Kinetics of the Thermal Decomposition of 2,4,6-Triazido-3,5-Difluoropyridine View Full Text


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Article Info

DATE

2018-11

AUTHORS

V. V. Nedel’ko, N. V. Chukanov, B. L. Korsunskiy, T. S. Larikova, S. V. Chapyshev, V. V. Zakharov

ABSTRACT

The kinetics and products of the thermal decomposition of 2,4,6-triazido-3,5-difluoropyridine in melt at temperatures of 120–160°C have been studied using pressure measurements, differential thermal analysis, and IR spectroscopy. The reaction occurs in two macroscopic steps, each described by a first-order kinetic equation. In the first, the activation energy and the common logarithm of the pre-exponential factor are 35.6 ± 1.2 kcal/mol and 15.1 ± 0.6 s–1, respectively. For the studied compound (and certain other heterocyclic azides, such as 2,4,6-triazido-1,3,5-triazine and 2,4,6-triazidopyrimidine), the pre-exponential factor is anomalously high. This is due to the fact that the 2,4,6-triazido-3,5-difluoropyridine molecule contains no hydrogen atoms. For such azides, the usual decomposition mechanism (cleavage of the azide group with subsequent attack of nitrene on a hydrogen atom of a neighboring molecule) is impossible, which favors the stability of the formed nitrene. In this case, the reaction occurs through a complex chain polymerization mechanism, which leads to the formation of specific condensed products: packs of planar polyconjugate carbon–nitrogen networks with a porphyrin-like structure. More... »

PAGES

997-1002

References to SciGraph publications

  • 2016-11. Thermal decomposition of 2,4,6-triazidopyridine in RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
  • 2016-08. Thermal decomposition of 2,4,6-triazidopyrimidine in the melt in RUSSIAN CHEMICAL BULLETIN
  • 2016-07. Thermal decomposition of 2,4,6-triazido-1,3,5-triazine in RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
  • 2018-01. 2,4,6-Triazido-1,3,5-Triazine, 2,4,6-Triazidopyrimidine, and 2,4,6-Triazidopyridine as Precursors of Carbon Nitride Materials in RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
  • Identifiers

    URI

    http://scigraph.springernature.com/pub.10.1134/s199079311806009x

    DOI

    http://dx.doi.org/10.1134/s199079311806009x

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