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

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Chemistry of Heterocyclic Compounds Aims and scope

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.

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  1. The DFT/B3LYP method has been applied before to high-fidelity structural and energy calculations of five-membered heterocycles with one heteroatom and the corresponding benzo-fused systems [15,17–20], as well as azoles (for example, pyrazole [21] and oxazole [22]). Similar results and conclusions for heterocyclic systems were also obtained with the HF method [15,19,20].

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Authors and Affiliations

  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Ave., Moscow, 119991, Russia

    L. I. Belen’kii, I. D. Nesterov & N. D. Chuvylkin

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  1. L. I. Belen’kii
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  2. I. D. Nesterov
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  3. N. D. Chuvylkin
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Correspondence to L. I. Belen’kii.

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*Dedicated with the warmest wishes to Academician J. Stradiņš on the occasion of his 80th birthday.

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1739-1751, November, 2013.

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Belen’kii, L.I., Nesterov, I.D. & Chuvylkin, N.D. Quantum-Chemical Investigation of Azoles 1. Alternative Electrophilic Substitution Mechanisms in 1,2- and 1,3-Azoles*. Chem Heterocycl Comp 49, 1611–1622 (2014). https://doi.org/10.1007/s10593-014-1412-8

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