Haloacetylated Enol Ethers, 19: [1] Synthesis of 3-(2-Thienyl)- and 3-(2-Furyl)-5-trihalomethyl Substituted Azoles

Abstract

Heterocyclization of 1,1,1-trifluoro[chloro]-4-methoxy-4-[2-tienyl]-3-buten-2-one and 1,1,1-trifluoro[chloro]-4-methoxy-4-[2-furyl]-3-buten-2-ones into isoxazoles and pyrazoles derivatives as a new type of trihalomethylated bicyclic heterocycles is reported.

Keywords

[3+2] cyclocondensation - furyl isoxazoles - thienyl isoxazoles - furyl pyrazoles - thienyl pyrazoles

References

• 1 For part 18 in this series, see: Martins MAP. Bastos GP. Sinhorin AP. Zimmermann NEK. Rosa A. Brondani S. Emmerich D. Bonacorso HG. Zanatta N. J. Fluorine Chem.  2003,  123:  249 
• 2a Frolund B. Jorgensen AT. Tagmose L. Stensbol TB. Vertergaard HT. Engblom C. Kristiansen U. Sanchez C. Krogsgaard-Laesen P. Liljefors T. J. Med. Chem.  2002,  45:  2454 
• 2b Frolund B. Tagmose L. Liljefors T. Stensbol TB. Engblom C. Kristiansen U. Krogsgaard-Larsen P. J. Med. Chem.  2000,  43:  4930 
• 2c Habeeb AG. Praveen Rao PN. Knaus EE. J. Med. Chem.  2001,  44:  3039 
• 2d Clark RD. J. Agric. Food Chem.  1996,  44:  3643 
• 2e Donohue BA. Michelotti EL. Reader JC. Reader V. Stirling M. Tice CM. J. Comb. Chem.  2002,  4:  23 
• 3a Grünanger P. Vita-Finzi P. In Chemistry of Heterocyclic Compounds: Isoxazoles   Vol. 49, Part 1:  Wiley; New York: 1991. 
• 3b Singh SP. Kumar D. Batra H. Naithani R. Rozas I. Elguero J. Can. J. Chem.  2000,  78:  1109 
• 3c Elguero J. In Comprehensive Heterocyclic Chemistry   Vol. 5, 1st ed.:  Katrittzky AR. Rees CW. Pergamon/Elsevier; Oxford: 1984.  p.167 
• 4a Baurle P. In Electronic Materials: The Oligomeric Approach   Müllen K. Wegner G. Wiley-VCH; Weinheim: 1998.  Chap. 2.
• 4b Otsubo T. Aso Y. Takimiya K. Bull. Chem. Soc. Jpn.  2001,  74:  1789 
• 4c Fichou D. J. Mater. Chem.  2000,  10:  571 
• 4d Dodabalapur A. Torsi H. Katz HE. Science  1995,  268:  270 
• 5a Martins MAP. Bastos GP. Bonacorso HG. Zanatta N. Flores AFC. Siqueira GM. Tetrahedron Lett.  1999,  40:  4309 
• 5b Bonacorso HG. Martins MAP. Bittencourt SRT. Lourega RV. Zanatta N. Flores AFC. J. Fluorine Chem.  1999,  99:  177 
• 6a In Organofluorine Chemistry: Principles and Commercial Applications   Banks RE. Smart BE. Tatlow JC. Plenum; New York: 1994. 
• 6b In Organic Chemistry in Medicinal Chemistry and Biochemical Applications   Filler R. Elsevier; Amsterdam: 1993. 
• 6c Sargent CR. Adv. Heterocyclic Chem.  1991,  28:  1 
• 6d Clark RD. J. Agric. Food Chem.  1996,  44:  3643 
• 6e Habeeb AG. Praveen Rao PN. Knaus EE. J. Med. Chem.  2001,  44:  3039 
• 7a Jiang B. Xu Y.-Y. Yang J. J. Fluorine Chem.  1994,  67:  83 
• 7b Plancquaert M.-A. Redon M. Janousek Z. Viehe HG. Tetrahedron  1996,  52:  4383 
• 7c Bravo P. Diliddo D. Resnati G. Tetrahedron  1994,  50:  8827 
• 7d Touzot A. Soufyane M. Berber H. Toupet L. Mirand C. J. Fluorine Chem.  2004,  125:  1299 
• 7e Sloop JC. Bumgardner CL. Loehle WD. J. Fluorine Chem.  2002,  118:  135 
• 7f Sevenard DV. Khomutov OG. Pashkevich KI. Lork E. Röschenthaler G.-V. Helv. Chim. Acta  2002,  85:  1960 
• 8a Martins MAP. Cunico W. Pereira CMP. Sinhorin A. Flores AFC. Bonacorso HG. Zanatta N. Curr. Org. Chem.  2004,  1:  391 
• 8b Martins MAP. Pereira CMP. Zimmermann NEK. Moura S. Sinhorin A. Cunico W. Zanatta N. Bonacorso HG. Flores AFC. Synthesis  2003,  2353 
• 9 Flores AFC. Brondani S. Zanatta N. Rosa A. Martins MAP. Tetrahedron Lett.  2002,  43:  8701 
• 11a Claramunt RM. Lopez C. Trofimenko S. Elguero J. Can. J. Chem.  1993,  71:  678 
• 11b Foces-Foces C. Trofimenko S. Lopez C. Santa Maria MD. Claramunt RM. Elguero J. J. Mol. Struct.  2000,  526:  59 
• 12 Martins MAP. Flores AFC. Bastos GP. Sinhorin AP. Zanatta N. Bonacorso HG. Tetrahedron Lett.  2000,  41:  293 
• 13 Chapman AV. Cook MJ. Katritzky AR. Aabraham MH. Danil de Namor AF. Dumont L. Reisse J. Tetrahedron  1978,  34:  1571 

10

¹⁹F NMR in CDCl₃ from external CFCl₃ (δ = 0.0 ppm): for 5-trifluoromethyl-4,5-dihydroisoxazoles and 5-trifluoromethyl-1-phenyl-4,5-dihydropyrazoles the δ were in range -78.1 to -82.9 ppm; for 5-trifluoromethylisoxazoles δ = -64.1 to -64.5 ppm; for 5-trifluoromethyl-1H-pyrazoles δ = -62.8 to -63.5 ppm; from a mixture of isomers ( [1,3] 15a′ and [1,5] 15a) were obtained two signals at -62.8 and -64.1 ppm with the same intensity.