Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Correlation of the Rates of Solvolyses of Cinnamyl Bromide

  • Koo, In-Sun (Department of Chemical Education and The Research Institute of Natural Science,Gyeongsang National University) ;
  • Cho, Jun-Mi (Department of Chemical Education and The Research Institute of Natural Science,Gyeongsang National University) ;
  • An, Sun-Kyoung (Department of Chemical Education and The Research Institute of Natural Science,Gyeongsang National University) ;
  • Yang, Ki-Yull (Department of Chemical Education and The Research Institute of Natural Science,Gyeongsang National University) ;
  • Lee, Jong-Pal (Department of Chemistry, Dong-A University) ;
  • Lee, I. (Department of Chemistry, Inha Univer)
  • Published : 2003.04.20
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Abstract

Solvolytic rate constants at 25℃ are reported for solvolyses of cinnamyl bromide (1) in binary mixtures of water with acetone, ethanol, methanol, methanol-d, and 2,2,2-trifluoroethanol. Product selectivities are reported for solvolyses of 1 in aqueous ethanol and methanol. Rate ratios in solvents of the same $Y_{Br}$ value and different nucleophilicity provide measures of the minimum extent of nucleophilic solvent assistance (e.g. $[k_{40EW}/k_{97TFE}]$Y = 2.88, EW = ethanol-water). With use of the extended Grunwald-Winstein equation, the l and m values are similar to the values of 0.43 and 0.88 obtained for the solvolyses of 1 using the equation (see below) which includes a parameter (I) for solvation of aromatic rings. The magnitude of l and m values associated with a change of solvent composition predicts the $S_{N1}$ reaction mechanism rather than an $S_{N2}$ channel. Product selectivities (S), defined by S = [ether product]/[alcohol product]×[water]/[alcohol solvent] are related to four rate constants for reactions involving one molecule of solvent as nucleophile and another molecule of solvent as general base catalyst. A linear relationship between 1/S and molar ratio of solvent is derived theoretically and validated experimentally for solvolyses of the above substrates from water up 75% 1/S = $(k_{wa}/k_{aw})$([alcohol solvent]/[water]) + $k_{ww}/k_{aw}$ alcohol-water. The results are best explained by product formation from a “free” carbocation intermediate rather than from a solvent-separated ion pair.

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References

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