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Expanding the Limits of Organic Energetic Materials: High-Performance Alliance of 1,3,4-Thiadiazole and Furazan Scaffolds

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    Expanding the Limits of Organic Energetic Materials: High-Performance Alliance of 1,3,4-Thiadiazole and Furazan Scaffolds
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    • Ilya D. Deltsov
      Ilya D. Deltsov
      N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow 119991, Russian Federation
      More by Ilya D. Deltsov
    • Ivan V. Ananyev
      Ivan V. Ananyev
      N. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, GSP-1, Leninsky Prospect, 31, Moscow 119991, Russian Federation
      More by Ivan V. Ananyev
      Orcidhttps://orcid.org/0000-0001-6867-7534
    • Dmitry B. Meerov
      Dmitry B. Meerov
      N. N. Semenov Federal Research Centre for Chemical Physics, Russian Academy of Sciences, 4 Kosygin Strasse, Moscow 119991, Russian Federation
      More by Dmitry B. Meerov
    • Leonid L. Fershtat*
      Leonid L. Fershtat
      N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow 119991, Russian Federation
      National Research University Higher School of Economics, Myasnitskaya strasse, 20, Moscow 101000, Russian Federation
      *[email protected]
      More by Leonid L. Fershtat
      Orcidhttps://orcid.org/0000-0002-0203-1025
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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2024, 89, 1, 174–182
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    https://doi.org/10.1021/acs.joc.3c01858
    Published December 11, 2023
    Copyright © 2023 American Chemical Society
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    Abstract

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    A majority of known and newly synthesized energetic materials comprise polynitrogen or nitrogen–oxygen heterocycles with various explosophores. However, available structural combinations of these organic scaffolds are finite and are about to reach their limits. Herein, we present the design and synthesis of a series of sulfur-containing polyazole structures comprising 1,3,4-thiadiazole and furazan rings linked by C–C bonds and enriched with energetic nitro and azo functionalities. In terms of detonation performance, all synthesized 1,3,4-thiadiazole-furazan assemblies (D = 7.7–7.9 km s–1; P = 26–28 GPa) lie between the powerful explosive TATB (D = 8.0 km s–1; P = 31 GPa) and melt-cast material TNT (D = 6.9 km s–1; P = 23 GPa). In the synthesized series, azo-bridged derivative 5 seems to be most practically interesting, as it combines a relatively high energetic performance (D = 7.9 km s–1; P = 28 GPa), a very high thermal stability (271 °C), and insensitivity to friction. By these functional properties, 5 outperforms the benchmark heat-resistant explosive hexanitrostilbene (HNS). To the best of our knowledge, this is the first example of an energetic alliance of furazan and 1,3,4-thiadiazole scaffolds and a rare case of sulfur-containing high-energy materials, which can certainly be considered as an evolutionary step in energetic materials science.

    Copyright © 2023 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.joc.3c01858.

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    CCDC 2285037 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

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    This article is cited by 14 publications.

    1. Ilya D. Deltsov, Dmitry B. Vinogradov, Konstantin A. Monogarov, Leonid L. Fershtat. Azobis(polynitrophenyl-1,2,5-oxadiazoles) as Heat-Resistant Friction-Insensitive Energetic Materials. The Journal of Organic Chemistry 2025, 90 (1) , 733-741. https://doi.org/10.1021/acs.joc.4c02678
    2. Ruyi Lu, Guangyuan Zhang, Shuaijie Jiang, Kejing Zhang, Ming Lu, Pengcheng Wang. Expanding the π -conjugate structures: Synthesis of high-energy and insensitive Tricyclic fused energetic material. Journal of Molecular Structure 2025, 1319 , 139551. https://doi.org/10.1016/j.molstruc.2024.139551
    3. Dmitry B. Vinogradov, Leonid L. Fershtat. Energetic azine N-oxides: State-of-the-art achievements in the synthesis and performance. Chemical Engineering Journal 2025, 504 , 158859. https://doi.org/10.1016/j.cej.2024.158859
    4. Parasar Kumar, Vikas D. Ghule, Srinivas Dharavath. Advancing energetic chemistry: the first synthesis of sulfur-based C–C bonded thiadiazole-pyrazine compounds with a nitrimino moiety. Dalton Transactions 2024, 53 (48) , 19112-19115. https://doi.org/10.1039/D4DT02919D
    5. Alexander V. Shaferov, Ivan V. Ananyev, Konstantin A. Monogarov, Igor V. Fomenkov, Alla N. Pivkina, Leonid L. Fershtat. Energetic Methylene‐Bridged Furoxan‐Triazole/Tetrazole Hybrids. ChemPlusChem 2024, 89 (12) https://doi.org/10.1002/cplu.202400496
    6. Chun Xiao, You Ran, Lei Yang, Baohui Zheng, Chuan Huang, Qing Ma, Jinshan Li. 3, 4-Bis (3-nitrofurazan-4-yl) furoxan (DNTF) and 4-methoxy-1-methyl-3, 5-dinitro-1 H-pyrazole (DMDNP) based molten carrier with high energy and low sensitivity: Eutectic design and desensitization effect. Materials Today Communications 2024, 41 , 110383. https://doi.org/10.1016/j.mtcomm.2024.110383
    7. Xun Huang, Pinxu Zhao, Haifeng Huang, Jun Yang. Introduction of an N-Amino Group onto 4-(Tetrazol-5-yl)-5-nitro-1,2,3-triazole: A Strategy for Enhancing the Density and Performance of Energetic Materials. Synlett 2024, 35 (17) , 1978-1984. https://doi.org/10.1055/a-2298-0282
    8. M. P. Egorov, V. P. Ananikov, E. G. Baskir, S. E. Boganov, V. I. Bogdan, A. N. Vereshchagin, V. A. Vil’, I. L. Dalinger, A. D. Dilman, O. L. Eliseev, S. G. Zlotin, E. A. Knyazeva, V. M. Kogan, L. O. Kononov, M. M. Krayushkin, V. B. Krylov, L. M. Kustov, V. V. Levin, B. V. Lichitsky, M. G. Medvedev, N. E. Nifantiev, O. A. Rakitin, A. M. Sakharov, I. V. Svitanko, G. A. Smirnov, A. Yu. Stakheev, M. A. Syroeshkin, A. O. Terent’ev, Yu. V. Tomilov, E. V. Tretyakov, I. V. Trushkov, L. L. Fershtat, V. A. Chaliy, V. Z. Shirinian. Current trends in organic chemistry: contribution of the N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences. Russian Chemical Bulletin 2024, 73 (9) , 2423-2532. https://doi.org/10.1007/s11172-024-4366-8
    9. Chao Zhang, Ting-wei Wang, Zu-jia Lu, Zhen-xin Yi, Mei-qi Xu, Yan Li, Qi-yao Yu, Zhi-min Li, Jian-guo Zhang. A new sulfur-containing laser-sensitive primary explosive based on thiazole-4-carbohydrazide. Energetic Materials Frontiers 2024, 5 (3) , 191-198. https://doi.org/10.1016/j.enmf.2024.02.005
    10. Prachi Bhatia, Pooja Jangra, Vikas D. Ghule, Dheeraj Kumar. Combination of N ‐amino‐1,2,4‐triazole and 4‐hydroxy‐3,5‐dinitropyrazole for the synthesis of high performing explosives. Journal of Heterocyclic Chemistry 2024, 61 (8) , 1299-1305. https://doi.org/10.1002/jhet.4856
    11. N. V. Lobanov, A. N. Rykov, A. V. Stepanova, A. A. Larin, L. L. Fershtat, I. F. Shishkov. Equilibrium Molecular Structure of 3-Cyano-4-Amino-1,2,5-Oxadiazole-2-Oxide in the Gas Phase. Journal of Structural Chemistry 2024, 65 (8) , 1603-1611. https://doi.org/10.1134/S0022476624080110
    12. Meiheng Lv, Yuhang Zhang, Tingting Wang, Yue Gao, Zexu Cai, Wenze Li, Fangjian Shang, Yinhua Ma, Jianyong Liu. The impact of electronic effect on the dissociation mechanism of oxadiazole-based regioisomeric energetic materials. Materials Today Communications 2024, 39 , 109207. https://doi.org/10.1016/j.mtcomm.2024.109207
    13. Nikita V. Muravyev, Leonid Fershtat, Qinghua Zhang. Synthesis, design and development of energetic materials: Quo Vadis?. Chemical Engineering Journal 2024, 486 , 150410. https://doi.org/10.1016/j.cej.2024.150410
    14. Meiheng Lv, Yuhang Zhang, Tingting Wang, Yue Gao, Zexu Cai, Wenze Li, Fangjian Shang, Yinhua Ma, Jianyong Liu. The Impact of Short-Range Electron Effects on the Dissociation Mechanism of Oxadiazole-Based Regioisomeric Energetic Materials. 2024https://doi.org/10.2139/ssrn.4764559
    15. Yuri A Sidunets, Valeriya G Melekhina, Leonid L Fershtat. Tandem diazotization/cyclization approach for the synthesis of a fused 1,2,3-triazinone-furazan/furoxan heterocyclic system. Beilstein Journal of Organic Chemistry 2024, 20 , 2342-2348. https://doi.org/10.3762/bjoc.20.200
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    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2024, 89, 1, 174–182
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.joc.3c01858
    Published December 11, 2023
    Copyright © 2023 American Chemical Society
    Request reuse permissions

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