Facile synthesis of 4-amino-3,5-dinitropyrazolated energetic derivatives via 4-bromopyrazole and their performances

Wu, Bo; Yang, Liu; Zhai, Diandian; Ma, Congming; Pei, Chonghua

doi:10.1016/j.fpc.2021.03.002

Cited by 9 publications

(5 citation statements)

References 32 publications

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“…Nitrogen-rich heterocyclic amines 1-methyl-4-amino-3,5-dinitropyrazole and 1-ethyl-4-amino-3,5-dinitropyrazole were synthesized according to previous work. 40 2.2. Characterization.…”

Section: Methodsmentioning

confidence: 99%

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Continuous-Flow Oxidation of Amines Based on Nitrogen-Rich Heterocycles: A Facile and Sustainable Approach for Promising Nitro Derivatives

Jiang

Yang

et al. 2022

Org. Process Res. Dev.

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The oxidation of amines based on nitrogen-rich heterocycles is one of the appealing alternatives for promising nitro derivatives. Herein, we present a continuous-flow process to achieve oxidation of these amines to their nitro derivatives, taking advantage of hydrogen peroxide as an environmentally benign and inexpensive oxidant. Facile and sustainable access to valuable nitro compounds was ensured. The utility of the present continuous-flow oxidation process was demonstrated by synthesizing promising energetic compounds 5-amino-3-nitro-1,2,4-triazole (ANTA) and 1-methyl-3,4,5-trinitropyrazole (MTNP) on a multigram scale.

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“…Nitrogen-rich heterocyclic amines 1-methyl-4-amino-3,5-dinitropyrazole and 1-ethyl-4-amino-3,5-dinitropyrazole were synthesized according to previous work. 40 2.2. Characterization.…”

Section: Methodsmentioning

confidence: 99%

“…All commercially available chemicals were purchased and used without further purification. Nitrogen-rich heterocyclic amines 1-methyl-4-amino-3,5-dinitropyrazole and 1-ethyl-4-amino-3,5-dinitropyrazole were synthesized according to previous work …”

Section: Methodsmentioning

confidence: 99%

Continuous-Flow Oxidation of Amines Based on Nitrogen-Rich Heterocycles: A Facile and Sustainable Approach for Promising Nitro Derivatives

Jiang

Yang

et al. 2022

Org. Process Res. Dev.

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“…Its symmetrical "butterfly" structure has also attracted extensive attention from researchers. Using 2,2-bis(tert-butyl-NNOazoxy)acetonitrile (17) as the raw material, TTTO was synthetized by Klenov et al [33] based on a 10-step synthetic strategy with a total yield of 1.1%(Scheme 4). The synthesis process was too complex and the yield was too low, and chromatographic separation was required for purifying key intermediates.…”

Section: Energetic Heterocyclic N-oxides Via Different Cyclization Re...mentioning

confidence: 99%

“…Since the advent of conventional energetic materials such as trinitrotoluene (TNT), RDX, and HMX, researchers worldwide have been extensively exploring energetic materials with chain, ring, and cage parent nucleus structures composed of C, H, and N as the main elements as well as new energetic parent frameworks such as tetrazine, triazole, and furazan [1][2][3][4][5][6][7][8][9][10][11]. Meanwhile, they strive to improve the performance of the compounds by introducing energetic groups, including nitroamino groups, trinitroethyl groups, fluoroacyl dinitroethyl groups, and azide groups [12][13][14][15][16][17]. As a typical energetic group for improving the detonation performance of compounds, the nitro group (-NO 2 ) could not only increase the energy density of CHONbased compounds but also enhance the oxygen balance of the energetic compounds, which is conducive to energy release.…”

Section: Introductionmentioning

confidence: 99%

Synthetic Methods towards Energetic Heterocyclic N-Oxides via Several Cyclization Reactions

She

Zhai³

et al. 2022

Crystals

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Due to the introduction of oxygen atoms, N-oxide energetic compounds have a unique oxygen balance, excellent detonation properties, and a high energy density, attracting the extensive attention of researchers all over the world. N-oxides are classified into two categories based on the structural characteristics of their skeletons: azine N-oxides and azole N-oxides, whose N→O coordination bonds are formed during cyclization. There are six kinds of azine N-oxides, namely 1,2,3,4-tetrazine-1,3-dioxide, 1,2,3,5-tetrazine-2-oxide, 1,2,3-triazine-3-oxide, 1,2,3-triazine-2-oxide, pyridazine-1,2-dioxide, and pyrazine-1-oxide. Azole N-oxides include 1,2,5-oxadiazole-2-oxide, pyrazole-1-oxide, and triazole-1-oxide. Synthetic strategies towards these two categories of N-oxides are fully reviewed. Corresponding reaction mechanisms towards the aromatic N-oxide frameworks and examples that use the frameworks to create high-energy substances are discussed. Moreover, the energetic properties of N-oxide energetic compounds are compared and summarized.

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“…However, thus far, the applications of Hofmann reactions in the synthesis of energetic materials have rarely been reported, especially in the construction of new framework structures. Nitropyrazoles are significant for the design and synthesis of energetic materials [ 8 , 9 ]. During the past few decades, our research interest was mainly focused on the structural diversity of fused-heterocyclic frameworks in energetic materials, among which, the pyrazolo [4,3-c]pyrazole structure was a successfully applied framework in the construction of 1 H ,4 H -3,6-dinitropyrazolo [4,3- c ]pyrazole (DNPP), as well as its insensitive derivative [ 10 , 11 , 12 , 13 ], 1,4-diamino-3,6-dinitropyrazolo[4,3-c]pyrazole (LLM-119) [ 14 ], which contains both amino and nitro groups.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Energetic 7-Nitro-3,5-dihydro-4H-pyrazolo[4,3-d][1,2,3]triazin-4-one Based on a Novel Hofmann-Type Rearrangement

Bi¹,

Luo²,

Zhang

et al. 2021

Molecules

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Rearrangement reactions are efficient strategies in organic synthesis and contribute enormously to the development of energetic materials. Here, we report on the preparation of a fused energetic structure of 7-nitro-3,5-dihydro-4H-pyrazolo[4,3-d][1,2,3]triazin-4-one (NPTO) based on a novel Hofmann-type rearrangement. The 1,2,3-triazine unit was introduced into the fused bicyclic skeleton from a pyrazole unit for the first time. The new compound of NPTO was fully characterized using multinuclear NMR and IR spectroscopy, elemental analysis as well as X-ray diffraction studies. The thermal behaviors and detonation properties of NPTO were investigated through a differential scanning calorimetry (DSC-TG) approach and EXPLO5 program-based calculations, respectively. The calculation results showed similar detonation performances between NPTO and the energetic materials of DNPP and ANPP, indicating that NPTO has a good application perspective in insensitive explosives and propellants.

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Facile synthesis of 4-amino-3,5-dinitropyrazolated energetic derivatives via 4-bromopyrazole and their performances

Cited by 9 publications

References 32 publications

Continuous-Flow Oxidation of Amines Based on Nitrogen-Rich Heterocycles: A Facile and Sustainable Approach for Promising Nitro Derivatives

Continuous-Flow Oxidation of Amines Based on Nitrogen-Rich Heterocycles: A Facile and Sustainable Approach for Promising Nitro Derivatives

Synthetic Methods towards Energetic Heterocyclic N-Oxides via Several Cyclization Reactions

Synthesis of Energetic 7-Nitro-3,5-dihydro-4H-pyrazolo[4,3-d][1,2,3]triazin-4-one Based on a Novel Hofmann-Type Rearrangement

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