Bulletin of the Korean Chemical Society

  • 제28권12호
  • /
  • Pages.2324-2328
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  • 2007
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  • 0253-2964(pISSN)
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  • 1229-5949(eISSN)
대한화학회 (Korean Chemical Society)
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Synthesis of N-Alkylated 4-Fluoro-5-phenylpyrrole-2-carboxylate via Isolable Pyrroline Ionic Intermediates

  • Kim, Sung-Kwan (Department of Bionanochemistry, Wonkwang University) ;
  • Jun, Chang-Soo (Department of Bionanochemistry, Wonkwang University) ;
  • Kwak, Kyung-Chell (Department of Bionanochemistry, Wonkwang University) ;
  • Park, Kwang-Yong (School of Chemical Engineering and Material Science, Chung-Ang University) ;
  • Chai, Kyu-Yun (Department of Bionanochemistry, Wonkwang University)
  • 발행 : 2007.12.20
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초록

Organic fluorine chemistry produces many useful products. This paper elucidates the reaction of ethyl-4,4- difluoro-2-iodo-5-oxo-5-phenylpentanoate (2) with primary amines in a one-pot scheme. The reaction produced a series of β-fluoropyrrole derivatives at ambient temperatures. In this reaction, the less bulky the primary amine the higher was the resultant yield. When (2) and aqueous methylamine (40%) were allowed to react below 0 oC, 5-(ethoxycarboxyl)-1-methyl-3,3-difluoro-2-hydroxy-2-phenylpyrrolidine, an intermediate molecule for 2-ethyl-4-flouro-1-methyl-5-phenylpyrrole-2-carboxylate (5), was isolated first. Then, (5) reacted with hydroperchloric acid and acetic anhydride to form 5-(ethoxycarboxyl)-1-methyl-3,3-difluoro-2- phenylpyrrolinium perchlorate (6), which was converted to 2-ethyl-4-flouro-1-methyl-5-phenylpyrrole-2- carboxylate gradually in the presence of a base. Our experiments demonstrate that the formation of 2-ethyl-4- flouro-1-methyl-5-phenylpyrrole-2-carboxylate occurs via both one-pot schemes and stepwise pathways, depending on the reaction conditions. The isolation and characterization of the isolated intermediate (6) suggest an anionic pathway for this reaction.

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참고문헌

  1. Welch, J. T. Tetrahedron Lett. 1987, 43, 3123 https://doi.org/10.1016/S0040-4020(01)90286-8
  2. Marquez, V. E.; Tseng, C. K.; Mitsuya, H. J. Med. Chem. 1990, 33, 978 https://doi.org/10.1021/jm00165a015
  3. Yamazaki, T.; Welch, J. T.; Plummer, J. S.; Gimi, R. Tetrahedron Lett. 1991, 32, 4267 https://doi.org/10.1016/S0040-4039(00)92145-2
  4. Davis, J. A.; Han, W. Tetrahedron Lett. 1992, 33, 1153 https://doi.org/10.1016/S0040-4039(00)91883-5
  5. Maqbool, A. S.; Victor, E, M. Ttrahedron Lett. 1994, 35, 3263 https://doi.org/10.1016/S0040-4039(00)76880-8
  6. Bass Jr., J. B.; Farer, L. S.; Hopewell, P. C.; O'Brian, R.; Jacobs, R. F.; Ruben, F.; Snider Jr., D. E.; Thornton, G. Am. J. Respir. Crit. Care Med. 1994, 149, 1359 https://doi.org/10.1164/ajrccm.149.5.8173779
  7. Davidson, P. T.; Le, H. Q. Drugs 1992, 43, 651 https://doi.org/10.2165/00003495-199243050-00003
  8. Grosset, J. H. Bull. Int. Union Tuberc. Lung Dis. 1990, 65, 86
  9. Fried, J.; Hallinan, E. A. J. Am Chem. Soc. 1984, 106, 3871 https://doi.org/10.1021/ja00325a033
  10. Thaisrivongs, S.; Pals, W. H.; Thomasco, L. M. J. Med. Chem. 1985, 28, 1555 https://doi.org/10.1021/jm00149a002
  11. Filler, R. Chem. Tech. 1974, 4, 752
  12. Buhr, G. Chem. Ber. 1973, 106, 3544 https://doi.org/10.1002/cber.19731061111
  13. Leroy, J.; Rubinstein, M.; Wakselman, C. J. Fluorine. Chem. 1984, 25, 255 https://doi.org/10.1016/S0022-1139(00)80954-9
  14. Onda, H.; Toi, H.; Aoyama, Y.; Ogoshi, H. Tetrahedron Lett. 1985, 26, 4221 https://doi.org/10.1016/S0040-4039(00)98997-4
  15. Barmes, K. D.; Hu, Y.; Hunt, D. A. Synthetic Communications 1994, 24, 1749 https://doi.org/10.1080/00397919408010180
  16. Qui, Z. M.; Burton, D. J. Tetrahedron Lett. 1994, 35, 1813 https://doi.org/10.1016/S0040-4039(00)73167-4
  17. Qui, Z. M.; Burton, D. J. Tetrahedron Lett. 1994, 35, 4319 https://doi.org/10.1016/S0040-4039(00)73343-0
  18. Boyd, G. V.; Wright, J. C. S. Perkin I 1972, 909 https://doi.org/10.1039/p19720000909
  19. Lee, Y.; Park, K.; Cho, I.; Chai, K. Journal of the Korean Chemical Society 1998, 42(3), 335-339
  20. Leroy, J.; Porhiel, E.; Bondon, A. Tetrahedron 2002, 58, 6713-6722 https://doi.org/10.1016/S0040-4020(02)00677-4
  21. Killean, R. C. G.; Lawrence, J. L. Acta Cryst. Sect B 1969, 25, 1750 https://doi.org/10.1107/S0567740869004687

피인용 문헌

  1. Efficient Preparation of 3-Fluoropyrrole Derivatives vol.31, pp.1, 2007, https://doi.org/10.5012/bkcs.2010.31.01.031