Improved Synthesis and Thermochemical Properties of Amino- and Hydrazino-1,2,4,5-Tetrazines
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Improved synthesis and thermochemical properties of amino- and hydrazino-1,2,4,5-tetrazines Tat'yana S. Kon'kova1*, Yurii N. Matyushin1, Evgeniy А. Miroshnichenko1, Nadezhda V. Palysaeva2, Aleksei B. Sheremetev2* 1
N. N. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, 4 Kosygina St., Moscow 119991, Russia; е-mail: [email protected] 2 N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Ave., Moscow 119991, Russia; е-mail: [email protected] Submitted August 17, 2020 Accepted after revision October 5, 2020
Translated from Khimiya Geterotsiklicheskikh Soedinenii, 2020, 56(11), 1449–1453
Improved protocols for the synthesis of 3,6-diamino- and 3,6-dihydrazino-1,2,4,5-tetrazines as well as 6-amino[1,2,4]triazolo[4,3-b][1,2,4,5]tetrazine were developed. Combustion energies were determined by the bomb calorimetry and the enthalpies of formation in the standard state were calculated for the compounds of this study. Based on the obtained data, the contribution of the 1,2,4,5-tetrazine moiety to the enthalpy of combustion of its derivatives was estimated. Keywords: 1,2,4,5-tetrazine, calorimetry, enthalpy of combustion, enthalpy of formation.
Precise experimental values of the enthalpies of formation (ΔHf) of compounds of various classes undoubtedly form the basis of fundamental thermochemistry and are also of great importance for applied science. Unfortunately, experimental values are available for less than 0.1% of known compounds. Since the experimental determination of thermochemical characteristics is a very laborious process, significant efforts are spent on the development of computational approaches. Various empirical and semiempirical methods require extensive parametrization and often lead to significant errors in the assessment of atypical molecules, in particular energy-rich molecules which are components of energetic materials (explosives, propellants, pyrotechnic compositions). When assessing the potential value of an energetic compound, the key performance indicators are usually the detonation velocity and pressure for explosives, and the specific impulse for propellants. The basic characteristic that determines these properties is the energy that is released during detonation or combustion which can be easily estimated by calculation methods1 if the heat of formation of the compound ΔHf is known.2 The decomposition energy is also related to the sensitivity of 0009-3122/20/56(11)-1449©2020 Springer Science+Business Media, LLC
energetic compounds to the initiation of detonation3 characterizing the risks of their use. Only having a reliable ΔHf value the performance and the safety of using an energetic compound can be correctly assessed. High nitrogen heterocycles are the most promising and environmentally attractive building blocks for designing new energetic compounds. Indeed, compounds with a high nitrogen content are characterized by high energy content, and their decomposition is accompanied by the release of a large amount of heat and the fo
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