The Korean Journal of Pesticide Science (농약과학회지)

The Korean Society of Pesticide Science (한국농약과학회)
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Understand the Molecular Orbital Theory on the Hydrolytic Reactivity of Herbicide Flumioxazine

제초제 Flumioxazine의 가수분해 반응성에 관한 분자 궤도론적 이해

  • Sung, Nack-Do (Division of Applied Biologies and Chemistry, College of Agriculture and Life Science, Chungnam National University) ;
  • Jung, Hoon-Sung (Division of Applied Biologies and Chemistry, College of Agriculture and Life Science, Chungnam National University)
  • 성낙도 (충남대학교 농업생명과학대학 응용생물화학부) ;
  • 정훈성 (충남대학교 농업생명과학대학 응용생물화학부)
  • Published : 2004.12.30
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Abstract

Hydrolytic reactivities of N-phenylphthalimid herbicide flumioxazine (S) were disccused using molecular orbital (MO) theoretical method. It is revealed that below pH 5.0, the protonation $(SH^+)$ to carbonyl oxygens atom $(O_{21})$ of 1,2-dicarboximino group by general acid catalysis $(k_A)$ with hydronium ion $(H_3O^+)$ proceeds via charge controled reaction. Whereas, the specific base catalysis $(k_{OH})$ with hydroxide anion via orbital controled reaction occurs above pH 8.0. We may concluded that in the range of pH $5.0\sim8.0$, the hydrolysis proceeds through nucleophilic addition elimination $(Ad_{N-E})$ reaction, these two reactions occur competitively.

제초제 flumioxazine의 가수분해 반응성을 분자 궤도(MO)론적으로 검토한 결과, pH 5.0 이하의 산성에서는 $A_{AC}1$형의 반응 메커니즘으로 1,2-dicarboximino group의 carbonyl oxygene 원자$(O_{21})$에 대하여 hydronium ion $(H_3O^+)$에 의한 양성자화$(SH^+)$가 일반 산-촉매반응(general acid catalysis)에 따른 전하조절(charge-control) 반응이 일어난다. pH 8.0이상의 염기성에서는 $B_{AC}2$형의 반응 메커니즘으로 hydroxide anion $(OH^-)$에 의한 특정 염기-촉매반응(specific base catalysis)에 따른 궤도조절(orbital-control) 반응이 일어난다. 그리고 pH $5.0\sim8.0$ 사이에서 두 반응은 경쟁적으로 일어나 친핵성 첨가-제거반응$(Ad_{N-E})$으로 진행된다.

Keywords

References

  1. Blackbum, R. A. M., Capon, B. and McRitchie, A. C. (1977) The mechanism of hydrolysis of phthalamic and N-phenylphthalamic acid: The spectrophotometric detection of phtalic anhydride as an intermediate, Bioorg. Chem., 6:71-78
  2. Brown, J., Su, S. C. K. and Shafer, J. A. (1966) The hydrolysis and cyclization of some phthalamic acid derivatives. J. Am. Chem. Soc., 88:4468-4474
  3. Dewar, M. J. S., Zoebish, E. G., Healy, E. F. and Stewart, J. J. P. (1985) AM1: A new general purpose quantum mechanical molecular model,. J. Am. Chem. Soc., 107:3902-3909
  4. Fleming, I. (1976) Frontier Orbitals and Organic Chemical Reactions, Ch 3., John Wiely & Sons, London
  5. Geoffery, A. and Bevington, J. C. (1989) Cationic Ring-Opening Polymerization: Cyclic Ethers. pp.813-823, In Comprehensive Polymer Science: The Synthesis, Chara-cterization, Reactions & Applications of Polymers. Vol. 3., (ed. Penclerk, S. and Slomkowski, J.), Pergamon Press, Toronto
  6. Issacs, N. S. (1987) Physical Organic Chemistry. Ch. 9. Longman, Scientific & Technical. pp.331-334 & 358
  7. Katagi, T (2003) Hydrolysis of N-phenylimide herbicide flumioxazin and its anilic acid derivative in aqueous solutions. J. Pesticide Sci., 28:44-50
  8. Klopman, G. (1974) Chemical Reactivity and Reaction Paths, John Wiely & Sons, New York. Ch.4., pp.55-165
  9. Lowry, T H. and Richardson, K. S. (1985) Mechanism and Theory in Organic Chemistry (3rd ed.), Harper & Row, Pub., New York. Ch.7
  10. Richards, W. G. (1977) Quantum Pharmacology, Butterworths, London, Boston
  11. Stewart, J. J. (1990) MOPAC: A semiempirical molecular orbital program, J. Comp.-Aided Mol. Design., 4:1-105
  12. Tomlin, C. ed., (1997) The Pesticide Mannual (11th ed.), Crop Protection Publications, Surrey, U. K., pp.140, pp.677 & pp.1163
  13. Yoshida, R, Sakaki, M., Sato, R, Haga, T., Nagano, E., Oshio, H. and Kamoshita, K. (1991) Brighton Crop Protection Conference-Weeds, Vol. 1, pp. 69-75
  14. 성낙도，윤태용，권기성，김태린 (1990) 살충성 2chloro-l-(2,4,5-trichlorophenyl)vinyl-dimethylphosphate (Gardona)의 가수분해 반응메카니즘，대한화학회지，34(5):483-489
  15. 성낙도，김현이，박천규 (1994a) 살충성 O,O-diethyl-a-cy anobenzylideneaminooxyphospho-rothioate (Volaton) 의 가수분해 반응메카니즘，한국농화학회지, 37(2): 124-129
  16. 성낙도 (1994b) 핵산 모델로서 phosphate diester의 가수분해，한국농화학회지, 37(6):447-450
  17. 성낙도，이찬복，류재옥, 김대황 (1995) 제초성 N-(2,6-dimethoxypyrimidin-2-yl)amino-carbonyl-2-치환(Z)-6-(1-hydroxy-2-fluoroethyl)benzenesulfonamide 유도체의 가수분해반응 메카니즘，한국농화학회지，38 (5):455-462
  18. 성낙도，이광재，김용집，김대황 (1996) 제초성 flazasulfuron의 smile 자리옮김반응，한국농화학회지, 38(5): 218-223
  19. 성낙도，유성재，강문성 (1997) 살충성 imidaclopride의 가수분해 반응메카니즘，한국농화학회지 40(1):53-57
  20. 성낙도，유성재，최경섭，권기성 (1998) 살충제 buprofezin의 가수분해 반응메카니즘，한국농약과학회지，2(5):45-52
  21. 성낙도 (2002a) 살충제 O,O-diethyl-O-(1-phenyl-3-trifluoromethylyrazol-5-yl)phosphoro-thioate (Flpyrazofos)의 가수분해 반응 메카니즘，한국농약과학회지, 6(3):218-223
  22. 성낙도 (2002b) 정량적인 구조-활성상관(QSAR) 기법에 의한 새로운 농약의 개발 II. 자유 에너지 직선관계(LFER)와 설명인자들，한국농약과학회지，6(4): 231-243