Russian Chemical Bulletin

, Volume 64, Issue 9, pp 2076–2082 | Cite as

Alkylation of toluene with dichloromethane in the presence of triisobutylaluminum and perfluorophenylborates

  • N. M. Bravaya
  • E. E. Faingol’d
  • A. N. Galiullin
  • O. N. Babkina
  • S. L. Saratovskikh
  • A. V. Chernyak
  • V. D. Makhaev
Full Articles


1H NMR method showed that in systems based on triisobutylaluminum (TIBA) and triphenylcyclopropenylium [Ph3C3]+[B(C6F5)4]–(CPB) or triphenylmethylium [Ph3C]+[B(C6F5)4]–(TB) perfluorophenylborates in a toluene–dichloromethane mixture the Friedel–Crafts process occurs with the formation of ditolylmethane (DTM) accompanied by the complete decomposition of TIBA to form isobutane. 19F NMR spectroscopy showed that the [B(C6F5)4]–anion decomposes in the systems to form B(C6F5)3 and HC6F5. The short-living [AlBu2 i]+ cation formed in the reaction of perfluorophenylborates with TIBA is assumed to be the species initiating the process. It has been shown that CPB is less reactive than TB. The addition of a stoichiometric amount of Ph2CCpFluHfMe2 exerts no effect on the process with the CPB-containing system but inhibits the reaction in the case of TB.

Key words

Friedel–Crafts reaction toluene dichloromethane alkylation triisobutylaluminum carbenium ions perfluorophenylborates metallocene NMR spectroscopy 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    S. Prajapati, A. P. Mishra, A. Srivastava, IJPCBS, 2012, 2, 52.Google Scholar
  2. 2.
    M. Rueping, B. J. Natchtsheim, Beilstein J. Org. Chem., 2010, 6, No.6.CrossRefGoogle Scholar
  3. 3.
    E. Y.-X. Chen, T. J. Marks, Chem. Rev., 2000, 100, 1391.CrossRefGoogle Scholar
  4. 4.
    J. Kuwabara, D. Takeuchi, T. Osakada, J. Mol. Catal., 2004, 208, 39.CrossRefGoogle Scholar
  5. 5.
    K. Song, H. Gao, F. Liu, J. Pan, L. Guo, S. Zai, Q. Wu, Eur. J. Inorg. Chem., 2009, 3016.Google Scholar
  6. 6.
    P. W. Dyer, J. Fawcett, M. J. Hanton, Organometallics, 2008, 27, 5082.CrossRefGoogle Scholar
  7. 7.
    S. O. Ojwach, I. A. Guzei, L. L. Benade, S. F. Mapolie, J. Darkwa, Organometallics, 2009, 28, 2127.CrossRefGoogle Scholar
  8. 8.
    A. Budhai, B. Omondi, S. O. Ojwach, C. Obuah, E. Y. OseiTwumb, J. Darkwa, Catal. Sci. Technol., 2013, 3, 3130.CrossRefGoogle Scholar
  9. 9.
    I. Vicente, K. Bernardo-Gusmão, M. O. de Souza, R. F. de Souza, J. Braz. Chem. Soc., 2014, 25, 2151.Google Scholar
  10. 10.
    V. D. Makhaev, A. N. Galiullin, E. E. Faingol´d, N. M. Bravaya, L. A. Petrova, Russ. Chem. Bull. (Int. Ed.), 2014, 63, 651–656 [Izv. Akad. Nauk, Ser. Khim., 2014, 651–656].CrossRefGoogle Scholar
  11. 11.
    H. Li, D. C. Neckers, Can. J. Chem., 2003, 81, 758.CrossRefGoogle Scholar
  12. 12.
    M. Bochmann, Topics Catal., 1999, 7, 9.CrossRefGoogle Scholar
  13. 13.
    M. Bochmann, M. J. Sarsfield, Organometallics, 1998, 17, 5908.CrossRefGoogle Scholar
  14. 14.
    Z. Yu, A. V. Korolev, M. J. Heeg, C. P. Winter, Polyhedron, 2002, 21, 1117.CrossRefGoogle Scholar
  15. 15.
    M. P. D. Mahindaratne, K. Wimalasena, J. Org. Chem., 1998, 63, 2858.CrossRefGoogle Scholar
  16. 16.
    R. Breslow, H. W. Chang, J. Am. Chem. Soc., 1961, 83, 2367.CrossRefGoogle Scholar
  17. 17.
    C. Götz, A. Rau, G. Luft, Macromol. Symp., 2002, 178, 93.CrossRefGoogle Scholar
  18. 18.
    C. R. Samanami, M. L. Amadoruge, C. H. Yoder, J. A. Colen, C. E. Moore, A. L. Rheingold, N. F. Materer, C. A. Weinert, Organometallics, 2011, 30, 1046.CrossRefGoogle Scholar
  19. 19.
    R. Ma, M. Chen, M. Zhou, J. Phys. Chem. A, 2009, 113, 12926.CrossRefGoogle Scholar
  20. 20.
    C. A. Reed, N. L. P. Fackler, K.-C. Kim, D. Stasko, D. R. Evans, J. Am. Chem. Soc., 1999, 121, 6314.CrossRefGoogle Scholar
  21. 21.
    P. Jutzi, C. Müller, A. Stammler, H.-G. Stammler, Organometallics, 2000, 19, 1442.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • N. M. Bravaya
    • 1
  • E. E. Faingol’d
    • 1
  • A. N. Galiullin
    • 1
  • O. N. Babkina
    • 1
  • S. L. Saratovskikh
    • 1
  • A. V. Chernyak
    • 1
  • V. D. Makhaev
    • 1
  1. 1.Institute of Problems of Chemical PhysicsRussian Academy of SciencesChernogolovka, Moscow RegionRussian Federation

Personalised recommendations