Abstract
The results of theoretical search for model transition states of the electrophilic substitution reaction in 2H-tetrazole (1) without the preliminary formation of N-protonated azolium salts are presented for two routes that were previously suggested by the authors and thermodynamically investigated: A, the attack of molecule 1 by the nucleophile (HO–(aq)) to form the anion to which the electrophile H3O+(aq)) is added and B, the attack of molecule 1 by the same electrophile followed by the addition of the same nucleophile to the specifically solvated protonated species formed in the preceding reaction step. The calculations were performed using the DFT/B3LYP/6-31G(d) method and the scanning procedure of the potential energy surface (PES). Both steps of route A turned out to be nearly barrierless, while in route B only its first step is barrierless and the second one is conjugated with passing an activation barrier of ∼45 kcal mol–1 between non-interacting or weakly interacting reactants and electrophilic substitution products. Unlike the specifically solvated protonated species of 1H-tetrazole in an aqueous solution, a similar species of 2H-tetrazole does not form a prereaction complex with the attacking nucleophile (HO–(aq)) and the five-membered ring is destroyed in fact in the nitrogen-containing reaction product formed after passing the activation barrier. The optimized structure of the transition state differs strongly from the nitrogen-containing structure of the reaction product with the destroyed ring, which was found by scanning of the PES.
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For Part 10, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 0941—0945, June, 2017.
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Chuvylkin, N.D., Subbotin, A.N., Belov, S.A. et al. Quantum chemical studies of azoles. Russ Chem Bull 66, 941–945 (2017). https://doi.org/10.1007/s11172-017-1835-3
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DOI: https://doi.org/10.1007/s11172-017-1835-3