Nucleophilic Substitution Reactions of Benzoic Anhyrides with Aniline in Methanol-Acetonitrile Mixtures

메탄올-아세토니트릴 혼합용매에서 벤조산 무수물과 아닐린의 친핵성 치환반응

  • 이병춘 (충북대학교 자연과학대학 화학과) ;
  • 신영국 (충북대학교 자연과학대학 화학과) ;
  • 이승우 (충북대학교 자연과학대학 화학과) ;
  • 이익춘 (인하대학교 이과대학 화학과) ;
  • 이원희 (인하대학교 이과대학 화학과)
  • Published : 19970200


Kinetic studies for the nucleophilic substitution reactions of the benzoic anhydrides with anilines in methanol-acetonitrile mixtures at$35.0{\circ}C$have been carried out in order to elucidate the reaction mechanism. Individual rate constants$k_{XY}$and$k_{XZ}$were decided from the ratios of the reaction products for the competitive substitution reaction at either one of the two carbonyl carbons in benzoic anhydride. Transition state structure and reaction mechanism were elucidated by the Hammett$p_x,\;p_y$and$p_z$values and cross interaction constant$p_x\;p_y$and$p_zvalues. The reaction of the benzoic anhydride has been proposed to proceed by a frontside attack$S_N2 $mechanism with four-membered ring transition state from unusually large magnitude of the$ρ_X,\;ρ_{XY},\;ρ_{XZ}$and positive$p_Y$values.



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