Nucleophilic Reactions of The Bis Ammonium Salt of 4,4′,5,5′-Tetranitro-2,2′-biimidazole

Abstract

The reactivity of the bis ammonium salt of 4,4′,5,5′-tetranitro-1,1′-biimidazole toward nucleophilic addition to the electrophiles dimethylsulfate and mesitylene-O-sulfonyl hydroxylamine has been studied. We have found that the tetranitrobiimidazolate bis anion has sufficient nucleophilicity to react with these electrophiles to form new products, 1,1′-dimethyl-4,4′,5,5′-tetranitro-2,2′-biimidazole (DMTNBI), 1,1′-diamino-4,4′,5,5′-tetranitro-2,2′-biimidazole, and ammonium 1-amino-4,4′,5,5′-tetranitro-2,2′-biimidazolate. These materials were characterized chemically and with respect to their thermal stability.

Key words

biimidazoles - heterocycles - N-amination - explosives - nitro compounds

• References

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• 13 Synthesis of Compounds 4 and 5: Mesitylene O-sulfonyl hydroxylamine (MSH; 0.43 g, 2 mmol) was added to a solution of bisammonium 4,4′,5,5′-tetranitro-2,2′-bi-1H-imidazolate, (0.348 g, 5.75 mmol) in DMF (5 mL) and stirred at 25 °C for 18 h without stirring. The reaction mixture was poured into H₂O (20 mL). The mixture was extracted with CHCl₃ (2 × 10 mL). The organics were dried with MgSO₄, and concentrated. The residue was purified by column chromatography (EtOAc) to provide compound 5; yield: 0.137 g (40%); mp 206 °C (dec.). IR (KBr): 3362, 3260, 1559, 1533, 1502, 1389, 1362, 1327, 1145, 1046, 851, 816, 760, 748, 708, 641 cm^–1. ¹H NMR (300 MHz, CD₃CN): δ = 7.1. ¹³C NMR (100 MHz, DMSO-d ₆): δ = 136.07, 138.70, 141.85. Anal. Calcd for C₆H₄O₈N₁₀: C, 20.94; H, 1.17; N, 40.70. Found: C, 20.92; H, 1.16; N, 40.71. The aqueous solution was allowed to stand for 3 d and compound 4 was crystallized from solution; yield: 0.104 g (30%); mp 233 °C (dec.). IR (KBr): δ = 3337, 3297, 2935, 2816, 1536, 1513, 1464, 1437, 1402, 1365, 1313, 1265, 1174, 1111, 1001, 935, 855, 818, 809, 772, 764, 722, 694 cm^–1. ¹H NMR (300 MHz, DMF-d ₇): δ = 7.2 (br s, 2 H), 7.69 (t, J = 12.9 Hz, 4 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 132.30, 135.85, 136.63, 137.98, 139.48, 141.10. Anal. Calcd for C₆H₄O₈N₁₀: C, 20.82; H, 1.75; N, 40.46. Found: C, 20.90; H, 1.77; N, 40.47.
• 14 CCDC 908704 and CCDC 908705 contain the supplementary crystallographic data for 2 and 4. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.