A Convenient Method for the Preparation of 4,10-Dinitro-2,6,8,12-tetraoxa-4,10-diazatetracyclo[5.5.0.0^5,90^3,11]dodecane via Nitration of 1,4-Diformyl-2,3,5,6-tetrahydroxypiperazine Using [Msim]NO₃

Abstract

Improvement of methods for the synthesis of high-energetic scaffolds such as 4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazaisowurtzitane or 4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazatetracyclo [5.5.0.0^5,90^3,11]dodecane (TEX) is in demand because these materials may be used as high explosives. Herein, we demonstrate that the ionic liquid 3-methyl-1-sulfonic acid imidazolium nitrate ([Msim]NO₃) is an efficient reagent for the synthesis of TEX via nitration of 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine (DFTHP) with high efficiency and short reaction time and under mild conditions.

Key words

TEX - DFTHP - [Msim]NO₃ - 1,4-diformyl-2,3,5,6-tetrahydroxypiperazine

• References and Notes

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• 17 Procedure for the Synthesis of TEX CAUTION: During the synthesis of TEX the temperature of the reaction should be slowly increased and, on workup, shock, heat, friction, and impact on the product must be avoided. A mixture of DFTHP (1 mmol, 0.2 g) and urea (1 mmol, 0.06 g) was added portionwise to a round-bottomed flask containing [Msim]NO₃ (10 mmol, 2.28 g) cooled to 0 °C under a nitrogen atmosphere. The temperature of the reaction mixture smoothly increased to 75 °C. After confirmed completion of the reaction by TLC, the reaction mixture was cooled to room temperature. Then, the reaction vessel was placed in an ice water bath (0 °C). After 10 min the product precipitated. The precipitate was washed with water, NaHCO₃ solution, MeOH, and dried under high vacuum at 40 °C to give 4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazaisowurtzitane/4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazatetracyclo [5.5.0.0⁵,⁹0³,¹¹] dodecane (TEX) as a pale yellow solid in 68% yield; mp 240 °C (dec.). IR (KBr): 3631, 3080, 3051, 1594, 1288, 902 cm^–1. ¹H NMR (300 MHz, DMSO): δ = 5.95 (s, 2 H), 6.96 (s, 4 H) ppm. ¹³C NMR (75 MHz, DMSO): δ = 82.6, 102.6 ppm. MS: m/z (%) = 263 [M + 1].
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• 19 General Procedure for the Preparation of DFTHP Triethylamine (0.25 mmol, 0.036 mL) was placed in 50 mL round-bottomed flask (pH 9). Then a mixture of glyoxal (20 mmol, 0.91 mL) and formamide (20 mmol, 0.79 mL) was added dropwise at room temperature. The progress of the reaction was followed by TLC (EtOAc–n-hexane, 4:1). After 45 min DFTHP precipitated as a white solid. The obtained crude product was washed with a mixture of EtOH and HCl, and finally DFTHP was obtained in 85% yield (Scheme 3) as white solid; mp 223 °C (dec.). IR (KBr): 3326, 3224, 1671 cm^–1. ¹H NMR (300 MHz, DMSO): δ = 4.96–4.98 (d, 2 H), 5.45 (s, 2 H), 5.90–6.02 (d, 4 H), 8.25 (s, 2 H) ppm. ¹³C NMR (75 MHz, DMSO): δ = 72.4, 72.7, 79.1, 79.5, 164.6, 164.7 ppm.