Advertisement

Catalysis Letters

, Volume 42, Issue 1–2, pp 5–13 | Cite as

Solid acid (superacid) catalyzed regioselective adamantylation of substituted benzenes

  • George A. Olah
  • Béla Török
  • Tatyana Shamma
  • Marianna Török
  • G. K. Surya Prakash
Article

Abstract

Adamantylation of substituted benzenes with 1-bromo-adamantane was catalyzed by solid acids including acidic ion exchange and ionomer resins, HY zeolite, sulfated zirconia and supported superacids on HY zeolite and SiO2. Adamantylation generally takes place in excellent yield giving predominantly para products without formation of byproducts. The reactions did not require the usual workup of Friedel-Crafts reactions as catalysts were simply filtered of. Cross-linked polystyrene resin sulfonic acid (Amberlyst) was found particularly suitable as besides its high catalytic activity, high regioselectivity was observed with almost exclusive formation ofp-adamantylated benzenes. AMI, PM3 and MNDO semiempirical calculations of heats of formation showed that of all regioisomers, the para isomer is the most stable. The temperature dependence of adamantylation was also investigated allowing the optimization ofp-substituted product in high yield and excellent selectivity. Lack of isomerization of 1-p-tolyla-damantane using solid (Amberlyst, Nafion-H) and liquid acids (neat and modified trifluoromethanesulfonic acid) indicates absence of product isomerization, while the intramolecular rearrangement of the intermediate arenium complex is still possible.

Keywords

regioselective adamantylation solid acid catalysis highp-selectivity positional protection 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. [1] (a)
    P. Batamack, I. Bucsi, A. Molnár and G.A. Olah, Catal. Lett. 25 (1994) 11;Google Scholar
  2. [1] (b)
    G.A. Olah, ed.,Friedel-Crafts and Related Reactions, Vol. II (Wiley Interscience, New York, 1964);Google Scholar
  3. [1] (c)
    G.A. Olah,Friedel-Crafts Chemistry (Wiley Interscience, New York, 1973);Google Scholar
  4. [1] (d)
    R.M. Roberts and A.A. Khalaf,Friedel-Crafts Alkylation Chemistry (Dekket, New York, 1984).Google Scholar
  5. [2]
    G.A. Olah, P.S. Iyer and G.K.S. Prakash, Synthesis (1986) 513.Google Scholar
  6. [3]
    K. Tanabe, M. Misono, Y. Ono and H. Hattori,New Solid Acids and Bases, Stud. Surf. Sci. Catal., Vol. 51 (Elsevier, Amsterdam, 1989).Google Scholar
  7. [4]
    M.J. Astle, in:Ion Exchangers in Organic and Biochemistry, eds. C. Calman and T.R. Kressman (Interscience, New York, 1957) ch. 36, p. 658.Google Scholar
  8. [5]
    Y. Ono and S. Suzuki, in:Acid-Base Catalysis, Proc. Int. Symp. on Acid-Base Catalysis, Sapporo 1988, p. 379.Google Scholar
  9. [6] a
    S.J. Sondheimer, N.J. Bunce and C.A. Fyfe, JMS Rev. Macromol. Chem. Phys. C 26 (1986) 353;Google Scholar
  10. [6] b
    S.J. Sondheimer, N.J. Bunce, M.E. Lemke and C.A. Fyfe, Macromolecules 19 (1986) 339;Google Scholar
  11. [6] c
    L.L. Ferry, J. Macromol. Sci. Chem. A 27 (1990) 1095.Google Scholar
  12. [7]
    M.L. Poutsma, in:Zeolite Chemistry and Catalysis, ed. J.A. Rabo, ACS Monographs 171 (Am. Chem. Soc., Washington, 1976) ch. 8, p. 439.Google Scholar
  13. [8]
    T. Yamaguchi, Appl. Catal. 61 (1990) 1.Google Scholar
  14. [9]
    G.A. Olah, R. Malhotra and S.C. Narang, J. Org. Chem. 43 (1978) 4628.Google Scholar
  15. [10]
    G.A. Olah, R. Malhotra, S.C. Narang and J.A. Olah, Synthesis (1978) 672.Google Scholar
  16. [11]
    G.A. Olah and D. Meidar, Nouv. J. Chem. 3 (1979) 269.Google Scholar
  17. [12]
    L. Testafari, M. Tiecco, P. Spagnolo, P. Zanirato and G. Martelli, J. Chem. Soc. Perkin Trans. 2 (1976) 662.Google Scholar
  18. [13]
    J. Newman, Synthesis (1972) 692.Google Scholar
  19. [14]
    I. Moiseev and R.I. Doroshenko, Zh. Org. Khim. 18 (1982) 1233.Google Scholar
  20. [15]
    R. Perkins, S. Bennett, E. Bowering, J. Burke, K. Reid and D. Wal, Chem. Ind. (London) (1980) 790.Google Scholar
  21. [16]
    G.A. Olah, O. Farooq, S.M.F. Farnia and A. Wu, J. Org. Chem. 55 (1990) 1516.Google Scholar
  22. [17]
    G.A. Olah, O. Farooq, S.M.F. Farnia and J.A. Olah, J. Am. Chem. Soc. 110 (1988) 2560.Google Scholar
  23. [18]
    G.A. Olah, K. Laali and O. Farooq, J. Org. Chem. 50 (1985) 1483.Google Scholar
  24. [19]
    S.M.F. Farnia, M. Stephenson and G.A. Olah, J. Org. Chem. 53 (1988) 2840.Google Scholar
  25. [20]
    M. Tashiro, H. Watanabe and O. Tsuge, Org. Prep. Proc. Int. 6 (1974) 117.Google Scholar
  26. [21]
    M. Tashiro, Synthesis (1979) 921.Google Scholar
  27. [22]
    T. Yamato, C. Hideshima, A. Miyazawa, M. Tashiro, G.K.S. Prakash and G.A. Olah, Catal. Lett. 6 (1990) 345.Google Scholar
  28. [23]
    T. Yamato, C. Hideshima, G.K.S. Prakash and G.A. Olah, J. Org. Chem. 56 (1991) 3192.Google Scholar
  29. [24]
    M.A. Harmer, W.E. Farneth and Q. Sun, J. Am. Chem. Soc., submitted.Google Scholar
  30. [25]
    SPARTAN program package, Version 2.0., Wavefunction, Inc., Irvine (1991).Google Scholar
  31. [26]
    J. March,Advanced Organic Chemistry, 4th Ed. (Wiley, New York, 1992).Google Scholar
  32. [27] (a)
    S. Saito, Y. Sato, T. Ohwada and K. Shudo, J. Am. Chem. Soc. 116 (1994) 2312;Google Scholar
  33. [27] (b)
    S. Saito, S.-I. Saito, T. Ohwada and K. Shudo, Chem. Pharm. Bull. 39 (1991) 2718.Google Scholar

Copyright information

© J.C. Baltzer AG, Science Publishers 1996

Authors and Affiliations

  • George A. Olah
    • 1
  • Béla Török
    • 1
  • Tatyana Shamma
    • 1
  • Marianna Török
    • 1
  • G. K. Surya Prakash
    • 1
  1. 1.Donald P. and Katherine B. Loker Hydrocarbon Research Institute and Department of ChemistryUniversity of Southern CaliforniaLos AngelesUSA

Personalised recommendations