CN-122010908-A - Novel imino bridged pyrazole triazole energetic compound and preparation method thereof

CN122010908ACN 122010908 ACN122010908 ACN 122010908ACN-122010908-A

Abstract

The invention discloses an imino bridged pyrazole triazole novel energetic compound which is (5-nitro-N- (5-nitro-1H-pyrazol-4-yl) -1H-1,2, 4-triazole-3-amine) and (N- (3, 5-dinitro-1H-pyrazol-4-yl) -5-nitro-1H-1, 2, 4-triazole-3-amine). The invention also discloses a preparation method of the novel imino bridged pyrazole triazole energetic compound. The invention utilizes imino groups to build a basic framework after bridging, and carries out energetic derivatization on the basic framework to obtain the novel imino bridged energetic compound. The compound prepared by the invention has novel structure and excellent comprehensive performance, and has great application potential in the field of high-energy insensitive explosive.

Inventors

LIAO SICHENG
LIU TIANLIN
Chen Shiluo
ZHOU ZHIYU

Assignees

中国工程物理研究院化工材料研究所

Dates

Publication Date: 20260512
Application Date: 20260108

Claims (4)

1. The novel imino bridged pyrazole triazole energetic compound is characterized by having the following structural formula 1 or 2: 。
2. a preparation method of an imino bridged pyrazole triazole novel energetic compound, which is characterized by comprising the following reaction formula: 。
3. The process for the preparation of an imino bridged pyrazole triazole novel energetic compound according to claim 2, characterized in that it comprises: Step one, synthesis of intermediate 1 Dispersing 4-aminopyrazole and N-cyano dimethyl dithioimine carbonate in a solvent in turn at room temperature, fully stirring, adding a small amount of organic base, continuously reacting for 8 hours at room temperature, filtering and collecting solid after the reaction is finished, washing the solid with the solvent for a plurality of times, and drying to obtain an intermediate 1; Step two, synthesis of intermediate 2 Dispersing the intermediate 1 in absolute ethyl alcohol under ice bath, slowly adding hydrazine hydrate into the solution while stirring, slowly heating and refluxing the mixed solution for reaction after the dripping is finished, and filtering and collecting solids after the system is cooled to room temperature after the reaction is finished to obtain an intermediate 2; Step three, synthesis of Compound 1 Dispersing the intermediate 2 into concentrated nitric acid in ice bath, adding a small amount of water for continuous stirring after full stirring, then slowly dripping sodium nitrite solution into a reaction mixed solution for continuous reaction in ice bath after dripping, dripping the reaction solution into excessive sodium nitrite solution dropwise after ice bath reaction is finished for continuous reaction, filtering after the reaction is finished, extracting filtrate with ethyl acetate for a plurality of times, and drying after rotary evaporation to remove solvent to obtain a compound 1, namely (5-nitro-N- (5-nitro-1H-pyrazol-4-yl) -1H-1,2, 4-triazole-3-amine); step four, synthesis of compound 2 Slowly dissolving the compound 1 in concentrated sulfuric acid, cooling in an ice bath, then slowly dropwise adding fuming nitric acid into the solution, continuing the ice bath reaction after the dropwise adding is completed, pouring the reaction solution into ice water after the reaction is completed, extracting with ethyl acetate for a plurality of times, removing the solvent by rotary evaporation, and drying to obtain the compound 2, namely (N- (3, 5-dinitro-1H-pyrazol-4-yl) -5-nitro-1H-1, 2, 4-triazole-3-amine).
4. A process for the preparation of the novel energy containing iminobridged pyrazolyl triazole compound according to claim 3, characterized by comprising: In the first step, the solvent is absolute ethanol or methanol, and the organic base is triethylamine, pyridine or piperidine.

Description

Novel imino bridged pyrazole triazole energetic compound and preparation method thereof Technical Field The invention relates to a bridged energetic compound and a preparation method thereof, in particular to an imino bridged pyrazole triazole novel energetic compound and a preparation method thereof, and belongs to the technical field of energetic material preparation. Background The triazole skeleton consists of two carbon atoms and three nitrogen atoms, compared with tetrazole with more nitrogen content, the triazole is more stable and has more modifiable sites, more energy-containing groups can be introduced, and compared with pyrazole with more carbon content, the triazole skeleton has better energy performance due to higher nitrogen content. Therefore, the triazole skeleton can well balance energy and sensitivity, and is a preferable skeleton for constructing novel low-sensitivity high-energy explosive molecules. The pyrazole nitrogen heterocycle is a five-membered heterocycle composed of two nitrogen atoms and three carbon atoms, the ring is provided with more modifiable sites, two reactive sites can be provided for energetic modification after the interlinkage skeleton is constructed, and the pyrazole compound generally has better detonation performance and thermal stability, and is a structural unit with the potential of constructing low-sense high-energy explosive. After the imino group is introduced, molecules are connected with each other through hydrogen bonds taking the imino group as a core, so that a rich three-dimensional hydrogen bond network is formed. The existence of abundant hydrogen bond acting force improves the stacking efficiency of compound crystals, improves the density, and further improves the final energy performance. Meanwhile, the strong hydrogen bond network can also relieve external stimulus through interaction of hydrogen bonds, so that sensitivity is reduced. The advantages of the three are combined, the imine is selected as a bridging structure, the triazole and the pyrazole are used as structural units to construct a novel energetic framework, and the novel energetic framework is derived on the basis to obtain the imine bridging explosive molecule, so that the method is an effective method for constructing the low-sensitivity high-energy explosive. Disclosure of Invention The invention aims to provide novel imino bridged pyrazole triazole energetic compounds. The invention is realized in the following way: Novel imino bridged pyrazole triazole energetic compound has the following structural formula: 。 The invention also aims to provide a preparation method of the novel imino bridged pyrazole triazole energetic compound, which has the following reaction formula: 。 specifically, the preparation method of the novel imino bridged pyrazole triazole energetic compound provided by the invention comprises the following steps: Step one, synthesis of intermediate 1 Dispersing 4-aminopyrazole and N-cyano dimethyl dithioimine carbonate in a solvent in turn at room temperature, fully stirring, adding a small amount of organic base, continuously reacting for 8 hours at room temperature, filtering, collecting solid after the reaction is finished, washing for a plurality of times by the solvent, and drying to obtain the intermediate 1. The reaction in the first step is carried out in ethanol, methanol or other solvents can be used, triethylamine can be used for the reaction, and other organic bases such as pyridine, piperidine and the like can be selected. Step two, synthesis of intermediate 2 Dispersing the intermediate 1 in absolute ethyl alcohol in ice bath, slowly adding hydrazine hydrate into the solution while stirring, slowly heating and refluxing the mixed solution after dripping, cooling the system to room temperature after the reaction is completed, and filtering and collecting solids to obtain the intermediate 2 Step three, synthesis of Compound 1 Dispersing the intermediate 2 into concentrated nitric acid in ice bath, adding a small amount of water for continuous stirring after fully stirring, slowly dripping sodium nitrite solution into the reaction mixed solution, and continuously reacting in ice bath after dripping. After the ice bath reaction is finished, dropwise adding the reaction solution into excessive sodium nitrite solution for continuous reaction, filtering after the reaction is finished, extracting filtrate with ethyl acetate for several times, removing solvent by rotary evaporation, and drying to obtain the compound 1, namely (5-nitro-N- (5-nitro-1H-pyrazol-4-yl) -1H-1,2, 4-triazole-3-amine). Step four, synthesis of compound 2 Compound 1 was slowly dissolved in concentrated sulfuric acid and cooled in an ice bath. And slowly dropwise adding fuming nitric acid into the solution, continuing ice bath reaction after dropwise adding, pouring the reaction solution into ice water after the reaction is finished, extracting with ethyl acetate for a plurality of times,