Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Influence of Solvents on Rates of Reactions of 2,4-Dinitro Substituted Halobenzenes with Substituted Anilines (III)

2,4-이니트로할로벤젠과 치환된 아닐린의 반응속도에 대한 용매효과 (제3보)

  • Hai Whang Lee (Department of Chemistry, College of Science, Inha University) ;
  • Ikchoon Lee (Department of Chemistry, College of Science, Inha University)
  • 이해황 (仁荷大學校 理科大學 化學科) ;
  • 이익춘 (仁荷大學校 理科大學 化學科)
  • Published : 1978.08.30
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Abstract

Rates of reactions of 2,4-dinitrofluorobenzene and 2,4-dinitrobromobenzene with para substituted anilines in acetonitrile-methanol binary mixtures have been measured. It has been shown that methanol acts as nucleophilic catalyst upon reaction of 2,4-dinitrobromobenzene with anilines and as bifunctional catalyst upon reaction of 2,4-dinitrofluorobenzene with anilines. The electrophilic catalysis by methanol probably consists of formation of hydrogen bond in the transition state between alcoholic hydrogen and leaving group, fluorine. Nucleophilic catalysis by methanol may be ascribed to formation of hydrogen bond between alcoholic oxygen and amine hydrogen in the transition state.

2,4-Dinitrohalo (F,Br) benzene과 파라치환아닐린간의 반응속도를 아세토니트릴-메탄올 혼합용매하에서 측정하였다. 2,4-Dinitrobromobenzene과 치환아닐간의 반응에서 메탄올은 친핵촉매 현상만을 보였으며, 2,4-dinitrofluorobenzene과 치환아닐린간의 반응에서는 메탄올은 양쪽성(친핵 및 친전자) 촉매현상을 보였다. 메탄올에 의한 친핵촉매현상은 아마도 천이상태에서 알코올기의 수소와 이탈기의 플루오르사이의 수소결합에 의해 설명될 수 있으며 친전자촉매현상은 알코올기의 산소와 아닐린의 아민기 수소사이의 수소결합에 기인되는 것임을 알았다.

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References

  1. J. Chem. Soc. B. O. Koniglio(et al.)
  2. J. Chem. Soc. A.J. Parker
  3. J. Org. Chem. v.29 C.A. Kingsbury
  4. Reakts. Sposobnost Organ. Soed. v.5 S.M. Shein;L.A. Suchkova
  5. Reakts. Sposobnost Organ. Soed. v.6 no.2 L.A. SuchKova;S.M. Shein
  6. Reakts. Sposobnost Organ. Soed. v.5 V.A. Savelova;L.W. Litvinenko
  7. J. Org. Chem. v.42 F.P. Bullestreri(et al.)
  8. J. Korean Chem. Soc. v.21 H.W. Lee;I. Lee
  9. J. Korean Chem. Soc. v.22 H.W. Lee;I. Lee
  10. Dictionary of Organic Compounds
  11. Spec. Publ. no.11;18 Tables of Interactomic Distances and Configuratio in Molecules and Ions L.E. Sutton(ed.)
  12. Coll. Czechos. Chem. Comm. v.37 J. Kavalek;J. Haasova;V. Sterba
  13. Science v.151 R.G. Pearson
  14. J. Amer. Chem. Soc. v.79 J.F. Bunnett;W.D. Merritt Jr.
  15. Chem. Reactivity and Reaction Paths G. Klopman