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Chemistry of Heterocyclic Compounds

, Volume 49, Issue 11, pp 1611–1622 | Cite as

Quantum-Chemical Investigation of Azoles 1. Alternative Electrophilic Substitution Mechanisms in 1,2- and 1,3-Azoles*

  • L. I. Belen’kiiEmail author
  • I. D. Nesterov
  • N. D. Chuvylkin
Article

Quantum-chemical calculations were performed for the molecular structures of 1,2-azoles (pyrazole, isoxazole, isothiazole), 1,3-azoles (imidazole, oxazole, thiazole), and the corresponding intermediates of electrophilic substitution reactions (with protons as the model electrophiles): azolium ions, bipolar ions (ylides/carbenes), cationic σ-complexes, as well as activation energy values were calculated for the decomposition of ylides. The calculations were performed for gas phase and aqueous solutions according to the B3LYP method in a 6-31G(d) basis set, with corrections for the zero-point vibration energy. The solvation effects were taken into account by using the overlapping spheres model (IEFPCM). The results of the calculations explained some features of electrophilic substitution in azoles according to two alternative mechanisms: the classical addition-elimination with cationic σ-complex intermediates, and the mechanism of elimination-addition that involves ylides (carbenes) as key intermediates.

Keywords

1,2-azoles 1,3-azoles B3LYP/6-31G(d) method electrophilic substitution quantum-chemical calculations 

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Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  • L. I. Belen’kii
    • 1
    Email author
  • I. D. Nesterov
    • 1
  • N. D. Chuvylkin
    • 1
  1. 1.N. D. Zelinsky Institute of Organic ChemistryRussian Academy of SciencesMoscowRussia

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