Skip to main content
SpringerLink
Log in

Through-space electronic interactions of [2.2]metacyclophane benzyl cations

  • Published:
Research on Chemical Intermediates Aims and scope Submit manuscript

Abstract

The hydrolysis of 8-bromomethyl[2.2]metacyclophanes 3 to the corresponding 8-hydroxymethyl derivatives 4 was carried out in 83% aqueous dioxane solution at 25°C. Substituent effect through space on the rate of the hydrolysis of bromomethyl groups attached on the opposite aromatic ring was first found in this investigation. Interestingly, the introduction of the substituents at the internal position 16 tends to enhance the hydrolysis reaction rate 10–100 times. It was found also that the stabilization by both the direct through-space cation-π-interaction and the interaction through the intra-annular 8,16-position are possible in the [2.2]metacyclophane 8-benzyl cations. The good correlation with log(K/KH) and σp + was observed for the hydrolysis of internally unsubstituted 5-bromomethyl[2.2]MCPs 7, in which the direct through-space cation-π-interactions are not possible.

TiCl4 and Nafion-H, a perfluorinated resinsulfonic acid, catalysed Friedel-Crafts benzylation of benzene and substituted benzenes with 8-bromomethyl- and 8-hydroxymethyl[2.2]metacyclophanes to afford 8-benzyl[2.2]metacyclophanes is described. A high substrate and positional selectivity were observed in the present benzylation reaction quite different from those obtained from the benzyl bromide and benzyl alcohol. The benzyl cation intermediate stabilized by the through-space electronic interaction among the opposite benzene ring was first demonstrated in the benzylation of [2.2]metacyclophane systems.

The mild and selective transannular reaction attributable to the highly strained character of [2.2]metacyclophane skeleton and the increased stabilization of the 5-benzyl cation intermediate arising from the electronic interactions among the opposite benzene ring through the intra-annular 8,16-positions was also observed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Part 42, T. Yamato, J. Matsumoto, M. Sato, K. Fujita, Y. Nagano, and M. Tashiro, submitted to J. Chem. Research (S).

  2. C.J. Brown, J. Chem. Soc. 3278 (1953).

  3. C.-F. Shieh, D. McNally, and R.H. Boyd, Tetrahedron 25, 3653 (1969).

    Article  CAS  Google Scholar 

  4. A.W. Hanson, Acta Crystallor. 15, 956 (1962).

    Article  CAS  Google Scholar 

  5. (a) P.M. Keehn and S.M. Rosenfield, Cyclophanes, Academic Press, New York, 1983; (b) D.J. Wilson, V. Boekelheide, and R.W. Griffin, Jr., J. Am. Chem. Soc. 82, 6302 (1960); (c) N.L. Allinger, M.A. Da Rooge, and R.B. Hermann, J. Am. Chem. Soc. 83, 1974 (1961); (d) H.S. Gutowsky and C. Juan, J. Chem. Phys. 37, 120 (1962); (e) T. Sato, S. Akabori, M. Kainosho, and K. Hata, Bull. Chem. Soc. Jpn 39, 856 (1966); (f) T. Sato, S. Akabori, M. Kainosho, and K. Hata, Bull. Chem. Soc. Jpn 41, 218 (1968); (g) M. Fujimoto, T. Sato, and K. Hata, Bull. Chem. Soc. Jpn 40, 600 (1967); (h) K. Burri and W. Jenny, Helv. Chim. Acta. 50, 1978 (1967); (i) N.L. Allinger, B.J. Gordon, S.-E. Hu, and R.A. Ford, J. Org. Chem. 32, 2272 (1967); (j) R. Flammang, H.P. Figeys, and R.H. Martin, Tetrahedron 24, 1171 (1968); (k) H. Blaschke, C.E. Ramey, I. Calder, and V. Boekelheide, J. Am. Chem. Soc. 92, 3675 (1970).

    Google Scholar 

  6. W.S. Lindsay, P. Stokes, L.G. Humber, and V. Boekelheide, J. Am. Chem. Soc. 83, 943 (1961).

    Article  CAS  Google Scholar 

  7. V. Boekelheide, C. Ramey, E. Sturm, T. Miyasaka, and B.A. Hess, Jr., J. Org. Chem. 34, 1956 (1969).

    Article  CAS  Google Scholar 

  8. Reviews: (a) R.W. Griffin, Jr., Chem. Rev. 63, 45 (1963); (b) B.H. Smith, Bridged Aromatic Compounds, Academic Press, New York, N.Y., 1964.

    Article  CAS  Google Scholar 

  9. (a) N.L. Allinger, B.J. Gordon, H.-E. Hu, and R.A. Ford, J. Org. Chem. 32, 2272 (1967); (b) T. Sato, E. Yamada, Y. Okamura, T. Amada, and K. Hata, Bull. Chem. Soc. Jap. 38, 1049 (1965); (c) M. Fujimoto, T. Sato, and K. Hata, Bull. Chem. Soc. Jap. 40, 600 (1967); (d) T. Sato, M. Wakabayashi, Y. Okamura, T. Amada, and K. Hata, Bull. Chem. Soc. Jap. 40, 2363 (1967).

    Article  CAS  Google Scholar 

  10. T. Sato and K. Nishiyama, J. Chem. Soc., Chem. Comm. 220 (1973).

  11. T. Sato, K. Nishiyama, S. Shimada, and K. Hata, Bull. Chem. Soc. Jap. 44, 2858 (1971).

    Article  CAS  Google Scholar 

  12. (a) S. Hayashi and T. Sato, Bull. Chem. Soc. Jap. 45, 2360 (1972); (b) T. Sato and K. Nishiyama, J. Org. Chem. 37, 3254 (1972).

    Article  CAS  Google Scholar 

  13. (a) T. Yamato, S. Ide, K. Tokuhisa, and M. Tashiro, J. Org. Chem. 57, 271 (1992); (b) T. Yamato, J. Matsumoto, S. Ide, K. Tokuhisa, K. Suehiro, and M. Tashiro, J. Chem. Research (S), 420 (1992).

    Article  CAS  Google Scholar 

  14. (a) M. Tashiro and T. Yamato, Synthesis 435 (1978); (b) M. Tashiro and T. Yamato, J. Org. Chem. 46, 1543 (1981).

  15. (a) M. Tashiro and T. Yamato, J. Org. Chem. 46, 4556 (1981); (b) M. Tashiro and T. Yamato, Chem. Lett. 61 (1982); (c) M. Tashiro and T. Yamato, J. Chem. Soc., Perkin Trans. 1, 2165 (1984).

    Article  CAS  Google Scholar 

  16. W.S. Lindsey, P. Stokes, L.G. Humber, and V. Boeckelheide, J. Am. Chem. Soc. 83, 943 (1961).

    Article  Google Scholar 

  17. L.P. Hammett, J. Am. Chem. Soc. 59, 96 (1937).

    Article  CAS  Google Scholar 

  18. G.A. Olah, Acc. Chem. Res. 4, 240 (1971).

    Article  CAS  Google Scholar 

  19. (a) T. Yamato, N. Sakaue, C. Hideshima, and M. Tashiro, Chem. Express 5, 773 (1990); (b) T. Yamato, C. Hideshima, G.K.S. Prakash, and G.A. Olah, J. Org. Chem. 56, 2089 (1991).

    CAS  Google Scholar 

  20. (a) G.A. Olah, P.S. Iyer, and G.K.S. Prakash, Synthesis 513 (1986); (b) T. Yamato, Yukigousei Kagaku Kyoukai-shi, 53, 487 (1995) and references therein.

  21. (a) T. Yamato, N. Hideshima, T. Furusawa, M. Tashiro, G.K.S. Prakash, and G.A. Olah, J. Chem. Res. (1991), (S), 242; (M) 2414; (b) T. Yamato, L.K. Doamekpor, H. Tsuzuki, and M. Tashiro, Chem. Lett. 89 (1995).

    Google Scholar 

  22. (a) G.A. Olah, S.J. Kuhn, and S.H. Flood, J. Am. Chem. Soc. 84, 1688 (1962); (b) G.A. Olah, S. Kobayashi, and M. Tashiro, J. Am. Chem. Soc. 94, 7448 (1972).

    Article  CAS  Google Scholar 

  23. M. Tashiro, S. Mataka, Y. Takezaki, M. Takeshita, T. Arimura, A. Tsuge, and T. Yamato, J. Org. Chem. 54, 451 (1989).

    Article  CAS  Google Scholar 

  24. M. Tashiro, T. Yamato, K. Kobayashi, and T. Arimura, J. Org. Chem. 52, 3196 (1987).

    Article  CAS  Google Scholar 

  25. T. Sato, K. Torizuka, R. Komaki, and H. Atobe, J. Chem. Soc., Perkin Trans. 2 561 (1980).

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Applied Chemistry, Faculty of Science and Engineering, Saga University, Honjo-machi, 840, Saga-shi, Saga, Japan

    Takehiko Yamato, Koji Fujita, Naoki Shinoda & Kozo Noda

  2. Department of Industrial Chemistry, Faculty of Science and Engineering, Tohwa University, 1-1 Chikushigaoka, Minami-ku, 815, Fukuoka, Japan

    Yoshiaki Nagano

  3. Institute of Advanced Material Study, Kyushu University, 6-1 Kasuga-kohen, 816, Kasuga-shi, Fukuoka, Japan

    Takashi Arimura & Masashi Tashiro

Authors
  1. Takehiko Yamato
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Koji Fujita
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Naoki Shinoda
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kozo Noda
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yoshiaki Nagano
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Takashi Arimura
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Masashi Tashiro
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Parts of the present paper have been published as a preliminary communication: M. Tahiro, T. Arimura, and T. Yamato, Chem. Pharm. Bull. 31, 370 (1983).

Rights and permissions

Reprints and permissions

About this article

Cite this article

Yamato, T., Fujita, K., Shinoda, N. et al. Through-space electronic interactions of [2.2]metacyclophane benzyl cations. Res. Chem. Intermed. 22, 871–897 (1996). https://doi.org/10.1163/156856796X00539

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1163/156856796X00539

Keywords

Search

Navigation