Quantum-chemical study of nucleophilic substitution of nitro group in N-alkyl-3-nitro-1,2,4-triazoles molecules in reactions with alicyclic alcohols and polyatomic phenols

  • Vadim E. Matulis Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieninhradskaja Street, Minsk 220006, Belarus
  • Yuri V. Grigoriev Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieninhradskaja Street, Minsk 220006, Belarus
  • Gennady T. Sukhanov Institute for Problems of Chemical and Energetic Technologies, Siberian Branch of the Russian Academy of Sciences, 1 Sotsialisticheskaya Street, Biysk 659322, Altai region, Russia
  • Irina A. Krupnova Institute for Problems of Chemical and Energetic Technologies, Siberian Branch of the Russian Academy of Sciences, 1 Sotsialisticheskaya Street, Biysk 659322, Altai region, Russia
  • Oleg A. Ivashkevich Belarusian State University, Niezaliežnasci Avenue, 4, 220030, Minsk, Belarus

Abstract

Nucleophilic substitution of nitro group in N-alkyl-3-nitro-1,2,4-triazoles molecules with alicyclic alcohols (cyclohexanol, menthol) and polyatomic phenols (pyrocatechol, resorcinol) in the gas phase and in aqueous solution was studied by means of quantum-chemical calculations. The results of calculations show that nucleophilic substitution of the nitro group attached to the triazole ring under action of alicyclic alcohols is thermodynamically possible both in the gas phase and in aqueous solution. Among the isomeric N-alkyl-3-nitro-1,2,4-triazoles, the lowest value of ∆rG corresponds to the N(2)-isomer. Calculated values of ∆rG are appreciably higher for polyatomic phenols in comparison with alicyclic alcohols. The reactions of 1-alkyl-3-nitro-1,2,4-triazoles with resorcinol and pyrocatechol in aqueous solution are characterized by small negative or positive values of ∆rG. So, nucleophilic substitution is reversible in this case. At the same time, the process is irreversible for the corresponding anions (when reactions take place in alkaline media).

Author Biographies

Vadim E. Matulis, Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieninhradskaja Street, Minsk 220006, Belarus

senior researcher

Yuri V. Grigoriev, Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieninhradskaja Street, Minsk 220006, Belarus

PhD (chemistry); head of the laboratory of chemistry of condensed systems

Gennady T. Sukhanov, Institute for Problems of Chemical and Energetic Technologies, Siberian Branch of the Russian Academy of Sciences, 1 Sotsialisticheskaya Street, Biysk 659322, Altai region, Russia

doctor of science (chemistry); head of the laboratory of chemistry and technology of high-energy azoles

Irina A. Krupnova, Institute for Problems of Chemical and Energetic Technologies, Siberian Branch of the Russian Academy of Sciences, 1 Sotsialisticheskaya Street, Biysk 659322, Altai region, Russia

junior researcher

Oleg A. Ivashkevich, Belarusian State University, Niezaliežnasci Avenue, 4, 220030, Minsk, Belarus

academician of the National Academy of Sciences of Belarus, doctor of science (chemistry), full professor; deputy vice chancellor

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Published
2018-04-30
Keywords: N-alkyl-3-nitro-1,2,4-triazoles, nucleophilic substitution of nitro group, alicyclic alcohols, polyatomic phenols, quantum-chemical calculations
Supporting Agencies This study is supported by Belarusian Republican Foundation for Fundamental Research (project No. Х15СО-018).
How to Cite
Matulis, V. E., Grigoriev, Y. V., Sukhanov, G. T., Krupnova, I. A., & Ivashkevich, O. A. (2018). Quantum-chemical study of nucleophilic substitution of nitro group in N-alkyl-3-nitro-1,2,4-triazoles molecules in reactions with alicyclic alcohols and polyatomic phenols. Journal of the Belarusian State University. Chemistry, 1, 35-42. Retrieved from https://journals.bsu.by/index.php/chemistry/article/view/1219
Issue
No 1 (2018): Journal of the Belarusian State University. Chemistry
Section
Original Articles

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