Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Aminolysis of 4-Nitrobenzenesulfenyl Chloride

  • Lee, Jong-Pal (Department of Chemistry, Dong-A University) ;
  • Lee, Sung-Sik (Department of Chemical Engneering, Dong-A University) ;
  • Koo, In-Sun (Department of Chemistry Education and Research Institute of Natural Science, Gyeongsang National University)
  • Received : 2010.12.03
  • Accepted : 2011.01.08
  • Published : 2011.03.20
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Abstract

The reactions of 4-nitrobenzenesulfenyl chloride with substituted benzylamines proceed through three pathways, the uncatalyzed ($k_2$) and catalyzed ($k_3$) paths including solvolysis ($k_o$) by the solvent. The large value of primary normal kinetic isotope effects imply that the proton transfer occurs concurrently from benzylamine to Cl atom of the substrate. The ${\beta}_x$ and ${\rho}_x$ values for the catalyzed path, $k_3$, are greater than those for the uncatalyzed path, indicating that greater degree of bond formation in the catalyzed TS compared to the uncatalyzed TS.

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