Theoretical study on the flash vacuum gas-phase pyrolysis reaction mechanism of 2-(2-benzylidenehydrazinyl)pyridine and analogous

Sebastián A. Cuesta, Edgar A. Márquez, Marcos Antonio Loroño Gonzalez, J. L. Paz, José R. Mora

Research output: Contribution to journalArticlepeer-review

Abstract

In the present study, the most favourable reaction mechanism in the flash vacuum pyrolysis of 2-[(2E)-2-benzylidenehydrazinyl]pyridine and analogous was theoretically studied using B3LYP-D3/6-311G(d,p) level. The influence of different substituents on the phenyl ring in the para position is evaluated at 500 K. A deep analysis of the mechanisms reveals the influence of the substituents in the activation energy, where the reactivity order OCH3 > CH3 > H > Cl > NO2 is found, following Hammet parameters (σp). To reach the transition state, geometric changes contribute more than 70% of the energy in agreement with the reaction force analysis. A recent independent gradient model (IGM) is also applied to establish an influence between the substituent and the strength of the bonds involved in the mechanism, through an intrinsic bond strength index (IBSI). Furthermore, the influence of the substituent was also evaluated in terms of interatomic distances and evolution percentages, finding high correlations with Hammet σp values.

Original languageEnglish
Article number113297
JournalComputational and Theoretical Chemistry
Volume1202
DOIs
StatePublished - Aug 2021
Externally publishedYes

Bibliographical note

Funding Information:
This study was supported by the Universidad San Francisco de Quito by the research grants 2019-2021. The authors have used the high-performance computing (HPC) system available in USFQ for the theoretical calculations presented in this work.

Publisher Copyright:
© 2021 Elsevier B.V.

Keywords

  • B3LYP-D3
  • Hammet σ
  • Hydrazines
  • IBSI
  • Pyrolysis
  • Reaction mechanism

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