Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Kinetics and Mechanism of the Hydrolysis of N-(Benzenesulfonyl) benzimidoyl Chlorides

  • Kim, Tae-Rin (Department of Chemistry, Korea University) ;
  • Kwon, Hyo-Shik (Department of Chemical Education, Chungbuk University)
  • Published : 1988.06.20
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Abstract

The rates of hydrolysis of N-(benzenesulfonyl) benzimidoyl chlorides (p-H, $p-CH_3,\;p-CH_3,\;p-NO_2\;and m-NO_2$) have been measured by UV spectrometry in 60% methanol-water at $25^{\circ}C$ and a rate equation which can be applied over wide pH range was obtained. Below pH 7.00, the substituent effect on the hydrolysis rate of N-(benzenesulfonyl) benzimidoyl chloride was found to conform to the Hammett ${\sigma}$ constant with ${\rho}$ = -0.91, whereas above pH 9.00, with ${\rho}$ = 0.94. On the basis of the rate equation obtained and the effect of solvent, substituents and salt, the following reaction mechanism were proposed; below pH 7.00, the hydrolysis of N-(benzenesulfonyl) benzimidoyl chloride proceeds by $S_N1$ mechanism, however, above pH 9.00, the hydrolysis is initiated by the attack of the hydroxide ion and in the range of pH 7.00-9.00, these two reactions occur competitively.

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References

  1. The Chemistry of the Carbon-Nitrogen Double Bond S. Patai
  2. J. Chem. Soc. E. R. H. Jones;F. G. Mann
  3. Brit. Pat., 970, 480
  4. Chem. Abstr. v.62
  5. Tetrahedron Letters F. L. Scott;D. A. Cronin
  6. Liebigs Ann. Chem. v.2 E. Stanoeva;M. Haimova;V. Ognyanov
  7. Heterocycles v.22 no.5 D. Prajapati;S. Attaluri
  8. Heterocycles v.22 no.5 D. Prajapati;S. Attaluri
  9. J. Prakt. Chem. v.324 no.6 R. Neumann;J. Beger
  10. J. Org. Che. v.49 no.3 John E. Mills;Robin M. Cosgrove
  11. Chem. Ber. v.95 I. Ugi;F. Beck;Fetzer
  12. J. Chem. Soc., Perkin II A. F. Hegarty;M. P. Cashman;F. L. Srott
  13. J. Chem. Soc., Perkin II A. F. Hegarty;K. J. Dignam
  14. USSR, Zh, Org. Khim. v.5 Y. L. Dubina;S. I. Brumistror
  15. J. Chem. Soc. no.B F. L. Scott;M. Cashman;A. F. Hegarty
  16. J. Chem. Soc. no.B F. L. Scott;M. Cashman;A. F. Hegarty
  17. J. Korean Chem. Soc. v.20 K. S. Kwon;T. R. Kim
  18. J. Chem. Soc., Perkin II A. F. Hegarty;J. D. Cronin;F. L. Srott
  19. Chem. Ber. v.94 I. Ugi;F. Beck;U. Fetzer
  20. Helv. Chem. Acta. v.42 H. H. Bonhard;H. Zollinger
  21. USSR, Zh, Org. Khim. v.2 no.10 V. L. Dubina;S. I. Brumistor

Cited by

  1. ChemInform Abstract: Kinetics and Mechanism of the Hydrolysis of N‐(Benzenesulfonyl)benzimidoyl Chlorides. vol.20, pp.1, 1988, https://doi.org/10.1002/chin.198901062