The Korean Journal of Pesticide Science (농약과학회지)

The Korean Society of Pesticide Science (한국농약과학회)
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A Synthesis of New Fluorine-containing Phenylformamidines Possessing N-Dialkylaminosulfenyl Group and Their Insecticidal Activities

N-Dialkylaminosulfenyl 치환체를 갖는 새로운 불소 함유 Phenylformamidine 유도체의 합성과 살충활성

  • Lee, Dong-Guk (Moghu Research center Ltd., Korea Research Institute of Bioscience and Biotechnology) ;
  • Chung, Kun-Hoe (Moghu Research center Ltd., Korea Research Institute of Bioscience and Biotechnology) ;
  • Ko, Young-Kwan (Bio-Organic Science Division, Korea Research Institute of Chemical Technology) ;
  • Ryu, Jae-Wook (Bio-Organic Science Division, Korea Research Institute of Chemical Technology) ;
  • Woo, Jae-Chun (Bio-Organic Science Division, Korea Research Institute of Chemical Technology) ;
  • Koo, Dong-Wan (Bio-Organic Science Division, Korea Research Institute of Chemical Technology) ;
  • Choi, Yong-Ho (Bio-Organic Science Division, Korea Research Institute of Chemical Technology) ;
  • Park, No-Joong (Bio-Organic Science Division, Korea Research Institute of Chemical Technology) ;
  • Kim, Tae-Joon (Dongbu Hannong Agrolife Research Institute) ;
  • Choi, In-Young (Dongbu Hannong Agrolife Research Institute)
  • Received : 2010.08.30
  • Accepted : 2010.09.10
  • Published : 2010.09.30
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Abstract

Phenylformamidine derivatives are well known as insecticides for their specific activity against the insects. It has now been established that they show insecticidal activity as agonists on the octopamine receptor. In order to get a highly active compound we have intensively exploited fluorine substituted-aromatic formamidines possessing N-dialkylaminosulfeny group. Up to now, there are several candidates we found: N-(dialkylamino)sulfenyl-N-methyl-N'-(4-fluoro-2-methylphenyl)formamidines. The miticidal activity of Compound 29 show five-fold higher than Amitraz.

Phenylformamidine계 유도체들은 곤충의 신경전달 물질인 octopamine과 경쟁적으로 octopamine receptor에 작용하여 생육 전 단계에 걸쳐 살충 활성을 나타내는 젓으로 알려져 있다. 본 연구에서는 고활성 화합물을 발견하기 위해 과거에 합성되지 않은 불소를 함유한 phenylformamidine 유도체에 N-dialkylaminosulfenyl 치환체를 도입하여 새로운 화합물을 합성하고 살충활성 시험을 한 결과 N-(dialkylamino)sulfenyl-N-methyl-N'-(4-fluoro-2-methyl-phenyl)formamidines 유도체들이 높은 살충 활성 나타내었으며 특히, 이들 중 가장 우수한 살충 활성을 갖는 화합물 29와 대조약제인 Amitraz의 점박이응애에 대한 $LD_{90}$는 각각 32.0 ppm, 150.4 ppm으로 화합물 29는 점박이응애에 대하여 Amitraz보다 5배 우수한 살충활성을 나타내었다.

Keywords

References

  1. Chen, J. S. and K. C. Kang (1989) Susceptibility of two bulb mites, Rhizoglyphus robini and R. setosus (Acarina: Acaridae), to some acaricides and insecticides. Experimental and Applied Acarology 6(1):55-66. https://doi.org/10.1007/BF01193233
  2. Evans, P. D. and J. D. Gee (1980) Action of formamidine pesticides on octopamine receptor. Nature 287:60-62. https://doi.org/10.1038/287060a0
  3. Fahmy, M. A., C. R. Harrison, G. P. Lahm and T. M. Stevenson (1993) N-sulfenylated pyrazolines, compositions and use. US patent 5,196,408 Al.
  4. Gall., J. M. McCall., R. E. TenBrink, P. F. VonVoigtlander, and J. S. Mohrland (1988) Arylformamdines with Antinociceptive Properties. J. Med. Chem. 31:1816-1820. https://doi.org/10.1021/jm00117a023
  5. Goto, T., T. Soeda, N. Asai and A. Tanak (1983) Aminosulfenyl chloride derivatives. US patent 4,421,693.
  6. Harrison, I. R., A. Kozlik, J. F. MeCarthy, B. H. Palmer, S. B. Wakerley, T. I. Watkins and D. M. Weighton (1972) 1,5-Bis(2,4-dimethylphenyl)-3-methyl-1,3,5-triazapenta-1,4-diene, a new acaricide active against strains of mites resistant to organophosphorus and bridged diphenyl compounds. Pestic. Sci., 3(6):679-680. https://doi.org/10.1002/ps.2780030603
  7. Harrison, I. R., A. Kozlik, J. F. McCarthy, B. H. Palmer, S. B. Wakerley, T. I. Watkins and D. M. Weighton (1973) 1,3,5-triazapenta-1,4-dienes. Chemical aspects of a new group of acaricides. Pestic. Sci., 4(6):679-686.
  8. Harrison, I. R., J. F. McCarthy, B. H. Palmer and J. Burton (1973) Pesticidal compounds and compositions. US patent 3,781,355.
  9. Hateh, C. E. (1978) Synthesis of N, N-Dialkylaminosulfenylcarbamate insecticides via carbamoyl fluorides. J. Org. Chem. 43:3953-3957. https://doi.org/10.1021/jo00414a033
  10. Holiingworth, R. M. (1976) Chemstry, Biological Activity, and Uses of Formamidine Pesticides. Environ. Health. Perspec., 14:57-69. https://doi.org/10.1289/ehp.761457
  11. John, W. E., J. C. Maurice and C. E. Hatch (1982) Trialkylamine/sulfur dioxide catalyzed sulfenylation of carbamates. US patent 4,329,293.
  12. Loewenstein, Y., M. Denarie, H. Zakut and H. Soreq (1993) Molecular dissection of cholinesterase domains responsible for carbamate toxicity. Chemico-Biological Interactions 87(1):209-216. https://doi.org/10.1016/0009-2797(93)90044-Y
  13. Renzi, B., E. Kriege, and I. Robert (1986) Sublethal acute toxicity of carbosulfan[2,3-dihydro-2,2-dimethyl-7-benzofuranyl(di-n-butylaminosulfenyl)-(methyl)carbamate] in the rat after intravenous and oral exposures. Fundamental and Applied Toxicology 6(1):7-15. https://doi.org/10.1016/0272-0590(86)90259-9
  14. Takeo, S. T., M. Ichiki and I. Yoshihiko (1971) Synthetic Reaction by Complex Catalysts. J. Org. Chem. 36(19):2876-2880. https://doi.org/10.1021/jo00818a033
  15. Umetsu, N., T. Fukuto and D. Roy (1982) Alteration of carbosulfan [2,3-dihydro-2,2-dimethyl-7-benzofuranyl(di-n-butylaminosulfenyl)methylcarbamate] in the rat stomach. J. Agr. and Food Chem. 30(3):555-557. https://doi.org/10.1021/jf00111a036
  16. 오만균, 안희근, 김현경, 윤창만, 김진주, 김태준, 이동국, 정근회, 김길하 (2008) 꿀벌응애에 대한 신규화합물 K16776의 살비효과. 한국농약과학회지 12(2):192-196.
  17. 이동국, 정근회, 고영관, 류재욱, 우재춘, 구동완, 최용호, 박노중, 홍미숙, 김태준 (2008) 새로운 불소함유 Phenylformamidine 유도체의 합성과 살충활성. 한국농약과학회지 12(3):295-301.
  18. 이동국, 정근회, 고영관, 류재욱, 우재춘, 구동완, 최용호, 박노중, 홍미숙, 김태준 (2009) 마이크로웨이브를 이용한 N', N'-Disubsitituted N-Fluorophenylformamidine 유도체의 편리한 합성과 살충활성. 한국농약과학회지 13(2):117-125.
  19. 정근회 (2008) 신규 곤충 신경전달 작용점을 이용한 살충제(Octopaminergic Agonist 살충제) 기술개발에 관한 연구. 지식경제부 과제 1단계 보고서.
  20. 정근회, 고영관, 류재욱, 우재춘, 구동완, 김대황, 이동국, 박노중, 최용호, 정봉진, 김태준, 조창섭, 홍미숙 (2009) 새로운 불소함유 페닐포름아미딘 유도체의 합성 및 생리활성. 대한민국 특허 10-0920771.