-propyl fluoroformate in a variety of pure and binary solvents have been studied at 40.0 {^{\circ}C}. The extended (two-term) Grunwald-Winstein equation has been applied to the specific rates of solvolysis of npropyl fluoroformate. The sensitivities (l = 1.80 ${\pm}$ 0.17 and m = 0.96 ${\pm}$ 0.10) to changes in solvent nucleophilicity and solvent ionizing power and the $k_F/k_{Cl}$ values are similar to those for solvolyses of n-octyl fluoroformate over the full range of solvents, suggesting that the addition step of an addition-elimination mechanism is ratedetermining. These observations are also compared with those previously reported for the corresponding chloroformate and fluoroformate esters.

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