Synthesis 2008(15): 2333-2336  
DOI: 10.1055/s-2008-1067170
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

A Facile and Improved Synthesis of 3-Fluorothiophene

Martin Pomerantz*, Nashaat Turkman
Department of Chemistry and Biochemistry, Box 19065, The University of Texas at Arlington, Arlington, TX 76019-0065, USA
Fax: +1(817)2723808; e-Mail: pomerantz@uta.edu;
Weitere Informationen

Publikationsverlauf

Received 29 January 2008
Publikationsdatum:
08. Juli 2008 (online)

Abstract

A new efficient and convenient route to 3-fluoro­thiophene in four steps and 49% overall yield is reported. The fluorine atom was successfully introduced into the thiophene ring in 67% yield using the Schiemann reaction on 2-methoxycarbonyl­thiophene-3-diazonium tetrafluoroborate. The product, methyl 3-fluorothiophene-2-carboxylate was saponified and the 3-fluorothiophene-2-carboxylic acid was decarboxylated to afford 3-fluorothiophene in 93% yield.

    References

  • 1 Kassmi AE. Fache F. Lemaire MJ. Electroanal. Chem.  1994,  373:  241 
  • 2 Hutchison GR. Ratner MA. Marks TJ. J. Am. Chem. Soc.  2005,  127:  16866 
  • 3 Irvin DJ. Witker DL. Closson AP. Stenger-Smith JD. Irvin JA. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.)  2008,  49:  552 
  • 4 Kuraki Y, and Funatsu E. inventors; Jpn. Kokai Tokkyo Koho JP  02282246.  1990; Chem. Abstr. 1991, 115, 123751
  • 5 Raos G. Famulari A. Meille SV. Gallazzi MC. Allegra G. J. Phys. Chem. A  2004,  108:  691 
  • 6 Parry DR, Matthews IR, Mitchell G, Williams AG, Barnes NJ, Cox JM, Gillen KJ, Ensminger MP, Khodayari K, and Nakayama H. inventors; Int. Patent WO  2000021928.  2000; Chem. Abstr. 2000, 132, 293663
  • 7 Miyata J, Yokota M, Naito R, Kamikawa A, Kawakami M, and Hattori K. inventors; Int. Patent Appl. WO  2006022375.  2005; Chem. Abstr. 2006, 144, 253996
  • 8 White JF, Shiosaki K, Hangauer DG, Solomon M, and Edgar DM. inventors; Int. Patent Appl. WO  2007022068.  2006; Chem. Abstr. 2007, 146, 244376
  • 9 Balz G. Schiemann G. Ber. Dtsch. Chem. Ges.  1927,  60:  1186 
  • 10 VanVleck TR. J. Am. Chem. Soc.  1949,  71:  3256 
  • 11 Flood DT. Org. Synth. Coll. Vol. II   Wiley; New York: 1943.  p.295 
  • 12 Rodmar S. Rodmar B. Sharma M. Gronowitz S. Christiansen H. Rosen R. Acta Chem. Scand.  1968,  22:  907 
  • 13 Peet JHJ. Rockett BW. J. Organomet. Chem.  1974,  82:  C57 
  • 14 Adcock W. Khor TC. J. Organomet. Chem.  1975,  91:  C20 
  • 15 Glinski MB. Freed JC. Durst T. J. Org. Chem.  1987,  52:  2749 
  • 16 Crestoni ME. Fornarini S. Gazz. Chim. Ital.  1989,  119:  203 
  • 17 Crestoni ME. J. Labelled Compd. Radiopharm.  1990,  28:  1109 
  • 18 Cerichelli G. Crestoni ME. Fornarini S. Gazz. Chim. Ital.  1990,  120:  749 
  • 19 Corral C. Lasso A. Lissavetzy J. Insua A. Valdeolmillos A. Heterocycles  1985,  23:  1431 
  • 20 Kobarfard F. Kauffman M. Boyko W. J. Heterocycl. Chem.  1999,  36:  1247 
  • 21 Taylor EC. Zhou P. Org. Prep. Proced. Int.  1997,  29:  221 
  • 22 Kiryanov A. Seed A. Sampson P. Tetrahedron Lett.  2001,  42:  8797 
  • 23 Foister S. Marques M. Doss R. Dervan P. Bioorg. Med. Chem.  2003,  11:  4333 
  • 24 El Kassmi A. Fache F. Lemaire M. Synth. Commun.  1994,  24:  95 
  • 25 Pomerantz M. Gu X. Zhang SX. Macromolecules  2001,  34:  1817 
  • 26 See, for example: Lisitsyn AS. Appl. Catal., A  2007,  332:  166 
  • See, for example:
  • 27a Goossen LJ. Deng G. Levy LM. Science  2006,  313:  662 
  • 27b Goossen LJ. Rodriquez N. Melzer B. Linder C. Deng G. Levy LM. J. Am. Chem. Soc.  2007,  129:  4824