Theoretical and Experimental Chemistry

, Volume 34, Issue 2, pp 86–92 | Cite as

Effect of structure on the kinetics of the nucleophilic substitution of acylonium ions

  • V. I. Rybachenko
  • G. Schroeder
  • K. Yu. Chotii
  • V. V. Kovalenko


A study was carried out on 67 reactions involving transfer of acyl groups from the corresponding N-, O-acylonium salts to pyridine N-oxides, highly basic pyridines, and N-methylimidazole in acetonitrile solution. PM3 calculations were carried out for the ionization potentials of the nucleophiles and electron affinities of the N-, O-acylonium cations. A multiparameter correlation was obtained predicting the rate of acyl group transfer.


Ionization Potential Electron Affinity Nucleophilic Substitution Acyl Transfer Physical Organic Chemistry 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    A. Williams, in: Advances in Physical Organic Chemistry, Vol. 27 (1992), pp. 1–55.CrossRefGoogle Scholar
  2. 2.
    V. I. Minkin, B. Ya. Simkin, and R. M. Minyaev, Quantum Chemistry of Organic Compounds. Reaction Mechanisms [in Russian], Khimiya, Moscow (1986).Google Scholar
  3. 3.
    L. M. Litvinenko and N. M. Oleinik, Mechanisms of Organic Catalysts [in Russian], Naukova Dumka, Kiev (1984).Google Scholar
  4. 4.
    A. N. Kost, S. K. Suminov, and A. K. Sheinkman, in: Iminium Salts in Organic Chemistry, H. Bohme and H. G. Viehe (eds.), Wiley, New York (1979), pp. 573–602.Google Scholar
  5. 5.
    V. I. Rybachenko, G. Schroeder, B. Leska, et al., Teor. Éksp. Khim.,33, No. 3, 143–148 (1997).Google Scholar
  6. 6.
    E. V. Titov, V. I. Rybachenko, and K. Yu. Chotii [C. Ju. Chotiy], J. Mol. Struct.,238, 289–305 (1990).CrossRefGoogle Scholar
  7. 7.
    S. S. Shaik, H. B. Schlegel, and S. Wolfe, Theoretical Aspects of Physical Organic Chemistry. TheS N2 Mechanism, Wiley, New York (1992).Google Scholar
  8. 8.
    K. H. Yew, H. J. Koh, H. W. Lee, and I. Lee, J. Chem. Soc., Perkin Trans. II, No. 11, 2263–2268 (1995).Google Scholar
  9. 9.
    M. Jedrzejczak, R. E. Motie, D. P. N. Satchel, et al., J. Chem. Soc., Perkin Trans. II, No. 7, 1471–1479 (1994).Google Scholar
  10. 10.
    I. V. Trushkov, D. N. Chuvylkin, A. S. Koz’min, and N. S. Zefirov, Izv. Akad. Nauk, Ser. Khim., No. 5, 804–826 (1995).Google Scholar

Copyright information

© Plenum Publishing Corporation 1998

Authors and Affiliations

  • V. I. Rybachenko
    • 1
  • G. Schroeder
    • 1
    • 2
  • K. Yu. Chotii
    • 1
  • V. V. Kovalenko
    • 1
  1. 1.L. M. Litvinenko Institute of Physical Organic and Coal ChemistryNational Academy of Sciences of UkraineDonetskUkraine
  2. 2.Chemistry DepartmentAdam Mickiewicz UniversityPoznanPoland

Personalised recommendations