Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Rate and Product Studies with 2-Methyl-2-Chloroadamantane under Solvolytic Conditions

  • Lee, Young-Hoon (Department of Food and Biotechnology, Hanseo University) ;
  • Seong, Mi-Hye (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Lee, Eun-Sung (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Lee, Yong-Woo (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Won, Ho-Shik (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Kyong, Jin-Burm (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Kevill, Dennis N. (Department of Chemistry and Biochemistry, Northern Illinois University)
  • Received : 2010.01.27
  • Accepted : 2010.03.02
  • Published : 2010.05.20
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Abstract

Reactions of 2-methyl-2-chloroadamantane (1) in a variety of pure and binary solvents have been studied at various temperatures and pressures up to 80 MPa. The sensitivity (m) to changes in solvent ionizing power of the Grunwald-Winstein equation, and the activation volume (${\Delta}V^{\ddag}$) are calculated from the specific rates. An excellent linear relationship (R = 0.997) for 1, log (k/$k_0$) = $0.80Y_{Cl}$ + 0.11, and the activation volume, ${\Delta}V^{\ddag}$ = -15.2 ~ -10.2 $mL{\cdot}mol^{-1}$ were observed. These values are similar to those for solvolyses of 1-adamantyl halides over the full range of solvents, suggesting that the unimolecular mechanism involving ion pairs is rate-determining. These observations are also compared with those previously reported for the corresponding 1-adamantyl derivatives and chloroformate esters.

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