Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of the Aminolysis of Benzenesulfonyl, Benzoyl and Benzyl Halides

  • Byung Choon Lee (Department of Chemistry, Choongbuk National University) ;
  • Dong Sook Sohn (Department of Chemistry, Choongbuk National University) ;
  • Ji Hyun Yoon (Department of Chemistry, Choongbuk National University) ;
  • Sun Mo Yang (Department of Chemistry, Choongbuk National University) ;
  • Ikchoon Lee (Department of Chemistry, Inha University)
  • Published : 1993.10.20
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Abstract

Kinetic studies are conducted for the reactions of Y-benzoyl, Y-benzenesulfonyl and Y-benzyl halides with X-anilines in acetonitrile, and the transition state (TS) structures and their variations with substituents X and Y are discussed. The magnitude of the cross-interaction constants, $\rho$xy, is the largest and the inverse secondary kinetic isotope effect (SKIE), $k_H/k_D$ < 1.0, with deuterated aniline nucleophiles is the smallest for benzoyl fluoride reflecting the tightest TS for this compound. The SKIEs for sulfonyl halides are relatively large due to a relatively large, diffuse nature of the reaction center, S, causing weaker steric hindrance to the vibrations of the two N-H(D) bonds. For benzoyl and sulfonyl halides, the trends in $k_H/k_D$ and $Ir_XI$ variations with $\sigma$Y contradict each other, which is rationalized by the negative charge accumulation on the reaction center, CO and SO$_2$, causing inefficient transfer for the substrate with an electron donating substituent.

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References

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