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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

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.

Keywords

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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