Journal of Life Science (생명과학회지)

Korean Society of Life Science (한국생명과학회)
권호 표지
DOI QR코드

DOI QR Code

Acid and Nucleophile Catalysed Hydrolyses of Benzenesulfinamides

벤젠술핀아미드의 가수분해반응에서 산 및 할라이드 이온의 촉매작용

  • Received : 2010.10.12
  • Accepted : 2010.12.15
  • Published : 2010.12.30
Download PDF
⟨ Previous Next ⟩

Abstract

Acid and halide ion catalyses for the hydrolysis of benzenesulfinamides were kinetically investigated. The rates of hydrolysis increased with increasing concentration of both acid and halide ions and also showed to speed up as the electron donating ability of the benzenesulfinyl moiety and the electron withdrawing ability in the leaving group increased. The reactivity of halide ions was in the order of $Br^-$ > $Cl^-$. The reaction mechanism may be accommodated by including a hypervalent intermediate and sulfonium cation.

Benzenesulfinamide류의 가수분해반응에서 산 및 할라이드 이온의 촉매작용을 속도론적으로 조사하였다. 반응속도는 산 및 할라이드 이온의 농도가 증가함에 따라 증가하였고, benzenesulfinyl group에 전자주게기와 이탈기에 전자받게기를 가진 반응기질에서 빠르게 나타났다. 할라이드 이온의 반응성은 브롬 이온이 염소이온 보다 크게 나타남을 알 수 있었다. 반응 메카니즘은 초원가 중간체와 술포늄 양이온을 거쳐 진행 될 것으로 예상 할 수 있었다.

Keywords

References

  1. Asefi, H. and J. G. Tillett. 1979. Nucleophilic substitution at Sulfur. J. Chem. Soc. Perkin Trans. 2, 1579-1582.
  2. Fife, T. H. 1993. Kinetic and mechanistic effects of C-N bond breaking in amide hydrolysis. Acc. Chem. Res. 26, 325-331. https://doi.org/10.1021/ar00030a005
  3. Fife, T. H., R. Najarajan, and M. H. Werner. 1987. Effect of the leaving group in the hydrolysis of N-acylimidazoles. J. Org. Chem. 52, 740-746. https://doi.org/10.1021/jo00381a006
  4. Finley, K. T., R. S. Kaiser, R. L. Reeves, and G Werimint. 1969. Adition of arenesulfinic acids to N,N,-dialkylquinonediimines J. Org. Chem. 34, 2083-2090. https://doi.org/10.1021/jo01259a012
  5. Kice, J. L. and G. Guaraldi. 1967. Mechanism of substitution at sulfinyl sulfur. J. Am. Chem. Soc. 89, 4113-4121. https://doi.org/10.1021/ja00992a028
  6. Lee, J. P., B. Ramesh, and T. H. Fife. 1997. Steric effect in the hydrolysis reactions of N-acylimidazoles. J. Org. Chem. 62, 2872-2876. https://doi.org/10.1021/jo960508d
  7. Lee, J. P., W. R. Kim., Y. H. Lee, and I. S. Koo. 2006. Kinetic evidence for hypervalent intermediate in acid hydrolysis of N-arylbenzenesulfinamides. Bull. Korean Chem. Soc. 27, 941-943. https://doi.org/10.5012/bkcs.2006.27.6.941
  8. Okuyama, T., J. P. Lee, and K. Ohnishi. 1994. Evidence for hypervalent intermediate in acid hydrolysis of sulfinamide. J. Am. Chem. Soc. 116, 6480-6481. https://doi.org/10.1021/ja00093a077
  9. Pearson, R. G. and J. Songstad. 1967. Application of the principle of hard and soft acids and bases to organic chemistry. J. Am. Chem. Soc. 89, 1827-1836. https://doi.org/10.1021/ja00984a014
  10. Rappoport, Z. 1969. Nucleophilic vinylic substitution, pp. 1-108, In Gold. V. (ed.), Adv. Phys. Org. Chem. Vol. 7, Academic Press Inc., New York.