Trimerization of 4‐Amino‐3,5‐dinitropyrazole: Formation, Preparation, and Characterization of 4‐Diazo‐3,5‐bis(4‐amino‐3,5‐dinitropyrazol‐1‐yl) pyrazole (LLM‐226)

Zhang, Maoxi; Pagoria, Philip F.; Imler, Gregory H.; Parrish, Damon A.

doi:10.1002/jhet.3434

Cited by 10 publications

(8 citation statements)

References 24 publications

(41 reference statements)

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“…The samples of LLM-116 and LLM-226 were supplied by Xi'an Modern Chemistry Research Institute. The compounds were synthesized through reported procedures [17,35] (Scheme 1) All the samples were characterized by 1 H NMR, 13 C NMR, FTIR and elemental analysis. The thermal analysis experiments were performed with a model TGDSC STA 449C instrument (NETZSCH, Germany).…”

Section: Methodsmentioning

confidence: 99%

“…With a highly acidic aromatic N-H bond, 4-amino-3,5-dinitropyrazole [13,14] (LLM-116) has been successfully applied as an active nucleophile in the design and synthesis of other heterocycle-based energetic materials [15,16]. 4-Diazo-3,5-bis(4-amino-3,5-dinitropyrazol-1-yl)pyrazole (LLM-226) is a novel trimer structure of LLM-116 which was recently beautifully prepared through a selfcoupling reaction [17]. (Figure 1) Compared with LLM-116, the trimerization retains the pyrazole backbones but removes the active H from their aromatic N-H moieties.…”

Section: Introductionmentioning

confidence: 99%

“…(Figure 1) Compared with LLM-116, the trimerization retains the pyrazole backbones but removes the active H from their aromatic N-H moieties. Due to the abundant nitro and amino groups, both LLM-116 and LLM-226 are promising candidates for insensitive high explosives, with their energetic properties as follows [17]: density of 1.90 and 1.83 g•cm −3 ; Dh 50 (2.5 kg weight) of 177 and 31cm; friction sensitivity (BAM) of 0/10 @ 36kg and 1/10 @ 32.4kg; Spark Sensitivity (J @ 0 Ohms) of 0.038 and 0.014; detonation velocity (calculated) of 8497 and 8220 m/s; detonation pressure (calculated) of 31.89 and 28.0 Gpa; enthalpy of formation (calculated) of 221.1 and 686.63 kJ/mol. Meanwhile, the novel structures and self-coupling manner make these dinitropyrazole derivatives ideal for comparative thermal studies to clarify how the heterocyclic units and coupling manners will affect corresponding thermal properties.…”

Section: Introductionmentioning

confidence: 99%

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Comparative Studies on Thermal Decompositions of Dinitropyrazole-Based Energetic Materials

Zhou

Zhang²,

Huo³

et al. 2021

Molecules

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Dinitropyrazole is an important structure for the design and synthesis of energetic materials. In this work, we reported the first comparative thermal studies of two representative dinitropyrazole-based energetic materials, 4-amino-3,5-dinitropyrazole (LLM-116) and its novel trimer derivative (LLM-226). Both the experimental and theoretical results proved the active aromatic N-H moiety would cause incredible variations in the physicochemical characteristics of the obtained energetic materials. Thermal behaviors and kinetic studies of the two related dinitropyrazole-based energetic structures showed that impressive thermal stabilization could be achieved after the trimerization, but also would result in a less concentrated heat-release process. Detailed analysis of condensed-phase systems and the gaseous products during the thermal decomposition processes, and simulation studies based on ReaxFF force field, indicated that the ring opening of LLM-116 was triggered by hydrogen transfer of the active aromatic N-H moiety. In contrast, the initial decomposition of LLM-226 was caused by the rupture of carbon-nitrogen bonds at the diazo moiety.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Comparative Studies on Thermal Decompositions of Dinitropyrazole-Based Energetic Materials

Zhou

Zhang²,

Huo³

et al. 2021

Molecules

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“…Ring-bridge is an important connector linking bis(nitropyrazoles) to obtain high performance energetic materials. Pagoria et al [125] reported the trimerization of LLM-116. 4-Diazo-3,5-bis(4-amino-3,5-dinitropyrazol-1-yl) pyrazole (93) containing a stable diazo group was synthesized, and the detailed route is shown in Figure 32.…”

Section: Ring-bridged Bis(nitropyrazoles)mentioning

confidence: 99%

Recent Advances in Synthesis and Properties of Nitrated-Pyrazoles Based Energetic Compounds

et al. 2020

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Nitrated-pyrazole-based energetic compounds have attracted wide publicity in the field of energetic materials (EMs) due to their high heat of formation, high density, tailored thermal stability, and detonation performance. Many nitrated-pyrazole-based energetic compounds have been developed to meet the increasing demands of high power, low sensitivity, and eco-friendly environment, and they have good applications in explosives, propellants, and pyrotechnics. Continuous and growing efforts have been committed to promote the rapid development of nitrated-pyrazole-based EMs in the last decade, especially through large amounts of Chinese research. Some of the ultimate aims of nitrated-pyrazole-based materials are to develop potential candidates of castable explosives, explore novel insensitive high energy materials, search for low cost synthesis strategies, high efficiency, and green environmental protection, and further widen the applications of EMs. This review article aims to present the recent processes in the synthesis and physical and explosive performances of the nitrated-pyrazole-based Ems, including monopyrazoles with nitro, bispyrazoles with nitro, nitropyrazolo[4,3-c]pyrazoles, and their derivatives, and to comb the development trend of these compounds. This review intends to prompt fresh concepts for designing prominent high-performance nitropyrazole-based EMs.

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“…Already in 2014, it was employed in a pilot scale study by Ek and Latypov and prepared in 200 g batches [7] . Due to its favorable properties, ADNP has been increasingly used for the synthesis of new energetic materials since 2011 [9–11] . Herein, we report an significantly improved synthesis of BMHMO, rendering it an even more attractive starting material for the synthesis of energetic oxetane monomers.…”

Section: Introductionmentioning

confidence: 99%

Oxetane Monomers Based On the Powerful Explosive LLM‐116: Improved Performance, Insensitivity, and Thermostability

et al. 2022

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3‐Bromomethyl‐3‐hydroxymethyloxetane represents an inexpensive and versatile precursor for the synthesis of 3,3‐disubstituted oxetane derivatives. In the present work, its synthesis was improved and energetic oxetanes based on the explosive LLM‐116 (4‐amino‐3,5‐dinitro‐1H‐pyrazole) prepared. Reaching detonation velocities and pressures of up to 7335 ms−1 and 20.9 GPa in combination with a high thermostability and insensitivity, these surpass the prior art by far. Next to a symmetric LLM‐116 derivative, three asymmetric compounds were prepared using azido‐, nitrato‐ and tetrazolyl‐moieties. All compounds were intensively characterized by vibrational‐, mass‐ and multinuclear (1H, 13C, 14N) NMR spectroscopy, differential scanning calorimetry and elemental analysis. The molecular structures were elucidated by single crystal X‐ray diffraction. Hirshfeld analysis allowed to estimate their sensitivity next to a practical evaluation using BAM standard procedures. Their performance was calculated using the EXPLO5 V6.04 code and a small‐scale shock reactivity test and initiation test demonstrated their insensitivity and performance.

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Trimerization of 4‐Amino‐3,5‐dinitropyrazole: Formation, Preparation, and Characterization of 4‐Diazo‐3,5‐bis(4‐amino‐3,5‐dinitropyrazol‐1‐yl) pyrazole (LLM‐226)

Cited by 10 publications

References 24 publications

Comparative Studies on Thermal Decompositions of Dinitropyrazole-Based Energetic Materials

Comparative Studies on Thermal Decompositions of Dinitropyrazole-Based Energetic Materials

Recent Advances in Synthesis and Properties of Nitrated-Pyrazoles Based Energetic Compounds

Oxetane Monomers Based On the Powerful Explosive LLM‐116: Improved Performance, Insensitivity, and Thermostability

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