Synthesis and structural identification of 3,6-Bis(3,5- dimethylpyrazol-1-yl)-1,2,4,5-tetrazine (BDT)
127 viewsDOI:
https://doi.org/10.54939/1859-1043.j.mst.IPE.2024.32-39Keywords:
BDT; Synthesis; Optimization structure; DFT.Abstract
3,6-Bis(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine (BDT) has emerged as a key intermediate for accessing other promising tetrazine-based high-energy-density compounds. The study presented the step-by-step process of synthesizing BDT while thoroughly analyzing and investigating its crystal structure. The chemical structure of BDT was characterized using spectroscopic techniques such as FT-IR, 1H-NMR, 13C-NMR, and data from PXRD and CCDC 254069. BDT was analyzed using various theoretical techniques, such as 2D fingerprint and Hirshfeld surface. The morphology of the BDT crystals was evaluated through optical microscope images. The results show that BDT crystallizes in a monoclinic space group P21/c, with four molecules per unit cell (Z=4) with the calculated lattice parameters as follows: a = 11.37 Å, b = 16.67 Å, c = 7.74 Å. The proportion of interactions of N...H and H...H of the total Hirshfeld surface area of BDT were 31.9% and 45.7%, respectively. ESP's maximum negative and positive values are -212.9 kJ.mol-1 and 65.6 kJ.mol-1, respectively.
References
[1]. Sifain, A.E., et al., "Photoactive excited states in explosive Fe (II) tetrazine complexes: A time-dependent density functional theory study". J. Phys. Chem. C. Vol. 120, No. 50, pp. 28762-28773, (2016). DOI: https://doi.org/10.1021/acs.jpcc.6b10333
[2]. Chavez, D.E., M.A. Hiskey, and R.D. Gilardi, "3, 3′‐Azobis (6‐amino‐1, 2, 4, 5‐tetrazine): A Novel High‐Nitrogen Energetic Material". Angew. Chem., Int. Ed. Engl. Vol. 39, No. 10, pp. 1791-1793, (2000). DOI: https://doi.org/10.1002/(SICI)1521-3773(20000515)39:10<1791::AID-ANIE1791>3.0.CO;2-9
[3]. Coburn, M., et al., "Oxidations of 3, 6‐diamino‐1, 2, 4, 5‐tetrazine and 3, 6‐bis (s, s‐dimethylsulfilimino)‐1, 2, 4, 5‐tetrazine". J. Heterocycl. Chem. Vol. 30, No. 6, pp. 1593-1595, (1993). DOI: https://doi.org/10.1002/jhet.5570300623
[4]. Sinditskii, V., et al., "Thermal behavior and combustion mechanism of high-nitrogen energetic materials DHT and BTATz". Thermochim. Acta. Vol. 535, pp. 48-57, (2012). DOI: https://doi.org/10.1016/j.tca.2012.02.014
[5]. Zhang, J.G., et al., "The Crystal Structure and Synthesis Mechanism of 3, 6‐Bis (3, 5‐dimethylpyrazol‐1‐yl)‐1, 4‐dihydro‐1, 2, 4, 5‐tetrazine (BDT): A Key Precursor of S‐tetrazine". J. Heterocycl. Chem. Vol. 51, No. S1, pp. E234-E240, (2014). DOI: https://doi.org/10.1002/jhet.1948
[6]. Zhang, T., et al., "Alkali metal salts of 3, 6-dinitramino-1, 2, 4, 5-tetrazine: Promising nitrogen-rich energetic materials". CrystEngComm. Vol. 21, No. 4, pp. 765-772, (2019). DOI: https://doi.org/10.1039/C8CE01827H
[7]. Stetsiuk, O., A. Abhervé, and N. Avarvari, "1, 2, 4, 5-Tetrazine based ligands and complexes". Dalton Trans. Vol. 49, No. 18, pp. 5759-5777, (2020). DOI: https://doi.org/10.1039/D0DT00827C
[8]. Ren, J., et al., "3-Nitramino-6-hydroxy-1, 2, 4, 5-tetrazine and its alkaline earth metal salts: an effective strategy to balance energy density and safety of energetic compounds". J. Energ. Mater. Vol. 39, No. 1, pp. 48-59, (2021). DOI: https://doi.org/10.1080/07370652.2020.1754968
[9]. Li, H., et al., "Nitrogen-rich salts of 3, 6-dinitramino-1, 2, 4, 5-tetrazine: syntheses, structures, and energetic properties". J. Energ. Mater. Vol. 40, No. 1, pp. 15-33, (2022). DOI: https://doi.org/10.1080/07370652.2020.1825544
[10]. Hu, L., et al., "Selecting suitable substituents for energetic materials based on a fused triazolo-[1, 2, 4, 5] tetrazine ring". ACS Appl. Energy Mater. Vol. 3, No. 6, pp. 5510-5516, (2020). DOI: https://doi.org/10.1021/acsaem.0c00487
[11]. Klapoetke, T.M., et al., "Highly Energetic Salts of 3, 6-Bishydrazino-1, 2, 4, 5-tetrazine". Cent. Eur. J. Energetic Mater. Vol. 10, No. 2, pp. 151-170, (2013).
[12]. Klapoetke, T.M., A. Preimesser, and J. Stierstorfer, "Thermally Stable 3, 6-Disubstituted 1, 2, 4, 5-Tetrazines". Z. fur Naturforsch. - B J. Chem. Sci. Vol. 68, No. 12, pp. 1310-1320, (2013). DOI: https://doi.org/10.5560/znb.2013-3237
[13]. Steinhauser, G. and T.M. Klapötke, "“Green” pyrotechnics: a chemists' challenge". Angew. Chem., Int. Ed. Engl. Vol. 47, No. 18, pp. 3330-3347, (2008). DOI: https://doi.org/10.1002/anie.200704510
[14]. Gong, Y.-H., "Synthesis electrochemical and fluorescence studies of 1, 2, 4, 5-tetrazine derivatives: towards molecular sensors for anions and electron-rich compounds and synthesis and electrochemical study of ferrocene-containing pyridinium salts", Cachan, Ecole normale supérieure, (2007).
[15]. Frisch M. J., e.a., "Gaussian 09, revision A. 01. Gaussian", Inc.: Wallingford, CT, (2009).
[16]. Spackman, P.R., et al., "CrystalExplorer: A program for Hirshfeld surface analysis, visualization and quantitative analysis of molecular crystals". J. Appl. Crystallogr. Vol. 54, No. 3, pp. 1006-1011, (2021). DOI: https://doi.org/10.1107/S1600576721002910
