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A simple new hydrazine-free synthesis of methyl 1,4,5-trisubstituted 1H-pyrazole-3-carboxylates

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Abstract

Conditions for successful syntheses of polysubstituted pyrazole-3-carboxylates have been found. The methodology consists in mixing equimolar amounts of diazonium tetrafluoroborates and enaminoesters in presence of sodium acetate. 1-Methylpyrrolidone has appeared to be the solvent of choice. The compounds prepared have been characterized by means of nuclear magnetic resonance (NMR) spectroscopy, elemental analysis, and in two cases, also by X-ray diffraction. The advantage of the methodology is a simple implementation without necessity of working under inert atmosphere. The presence of other functional groups enables further synthetic transformations of the products.

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References

  1. Schröter HB, Neumann D, Katritzky AR, Swinbourne FJ (1966) Tetrahedron 22:2895

    Article  Google Scholar 

  2. Doyle Daves G, Cheng CC (1976) In: Ellis GP, West GB (eds) Progress in Medicinal Chemistry, vol 13. North-Holland, Amsterdam, p 327

    Google Scholar 

  3. Orth RE (1968) J Pharm Sci 57:537

    Article  CAS  Google Scholar 

  4. Lamberth C (2007) Heterocycles 71:1467

    Article  CAS  Google Scholar 

  5. Stanovnik B, Svete J (2002) In: Neier R (ed) Science of Synthesis, vol 12. Thieme, Stuttgart, p 15

    Google Scholar 

  6. Schmidt A, Dreger A (2011) Curr Org Chem 15:1423

    Article  CAS  Google Scholar 

  7. Schmidt A, Dreger A (2011) Curr Org Chem 15:2897

    Article  CAS  Google Scholar 

  8. Fustero S, Simón-Fuentes A, Sanz-Cervera JF (2009) Org Prep Proced Int 41:253

    Article  CAS  Google Scholar 

  9. Elguero J (1996) In: Katritzky AR, Scriven EFV (eds) Comprehensive Heterocyclic Chemistry II, vol 3. Elsevier, Oxford

    Google Scholar 

  10. Makino K, Kim HS, Kurasawa Y (1999) J Heterocycl Chem 36:321

    Article  CAS  Google Scholar 

  11. Fustero S, Sanchez-Rosello M, Barrio P, Simon-Fuentes A (2011) Chem Rev 111:6984

    Article  CAS  Google Scholar 

  12. Bekhit AA, Hymete A, Bekhit AEA, Damtew A, Aboul-Enein HY (2010) Mini-Rev Med Chem 10:1014

    Article  CAS  Google Scholar 

  13. Šimůnek P, Svobodová M, Bertolasi V, Macháček V (2008) Synthesis 2008(11):1761–1766

  14. Šimůnek P, Svobodová M, Macháček V (2009) J Heterocycl Chem 46:650

    Article  Google Scholar 

  15. Vohra RK, Renaud JL, Bruneau C (2005) Collect Czech Chem Commun 70:1943

    Article  CAS  Google Scholar 

  16. Burnett MN, Johnson CK (1996) ORTEP III, Report ORNL-6895. Oak Ridge National Laboratory, Oak Ridge

    Google Scholar 

  17. Allen FH, Kennard O, Watson DG, Brammer L, Orpen AG, Taylor R (1987) J Chem Soc Perkin Trans 2:S1

    Google Scholar 

  18. Gieren A, Lamm V (1982) Acta Crystallogr Sect B 38:844

    Article  Google Scholar 

  19. El-Abadelah MM, Sabri SS, Khanfar MA, Voelter W, Maichle-Moessmer C (1999) Z Naturforsch B 54:1323

    CAS  Google Scholar 

  20. Boyd M, Atwell GJ, Denny WA (1993) Acta Crystallogr Sect C 49:1429

    Article  Google Scholar 

  21. Brady T, Khang V, Barber JR, Chung Ng S, Zhou Y (2009) Tetrahedron Lett 50:6223

    Article  CAS  Google Scholar 

  22. Ibrahim HM, Behbehani H, Makhseed S, Elnagdi MH (2011) Molecules 16:3723

    Article  CAS  Google Scholar 

  23. Berger S, Braun S, Kalinowski HO (1997) NMR Spectroscopy of the Non-metallic Elements. Wiley, Chichester

    Google Scholar 

  24. Otwinowski Z, Minor W (1997) Processing of X-ray diffraction data collected in oscillation mode. In: Carter CW, Sweet RM (eds) Methods in Enzymology, vol 276, part A. London pp 307–326

  25. Coppens P (1970) In: Ahmed FR, Hall SR, Huber CP (eds) Crystallographic Computing. Munksgaard, Copenhagen, p 255

    Google Scholar 

  26. Altomare A, Cascarano G, Giacovazzo C, Guagliardi A (1994) J Appl Crystal 27:1045

    Article  CAS  Google Scholar 

  27. Sheldrick GM (2008) SHELXL-97. University of Göttingen, Göttingen

    Google Scholar 

  28. Altomare A, Burla MC, Camalli M, Cascarano GL, Giacovazzo C, Guagliardi A, Moliterni AGG, Polidori G, Spagna R (1999) J Appl Crystallogr 32:115

    Article  CAS  Google Scholar 

  29. Augustine RL, Bellina RF, Gustavsen AJ (1968) J Org Chem 33:1287

    Article  CAS  Google Scholar 

  30. Ohashi T, Oguro Y, Tanaka T, Shiokawa Z, Tanaka Y, Shibata S, Sato Y, Yamakawa H, Hattori H, Yamamoto Y, Kondo S, Miyamoto M, Nishihara M, Ishimura Y, Tojo H, Baba A, Sasaki S (2012) Bioorg Med Chem 20:5507

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Faculty of Chemical Technology, Institute of Organic Chemistry and Technology, University of Pardubice, Studentská 573, 532 10, Pardubice, Czech Republic

    Břetislav Brož & Petr Šimůnek

  2. Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 532 10, Pardubice, Czech Republic

    Zdeňka Padělková

  3. Dipartimento di Scienze Chimiche e Farmaceutiche, Centro di Strutturistica Diffrattometrica, Università di Ferrara, Via L. Borsari 46, 441 00, Ferrara, Italy

    Valerio Bertolasi

Authors
  1. Břetislav Brož
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  2. Zdeňka Padělková
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  3. Valerio Bertolasi
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  4. Petr Šimůnek
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Correspondence to Petr Šimůnek.

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Brož, B., Padělková, Z., Bertolasi, V. et al. A simple new hydrazine-free synthesis of methyl 1,4,5-trisubstituted 1H-pyrazole-3-carboxylates. Monatsh Chem 144, 1013–1019 (2013). https://doi.org/10.1007/s00706-013-0962-2

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  • DOI: https://doi.org/10.1007/s00706-013-0962-2

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