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Volumn 51, Issue 1, 2010, Pages 79-81

Electrophilic fluorination: the aminopyridine dilemma

Author keywords

Aminopyridine; Electrophilic fluorination; F TEDA

Indexed keywords

AMINOPYRIDINE DERIVATIVE; ELECTROPHILE; HOT WATER; PYRIDINE DERIVATIVE;

EID: 70649103936     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2009.10.089     Document Type: Article
Times cited : (16)

References (37)
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    • Common name 4-amino-3,6-dichloropicolinic acid, sold under the tradename Milestone™ (among others): Alexander, A. L.; Balko, T. W.; Bjelk, L. A.; Buysse, A. M.; Fields, S. C.; Keese, R.; Krumel, K. L.; Lo, W. C.; Lowe, C. T.; Richburg, J. S.; Ruiz, J. M. 4-Aminopicolinates and Their Use as Herbicides. U.S. Patent 6,297,197, Oct. 2, 2001; Chem. Abstr. 2001, 135, 107254.
    • Common name 4-amino-3,6-dichloropicolinic acid, sold under the tradename Milestone™ (among others): Alexander, A. L.; Balko, T. W.; Bjelk, L. A.; Buysse, A. M.; Fields, S. C.; Keese, R.; Krumel, K. L.; Lo, W. C.; Lowe, C. T.; Richburg, J. S.; Ruiz, J. M. 4-Aminopicolinates and Their Use as Herbicides. U.S. Patent 6,297,197, Oct. 2, 2001; Chem. Abstr. 2001, 135, 107254.
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    • Johnston, H.; Tomita, M. S. Amino-trichloropicolinic acid compounds. U.S. Patent 3,285,925, Nov. 15, 1966; Chem. Abstr. 1967, 66, 46338.
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    • Balko, T. W.; Buysse, A. M.; Epp, J. B.; Fields, S. C.; Lowe, C. T.; Keese, R. J.; Richburg, J. S., III; Ruiz, J. M.; Weimer, M. R.; Green, R. A.; Gast, R. E.; Bryan, K.; Irvine, N. M.; Lo, W. C.-L.; Brewster, W. K.; Webster, J. D. 6-Aryl-4-aminopicolinates and Their Use as Herbicides. U. S. Patent 6,784,137, Aug. 31, 2004; Chem. Abstr. 2003, 138, 153444.
    • Balko, T. W.; Buysse, A. M.; Epp, J. B.; Fields, S. C.; Lowe, C. T.; Keese, R. J.; Richburg, J. S., III; Ruiz, J. M.; Weimer, M. R.; Green, R. A.; Gast, R. E.; Bryan, K.; Irvine, N. M.; Lo, W. C.-L.; Brewster, W. K.; Webster, J. D. 6-Aryl-4-aminopicolinates and Their Use as Herbicides. U. S. Patent 6,784,137, Aug. 31, 2004; Chem. Abstr. 2003, 138, 153444.
  • 4
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    • Aminopyralid (3) is currently synthesized by the electrochemical reduction of picloram (4) at Dow on production scale.
    • Aminopyralid (3) is currently synthesized by the electrochemical reduction of picloram (4) at Dow on production scale.
  • 5
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    • Krumel, K. L.; Bott, C. J.; Gullo, M. F.; Hull, J. W., Jr.; Scortichini, C. L. Selective electrochemical reduction of halogenated 4-aminopicolinic acids. U. S. Patent 6,352,635, Mar. 5, 2002; Chem. Abstr. 2001, 135, 98860.
    • Krumel, K. L.; Bott, C. J.; Gullo, M. F.; Hull, J. W., Jr.; Scortichini, C. L. Selective electrochemical reduction of halogenated 4-aminopicolinic acids. U. S. Patent 6,352,635, Mar. 5, 2002; Chem. Abstr. 2001, 135, 98860.
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    • N-F pyridines rearrange to 2-C-F pyridines, however this does not appear to be general:
    • N-F pyridines rearrange to 2-C-F pyridines, however this does not appear to be general:. Umemoto T., and Tomizawa G. J. Org. Chem. 54 (1989) 1726
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    • Direct nucleophilic substitution of N-F pyridines:
    • Direct nucleophilic substitution of N-F pyridines:. Kiselyov A., and Strekowski L. J. Org. Chem. 58 (1993) 4476
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    • note
    • N-Fluorination of pyridine substrates is a problematic competing reaction because it renders the pyridine less reactive toward ring fluorination.
  • 18
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    • Umemoto reagents are supplied by Allied Signal Inc., Buffalo Research Laboratories, Buffalo, NY:
    • Umemoto reagents are supplied by Allied Signal Inc., Buffalo Research Laboratories, Buffalo, NY:. Umemoto T., Fukami S., Tomizawa G., Harasawa K., Kawada K., and Tomita K. J. Am. Chem. Soc. 112 (1990) 8563
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    • Appears to be effective on Grignards and electron rich phenols, but no specific mention of heterocycles:
    • Appears to be effective on Grignards and electron rich phenols, but no specific mention of heterocycles:. Barnette W.E. J. Am. Chem. Soc. 106 (1984) 452
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    • Also known as SELECTFLUOR, and Banks' Reagent: Banks, R. E. Preparation of N-fluorodiazoniabicycloalkanes as fluorinating agents. U. S. Patent 5,086,178, Feb. 4, 1992; Chem. Abstr. 1992, 116, 194355. Supplied by Air Products and Chemicals Inc., 7201 Hamilton Blvd, Allentown, PA 18195.
    • Also known as SELECTFLUOR, and Banks' Reagent: Banks, R. E. Preparation of N-fluorodiazoniabicycloalkanes as fluorinating agents. U. S. Patent 5,086,178, Feb. 4, 1992; Chem. Abstr. 1992, 116, 194355. Supplied by Air Products and Chemicals Inc., 7201 Hamilton Blvd, Allentown, PA 18195.
  • 26
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    • note
    • F-TEDA is a white salt which is safe, stable, and easily handled in air.
  • 29
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    • F-TEDA also has been used deliberately to effect chlorination and other electrophilic substitutions:
    • F-TEDA also has been used deliberately to effect chlorination and other electrophilic substitutions:. Syvret R.G., Butt K.M., Nguyen T.P., Bulleck V.L., and Rieth R.D. J. Org. Chem. 67 (2002) 4487
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    • Syvret, R.G.1    Butt, K.M.2    Nguyen, T.P.3    Bulleck, V.L.4    Rieth, R.D.5
  • 32
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    • note
    • Honeywell scientists, led by Dr. Andy Poss, attempted a fluorination of 3 with divalent fluorine in aqueous suspension at 25 °C and observed similar results, with respect to mass balance and picloram formation (personal communication).
  • 33
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    • There has been a noted solvent dependence with these reagents:
    • There has been a noted solvent dependence with these reagents:. Zupan M., Iskra J., and Stavber S. J. Fluorine Chem. 70 (1995) 7
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    • Zupan, M.1    Iskra, J.2    Stavber, S.3
  • 35
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    • note
    • 24 additional work is now underway to provide more details on the origin of 4. Our results will be forthcoming.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.