Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Linear Free Energy Relationship on the Chemical Shift of Imidoyl Proton in N-benzylideneaniline Derivatives by PMR Spectrometry

核磁氣 共鳴分光法에 義한 N-Benzylideneaniline 誘導體중 Imidoyl Proton 의 Chemical Shift 에 미치는 自由에너지 關係

  • Nack Do Sung (Department of Agricultural Chemistry, Chungnam National University) ;
  • Cheon Kyu Park (Department of Chemistry, Chungnam National University) ;
  • Moon kyu Park (Department of Chemistry, Chungnam National University) ;
  • Ki Sung Kwon (？÷？？？Þ？？？？ ？？？¡？Þ？？ ？？？？？¡) ;
  • Kim, Tae Rin (？÷？？？Þ？？？？ ？？？¡？Þ？？ ？？？？？¡)
  • 성낙도 (忠南大學校 農科大學 農化學科) ;
  • 박천규 (忠南大學校 理科大學 化學科) ;
  • 박문규 (忠南大學校 理科大學 化學科) ;
  • 권기성 (충남대학교 이과대학 화학과) ;
  • 김태린 (고려대학교 이과대학 화학과)
  • Published : 1985.06.20
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Abstract

The effects of linear free energy relationship (LFER) on the imidoyl proton (H${\alpha}$)-substituent chemical shift (SCS) in case of varying para-substituted C-phenyl group in N-benzylideneaniline derivatives were studied. The H${\alpha}$-SCS values and LFER parameters such as ${\sigma}$,${\sigma}^+$, ${\sigma}_I$,${\sigma}_R, F and R were applied to the Hammett, Okamoto-Brown, and Taft, Swain-Lupton's dual substituents parameter (DSP) equations. The results were: (1) the blending coefficient values, ${\lambda}$ = 2.8∼3.2, it's means that the resonance effect (R) was larger than inductive effect (I) and field effect (F), and (2) the values of percent resonance and percent field effects were %R = 66.6 and %F = 33.4, respectively, yielding the ratio of resonance effect (R) to field effect (F) of 2 : 1.

N-benzylideneaniline 유도체의 C-phenyl group 파라위치에 치환기가 변화함에 따라 imidoyl양성자의 화학적 이동 (H${\alpha}$-SCS)에 미치는 자유에너지 직선관계(LFER)를 검토하기 위하여 치환기별 H$_{\alpha}$-SCS와 ${\sigma}$,${\sigma}^+$, ${\sigma}_I$,${\sigma}_R$, F 및 R등의 여러가지 자유에너지 관계 파라미터를 Hammett, Okamoto-Brown식과 그리고 Taft, Swain-Lupton의 DSP식에 적용한 바, 2.8∼3.2의 섞임계수(blending coefficient values, ${\lambda}$)값을 얻음으로써 공명효과(R)가 유발효과(I)나 장효과(F)보다 H_${\sigma}$-SCS에 크게 영향을 미친다는 사실을 알 수 있었으며 Swain-Lupton의 식으로 구한 %R = 66.6 and %F = 33.4의 값으로 부터 H$_{\sigma}$-SCS에 미치는 공명효과(R)와 장효과(F)의 비가 2:1이라는 정량적인 관계를 알았다.

Keywords

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