Effect of structure on the kinetics of the nucleophilic substitution of acylonium ions
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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.
KeywordsIonization Potential Electron Affinity Nucleophilic Substitution Acyl Transfer Physical Organic Chemistry
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- 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.L. M. Litvinenko and N. M. Oleinik, Mechanisms of Organic Catalysts [in Russian], Naukova Dumka, Kiev (1984).Google Scholar
- 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.V. I. Rybachenko, G. Schroeder, B. Leska, et al., Teor. Éksp. Khim.,33, No. 3, 143–148 (1997).Google Scholar
- 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.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.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.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