Preparation of Imidazolium 2,4,5-Trinitroimidazolate from Derivatives of Imidazole and Its Oxidation Under Nitration Conditions

• Autorzy: Lian Pengbao , Hou Changming , Chen Lizhen , Xu Jianxin , Xu Zishuai , Wang Jianlong

Identyfikatory

DOI

10.22211/cejem/158311

• Języki publikacji: EN

Abstrakty

EN

In this study, the nitration reactions of imidazole and its nitro derivatives with a mixture of 98% HNO₃ and 98% H₂SO₄ (or 15% SO₃ in H₂SO₄) were reinvestigated. When imidazole or 4(5)-nitroimidazole was nitrated with a mixture of 98% HNO₃ and 98% H₂SO₄ (or 15% SO₃ in H₂SO₄), only 4,5-dinitroimidazole was obtained. Imidazolium 2,4,5-trinitroimidazolate was prepared from 2-nitroimidazole or 2,4(5)-dinitroimidazole with a mixture of 98% HNO₃ and 98% H₂SO₄ (or 15% SO₃ in H₂SO₄); the highest yields were 57.8 and 62.8%, respectively. However, on increasing the reaction temperature, duration, amount of H₂SO₄ or HNO₃, the by-product ethanedioic acid was produced. A possible reaction mechanism for the formation of ethanedioic acid from 2,4,5-trinitroimidazole is suggested. The compounds 4,5-dinitroimidazole, imidazolium 2,4,5-trinitroimidazolate and ethanedioic acid were characterized by infrared spectroscopy, multinuclear ¹H and ¹³C NMR spectroscopy, and elemental analysis. The structures of 4,5-dinitroimidazole and ethanedioic acid were further confirmed by single-crystal X-ray diffraction.

Słowa kluczowe

EN

imidazole; imidazole nitro derivatives; imidazolium 2,4,5-trinitroimidazolate; ethanedioic acid; nitration reaction; reaction mechanism

• Wydawca: Sieć Badawcza Łukasiewicz - Instytut Przemysłu Organicznego
• Czasopismo: Central European Journal of Energetic Materials
• Rocznik: 2022
• Tom: Vol. 19, no. 4
• Strony: 379--392
• Opis fizyczny: Bibliogr. 25 poz., rys., tab.

Twórcy

autor

Lian Pengbao

• Shanxi North Xingan Chemical Industry Co., Ltd., China
• School of Chemical Engineering and Technology, North University of China, Taiyuan 030051, China

autor

Hou Changming

• School of Chemical Engineering and Technology, North University of China, Taiyuan 030051, China

autor

Chen Lizhen

• School of Chemical Engineering and Technology, North University of China, Taiyuan 030051, China

autor

Xu Jianxin

• Gansu Yinguang Cherical Industry Group Co., Ltd., Baiyin 730900, China

autor

Xu Zishuai

• Gansu Yinguang Cherical Industry Group Co., Ltd., Baiyin 730900, China

autor

Wang Jianlong

• School of Chemical Engineering and Technology, North University of China, Taiyuan 030051, China

Bibliografia

• [1] Novikov, S.S.; Khmel’nitskii, L.I.; Lebedev, O.V.; Sevast’yanova, V.V.; Epishina, L.V. Nitration of Imidazoles with Various Nitrating Agents. Chem. Heterocycl. Compd. 1970, 6(4): 465-469.
• [2] Novikov, S.S.; Khmel’nitskii, L.I.; Lebedev, O.V.; Epishina, L.V.; Sevost’yanova, V.V. The Nitration of Iodoimidazoles. Chem. Heterocycl. Compd. 1970, 6(5): 614-618.
• [3] Cho, J.R.; Kim, K.J.; Cho, S.G.; Kim, J.K. Synthesis and Characterization of 1-Methyl-2,4,5-trinitroimidazole (MTNI). J. Heterocycl. Chem. 2002, 39(1): 141-147; DOI: 10.1002/jhet.5570390121.
• [4] Gao, H.; Ye, C.; Gupta, O.D.; Xiao, J.-C.; Hiskey, M.A.; Twamley, B.; Shreeve, J.M. 2,4,5-Trinitroimidazole-based Energetic Salts. Chem. Eur. J. 2007, 13(14): 3853-3860; DOI: 10.1002/chem.200601860.
• [5] Damavarapu, R.; Surapaneni, C.R.; Gelber, N.; Duddu, R.G.; Zhang, M.; Dave, P.R. Melt-cast Explosive Material. Patent US 7304164, 2007.
• [6] Badgujar, D.M.; Talawar, M.B.; Asthana, S.N.; Mahulikar, P.P. Advances in Science and Technology of Modern Energetic Materials: an Overview. J. Hazard. Mater. 2008, 151(2-3): 289-305; DOI: 10.1016/j.jhazmat.2007.10.039.
• [7] Coburn, M.D. Ammonium 2,4,5-Trinitroimidazole. Patent US 4028154, 1977.
• [8] Chen, J.; Lian, P.; Chen, L.; Wang, J.; Chen, J. Crystal Structure and Thermal Behaviour of Imidazolium 2,4,5-Trinitroimidazolate. Cent. Eur. J. Energ. Mater. 2019, 16(5): 547-563; DOI: 10.22211/cejem/113123.
• [9] Lian, P.; Chen, J.; Yuan, Y.; Chen, L.; Wang, J. The Nitration of 2,4,5-Triiodoimidazole and Its Oxidation Under Nitration Conditions. J. Energ. Mater. 2020, 39(3): 333-343; DOI: 10.1080/07370652.2020.1797928.
• [10] Katritzky, A.R.; Cundy, D.J.; Chen, J. Polyiodoimidazoles and Their Nitration Products. J. Energ. Mater. 1993, 11(4-5): 345-352.
• [11] Grimmett, M.R.; Hua, S.-T.; Channg, K.-C.; Foley, S.A.; Simpson, J. 1,4-Dinitroimidazole and Derivatives. Structure and Thermal Rearrangement. Aust. J. Chem. 1989, 43(8): 1281-1289.
• [12] Fargher, R.G.; Pyman, F.L. Nitro-, Arylazo-, and Amino-glyoxalines. J. Chem. Soc., Trans. 1919, 115(2).
• [13] Zhao, X.X.; Zhang, J.C.; Li, S.H.; Yang, Q.P.; Li, Y.C.; Pang, S.P. A Green and Facile Approach for Synthesis of Nitro Heteroaromatics in Water. Org. Process Res. Dev. 2014, 18(7): 886-890: 217-260; DOI: 10.1021/op5000754.
• [14] Sheldrick, G.M. SHELXT ‒ Integrated Space-Group and Crystal-Structure Determination. Acta Crystallogr. Sect. A Found. Crystallogr. 2015, A71(1): 3-8.
• [15] Sheldrick, G.M. Crystal Structure Refinement with SHELXL. Acta Crystallogr. Sect. C Struct. Chem. 2015, C71(1): 3-8; DOI: 10.1107/S2053229614024218.
• [16] Dolomanov, O.V.; Bourhis, L.J.; Gildea, R.J.; Howard, J.A.K.; Puschmann, H. OLEX2: a Complete Structure Solution, Refinement and Analysis Program. J. Appl. Crystallogr. 2009, 42(2): 339-341; DOI: 10.1107/S0021889808042726.
• [17] Latypov, N.V.; Bergman, J. Synthesis and Reactions of 1,1-Diamino-2,2-dinitroethylene. Tetrahedron 1998, 54(38): 11525-11536.
• [18] Cai, H.-Q.; Shu, Y.-J.; Yu, W.-F.; Li, J.-S.; Cheng, B.-B. Study on Synthesis of FOX-7 and Its Reaction Mechanism. Acta Chim. Sinica 2004, 64(3): 295-301.
• [19] Marlin, J.E.; Killpack, M. Nitroimidazolones. Synthesis of Deaza Analogues of 3-Nitro-1,2,4- triazol-5-one. Heterocycles 1992, 34(7): 1385-1393.
• [20] Cady, H.H.; Coburn, M.D.; Harris, B.W.; Rogers, R.N. Synthesis and Thermochemistry of Ammonium 2,4,5-Trinitroimidazole. Los Alamos Scientific Laboratory, Report No. LA-6802-MS, 1977.
• [21] Lian, P.; Chen, L.; Chen, J.; Wang, J.; Wang, J.; Chen, J. The Nitration of 1-Methyl2,4,5-triiodoimidazole and Its Oxidation by-Product Under Nitration Conditions. J. Energ. Mater. 2020, 40(1): 46-60; DOI: 10.1080/07370652.2020.1827313.
• [22] Lian, P.-B.; Chen, J.; Chen, L.-Z.; Zhao, C.-Y.; Wang, J.-L.; Shen, F.-F. Preparation of 1-Methyl-2,4,5-trinitroimidazole from Derivatives of 1-Methylimidazole and Its Oxidation Under Nitration Conditions. Chem. Heterocycl. Compd. 2020, 56(1): 55-59; DOI: 10.1007/s10593-020-02622-7.
• [23] Lian, P.-B.; Yuan, Y.; Chen, J.; Chen, L.-Z.; Wang, J.-L. Study of the Methylation Reaction of 2,4-Dinitroimidazole and Potassium 2,4,5-Trinitroimidazol-1-ide with Dimethyl Sulfate. Chem. Heterocycl. Compd. 2020, 56(8): 1010-1014; DOI: 10.1007/s10593-020-02767-5.
• [24] Bracuti, A.J. Crystal Structure of 4,5-Dinitroimidazole (45DNI). J. Chem. Crystallgraphy 1998, 28(5): 367-371; DOI: 10.1023/A:1022412208854.
• [25] Martin, A.; Pinkerton, A.A. Charge Density Studies Using CCD Detectors Oxalic Acid at 100 K Revisited. Acta Crystallogr. Sect. B Struct. Sci. 1998, B54(4): 471-477; DOI: 10.1107/S0108768197014596.