Pyridine analogue of macrocyclic polyyne C58H4N2 as a precursor to diazafullerene C58N2

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Yoshito Tobe, Hironobu Nakanishi, Motohiro Sonoda, Tomonari Wakabayashi and Yohji Achiba


Abstract

(1,3,5)Pyridinophanes having [4.3.2]propellatriene units were synthesized as precursors to macrocyclic polyyne C58H4N2; diazafullerene anion C58N2 was detected in the laser desorption mass spectrum of the pyridinophanes.


References

  1. J. C. Hummelen, B. Knight, J. Pavlovich, R. González and F. Wudl, Science, 1995, 269, 1554 CrossRef CAS; I. Lamparth, B. Nuber, G. Schick, A. Skiebe, T. Grösser and A. Hirsch, Angew. Chem., Int. Ed. Engl., 1995, 34, 2257 CrossRef CAS.
  2. M. Keshavarz-K., R. González, R. G. Hicks, G. Srdanov, V. I. Srdanov, T. G. Collins, J. C. Hummelen, C. Bellavia-Lund, J. Pavlovich, F. Wudl and K. Holczer, Nature, 1996, 383, 147 CrossRef; C. Bellavia-Lund, R. González, J. C. Hummelen, R. G. Hicks, A. Sastre and F. Wudl, J. Am. Chem. Soc., 1997, 119, 2946 CrossRef CAS; B. Nuber and A. Hirsch, Chem. Commun., 1996, 1421 RSC.
  3. T. Pradeep, V. Vijayakrishnan, A. K. Santra and C. N. R. Rao, J. Phys. Chem., 1991, 95, 10 564 CrossRef CAS.
  4. Z. Chen, K. Ma, Y. Pan, X. Xhao, A. Tang and J. Feng, J. Chem. Soc., Faraday Trans., 1998, 94, 2269 RSC; J. Aihara, unpublished results.
  5. Y. Tobe, N. Nakagawa, K. Naemura, T. Wakabayashi, T. Shida and Y. Achiba, J. Am. Chem. Soc., 1998, 120, 4544 CrossRef CAS.
  6. Y. Rubin, T. C. Parker, S. J. Pastor, S. Jalistagi, C. Boulle and C. L. Wilkins, Angew. Chem., Int. Ed., 1998, 37, 1226 CrossRef CAS.
  7. Y. Rubin, Chem. Eur. J., 1997, 3, 1009 CrossRef; U. H. F. Bunz, Y. Rubin and Y. Tobe, Chem. Soc. Rev., 1999, 28, 107 RSC; Y. Tobe, Advances in Strained and Interesting Organic Molecules, ed. B. Halton, JAI Press, Stamford, 1999, vol. 7, p. 153 Search PubMed.
  8. There are many possible isomers for 3 and 4 due to the orientation of the propellane units. Only one of the isomers of 3 and 4 are depicted in this paper for clarity.
  9. E. J. Corey and P. L. Fuchs, Tetrahedron Lett., 1972, 3769 CrossRef CAS.
  10. R. Graf and A. Weinberg, J. Prakt. Chem., 1932, 134, 180 CrossRef.
  11. For a review; K. Sonogashira, Comprehensive Organic Synthesis, ed. B. M. Trost and I. Fleming, Pergamon, Oxford, 1991, vol. 3, p. 521 Search PubMed.
  12. C. Cai and A. Vasella, Helv. Chim. Acta, 1995, 78, 2053 CrossRef CAS.
  13. There are so many possible isomers for the oxidative coupling product of 13 that it is not possible to determine the ratio of 3 and 4 nor even confirm whether it is indeed a mixture of the two by spectroscopic and chromatographic techniques.
  14. Only one isomer, 1,49-diazafullerene, would result from the C58N2 isomer 5, while two isomers, 1,49- and 1,60-diaza derivatives, would be formed from 6, provided that the cyclization of the polyyne chain takes place without bond breaking through a transition state with minimal bond angles of the alkyne chains as depicted in ref. 7.
  15. K. Kaizu, M. Kohno, S. Suzuki, H. Shiromaru, T. Moriwaki and Y. Achiba, J. Phys. Chem., 1997, 106, 9954 Search PubMed.
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