Modification of an N-Methyl Group toward a New Energetic Melt-Castable Material with a Good Energy-Stability Balance

Fang Chen; Siwei Song; Qinghua Zhang; Yi Wang

doi:10.1055/a-2256-2800

Synlett, Table of Contents

Synlett 2024; 35(17): 2015-2021
DOI: 10.1055/a-2256-2800

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Energetic Molecules

Modification of an N-Methyl Group toward a New Energetic Melt-Castable Material with a Good Energy-Stability Balance

Fang Chen

^aInstitute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900, P. R. of China

,

Siwei Song

^bSchool of Astronautics, Northwestern Polytechnical University, Xi’an, 710072, P. R. of China

,

Qinghua Zhang∗

^aInstitute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900, P. R. of China

^bSchool of Astronautics, Northwestern Polytechnical University, Xi’an, 710072, P. R. of China

,

Yi Wang∗

^aInstitute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900, P. R. of China

^bSchool of Astronautics, Northwestern Polytechnical University, Xi’an, 710072, P. R. of China

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Abstract

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Abstract

The energy and stability properties of energetic materials are often contradictory to each other (e.g., high energy vs low thermal stability). There is no doubt that it is still challenging to explore the effective balance between energetic performance and molecular stability, especially for melt-castable materials. In this study, we selected the 4-methoxy-3,5-dinitropyrazole framework and a stable nitro group to design a new energetic melt-castable compound, namely 4-methoxy-3,5-dinitro-1-(nitromethyl)-1H-pyrazole (MDNNMP). Compared with the N-methylation product DMDNP and the nitrato-substituted derivative MC-7, MDNNMP exhibits a better balanced performance, including good thermal stability (T_d : 203.7 °C), detonation velocity (D_v : 8099 m s^–1) and impact sensitivity (20 J). The favorable balanced performance of MDNNMP suggests that it is a suitable candidate as a high-performance melt-castable material. Additionally, compared with the nitratomethyl group, the nitromethyl group demonstrates superior advantages in performance regulation.

Key words

energetic material - melt-castable material - balanced properties - energy - stability

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References and Notes

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13 4-Methoxy-3,5-dinitro-1-(nitromethyl)-1H-pyrazole (MDNNMP) Compound 1 (0.5 g, 2.66 mmol) in DMF (5 mL) was treated with ammonium hydroxide (0.3 g, 8.57 mmol) and stirred for 1 h at ambient temperature. A mixture of the resulting ammonium 4-methoxy-3,5-dinitropyrazolate (0.5 g, 2.44 mmol) in DMF (5 mL) was treated with bromonitromethane (0.5 g, 3.66 mmol) and the resulting mixture was stirred at 50 °C for 3 h. After the reaction was complete, the mixture was poured into water and extracted with ethyl acetate. The combined organic layer was dried, filtered and purified by column chromatography (petroleum ether/ethyl acetate, 9:1) to yield the target product (0.18 g, 30%) as a white solid. ¹H NMR (400 MHz, DMSO-d ₆): δ = 7.15 (s, 2 H, CH₂), 4.09 (s, 3 H, CH₃). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 147.11, 138.04, 136.14, 83.75, 64.24. HRMS (ESI): m/z [M – H]^– calcd for C₅H₄N₅O₇: 246.0111; found: 246.0117. Anal. Calcd for C₅H₅N₅O₇: C, 24.30; H, 2.04; N, 28.34. Found: C, 24.31; H, 2.06; N, 28.32.

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