Carbon-nitrogen bond biazole energetic compound with polynitro modification or its usable salt and preparation method thereof

Abstract

The present invention discloses a polynitro-modified carbon-nitrogen biazole energetic compound or its usable salt. By introducing a C-N bond into the biazole ring energetic skeleton, a series of polynitro-modified carbon-nitrogen biazole energetic compounds and their usable salts are obtained. More C-N bonds and modifiable sites are provided, and the number of acidic hydrogens can be reduced, thereby enriching the types of energetic compounds and improving the detonation performance and mechanical sensitivity of the energetic molecules.

Description

Technical Field

[0001] The present invention relates to the technical field of energetic materials, and in particular to a method for preparing a polynitro-modified carbon-nitrogen bond biazole energetic compound or an available salt thereof. Background Art

[0002] Nitrogen-rich azole compounds are a class of polynitrogen-rich five-membered heterocyclic compounds with advantages such as high density, high positive formation enthalpy, good stability, and relatively green decomposition products. They have attracted much attention in the field of energetic materials. Monocyclic azole energetic skeletons are limited in variety and have a small number of modifiable sites. Many researchers are focusing on developing new linked cyclic energetic skeletons. Linked cyclic skeletons not only increase the variety of compounds, formation enthalpy, and modifiable sites, but also increase the directionality of the compounds, reduce steric hindrance, and facilitate planar stacking of the crystal structure. Compared to C-C bonded biazole energetic compounds, C-N bonded biazole energetic compounds can provide more C-N bonds and modifiable sites and reduce the number of acidic hydrogens.

[0003] Therefore, the development of new CN-linked bisazole energetic skeletons is of great significance for enriching the types of energetic compounds and regulating the properties of energetic compounds. Summary of the Invention

[0004] An object of the present invention is to solve at least the above problems and / or disadvantages and to provide at least the advantages which will be described hereinafter.

[0005] Another object of the present invention is to provide a polynitro-modified carbon-nitrogen bonded biazole energetic compound or its usable salt, which provides more CN bonds and modifiable sites and can reduce the number of acidic hydrogens, thereby enriching the types of energetic compounds and improving the detonation performance and mechanical sensitivity of the energetic molecules.

[0006] Yet another object of the present invention is to provide a method for preparing a polynitro-modified carbon-nitrogen-bonded biazole energetic compound or its usable salt. Starting from known available raw materials, the method achieves the synthesis of novel CN-bonded biazole energetic compounds and their usable salts through a multi-step reaction, thereby enriching the types of energetic compounds and having great significance for regulating the properties of energetic compounds.

[0007] In order to achieve these purposes and other advantages according to the present invention, there is provided a carbon-nitrogen bond biazole energetic compound having a polynitro modification or a salt thereof, wherein the energetic compound has the structure of the following formula (I):

[0008]

[0009] Wherein, R is monosubstituted or polysubstituted NH2, NO2, X is C or N, Y is C or N, Z is C or N, and W is N or C-NO2.

[0010] Preferably, the polynitro-modified carbon-nitrogen bond biazole energetic compound or its usable salt has a structure of the following formula (II) or (III) or (IV) or (V) or (VI):

[0011]

[0012]

[0013] Preferably, the polynitro-modified carbon-nitrogen bond biazole energetic compound or its usable salt has the following structure:

[0014]

[0015] Wherein, W is N or C-NO2.

[0016] Preferably, the polynitro-modified carbon-nitrogen bond biazole energetic compound or its usable salt has the following structure:

[0017]

[0018] Preferably, the carbon-nitrogen bond biazole energetic compound modified with multiple nitro groups or its usable salt is a potassium salt.

[0019] The present invention provides a method for preparing a polynitro-modified carbon-nitrogen bond biazole energetic compound or a usable salt thereof, which comprises the following steps:

[0020] Step 1, synthesis of the intermediate compound of formula (IX):

[0021] 3-nitro-1,2,4-triazole is reacted with ammonium nitrate and trifluoroacetic anhydride to obtain a compound of formula (IX);

[0022] Step 2: Synthesis of intermediate compound (X):

[0023] 3,4-dinitro-pyrazole is treated with trifluoroacetic anhydride and fuming nitric acid to obtain a compound of formula (X);

[0024]

[0025]

[0026] Step 3: Synthesis of compounds of formula (II), (III), (IV), (VI), (VI):

[0027] The compound of formula (X) obtained in step 2 is mixed with 4-nitro-3,5-diaminopyrazole (DANP), 3,5-dinitro-4-aminopyrazole (LLM-116), 3,4-dinitro-5-aminopyrazole (ADNP), 3-nitro-5-amino-1,2,4-triazole (ANTA), and 5-aminotetrazole (5AT), respectively, and the corresponding potassium salts are obtained under the action of anhydrous potassium carbonate, and the potassium salts are then acidified to obtain compounds of formula (II), (III), (IV), (VI), and (VI);

[0028] Step 4: Synthesis of the compound of formula (VIII):

[0029] The compound of formula (IX) obtained in step 1 is mixed with 3,4-dinitro-5-aminopyrazole (ADNP), and under the action of anhydrous potassium carbonate, the potassium salt corresponding to the compound of formula (VIII) is obtained, and the potassium salt is then acidified to obtain the compound of formula (VIII).

[0030] Preferably, the method for preparing the polynitro-modified carbon-nitrogen bond biazole energetic compound or its usable salt, step 1 specifically comprises: dissolving 3-nitro-1,2,4-triazole in dichloromethane, adding ammonium nitrate at room temperature, and then adding trifluoroacetic anhydride dropwise to the reaction system at 30°C. After the addition is complete, the mixture is reacted at room temperature for 10 hours. After the reaction is completed, the mixture is sequentially extracted, washed with a saturated sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent is removed under reduced pressure to obtain a compound of formula (IX).

[0031] Preferably, in the method for preparing the polynitro-modified carbon-nitrogen bond biazole energetic compound or its available salt, step 2 is specifically as follows: dissolving 3,4-dinitro-pyrazole in trifluoroacetic anhydride, then adding fuming nitric acid dropwise at 5° C., reacting at room temperature for 10 hours after the addition is completed, and then extracting, washing with a saturated sodium chloride solution, drying with anhydrous sodium sulfate, and removing the solvent under reduced pressure to obtain a compound of formula (X).

[0032] Preferably, the method for preparing the polynitro-modified carbon-nitrogen bond biazole energetic compound or its available salt, wherein step three is specifically: mixing the compound of formula (X) obtained in step two with 4-nitro-3,5-diaminopyrazole (DANP), 3,5-dinitro-4-aminopyrazole (LLM-116), 3,4-dinitro-5-aminopyrazole (ADNP), 3-nitro-5-amino-1,2,4-triazole (ANTA), and 5-aminotetrazole (5AT) in anhydrous methanol, and then adding anhydrous potassium carbonate solid to the reaction system, heating to 80 ° C., and reacting at a constant temperature for 8 hours. After the reaction is completed, cooling to room temperature, filtering to obtain the corresponding potassium salts of the compounds of formula (II), (III), (IV), (VI), and (VI), and acidifying the potassium salts of the above compounds with 10% mass fraction of hydrochloric acid, and filtering to obtain compounds of formula (II), (III), (IV), (VI), and (VI).

[0033] Preferably, the method for preparing the polynitro-modified carbon-nitrogen bond biazole energetic compound or its available salt, step four is specifically: mixing the compound of formula (IX) obtained in step 1 with 3,4-dinitro-5-aminopyrazole (ADNP) in anhydrous methanol, then adding anhydrous potassium carbonate solid to the reaction system, heating to 80 ° C, and reacting at a constant temperature for 8 hours. After the reaction is completed, cooling to room temperature, filtering to obtain the potassium salt corresponding to the compound of formula (VIII), acidifying with 10% mass fraction of potassium hydrochloride of the compound of formula (VIII), and filtering to obtain the compound of formula (VIII).

[0034] The present invention has at least the following beneficial effects:

[0035] 1. The present invention introduces a CN bond into an energetic compound of a biazole ring, thereby providing more CN bonds and modifiable sites and reducing the number of acidic hydrogens, thereby enriching the types of energetic compounds and improving the detonation performance and mechanical sensitivity of the energetic molecules.

[0036] 2. Provide a method for preparing a polynitro-modified carbon-nitrogen-bonded biazole energetic compound or its usable salt, which starts from known available raw materials and realizes the synthesis of novel CN-bonded biazole energetic compounds and their usable salts through multi-step reactions, enriching the types of energetic compounds and having great significance for regulating the performance of energetic compounds.

[0037] Other advantages, objectives and features of the present invention will be reflected in part from the following description and will be understood by those skilled in the art through study and practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 Schematic diagram of the single crystal structure of Compound 1 synthesized in Example 1 of the present invention;

[0039] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of compound 1 synthesized in Example 1 of the present invention;

[0040] Figure 3 This is the carbon NMR spectrum of compound 1 synthesized in Example 1 of the present invention;

[0041] Figure 4 is the DSC graph of compound 1 synthesized in Example 1 of the present invention;

[0042] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of compound 2 synthesized in Example 2 of the present invention;

[0043] Figure 6 This is the carbon NMR spectrum of compound 2 synthesized in Example 2 of the present invention;

[0044] Figure 7 is the DSC graph of compound 2 synthesized in Example 2 of the present invention;

[0045] Figure 8 Schematic diagram of the single crystal structure of compound 3 synthesized in Example 3 of the present invention;

[0046] Figure 9 is the H NMR spectrum of compound 3 synthesized in Example 3 of the present invention;

[0047] Figure 10 This is the carbon NMR spectrum of compound 3 synthesized in Example 3 of the present invention;

[0048] Figure 11 is the DSC graph of compound 3 synthesized in Example 3 of the present invention;

[0049] Figure 12 Schematic diagram of the single crystal structure of compound 4 synthesized in Example 4 of the present invention;

[0050] Figure 13 is the hydrogen nuclear magnetic resonance spectrum of compound 4 synthesized in Example 4 of the present invention;

[0051] Figure 14 This is the carbon NMR spectrum of compound 4 synthesized in Example 4 of the present invention;

[0052] Figure 15 is the DSC graph of compound 4 synthesized in Example 4 of the present invention;

[0053] Figure 16 is the hydrogen nuclear magnetic resonance spectrum of compound 5 synthesized in Example 5 of the present invention;

[0054] Figure 17This is the carbon NMR spectrum of compound 5 synthesized in Example 5 of the present invention;

[0055] Figure 18 is the DSC chart of compound 5 synthesized in Example 5 of the present invention;

[0056] Figure 19 Schematic diagram of the single crystal structure of compound 6 synthesized in Example 6 of the present invention;

[0057] Figure 20 is the H NMR spectrum of compound 6 synthesized in Example 6 of the present invention;

[0058] Figure 21 This is the carbon NMR spectrum of compound 6 synthesized in Example 6 of the present invention;

[0059] Figure 22 This is the DSC chart of compound 6 synthesized in Example 6 of the present invention. DETAILED DESCRIPTION

[0060] The present invention will be described in further detail below in conjunction with the accompanying drawings so that those skilled in the art can implement the invention with reference to the description.

[0061] It should be understood that terms such as “having,” “including,” and “comprising” used herein do not prescribe the existence or addition of one or more other elements or combinations thereof.

[0062] It should be noted that the experimental methods described in the following embodiments are conventional methods unless otherwise specified, and the reagents and materials can be obtained from commercial channels unless otherwise specified.

[0063] <Example 1>

[0064] Compound 1 has the following structural formula:

[0065]

[0066] The specific synthetic route is as follows:

[0067]

[0068] The specific synthesis steps are as follows:

[0069] Step 1, Synthesis of 1,3,4-trinitro-pyrazole:

[0070] At low temperature (0°C), 3,4-dinitro-pyrazole (3.16 g, 20 mmol) was dissolved in 15 mL of trifluoroacetic anhydride in an eggplant-shaped flask. Then, 4.2 mL of fuming nitric acid was added dropwise to the above system. The temperature was kept below 5°C during the entire addition process. After the addition was completed, the temperature was gradually returned to room temperature and the reaction was continued for 10 h. The reaction of the raw materials was monitored by TLC to ensure complete reaction. The system was poured into 200 g of crushed ice to quench the reaction and extracted with dichloromethane (100 mL × 3 times), washed with saturated sodium chloride solution (20 mL × 3 times), dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation under reduced pressure to obtain the product;

[0071] Step 2: Synthesis of 4-nitro-3,5-diaminopyrazole (DANP):

[0072] Place 120 mL of dichloromethane in a two-necked flask, weigh 20 g of the compound 4,6-dichloro-5-nitropyrimidine, and add it to the flask while stirring at room temperature. Once completely dissolved, place the flask in a cryocirculator set at -70°C, controlling the temperature fluctuation within 10°C. Add 10 mL of dimethylamine dropwise over 10 minutes using a constant pressure funnel. Stir for 5 minutes, then add 28 mL of N,N-diisopropylethylamine dropwise. After reacting at -70°C for 1 hour, slowly warm the reaction mixture to room temperature and extract and wash five times with a 20% (mass fraction) K₂CO₃ solution. Separate the organic dichloromethane phase and decolorize it by adsorption using activated carbon (AC). Allow to stand overnight for approximately 8 hours, then filter out the activated carbon. The dichloromethane is then spin-dried at room temperature and dried under vacuum to yield a crude brown-yellow solid. The product was recrystallized and washed out using anhydrous ether, and then spin-dried and vacuum-dried to obtain a relatively pure bright yellow crystalline intermediate product 6-chloro-N,N-dimethyl-5-nitropyrimidin-4-amine.

[0073] In an ice-water bath, the prepared 6-chloro-N,N-dimethyl-5-nitropyrimidin-4-amine intermediate was weighed and dissolved in 100 mL of anhydrous ethanol. 10 mL of 85% hydrazine hydrate was slowly added dropwise to the reaction solution with stirring. The reaction solution turned from yellow to a transparent red solution. After stirring for approximately 10 minutes, the reaction system was heated to 75°C and refluxed for 4 hours. An orange-red turbidity precipitated in the reaction solution. The reaction flask was placed in an ice-water bath and cooled to low temperature. The reaction solution was filtered to obtain an orange-red solid. The filtrate was concentrated and filtered to obtain the orange-red solid product, 4-nitro-3,5-diaminopyrazole (DANP) (13.54 g, 66.87%). 1HNMR(400MHz,DMSO-d6)δ10.78(s,1H),6.38(s,4H).13C NMR(101MHz,DMSO-d6)δ148.33,108.61ppm.IR(FTIR) 3293,1614,1571,1493,1413,1380,1225,1166,1126,1087cm-1 .EA(C3H5N5O2, 143.106): Calcd, C 25.18, H 3.52, N 48.94%. Found=C 24.82, H3.76, N 49.15%.

[0074] Step 3, synthesis of compound 1:

[0075] Disperse 2 mmol of 4-nitro-3,5-diaminopyrazole (DANP) in 10 mL of anhydrous methanol, then add 2 mmol of a methanol solution of 1,3,4-trinitro-pyrazole and an equivalent amount of anhydrous potassium carbonate solid. Heat to 80°C and react for 8 hours. TLC monitoring of the reaction indicates completion. After cooling to room temperature, the solid potassium salt of Compound 1, Compound 1-1, is obtained by filtration. The potassium salt of Compound 1-1 is acidified with 10% hydrochloric acid and filtered to yield neutral Compound 1 (Compound 1, 514.3 mg, 86% yield).

[0076] Compound 1: mp-℃; T dec :186.3℃; 1 H NMR (400MHz, d6-DMSO): δ8.08 (s, 2H). 13 CNMR(101MHz,d6-DMSO):δ107.8,120.5,135.9,148.1,148.3.150.7.IR(KBr pellet): 3481,3444,3373,3331,1621,1569,1493,1421,1398,1357,1339,1324,12 17,1177,1131,1062,986,846,814,799,768,752,698,644,593,477,431cm -1 .EA(C6H5N9O6, 299.0):Calcd,C24.09,H 1.68,N 42.14.Found:C 23.99,H 1.56,N 42.10.

[0077] The single crystal structure of compound 1 is shown in Figure 1 , hydrogen spectrum see Figure 2 , carbon spectrum see Figure 3 , DSC diagram see Figure 4 .

[0078] <Example 2>

[0079] Compound 2 has the following structural formula:

[0080]

[0081] The specific synthetic route is as follows:

[0082]

[0083] The specific synthesis steps are as follows:

[0084] Step 1, Synthesis of 1,3,4-trinitro-pyrazole:

[0085] At low temperature (0°C), 3,4-dinitro-pyrazole (3.16 g, 20 mmol) was dissolved in 15 mL of trifluoroacetic anhydride in an eggplant-shaped flask. Then, 4.2 mL of fuming nitric acid was added dropwise to the above system. The temperature was kept below 5°C during the entire addition process. After the addition was completed, the temperature was gradually returned to room temperature and the reaction was continued for 10 h. The reaction of the raw materials was monitored by TLC to ensure complete reaction. The system was poured into 200 g of crushed ice to quench the reaction and extracted with dichloromethane (100 mL × 3 times), washed with saturated sodium chloride solution (20 mL × 3 times), dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation under reduced pressure to obtain the product;

[0086] Step 2: Synthesis of 4-amino-3,5-dinitro-pyrazole (LLM-116):

[0087] Synthesis of 4-chloro-3,5-dinitropyrazole: In a 500-mL three-necked flask equipped with a thermometer and a stirrer, completely dissolve 4-chloropyrazole (10 g, 0.1 mmol) in 100 mL of concentrated sulfuric acid. Slowly add fuming nitric acid (20 mL) dropwise using a constant-pressure titration funnel at 40-50°C, carefully controlling the temperature during the addition. After the addition of the fuming nitric acid, stir at room temperature for a while, then gradually increase the temperature to 120°C and react for 16 hours. After the reaction, pour the reaction mixture into ice and extract with ethyl acetate (100 mL x 4). The organic phase is washed with saturated NaCl solution (100 mL x 3), dried over anhydrous sodium sulfate, air-dried, and vacuum-dried to obtain 4-chloro-3,5-dinitropyrazole as a white solid in an 83% yield.

[0088] Synthesis of 4-amino-3,5-dinitropyrazole ammonium salt monohydrate (LLM-116): 4-chloro-3,5-dinitropyrazole (19.19 g, 0.1 mmol) and 90 mL of aqueous ammonia were added to a 300 mL autoclave. It should be noted that the solvent should not exceed half of the volume of the autoclave, and then the autoclave was tightened. The reaction temperature was controlled at 230 ° C and the reaction pressure was controlled at 2 MPa for 24 hours. After the reaction was completed, the temperature of the reaction system was lowered to room temperature, the pressure of the autoclave was 0 MPa, the autoclave was opened, and the excess aqueous ammonia was removed by filtration to finally obtain the crystalline compound 4-amino-3,5-dinitropyrazole ammonium salt monohydrate with a yield of 78%.

[0089] Step 3, synthesis of compound 2:

[0090] 2 mmol of 4-amino-3,5-dinitro-pyrazole (LLM-116) was dispersed in 10 mL of anhydrous methanol. A 2 mmol methanol solution of 1,3,4-trinitro-pyrazole and an equivalent amount of solid anhydrous potassium carbonate were then added. The reaction was heated to 80°C and allowed to react for 8 hours. The reaction was monitored by TLC. After cooling to room temperature, the solid potassium salt of Compound 2, Compound 2-1, was obtained by filtration. The potassium salt of Compound 2-1 was acidified with 10% hydrochloric acid and filtered to yield the neutral Compound 2 (Compound 2, 394.8 mg, 60% yield).

[0091] Compound 2: mp 219.8℃; T dec :234.3℃; 1 H NMR (400MHz, d6-DMSO): δ7.17 (s, 2H). 13 CNMR(101MHz,d6-DMSO):δ113.1,119.4,136.4,138.2,150.6,157.4.IR(KBr pellet): 3594,3429,3360,3146,1644,1540,1477,1352,1310,1275,1219,1156,1003,963,865,849,829,814,754,659,453cm -1 .EA(C6H3N9O8,329.0):Calcd,C 21.89,H 0.92,N 38.30.Found:C21.36,H 1.28,N 37.89.

[0092] The hydrogen spectrum of compound 2 is shown in Figure 5 , carbon spectrum see Figure 6 , DSC diagram see Figure 7 .

[0093] <Example 3>

[0094] Compound 3 has the following structural formula:

[0095]

[0096] The specific synthetic route is as follows:

[0097]

[0098] The specific synthesis steps are as follows:

[0099] Step 1, Synthesis of 1,3,4-trinitro-pyrazole:

[0100] At low temperature (0°C), 3,4-dinitro-pyrazole (3.16 g, 20 mmol) was dissolved in 15 mL of trifluoroacetic anhydride in an eggplant-shaped flask. Then, 4.2 mL of fuming nitric acid was added dropwise to the above system. The temperature was kept below 5°C during the entire addition process. After the addition was completed, the temperature was gradually returned to room temperature and the reaction was continued for 10 h. The reaction of the raw materials was monitored by TLC to ensure complete reaction. The system was poured into 200 g of crushed ice to quench the reaction and extracted with dichloromethane (100 mL × 3 times), washed with saturated sodium chloride solution (20 mL × 3 times), dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation under reduced pressure to obtain the product;

[0101] Step 2: Synthesis of 3,4-dinitro-5-aminopyrazole (ADNP):

[0102] 1) Synthesis of 3,4-dinitropyrazole (DNP): Dissolve 3-nitropyrazole (5.7 g) in 100% sulfuric acid (30 mL) at 40°C. Add nitric acid (9.6 g, 100%) dropwise to the solution, maintaining the temperature below 55°C. Stir the solution at 40°C for 24 hours, pour into ice, extract with ethyl acetate (3 times with 150 mL), and wash with water (3 times with 150 mL). Dry the organic phase over anhydrous magnesium sulfate, and remove the solvent by rotary evaporation to obtain 3,4-dinitropyrazole as a pale yellow solid.

[0103] 2) Synthesis of 1,3,4,N-trinitropyrazole (TNP): Ammonium nitrate (0.83 g, 0.01 mol) was added portionwise to a suspension of dinitropyrazole (1.1 g, 0.01 mol) in dichloromethane (4.5 mL) at 15-18°C. At this temperature, a mixture of trifluoroacetic anhydride (3.5 mL) and dichloromethane (3 mL) was added dropwise to the suspension. The mixture was stirred at 20°C for 6 h and then poured into ice. The organic phase was separated and the aqueous phase was extracted three times with 5 mL of dichloromethane. The organic phases were confirmed to be the same by spotting. If they were the same, the organic phases were combined, washed with water, and dried over anhydrous magnesium sulfate. The solvent was evaporated to dryness. 1.35 g of the target compound was obtained as an oil (yield 98%).

[0104] 3) Synthesis of 3,4-dinitro-5-aminopyrazole-1H (ADNP): At room temperature, 6.5 g of sodium azide was dispersed in 130 mL of ethanol and 10 mL of water. A solution of 2.03 g of TNP in 20 mL of ether was added dropwise. After stirring for 30 min, 20% H2SO4 was added dropwise to adjust the pH to 1. 130 mL of anhydrous ether was added and anhydrous Na2SO4 was removed by filtration. The filtrate was washed with 100 mL of saturated brine. The organic phase was dried and used directly in the next step. Triphenylmethane was added to the dried and filtered ether solution from the previous step. The reaction solution turned from light yellow to orange-red, and triphenylphosphine dissolved. After stirring for 1 hour, 60 mL of NaOH (9.0 g) was added to the reaction solution to adjust the pH to >12. The reaction solution separated into a dark orange-red lower layer and a light yellow upper layer (triphenylphosphine byproduct). The organic phase was removed, and the aqueous phase was washed with a 5:1 mixture of PE and EA until no impurities were detected on the spot plate. The aqueous phase was acidified to pH 1 with hydrochloric acid, extracted with EA, washed with saturated brine, dried, and spin-dried to obtain the product, 3,4-dinitro-5-aminopyrazole-1H (ADNP). 1H NMR (400 MHz, DMSO-d6) δ 13.22 (s, 1H), 7.75 (s, 2H) ppm. 13C NMR (101 MHz, DMSO) δ 148.73, 147.78, 108.41 ppm.

[0105] Step 3, synthesis of compound 3:

[0106] Disperse 2 mmol of 3,4-dinitro-5-aminopyrazole (ADNP) in 10 mL of anhydrous methanol. Add 2 mmol of a methanol solution of 1,3,4-trinitro-pyrazole and an equivalent amount of solid anhydrous potassium carbonate. Heat to 80°C and react for 8 hours. Monitor the reaction by TLC. Cool to room temperature and filter to obtain the potassium salt of compound 3, compound 3-1. Acidify the potassium salt with 10% hydrochloric acid and filter to obtain neutral compound 3 (513.2 mg, 78% yield).

[0107] Compound 3: mp-℃; T dec :214.7℃; 1 H NMR (400MHz, d6-DMSO): δ8.34(s,2H),10.57(s,1H). 13 C NMR (101MHz, d6-DMSO): δ107.5,120.5,137.1,148.5,149.3,150.4.IR(KBrpellet): 3431,3329,3159,2983,1648,1556,154,1514,1501,1455,1391,1372,1332,12 51,1194,1071,987,864,845,816,775,762,724,673,652,618,587,499,454cm -1 .EA(C6H3N9O8,329.0):Calcd,C 21.89H 0.92,N 38.30.Found:C 21.93,H 0.79,N 38.41. The single crystal structure of compound 3 is shown in Figure 8 , hydrogen spectrum see Figure 9 , carbon spectrum see Figure 10 , DSC diagram see Figure 11 .

[0108] <Example 4>

[0109] Compound 4 has the following structural formula:

[0110]

[0111] The specific synthetic route is as follows:

[0112]

[0113] The specific synthesis steps are as follows:

[0114] Step 1: Synthesis of 1,3-dinitro-1,2,4-triazole

[0115] 3-nitro-1,2,4-triazole (2.26 g, 20 mmol) was dissolved in 20 mL of dichloromethane in an eggplant-shaped flask at room temperature (25-30°C), followed by the addition of ammonium nitrate (3.32 g, 20 mmol). 10 mL of trifluoroacetic anhydride and 10 mL of dichloromethane were then mixed and added dropwise to the above system. The temperature was maintained at no higher than 30°C during the entire addition process. After the addition was complete, the reaction was maintained at room temperature for 10 h. The reaction of the raw materials was monitored by TLC to ensure complete reaction. The system was poured into 200 g of crushed ice to quench the reaction and extracted with dichloromethane (100 mL × 3 times), washed with saturated sodium chloride solution (20 mL × 3 times), dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation under reduced pressure to obtain the product.

[0116] Step 2, synthesis of 3,4-dinitro-5-aminopyrazole (ADNP): the specific synthesis steps refer to step 2 of Example 3;

[0117] Step 3, synthesis of compound 4:

[0118] Disperse 2 mmol of 3,4-dinitro-5-aminopyrazole (ADNP) in 10 mL of anhydrous methanol. Then, add 2 mmol of a methanol solution of 1,3-dinitro-1,2,4-triazole and an equivalent amount of anhydrous potassium carbonate solid. Heat to 80°C and react for 8 h. Monitor the reaction by TLC. Cool to room temperature and filter to obtain a solid potassium salt of Compound 4, Compound 4-1. Acidify Compound 4-1 with 10% potassium hydrochloride and filter to obtain a neutral Compound 4 (456 mg, 80% yield).

[0119] Compound 4: mp-℃; T dec :288.3℃; 1 H NMR (400MHz, d6-DMSO): δ8.55 (s, 2H). 13 CNMR(101MHz,d6-DMSO):δ108.7,146.8,149.8,150.2,160.6.IR(KBr pellet): 3423,3305,3214,1652,1604,1561,1535,1517,1488,1468,1452,1373,133 9,1309,1209,1174,1149,1038,861,835,821,761,689,641,591,529,449cm -1 .EA(C5H3N9O6,285.0):Calcd,C 21.06,H1.06,N 44.21.Found:C 21.36,H 1.28,N 45.06. The single crystal structure of compound 4 is shown in Figure 12 , hydrogen spectrum see Figure 13 , carbon spectrum see Figure 14 , DSC diagram see Figure 15 .

[0120] <Example 5>

[0121] Compound 5 has the following structural formula:

[0122]

[0123] The specific synthetic route is as follows:

[0124]

[0125] The specific synthesis steps are as follows:

[0126] Step 1, Synthesis of 1,3,4-trinitro-pyrazole:

[0127] At low temperature (0°C), 3,4-dinitro-pyrazole (3.16 g, 20 mmol) was dissolved in 15 mL of trifluoroacetic anhydride in an eggplant-shaped flask. Then, 4.2 mL of fuming nitric acid was added dropwise to the above system. The temperature was kept below 5°C during the entire addition process. After the addition was completed, the temperature was gradually returned to room temperature and the reaction was continued for 10 h. The reaction of the raw materials was monitored by TLC to ensure complete reaction. The system was poured into 200 g of crushed ice to quench the reaction and extracted with dichloromethane (100 mL × 3 times), washed with saturated sodium chloride solution (20 mL × 3 times), dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation under reduced pressure to obtain the product;

[0128] Step 2: Synthesis of 3-nitro-5-amino-1,2,4-triazole (ANTA):

[0129] 1) Weigh 55g of NaNO2 and dissolve it in approximately 80mL of water. Pour the sodium nitrite solution into a three-necked flask in an oil bath and heat to 40°C. Weigh 3,5-diamino-1,2,4-triazole and dissolve it in 130mL of approximately 12% dilute sulfuric acid. Slowly add this solution dropwise to the sodium nitrite solution reaction system, maintaining the temperature below 50°C. Subsequently, under vigorous stirring, slowly add approximately 60mL of 80% concentrated sulfuric acid dropwise over 2 hours. After stirring for approximately 10 minutes, add 5.0g of urea to catalyze the oxidation reaction and allow it to fully react. Heat to 80°C and reflux for 1 hour. Cool to room temperature, add 2.5g of activated carbon, and stir at room temperature for 8 hours to decolorize. Filter the filtrate and extract it with ethyl acetate (EA). The organic phase is washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated by rotary evaporation at room temperature to yield an oily product: 3,5-dinitro-1,2,4-triazole (DNT). Then it was dissolved in 50 mL of acetone solution, 15 g of K2CO3 was added, and the mixture was stirred at room temperature for 2 h. The acetone was filtered and washed, and the acetone solution was spin-dried and vacuum-dried to obtain the potassium salt of 3,5-dinitro-1,2,4-triazole (KDNT).

[0130] 2) 9.3 g of KDNT solid was dissolved in 5 mL of 80% by mass hydrazine hydrate solution at low temperature with stirring. The temperature was raised to 80°C and refluxed for 2.5 h. The reaction solution was cooled to room temperature and poured into ice water with stirring. 20% dilute hydrochloric acid was then added dropwise to the ice water to a pH of 3-4. The solution was stirred for about 30 min. A yellow solid precipitated from the solution. After standing in a refrigerator overnight, the solution was filtered, washed with water, and dried in vacuo to obtain a yellow powder product, 3-amino-5-nitro-1,2,4-triazole (ANTA).

[0131] Step 3, synthesis of compound 5:

[0132] 2 mmol of 3-nitro-5-amino-1,2,4-triazole (ANTA) was dispersed in 10 mL of anhydrous methanol. A 2 mmol methanol solution of 1,3,4-trinitro-pyrazole and an equivalent amount of anhydrous potassium carbonate solid were then added. The reaction was heated to 80°C and allowed to react for 8 hours. The reaction was monitored by TLC. The mixture was cooled to room temperature and filtered to obtain the potassium salt of compound 5, compound 5-1. The potassium salt of compound 5-1 was acidified with 10% hydrochloric acid and filtered to obtain the neutral compound 5 (compound 5, 444.6 mg, yield: 78%).

[0133] Compound 5: mp-℃; T dec :212.3℃; 1 H NMR (400MHz, d6-DMSO): δ7.47(s,1H),6.39(s,2H). 13 C NMR(101MHz,d6-DMSO):δ119.8,137.6,150.4,157.7,160.8.IR(KBr pellet): 3617,3544,3424,3149,2431,1643,1541,1518,1394,1366,1332,1305,1148 ,1104,1028,973,842,815,774,763,755,724,708,682,617,585,539,468cm -1 .EA(C5H3N9O6,285.0):Calcd,C 21.06,H 1.06,N 44.21.Found:C 21.16,H 1.09,N 44.69.Hydrogen spectrum of compound 5 is shown Figure 16 , carbon spectrum see Figure 17 , DSC diagram see Figure 18 .

[0134] <Example 6>

[0135] Compound 6 has the following structural formula:

[0136]

[0137] The specific synthetic route is as follows:

[0138]

[0139] The specific synthesis steps are as follows:

[0140] Step 1, Synthesis of 1,3,4-trinitro-pyrazole:

[0141] At low temperature (0°C), 3,4-dinitro-pyrazole (3.16 g, 20 mmol) was dissolved in 15 mL of trifluoroacetic anhydride in an eggplant-shaped flask. Then, 4.2 mL of fuming nitric acid was added dropwise to the above system. The temperature was kept below 5°C during the entire addition process. After the addition was completed, the temperature was gradually returned to room temperature and the reaction was continued for 10 h. The reaction of the raw materials was monitored by TLC to ensure complete reaction. The system was poured into 200 g of crushed ice to quench the reaction and extracted with dichloromethane (100 mL × 3 times), washed with saturated sodium chloride solution (20 mL × 3 times), dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation under reduced pressure to obtain the product;

[0142] Step 2, synthesis of compound 6:

[0143] 2 mmol of 5-aminotetrazole (5AT) (commercially available at Shanghai Aladdin) was dispersed in 10 mL of anhydrous methanol. A 2 mmol methanol solution of 1,3,4-trinitro-pyrazole and an equivalent amount of anhydrous potassium carbonate solid were then added. The reaction was heated to 80°C for 8 h. The reaction was monitored by TLC. The reaction was then cooled to room temperature and filtered to obtain the potassium salt of compound 6, compound 6-1. The potassium salt of compound 6-1 was acidified with 10% hydrochloric acid and filtered to obtain the neutral compound 6 (compound 6, 400.1 mg, yield: 83%).

[0144] Compound 6: mp-℃; T dec :203.2℃;IR(cm -1 ) 1 H NMR (400 MHz, d6-DMSO): 13 C NMR(101MHz,d6-DMSO):δ111.6,140.2,148.7,153.1.IR(KBr pellet): 3589,3462,3277,3173,1623,1555,1504,1461,1417,1358,1323,1286,120 2,1134,1059,1033,1022,937,853,835,822,789,760,746,670,530,436cm -1 .EA(C4H2KN9O6,241.0):Calcd,C 19.92,H1.25,N 52.28.Found:C 19.56,H 1.28,N 52.39. The single crystal structure of compound 6 is shown in Figure 19 , hydrogen spectrum see Figure 20 , carbon spectrum see Figure 21 , DSC diagram see Figure 22 .

[0145] <Example 7>

[0146] Comparison of the performance of compounds 1 to 6 synthesized in the examples of the present invention and existing explosives RDX and Octogen:

[0147] The performance comparison of compounds 1 to 6 and RDX (hexogenin) and HMX (octogenin) is shown in Table 1.

[0148] Table 1: Tested and calculated properties of compounds 1-6, RDX, and HMX

[0149]

[0150] Remark: a Decomposition temperature (heating rate 5℃ min -1 ). b Density, density tester test (25℃). c Calculation of formation enthalpy – calculation software Gaussian 09 (Revision E.01). d Detonation velocity – EXPLO5 V6.01. e Detonation Pressure – EXPLO5 V6.05. f Impact sensitivity. g Friction sensitivity. h CaHbOcNd oxygen balance, 1600(c–a–b / 2) / Mw; Mw = molecular weight – oxygen balance (calculated with CO as the product).

[0151] Following a rearrangement strategy, six amino- and nitro-modified CN-linked energetic biazoles were obtained in a single step using DANP, LLM-116, ADNP, ANTA, and 5-AT as starting materials for rearrangement with 1,3-dinitrotriazole and 1,3,4-trinitropyrazole. These six novel energetic compounds exhibited excellent detonation performance (vD = 8053–8931 m / s, P = 26.5–34.1 GPa) and mechanical sensitivity (IS = 11–30 J, FS = 192–240 N), demonstrating the enormous potential of CN-linked energetic biazole frameworks and providing guidance for the subsequent development of novel CN-linked energetic compounds.

[0152] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and exemplary embodiments. They can be applied to a variety of fields suitable for the present invention. Further modifications will be readily apparent to those skilled in the art. Therefore, the present invention is not limited to the specific details and illustrations shown and described herein without departing from the general concept defined by the claims and their equivalents.

Claims

1. A polynitro-modified carbon-nitrogen bond biazole energetic compound or a usable salt thereof, characterized in that: The energetic compound has the following formula ( ) structure: （ ）。 2. The carbon-nitrogen bonded biazole energetic compound modified with multiple nitro groups or a usable salt thereof according to claim 1, wherein: A useful salt is the potassium salt.

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