Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Hydrolysis Mechanism of N-(benzenesulfonyl)-C-(N-methylanilino)imidoyl Chloride Derivatives

N-(benzenesulfonyl)-C-(N-methylanilino)imidoyl Chloride 유도체의 가수분해 반응 메카니즘

  • Kwon, Ki-Sung (Department of Chemistry, Chungnam National University) ;
  • Song, Yun-Yi (Department of Chemistry, Chungnam National University)
  • 권기성 (충남대학교 자연과학대학 화학과) ;
  • 송윤이 (충남대학교 자연과학대학 화학과)
  • Published : 19950800
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Abstract

Rate Constants of hydrolysis of N-(benzenesulfonyl)-C-(N-methylanilino)imidoyl chlorides were determined by UV spectrophotometry in 50% (v/v) aqueous methanol at 25$^{\circ}C.$ On the basis of rate equation, substituent effect, solvent effect, salt effect, thermodynamic parameters and hydrolysis product analysis, it may be concluded that the hydrolysis of N-(benzenesulfonyl)-C-(N-methylanilino)imidoyl chlorides proceed through $S_N1$ mechanism via azocarbonium ion intermediate below pH 9.0, while aebove pH 10.0 the hydrolysis proceeds through nucleophilic addition-elimination ($Ad_{N-E}$) mechanism.

25$^{\circ}C$의 50%(v/v) 메탄올-물의 혼합용매 속에서 N-(benzenesulfonyl)-C-(N-methylanilino)imidoyl Chloride 유토체의 가수분해 반응 속도 상수를 자외선 분광광도법으로 측정하여 반응속도식, 치환기효과, 용매효과, 염효과, 열역학적 할성화 파라미터 및 가수분해 생성물의 분석 등의 결과로부터 pH9.0 이하의 범위에서는 azocarbonium ion 중간체를 지나는 $S_N1$형 반응, pH 10.0 이상의 pH에서는 사면체 중간체를 지나는 친핵성 첨가-제거반응($Ad_{N-E}$)이 일어남을 제안하였다.

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References

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