Synthesis of 3,4′-dibromo-2,2′-bithiophene: a useful intermediate for 3,4′-disubstituted 2,2′-bithiophenes. X-Ray molecular structure of 3,4′-dibromo-2,2′-bithiophene

(Note: The full text of this document is currently only available in the PDF Version )

Luciano Antolini, Francesca Goldoni, Dario Iarossi, Adele Mucci and Luisa Schenetti


Abstract

The first synthesis of 3,4′-dibromo-2,2′-bithiophene via metal-catalysed cross-coupling between a metallated and a halogenated thiophene derivative is described. An X-ray crystal structure of 3,4′-dibromo-2,2′-bithiophene is reported. 3,4′-Dibromo-2,2′-bithiophene was converted into corresponding bis(alkylsulfanyl) derivatives through bromine–lithium exchange, followed by reaction with two dialkyl disulfides (Me2S2 or Bu2S2). The 1H and 13C NMR data are discussed.


References

  1. J. Roncali, Chem. Rev., 1992, 92, 711 CrossRef CAS.
  2. M. R. Andersson, M. Berggren, O. Inganäs, G. Gustafsson, J. C. Gustafsson-Carlberg, D. Selse, T. Hjertberg and O. Wennerström, Macromolecules, 1995, 28, 7525 CrossRef CAS.
  3. N. Noma, T. Tsuzuki and Y. Shirota, Adv. Mater., 1995, 7, 647 CrossRef CAS.
  4. G. Horowitz, F. Garnier, A. Yassar, R. Hajlaoui and F. Kouki, Adv. Mater., 1996, 8, 52 CAS.
  5. H. Higuchi, H. Koyama, H. Yokota and J. Ojima, Tetrahedron Lett., 1996, 37, 1617 CrossRef CAS; C. Branger, M. Lequan, R. M. Lequan, M. Barzoukas and A. Fort, J. Mater. Chem., 1996, 6, 555 RSC.
  6. Z. Gao, K. S. Siow and H. S. O. Chan, Synth. Met., 1995, 75, 5 CrossRef CAS.
  7. R. Rossi, A. Carpita, M. Ciofalo and J. L. Houben, Gazz. Chim. Ital., 1990, 120, 793 CAS; A. MacEachern, C. Soucy, L. C. Leitch, J. T. Arnason and P. Morand, Tetrahedron, 1988, 44, 2403 CrossRef.
  8. P. Bäuerle, G. Götz, A. Synowczyk and J. Heinze, Liebigs Ann. Chem., 1996, 279 Search PubMed.
  9. L. L. Miller and Y. Yu, J. Org. Chem., 1995, 60, 6813 CrossRef CAS.
  10. P. Bäuerle, F. Pfau, H. Schlupp, F. Würthner, K.-U. Gaudl, M. Balparda Caro and P. Fischer, J. Chem. Soc., Perkin Trans. 2, 1993, 489 RSC.
  11. G. Zotti, M. C. Gallazzi, G. Zerbi and S. V. Meille, Synth. Met., 1995, 73, 217 CrossRef CAS; F. Demanze, A. Yassar and F. Garnier, Synth. Met., 1996, 76, 269 CrossRef CAS; P. Bäuerle, G. Gotz, U. Segelbacher, D. Huttenlocher and M. Mehring, Synth. Met., 1993, 55–57, 4768 CrossRef; G. Horowitz, P. Delannoy, H. Bouchriha, F. Deloffre, J.-L. Fave, F. Garnier, R. Hajlaoui, M. Heyman, F. Kouki, P. Valat, V. Wintgens and A. Yassar, Adv. Mater., 1994, 6, 752 CrossRef CAS.
  12. P. Bäuerle, T. Fisher, B. Bidlingmeier, A. Stabel and J. P. Rabe, Angew. Chem., Int. Ed. Engl., 1995, 34, 303 CrossRef; H. Higuchi, T. Nakayama, H. Koyama, J. Ojima, T. Wada and H. Sasabe, Bull. Chem. Soc. Jpn., 1995, 68, 2363 CAS; J. M. Tour and R. Wu, Macromolecules, 1992, 25, 1901 CrossRef CAS.
  13. T.-A. Chen, X. Wu and R. D. Rieke, J. Am. Chem. Soc., 1995, 117, 233 CrossRef CAS; M. D. McClain, D. A. Whittington, D. J. Mitchell and M. D. Curtis, J. Am. Chem. Soc., 1995, 117, 3887 CrossRef CAS; R. D. McCullough, S. P. Williams, S. Tristam-Nagle, M. Jayaraman, P. C. Ewbank and L. Miller, Synth. Met., 1995, 69, 279 CrossRef CAS; Y. Miyazaki and T. Yamamoto, Synth. Met., 1994, 64, 69 CrossRef CAS.
  14. M. J. Marsella, P. J. Carroll and T. M. Swager, J. Am. Chem. Soc., 1994, 116, 9347 CrossRef CAS.
  15. C. Arbizzani, G. Barbarella, A. Bongini, M. Mastragostino and M. Zambianchi, Synth. Met., 1992, 52, 329 CrossRef CAS.
  16. U. Folli, D. Iarossi, M. Montorsi, A. Mucci and L. Schenetti, J. Chem. Soc., Perkin Trans. 1, 1995, 537 RSC.
  17. K. Faïd, R. Cloutier and M. Leclerc, Macromolecules, 1993, 26, 2501 CrossRef CAS.
  18. U. Folli, F. Goldoni, D. Iarossi, A. Mucci and L. Schenetti, J. Chem. Res. (S), 1996, 69 Search PubMed.
  19. E. Khor, S. C. Ng, H. C. Li and S. Chai, Heterocycles, 1991, 32, 1805 CAS.
  20. E. Schulz, K. Fahmi and M. Lemaire, Acros Organics Acta, 1995, 1, 10 Search PubMed.
  21. (a) S. Gronowitz, Y. Zhang and A.-B. Hörnfeldt, Acta Chem. Scand., 1992, 46, 654 CAS; (b) M. J. Naujan, V. Kannappan and R. Z. Ganesan, Phys. Chem., 1981, 127, 13 Search PubMed.
  22. F. Sauter, H. Fröhlich and W. Kalt, Synthesis, 1989, 771 CrossRef CAS.
  23. H. Fröhlich and W. Kalt, J. Org. Chem., 1990, 55, 2993 CrossRef.
  24. L. Brandsma and H. D. Verkruijsse, Preparative Polar Organometallic Chemistry, Springer-Verlag, Berlin, 1987, vol. 1, pp. 123 and 160 Search PubMed.
  25. E. Negishi, T. Takahashi and A. O. King, Org. Synth., 1988, 66, 67 CAS and references therein.
  26. J. K. Stille, Pure Appl. Chem., 1985, 57, 1771 CrossRef.
  27. E. W. Colvin, Chem. Soc. Rev., 1978, 7, 15 RSC.
  28. T. H. Chan and I. Fleming, Synthesis, 1979, 761 CrossRef CAS.
  29. D. Habich and F. Effenberger, Synthesis, 1979, 841 CrossRef.
  30. G. Barbarella, M. Zambianchi, A. Bongini and L. Antolini, J. Org. Chem., 1996, 61, 4708 CrossRef CAS.
  31. G. Barbarella, M. Zambianchi, A. Bongini and L. Antolini, Adv. Mater., 1993, 5, 834 CAS.
  32. S. Hotta and K. Waragai, Adv. Mater., 1993, 5, 896 CAS.
  33. G. J. Pyrka, Q. Fernando, M. B. Inoue, M. Inoue and E. Velazquez, Acta Crystallogr., Sect. C, 1988, 44, 562 CrossRef.
  34. L. Antolini, unpublished results.
  35. W. Porzio, S. Destri, M. Mascherpa and S. Brükner, Acta Polym., 1993, 44, 266 CrossRef CAS.
  36. A. Bax, R. H. Griffey and B. L. Hawkins, J. Magn. Reson., 1983, 55, 301 CAS.
  37. A. Bax and M. F. Summers, J. Am. Chem. Soc., 1986, 108, 2093 CrossRef CAS.
  38. F. W. Wehrli and T. Wirthlin, Interpretation of Carbon-13 NMR Spectra, Heyden, Bristol, 1978 Search PubMed.
  39. F. Goldoni, D. Iarossi, A. Mucci, L. Schenetti and M. Zambianchi, J. Mater. Chem., 1997, 7, 593 RSC.
  40. G. M. Sheldrick, SHELXS86, Acta Crystallogr., Sect. A, 1990, 46, 467 CrossRef.
  41. G. M. Sheldrick, SHELXL93: Program for the Refinement of Crystal Structures, University of Göttingen, Germany, 1993.