Linear Free Energy Relationship on the Phosphorylation of Acetylcholinesterase by Insecticidal O,O-Diethylphenylphosphate Derivatives

살충성(殺蟲性) O,O-Diethylphenylphosphate유도체(誘導體)들에 의(依)한 Acetylcholinesterase의 Phosphorylation에 미치는 자유(自由)에너지 관계(關係)

  • Sung, Nack-Do (Department of Agricultural Chemistry, College of Agriculture, Chungnam National University)
  • 성낙도 (충남대학교 농과대학 농화학과)
  • Published : 1984.06.30

Abstract

Linear free energy relation ship(LFER) on the insecticidal activity of O,O-diethylphenylphosphate (A) and 3,5-dimethylphenyl-O,O-diethylphosphate (B) derivatives were studied by EHT MO calculation method and regression analysis method. LFER between varying substituent constants and $pI_{50}$ constants of phosphates, (A) & (B) were calculated with applying Hammett, Okamoto-Brown, Taft and Swain-Lupton's DSP equations;percent resonance effect(R) and field effect(F) of (A) were %R=33.5 & %F=66.5 and also that of (B) were %R=2 & %F=98, respectively. On the basis of above findings, the insecticidal activities were similar for both (A) and (B), but (B) have larger field and inductive contribution than (A), due to the 3,5-dimethyl group of (B).

살충성 O,O-diethylphenylphosphate (A)와 3,5-dimethylphenyl-O,O-diethylphosphate 유도체 (B)에 의한 acetylcholinesterase(Ach E)의 phosphorylation 반응에 미치는 정량적인 자유에너지 관계(LFER)를 알아보기 위하여 Ach E의 두 작용점인 esteratic-anionic site에 대응하는 (A) 및 (B)의 P원자 및 meta 위치간의 공간직선 거리 및 알짜전하를 확장 H$\ddot{u}$ckel이론(EHT)에 의한 MO 계산 방법으로 계산하고 여러 가지 치환기상수와 $pI_{50}$ 상수를 Hammett 및 Okamoto-Brown식, Taft와 Swaln-Lupton의 DSP식에 적용한 회귀분석 결과로부터 살충작용에 미치는 정량적인 자유에너지 관계, %R과 %F를 계산하여 검토하였다. 즉, (A) 및 (B)의 살충효과는 서로 비슷하였으며 blending coefficient (${\lambda}$)는 모두 ${\lambda}$<1의 값을 나타내었다. (A) 및 (B)의 resonance effect (%R)와 field effect (%F)는 각각 %R=33.5, %F=66.5 그리고 %R=2, %F=98로 각각 계산되었는데(B)와 같이 phenyl group에 bulky한 소수성의 methyl group이 결합될수록 resonance effect($R_{\pi}$)보다는 direct through space field effect ($F_D$)가 아닌 through space field effect가 더 크게 영향을 미치게 된다는 사실을 알 수 있었다.

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