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In search of the most thermostable 1,1,1-trinitrocompounds: polynitroethyl-substituted sym-tetrazine and bistriazolotetrazine

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Abstract

In search of the most thermally stable 1,1,1-trinitrocompounds, several well-known and new energetic 1,2,4,5-tetrazines have been synthesized. The thermal stability of obtained compounds has been investigated by the methods of isothermal and non-isothermal kinetics. The introduction of the OCH2 or NHCH2 bridge between the heterocycle and the trinitromethyl moiety has been confirmed to result in a significant increase in thermal stability. An increase in stability is accompanied by a decrease in the C–NO2 bond length by 0.025–0.029 Å. An additional increase in the thermal stability of 1.1,1-trinitro derivatives is possible due to the creation of high-melting compounds, the decomposition of which proceeds before melting. Trinitroethylamine derivatives are most preferred due to the strong hydrogen bonds of the NH group. However, in some cases, the actual stability of a substance is reduced by the appearance of autocatalysis. On the basis of experimental data of manometry, analysis of condensed decomposition products by HPLC and IR spectroscopy, a mechanism for the decomposition of 1,1,1-trinitrocompounds was proposed. The compounds studied were found to have favorable detonation properties, which were close to those of RDX, a commonly used explosive. At the same time, some of the obtained polynitro compounds have increased burning rates in comparison with the known nitramines HMX and RDX.

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Acknowledgements

This research was supported by the Ministry of Science and Higher Education of the Russian Federation (Agreement with Zelinsky Institute of Organic Chemistry RAS No. 075-15-2020-803). X-ray diffraction data were collected using the equipment of Center for molecular composition studies of INEOS RAS with the financial support from Ministry of Science and Higher Education of the Russian Federation (Contract/Agreement No. 075-03-2023-642).The authors would like to acknowledge to Mrs. N.N. Kondakova for the assistance with thermoanalytical experiments.

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Authors and Affiliations

  1. D.I. Mendeleev University of Chemical Technology of Russia, Miusskaya Sq., 9, Moscow, Russia, 125047

    Gennady F. Rudakov, Valery P. Sinditskii, Valery V. Serushkin, Viacheslav Yu. Egorshev, Svetlana S. Zinchenko, Anastasya I. Botnikova, Alexandra I. Kalinichenko & Polina R. Veselkina

  2. A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilova Str., 28, Moscow, Russia, 119991

    Svetlana A. Aksenova

  3. Moscow Institute of Physics and Technology (National Research University), Institutskiy Per., 9, Dolgoprudny, Moscow Region, Russia, 141700

    Svetlana A. Aksenova

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  1. Gennady F. Rudakov
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  2. Valery P. Sinditskii
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Contributions

GFR contributed to conceptualization, visualization, writing—original draft, writing—review and editing; VPS contributed to conceptualization, visualization, writing—original draft, writing—review and editing; VVS contributed to methodology, formal analysis; VYE contributed to methodology, formal analysis, writing—original draft; SSZ contributed to investigation; AIB contributed to investigation; AIK contributed to investigation; PRV contributed to investigation; and SAA contributed to investigation, visualization, formal analysis, writing—original draft.

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Correspondence to Valery P. Sinditskii.

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Rudakov, G.F., Sinditskii, V.P., Serushkin, V.V. et al. In search of the most thermostable 1,1,1-trinitrocompounds: polynitroethyl-substituted sym-tetrazine and bistriazolotetrazine. J Therm Anal Calorim 149, 2119–2136 (2024). https://doi.org/10.1007/s10973-023-12795-w

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