Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Correlation of the Rates of Solvolysis of Phenyl Fluorothionoformate

  • Choi, Song-Hee (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Seong, Mi-Hye (Department of Chemistry and Applied Chemistry, Hanyang University) ;
  • Lee, Yong-Woo (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 : 2011.01.29
  • Accepted : 2011.02.15
  • Published : 2011.04.20
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Abstract

The specific rates of solvolysis of phenyl fluorothionoformate (PhOCSF, 1) have been determined in 22 pure and binary solvents at $10.0^{\circ}C$. The extended Grunwald-Winstein equation has been applied to the specific rates of solvolysis of 1 over the full range of solvents. The sensitivities (l = $1.32{\pm}0.13$ and m = $0.39{\pm}0.08$) toward the changes in solvent nucleophilicity and solvent ionizing power, and the $k_F/k_{Cl}$ values are similar to those previously observed for solvolyses of acyl haloformate esters, consistent with the addition step of an additionelimination pathway being rate-determining. The large negative values for the entropies of activation are consistent with the bimolecular nature of the proposed rate-determining step. The results are compared with those reported earlier for phenyl chloroformate and chlorothionoformate esters and mechanistic conclusions are drawn.

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References

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