View PDF Version
 
DOI: 10.1039/A701549F (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1997, 1679-1684

Synthesis, separation and characterisation of the first pure multiple adducts of C2v- and D3-C78

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

Andreas Herrmann and François Diederich

Abstract

Multiple cyclopropanation of an isomeric mixture of C2v- and D3-C78 (ca. 3∶1) with diethyl 2-bromomalonate yielded two C1-symmetrical bis-adducts, one of which was isolated without HPLC, and at least eight isomeric tris-adducts. Most of the adducts were isolated in pure state by HPLC and characterised by UV–VIS, 1H and 13C NMR spectroscopy, as well as by mass spectrometry. In the case of the tris-adducts, three isomers displayed a higher symmetry than C1 and could therefore be unambiguously assigned to the C78 isomer from which they arise. Three possible structures were finally proposed for a C2-symmetrical tris-adduct of C2v-C78, and two structures for a C3-symmetrical tris-adduct of D3-C78. Based on the comparison of the spectra obtained for the C2-symmetrical tris-adduct with those of the bis-adducts, three possible structures were proposed for one of the C1-symmetrical bis-adducts, being the direct precursor of the corresponding tris-adduct. The compounds described in this work represent the first adducts of C2v- and D3-C78 isolated and characterised in a pure state.

References

  1. F. Diederich, R. L. Whetten, C. Thilgen, R. Ettl, I. Chao and M. M. Alvarez, Science, 1991, 254, 1768 CAS.
  2. F. Diederich and R. L. Whetten, Acc. Chem. Res., 1992, 25, 119 CrossRef CAS.
  3. C. Thilgen, F. Diederich and R. L. Whetten, in Buckminsterfullerenes, ed. W. E. Billups and M. A. Ciufolini, VCH, New York, 1993, p. 59 Search PubMed.
  4. K. Kikuchi, N. Nakahara, T. Wakabayashi, S. Suzuki, H. Shiromaru, Y. Miyake, K. Saito, I. Ikemoto, M. Kainosho and Y. Achiba, Nature (London), 1992, 357, 142 CrossRef CAS.
  5. R. Taylor, G. J. Langley, A. G. Avent, T. J. S. Dennis, H. W. Kroto and D. R. M. Walton, J. Chem. Soc., Perkin Trans. 2, 1993, 1029 RSC.
  6. For the numbering and π-bond orders, see: R. Taylor, J. Chem. Soc., Perkin Trans. 2, 1993, 813 Search PubMed.
  7. J. M. Hawkins, M. Nambu and A. Meyer, J. Am. Chem. Soc., 1994, 116, 7642 CrossRef CAS.
  8. D. Heymann and L. P. F. Chibante, Recl. Trav. Chim. Pays-Bas, 1993, 112, 639 CAS.
  9. A. D. Darwish, H. W. Kroto, R. Taylor and D. R. M. Walton, J. Chem. Soc., Perkin Trans. 2, 1996, 1415 RSC.
  10. O. V. Boltalina, L. N. Sidorov, V. F. Bagryantsev, V. A. Seredenko, A. S. Zapolskii, J. M. Street and R. Taylor, J. Chem. Soc., Perkin Trans. 2, 1996, 2275 RSC.
  11. P. R. Birkett, A. D. Darwish, H. W. Kroto, G. J. Langley, R. Taylor and D. R. M. Walton, J. Chem. Soc., Perkin Trans. 2, 1995, 511 RSC.
  12. C. Bingel, Chem. Ber., 1993, 126, 1957 CrossRef CAS; C. Bingel and H. Schiffer, Liebigs Ann., 1995, 1551 CAS.
  13. A. Herrmann, M. Rüttimann, C. Thilgen and F. Diederich, Helv. Chim. Acta, 1995, 78, 1673 CrossRef CAS.
  14. A. Herrmann and F. Diederich, Helv. Chim. Acta, 1996, 79, 1741 CrossRef CAS.
  15. A. Herrmann, F. Diederich, C. Thilgen, H.-U. ter Meer and W. H. Müller, Helv. Chim. Acta, 1994, 77, 1689 CrossRef CAS.
  16. C. J. Welch and W. H. Pirkle, J. Chromatogr., 1992, 609, 89 CrossRef CAS.
  17. A. Kitaygorodskiy, G. E. Lawson and Y.-P. Sun, Ber. Bunsenges. Phys. Chem., 1995, 99, 1046 CAS.
  18. A. Hirsch, I. Lamparth, T. Grösser and H. R. Karfunkel, J. Am. Chem. Soc., 1994, 116, 9385 CrossRef CAS.
Click here to see how this site uses Cookies. View our privacy policy here.