Condensed ring high-energy density compound and preparation method thereof

Abstract

The invention relates to a fused ring high-energy density compound and a preparation method thereof, and belongs to the technical field of energetic materials, a 5-6 fused ring skeleton is adopted, 3-((tetrazole-5-yl) amido)-6-(3, 5-dimethylpyrazole-1-yl)-[1, 2, 4, 5] tetrazine is used as a raw material, and a ring closing reaction, a nitration reaction, an amination reaction and an oxidation reaction are sequentially performed to prepare 3-amino-7-nitro-[1, 2, 4, 5] tetrazine. The invention relates to 1, 2, 4] triazole [1, 5-b] [1, 2, 4, 5] tetrazine-2-oxide. The room temperature single crystal density of the prepared fused ring type high-energy-density compound is 1.973 g / cm < 3 >, the initial thermal decomposition temperature reaches 212 DEG C, the actually measured impact sensitivity is 20 J, the friction sensitivity is 324 N, the calculated detonation velocity is 9584 m / s, and the calculated detonation pressure is 40.0 GPa, which indicates that the fused ring type high-energy-density compound has high theoretical energy level and high safety, and is a high-energy low-sensitivity explosive with great potential.

Description

Technical Field

[0001] The present invention relates to the technical field of energetic materials, and in particular to a polycyclic high energy density compound and a preparation method thereof, which are applicable to the requirements of high energy and low sensitivity explosives in the fields of national defense equipment, aerospace, civil blasting, etc. Background Art

[0002] Energetic materials are widely used in the fields of national defense equipment, aerospace, civil blasting, etc., and are the basic energy materials for realizing functions such as damage, blasting, work, propulsion, etc. The energy density of energetic materials directly affects their ability to realize corresponding functions, and their safety determines their safety during storage, transportation, assembly, use and other processes.

[0003] Currently widely used high energy explosives such as cyclotrimethylenetrinitramine (RDX), octogen (HMX), etc., although having high energy density, have insufficient mechanical sensitivity and thermal stability, and are prone to explosion due to accidental stimulation, resulting in potential safety hazards during storage, transportation and use. And typical high safety explosives such as 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), etc., although having excellent safety, have significantly lower energy density than high energy explosives, with low energy, and it is difficult to meet the requirements of the working environment for high power explosives.

[0004] In view of the above technical phenomena, developing new high energy density compounds with higher safety is of great significance in the fields of national defense industry, civil blasting, and aerospace. Summary of the Invention

[0005] The purpose of the present invention is to provide a polycyclic high energy density compound and a preparation method thereof, aiming to break through the contradictory limitations between energy density and safety through molecular structure innovation.

[0006] On the one hand, a polycyclic high energy density compound provided by the present invention adopts the following technical solution:

[0007] A polycyclic high energy density compound, the structural formula of the polycyclic high energy density compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide (NATTO) is:

[0008]

[0009] Preferably, the preparation process of the polycyclic high energy density compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide is as follows:

[0010]

[0011] On the other hand, a preparation method of a fused-ring high-energy density compound provided by the present invention adopts the following technical scheme:

[0012] A preparation method of a fused-ring high-energy density compound includes the following preparation steps:

[0013] S1. Synthesize the compound 3-(3,5-dimethylpyrazol-1-yl)-7-amino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine (3-DMP-TT):

[0014] Add 3-((tetrazol-5-yl)amino)-6-(3,5-dimethylpyrazol-1-yl)-[1,2,4,5]tetrazine (TADPTz) into preheated and softened polyphosphoric acid. After adding, raise the reaction temperature at a heating rate of 2-10 °C / min, stir and react for 0.5-24 h, stop heating. After the system temperature returns to room temperature, dilute with water, neutralize with alkali, extract with an organic solvent, and rotary evaporate to obtain the crude product 3-DMP-TT. The crude product 3-DMP-TT is purified, filtered, and dried to obtain the pure product 3-DMP-TT;

[0015] S2. Synthesize the compound 3-(3,5-dimethyl-4-nitropyrazol-1-yl)-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine:

[0016] In an ice-water bath, slowly add the 3-DMP-TT prepared in step S1 into concentrated sulfuric acid, and slowly add fuming nitric acid. After adding, raise the reaction temperature at a heating rate of 2-10 °C / min, stir and react for 0.5-24 h, stop heating. After the system temperature returns to room temperature, quench, filter, wash, and dry in sequence to obtain the compound 3-(3,5-dimethyl-4-nitropyrazol-1-yl)-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine;

[0017] S3. Synthesize the compound 3,7-diamino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine:

[0018] Add the compound 3-(3,5-dimethyl-4-nitropyrazol-1-yl)-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine prepared in step S2 into a solvent, add ammonia water. After adding, seal the reactor, raise the reaction temperature at a heating rate of 2-10 °C / min, stir and react for 0.5-24 h, stop heating. After the system temperature returns to room temperature, concentrate, filter, wash, and dry in sequence to obtain the compound 3,7-diamino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine;

[0019] S4. Synthesis of compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide:

[0020] In an ice-water bath, slowly add hydrogen peroxide to concentrated sulfuric acid, then slowly add an oxidizing agent, and subsequently slowly add the compound 3,7-diamino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine prepared in step S3. After adding, raise the reaction temperature to room temperature at a heating rate of 2-10 °C / min, stir the reaction for 0.5-72 h, and successively carry out quenching, filtration, washing, and drying to obtain the compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide.

[0021] Preferably, the reaction temperature in step S1 is room temperature to 200 °C;

[0022] The mass ratio of polyphosphoric acid to 3-((tetrazol-5-yl)amino)-6-(3,5-dimethylpyrazol-1-yl)-[1,2,4,5]tetrazine in step S1 is (2-20) g:1 g.

[0023] Preferably, the base for base neutralization in step S1 includes any one of inorganic bases or organic bases;

[0024] The inorganic base includes any one or more of carbonates, bicarbonates, oxides, and hydroxides of alkali metals / alkaline earth metals;

[0025] The organic base includes any one or more of ammonia water, hydrazine hydrate, hydroxylamine, guanidine, triethylamine, aminoguanidine, methylamine, dimethylamine, trimethylamine;

[0026] The organic solvent in step S1 is selected from any one or more of ethyl acetate, methyl acetate, dichloromethane, chloroform, petroleum ether;

[0027] The purification process of the crude 3-DMP-TT in step S1 includes any one of medium column chromatography or recrystallization;

[0028] The solvents used in medium column chromatography or recrystallization are selected from any one or more of water, methanol, ethanol, isopropanol, ethylene glycol, DMF, DMSO, THF, acetonitrile, dichloromethane, chloroform, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycerol, acetone, triethanolamine, pyridine, benzene, toluene, xylene, ammonia water.

[0029] Preferably, in step S2, the mass ratio of the dosages of concentrated sulfuric acid, fuming nitric acid, and 3-(3,5-dimethylpyrazol-1-yl)-7-amino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine is (0.01 - 20) mL : (0.01 - 20) mL : 1 g;

[0030] The reaction temperature in step S2 is from room temperature to 100 °C.

[0031] Preferably, in step S3, the mass ratio of the volume dosage of the solvent, the dosage of ammonia water, and 3-(3,5-dimethyl-4-nitropyrazol-1-yl)-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine is (1 - 30) mL : (0.5 - 15) mL : 1 g;

[0032] The reaction temperature in step S3 is from room temperature to 150 °C;

[0033] The reactor in step S3 is any one of a pressure-resistant bottle, a pressure-resistant autoclave, a glass bottle with a reflux condenser, and a jacketed reactor.

[0034] Preferably, the solvent in step S3 is selected from any one or more of water, methanol, ethanol, isopropanol, ethylene glycol, DMF, DMSO, THF, acetonitrile, dichloromethane, chloroform, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycerol, acetone, triethanolamine, pyridine, benzene, toluene, and xylene.

[0035] Preferably, in step S4, the mass ratio of the dosages of concentrated sulfuric acid, hydrogen peroxide, the oxidant, and 3,7-diamino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine is (2 - 50) mL : (0.1 - 70) mL : (0.1 - 20) g : 1 g.

[0036] Preferably, the concentration of hydrogen peroxide in step S4 is 1% - 98%;

[0037] The oxidant in step S4 includes any one of inorganic oxidants or organic oxidants;

[0038] The inorganic oxidants include any one or more of sodium tungstate, potassium permanganate, potassium persulfate, and potassium dichromate;

[0039] The organic oxidants include any one or more of m-chloroperoxybenzoic acid and Dess-Martin reagent.

[0040] In summary, the present invention includes the following beneficial technical effects:

[0041] The preparation of this high-energy density compound is carried out through four steps using 3-((tetrazol-5-yl)amino)-6-(3,5-dimethylpyrazol-1-yl)-[1,2,4,5]tetrazine (TADPTz) as the raw material. The room-temperature single-crystal density of 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide (NATTO, or ICM-107) is 1.973 g / cm 3 , and its initial thermal decomposition temperature reaches 212 °C. The measured impact sensitivity is 20 J, and the friction sensitivity is 324 N; the calculated detonation velocity is 9584 m / s, and the calculated detonation pressure is 40.0 GPa. This indicates that NATTO (ICM-107) not only has a relatively high theoretical energy level but also has high safety, making it a high-energy and low-sensitivity explosive with great potential. Description of the Drawings

[0042] Figure 1 is the crystal structure of the compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide (NATTO, or ICM-107).

[0043] Figure 2 is the DSC-TG diagram of the compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide (NATTO, or ICM-107).

[0044] Figure 3 is the 1H NMR spectrum of the compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide (NATTO, or ICM-107).

[0045] Figure 4 is the 13C NMR spectrum of the compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide (NATTO, or ICM-107). Detailed Description of the Invention

[0046] The following further elaborates on the present invention in conjunction with examples and Figures 1-4 drawings.

[0047] A preparation method of a fused-ring high-energy density compound includes the following preparation steps:

[0048] S1. Synthesize the compound 3-(3,5-dimethylpyrazol-1-yl)-7-amino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine (3-DMP-TT):

[0049] 3-((Tetrazol-5-yl)amino)-6-(3,5-dimethylpyrazol-1-yl)-[1,2,4,5]tetrazine (TADPTz) was added to preheated and softened polyphosphoric acid (PPA). After the addition, the reaction temperature was raised at a heating rate of 2 - 10 °C / min, and the reaction was stirred for 0.5 - 24 h. Then, the heating was stopped. After the system temperature returned to room temperature, it was diluted with water, neutralized with base, extracted with organic solvent, and rotary evaporated to obtain the crude compound 3-(3,5-dimethylpyrazol-1-yl)-7-amino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine (3-DMP-TT). The crude 3-DMP-TT was purified (by column chromatography or recrystallization), filtered, and dried to obtain the pure 3-DMP-TT;

[0050] S2. Synthesis of compound 3-(3,5-dimethyl-4-nitropyrazol-1-yl)-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine:

[0051] In an ice-water bath, the 3-DMP-TT prepared in step S1 was slowly added to concentrated sulfuric acid, and fuming nitric acid was slowly added. After the addition, the reaction temperature was raised at a heating rate of 2 - 10 °C / min, and the reaction was stirred for 0.5 - 24 h. Then, the heating was stopped. After the system temperature returned to room temperature, it was quenched, filtered, washed, and dried in sequence to obtain the compound 3-(3,5-dimethyl-4-nitropyrazol-1-yl)-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine;

[0052] S3. Synthesis of compound 3,7-diamino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine:

[0053] The compound 3-(3,5-dimethyl-4-nitropyrazol-1-yl)-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine prepared in step S2 was added to a solvent, and ammonia water was added. After the addition, the reactor was sealed, and the reaction temperature was raised at a heating rate of 2 - 10 °C / min, and the reaction was stirred for 0.5 - 24 h. Then, the heating was stopped. After the system temperature returned to room temperature, it was concentrated, filtered, washed, and dried in sequence to obtain the compound 3,7-diamino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine;

[0054] S4. Synthesis of compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide (NATTO or ICM-107):

[0055] In an ice-water bath, hydrogen peroxide was slowly added to concentrated sulfuric acid, an oxidizing agent was slowly added, and then compound 3,7-diamino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine was slowly added. After the addition, the reaction temperature was raised to room temperature at a heating rate of 2-10 °C / min, and the reaction was stirred for 0.5-72 h. After quenching, filtration, washing, and drying in sequence, compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide (NATTO or ICM-107) was obtained.

[0056] Example

[0057] A preparation method of a polycyclic high energy density compound, comprising the following preparation steps:

[0058] S1. Weigh 30 g of polyphosphoric acid (PPA) and preheat it to 100 °C, then add 2.33 g of 3-((tetrazol-5-yl)amino)-6-(3,5-dimethylpyrazol-1-yl)-[1,2,4,5]tetrazine (TADPTz) monohydrate. After the addition, the reaction temperature was raised to 160 °C at a heating rate of 5 °C / min, and the reaction was stirred for 5 h. Heating was stopped. After the temperature of the system returned to room temperature, it was diluted with 450 mL of water, neutralized with sodium bicarbonate to a pH of about 6, and then extracted with 5×150 mL of ethyl acetate. The organic phase was washed with saturated brine and dried over anhydrous sodium sulfate, and then concentrated by rotary evaporation to obtain the crude product 3-DMP-TT. The crude product 3-DMP-TT was purified (by column chromatography or recrystallization), filtered (or rotary evaporated), and dried to obtain the pure product 3-DMP-TT, with a yield of about 40%;

[0059] S2. In an ice-water bath, 0.924 g of 3-DMP-TT was slowly added to 3.2 mL of concentrated sulfuric acid, and then 0.24 mL of fuming nitric acid was slowly added. After the addition, the reaction temperature was raised to 50 °C at a heating rate of 5 °C / min, and the reaction was stirred for 5 h. Heating was stopped. After the temperature of the system returned to room temperature, it was quenched with ice water, filtered, washed, and dried in sequence to obtain compound 3-(3,5-dimethyl-4-nitropyrazol-1-yl)-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine, with a yield of about 95%;

[0060] S3. At room temperature, add 12 mL of acetonitrile into a pressure-resistant reaction flask. Subsequently, add 0.83 g of the compound 3-(3,5-dimethyl-4-nitropyrazol-1-yl)-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine prepared in step S2 into the acetonitrile, then add 1.2 mL of 25% ammonia water. After adding, seal the reactor and increase the reaction temperature to 100 °C at a heating rate of 5 °C / min, stir the reaction for 24 h, stop heating. After the system temperature returns to room temperature, successively concentrate the reaction solution, filter, wash, and dry to obtain the compound 3,7-diamino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine, with a yield of about 81%;

[0061] S4. In an ice-water bath, slowly drop 3 mL of concentrated sulfuric acid into 10 mL of 50% hydrogen peroxide while stirring. Subsequently, slowly add 1.66 g of sodium tungstate dihydrate oxidant, and then slowly add 0.152 g of the compound 3,7-diamino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine prepared in step S3. After adding, increase the reaction temperature to room temperature at a heating rate of 2 °C / min, stir the reaction for 48 h, successively quench with ice water, filter, wash, and dry to obtain the compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide (NATTO or ICM-107), with a yield of about 42%.

[0062] Refer to Figures 1-4 , the high energy density compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide (NATTO or ICM-107), the structural formula is as follows:

[0063]

[0064] It is prepared through four-step reactions of ring closure, nitration, amination, and oxidation. The preparation reaction equation is as follows:

[0065]

[0066] DSC(T onset : 212 °C, T p : 214 °C, 50 - 500 °C, 5 °C·min -1 ); 1 H NMR (400 MHz, DMSO-d6, 25 °C) δ (ppm): 9.00 (2H, NH2); 13 C NMR (100 MHz, DMSO-d6, 25 °C) δ (ppm): 158.62, 151.42, 144.15; HRMS (C3HN8O3 -):Theoretical value: 197.0177, Measured value: 197.0177.

[0067] The above are all preferred embodiments of the present invention, and do not limit the protection scope of the present invention accordingly. Therefore, all equivalent changes made according to the structure, shape and principle of the present invention shall be covered within the protection scope of the present invention.

Claims

1. A fused-ring high-energy density compound, characterized in that, The structural formula of the fused-ring high-energy density compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide (NATTO) is as follows:

2. The fused-ring high energy density compound according to claim 1, characterized in that, The preparation process of the fused-ring high-energy density compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide is as follows:

3. A method for preparing a polycyclic high-energy density compound as described in any one of claims 1 or 2, characterized in that, It includes the following preparation steps: S1. Synthesize the compound 3-(3,5-dimethylpyrazol-1-yl)-7-amino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine (3-DMP-TT): Add 3-((tetrazol-5-yl)amino)-6-(3,5-dimethylpyrazol-1-yl)-[1,2,4,5]tetrazine (TADPTz) to preheated and softened polyphosphoric acid. After adding, raise the reaction temperature at a heating rate of 2 - 10 °C / min, stir and react for 0.5 - 24 h, stop heating. After the system temperature returns to room temperature, dilute with water, neutralize with alkali, extract with an organic solvent, and rotary evaporate to obtain the crude product 3-DMP-TT. The crude product 3-DMP-TT is purified, filtered, and dried to obtain the pure product 3-DMP-TT; S2. Synthesize the compound 3-(3,5-dimethyl-4-nitropyrazol-1-yl)-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine: In an ice-water bath, slowly add the 3-DMP-TT prepared in step S1 to concentrated sulfuric acid, and slowly add fuming nitric acid. After adding, raise the reaction temperature at a heating rate of 2 - 10 °C / min, stir and react for 0.5 - 24 h, stop heating. After the system temperature returns to room temperature, quench, filter, wash, and dry in sequence to obtain the compound 3-(3,5-dimethyl-4-nitropyrazol-1-yl)-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine; S3. Synthesize the compound 3,7-diamino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine: Add the compound 3-(3,5-dimethyl-4-nitropyrazol-1-yl)-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine prepared in step S2 to a solvent, add ammonia water. After adding, seal the reactor, raise the reaction temperature at a heating rate of 2 - 10 °C / min, stir and react for 0.5 - 24 h, stop heating. After the system temperature returns to room temperature, concentrate, filter, wash, and dry in sequence to obtain the compound 3,7-diamino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine; S4. Synthesize the compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide: In an ice-water bath, slowly add hydrogen peroxide to concentrated sulfuric acid, then slowly add an oxidizing agent, and subsequently slowly add the compound 3,7-diamino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine prepared in step S3. After adding, raise the reaction temperature to room temperature at a heating rate of 2 - 10 °C / min, stir and react for 0.5 - 72 h, and successively carry out quenching, filtration, washing, and drying to obtain the compound 3-amino-7-nitro-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine-2-oxide.

4. The preparation method of the fused-ring high energy density compound according to claim 3, characterized in that, The reaction temperature in step S1 is from room temperature to 200 °C; In step S1, the mass ratio of polyphosphoric acid to 3-((tetrazol-5-yl)amino)-6-(3,5-dimethylpyrazol-1-yl)-[1,2,4,5]tetrazine in the feed is (2 - 20) g:1 g.

5. The preparation method of the fused-ring high-energy density compound according to claim 3, wherein The base for base neutralization in step S1 includes any one of inorganic bases or organic bases; The inorganic base includes any one or more of carbonates, bicarbonates, oxides, and hydroxides of alkali metals / alkaline earth metals; The organic base includes any one or more of ammonia water, hydrazine hydrate, hydroxylamine, guanidine, triethylamine, aminoguanidine, methylamine, dimethylamine, trimethylamine; The organic solvent in step S1 is selected from any one or more of ethyl acetate, methyl acetate, dichloromethane, chloroform, petroleum ether; The purification process of the crude 3-DMP-TT in step S1 includes any one of medium column chromatography or recrystallization; The solvents used in medium column chromatography or recrystallization are selected from any one or more of water, methanol, ethanol, isopropanol, ethylene glycol, DMF, DMSO, THF, acetonitrile, dichloromethane, chloroform, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycerol, acetone, triethanolamine, pyridine, benzene, toluene, xylene, ammonia water.

6. The preparation method of the fused-ring high energy density compound according to claim 3, characterized in that, In step S2, the mass ratio of the dosage of concentrated sulfuric acid, fuming nitric acid to the feed of the compound 3-(3,5-dimethylpyrazol-1-yl)-7-amino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine is (0.01 - 20) mL:(0.01 - 20) mL:1 g; The reaction temperature in step S2 is from room temperature to 100 °C.

7. The preparation method of the fused-ring high-energy density compound according to claim 3, wherein In step S3, the volume ratio of the solvent dosage, ammonia water dosage to the feed of the compound 3-(3,5-dimethyl-4-nitropyrazol-1-yl)-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine is (1 - 30) mL:(0.5 - 15) mL:1 g; The reaction temperature in step S3 is from room temperature to 150 °C; The reactor in step S3 is any one of a pressure-resistant bottle, a pressure-resistant autoclave, or a glass bottle with a reflux condenser, a jacketed reactor.

8. The preparation method of the fused-ring high-energy density compound according to claim 3, characterized in that, The solvent in step S3 is selected from any one or more of water, methanol, ethanol, isopropanol, ethylene glycol, DMF, DMSO, THF, acetonitrile, dichloromethane, chloroform, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycerol, acetone, triethanolamine, pyridine, benzene, toluene, xylene.

9. The preparation method of the fused-ring high energy density compound according to claim 3, characterized in that, In the step S4, the mass ratio of the amounts of concentrated sulfuric acid, hydrogen peroxide, oxidant, and compound 3,7-diamino-[1,2,4]triazolo[1,5-b][1,2,4,5]tetrazine is (2 - 50) mL : (0.1 - 70) mL : (0.1 - 20) g : 1 g.

10. The preparation method of the fused-ring high-energy density compound according to claim 3, characterized in that, In the step S4, the concentration of hydrogen peroxide is 1% - 98%; The oxidant in the step S4 includes any one of inorganic oxidants or organic oxidants; The inorganic oxidants include any one or more of sodium tungstate, potassium permanganate, potassium persulfate, and potassium dichromate; The organic oxidants include any one or more of m-chloroperoxybenzoic acid and Dess-Martin reagent.

Images