A novel energetic compound TNDATO and its synthesis method and application

Abstract

The present invention discloses a novel energetic compound, TNDATO, and its synthesis method and application, relating to the technical field of energetic materials. The energetic compound, TNDATO, is N-(3-(5-amino-1,3,4-oxadiazole-2-yl)-1-trinitromethyl-1H-1,2,4-triazole-5-yl) nitramide, and has the chemical structural formula: #imgabs0# The present invention synthesizes the novel energetic compound, TNDATO, by using 1,3,4-oxadiazole and 1,2,4-triazole rings as primary structural units and amino, nitramine, and trinitromethyl groups as modifying functional groups. TNDATO has excellent detonation performance and high density, and has great potential as a high-energy-density material. It can be used to prepare explosives or pyrotechnic devices, and has important application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of energetic materials, and in particular to a novel energetic compound TNDATO, a synthesis method and application thereof. Background Art

[0002] Energetic materials are essential key components in defense weaponry and serve as a crucial energy source for mining, construction, the petroleum industry, and space propulsion systems. Energetic materials have evolved through three generations: the first, represented by trinitrotoluene (TNT), the second, represented by RDX and octogenol (HMX), and the third, represented by CL-20. Each new generation of energetic materials improves the effectiveness of weapon systems, requiring them to possess higher energy density and lower sensitivity. However, there is a conflict between the energy and safety of energetic materials, and finding a perfect balance between these two factors has long been a goal for researchers.

[0003] The emergence of new aromatic nitrogen-rich azole heterocyclic energetic compounds provides a new molecular design strategy for solving this problem. Nitrogen-rich azole energetic compounds release energy through their own redox reactions and the breaking of a large number of high-energy bonds in their structure (such as CN, NN and N=N bonds). This makes the energetic materials have higher energy, low signal characteristics and environmental friendliness. The present invention intends to use the molecular design strategy of aromatic nitrogen-rich azole heterocyclic energetic compounds to develop a compound with excellent detonation performance and high density, thereby providing a new compound for the preparation of high-energy density materials. Summary of the Invention

[0004] The present invention aims to provide a novel energetic compound, TNDATO, and its synthesis method and application to address the aforementioned problems of the prior art. TNDATO exhibits excellent detonation performance and high density, and has great potential as a high-energy-density material, possessing significant application prospects.

[0005] To achieve the above object, the present invention provides the following solutions:

[0006] The present invention provides an energetic compound TNDATO, which is N-(3-(5-amino-1,3,4-oxadiazol-2-yl)-1-trinitromethyl-1H-1,2,4-triazol-5-yl) nitramide, and has the following chemical structure:

[0007]

[0008] The present invention also provides a method for synthesizing the above-mentioned energetic compound TNDATO, comprising the following steps:

[0009] Using aminoguanidine hydrochloride and oxalic acid dihydrate as starting compounds, 5-(3-amino-1H-1,2,4-triazol-5-yl)-1,3,4-oxadiazol-2-amine was synthesized through cyclization, esterification, and aminohydrazide formation reactions.

[0010] Under alkaline conditions, reacting the 5-(3-amino-1H-1,2,4-triazol-5-yl)-1,3,4-oxadiazol-2-amine with bromoacetone to obtain 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one;

[0011] The 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one is subjected to a nitration reaction to obtain the energetic compound TNDATO.

[0012] Furthermore, the synthesis method of the 5-(3-amino-1H-1,2,4-triazol-5-yl)-1,3,4-oxadiazole-2-amine comprises the following steps:

[0013] Add oxalic acid dihydrate to an aqueous solution containing aminoguanidine hydrochloride, heat and reflux for 3 to 6 hours, cool to room temperature, filter to obtain a first filter cake, wash with deionized water, and then dissolve in an aqueous solution. Then, add sodium hydroxide in batches to adjust the pH to 9 to 11, heat and reflux again, adjust the pH to 1 to 2 with dilute sulfuric acid, filter, and dry to obtain 3-amino-1H-1,2,4-triazole-5-carboxylic acid.

[0014] Slowly adding thionyl chloride to an anhydrous ethanol solution containing the 3-amino-1H-1,2,4-triazole-5-carboxylic acid, heating and reflux for reaction for 2 to 4 hours, cooling to room temperature, and concentrating to obtain a reaction solution. The reaction solution is added to a saturated sodium acetate solution, stirred, and filtered to obtain a second filter cake, which is washed with water and dissolved in hydrazine hydrate. After heating and reaction, the pH is adjusted to 5 to 6, filtered, and dried to obtain 3-amino-1H-1,2,4-triazole-5-carbohydrazide;

[0015] Potassium hydroxide is added to an aqueous solution containing the 3-amino-1H-1,2,4-triazole-5-carbohydrazide, and the mixture is cooled to a temperature of -5 to 5°C, followed by slow addition of hydrogen bromide. The mixture is then heated to room temperature, and the reaction is followed by filtration to obtain a third filter cake, which is then washed with water and dried to obtain the 5-(3-amino-1H-1,2,4-triazole-5-yl)-1,3,4-oxadiazole-2-amine.

[0016] The molar ratio of the oxalic acid dihydrate to the aminoguanidine hydrochloride is (1-1.3):1.

[0017] Furthermore, the synthesis step of the 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one includes: adding the 5-(3-amino-1H-1,2,4-triazol-5-yl)-1,3,4-oxadiazol-2-amine to an aqueous solution containing sodium hydroxide, and then dropwise adding an acetone solution containing bromoacetone to react. After the reaction is completed, filtering and drying to obtain the 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one.

[0018] Furthermore, the molar ratio of the 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one, the sodium hydroxide and the bromoacetone is (1.0-2.0):2.4:(1-1.5); the reaction temperature is 20-90° C., and the reaction time is 10-16 h.

[0019] Furthermore, the nitration reaction step includes: slowly adding the 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one and fuming nitric acid dropwise into concentrated sulfuric acid in sequence, reacting at -5 to 5°C for 20 to 26 hours, and then separating to obtain the energetic compound TNDATO.

[0020] Furthermore, the volume ratio of the concentrated sulfuric acid to the fuming nitric acid is 1:(1-1.5).

[0021] The present invention also provides the use of the above-mentioned energetic compound TNDATO in the preparation of high energy density materials.

[0022] The present invention also provides a high energy density material, the active ingredient of which includes the above-mentioned energy-containing compound TNDATO.

[0023] The present invention also provides the use of the above-mentioned energetic compound TNDATO or high energy density material in the preparation of explosives or pyrotechnic products.

[0024] The present invention discloses the following technical effects:

[0025] The present invention provides a novel energetic compound N-(3-(5-amino-1,3,4-oxadiazole-2-yl)-1-trinitromethyl-1H-1,2,4-triazole-5-yl)nitramide (TNDATO) and a method for synthesizing the same. The present invention uses 1,3,4-oxadiazole ring and 1,2,4-triazole ring as main structural units, and amino, nitramine and trinitromethyl as modified functional groups to synthesize the novel energetic compound N-(3-(5-amino-1,3,4-oxadiazole-2-yl)-1-trinitromethyl-1H-1,2,4-triazole-5-yl)nitramide (TNDATO). Specifically, aminoguanidine hydrochloride and oxalic acid dihydrate, which are known to be commercially inexpensive and readily available, are used as starting compounds. 5-(3-amino-1H-1,2,4-triazol-5-yl)-1,3,4-oxadiazol-2-amine is synthesized through cyclization, esterification, and aminohydrazide formation. This is then reacted with bromoacetone under alkaline conditions to yield 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one. Finally, nitration is carried out using a nitric-sulfuric acid system to synthesize TNDATO. This compound, TNDATO, exhibits excellent detonation properties and high density, showing great potential as a high-energy-density material for the preparation of explosives or pyrotechnic devices, possessing significant application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0027] Figure 1 Schematic diagram of the crystal structure of compound TNDATO;

[0028] Figure 2 is the hydrogen spectrum of compound TNDATO;

[0029] Figure 3 is the carbon spectrum of compound TNDATO;

[0030] Figure 4 is the differential scanning calorimetry diagram of compound TNDATO;

[0031] Figure 5 is the X-ray diffraction (XRD) pattern of compound TNDATO. DETAILED DESCRIPTION

[0032] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0033] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. The intermediate value within any stated value or stated range, and each smaller range between any other stated value or intermediate value within the stated range, is also encompassed within the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0034] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0035] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be illustrative only.

[0036] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0037] Example 1

[0038] (1) Synthesis of Compound 4 - 3-amino-1H-1,2,4-triazole-5-carboxylic acid

[0039]

[0040] At room temperature, oxalic acid dihydrate (1.64 g, 13 mmol) was added to a water (6 mL) solution containing aminoguanidine hydrochloride (1.11 g, 10 mol). The reaction system was heated to reflux for 4 h, then cooled to room temperature, filtered, and the filter cake was washed with deionized water. The filter cake was dissolved in an aqueous solution (8 mL), and sodium hydroxide was added in batches to adjust the pH to 10.5. The reaction system was heated to reflux for 2 h, and then the pH was adjusted to 2 with 45% sulfuric acid. The filter cake was filtered and dried at room temperature to obtain compound 4 (0.96 g) as a white solid product with a yield of 75%.

[0041] (2) Synthesis of Compound 5 - 3-amino-1H-1,2,4-triazole-5-carbohydrazide

[0042]

[0043] At 0°C, thionyl chloride (0.5 mL) was slowly added to an anhydrous ethanol solution (6.5 mL) containing compound 4 (0.64 g, 5 mmol), and the reaction system was heated to 90°C and refluxed for 2 h. After the reaction was completed, the temperature of the reaction system was lowered to room temperature, and the reaction solution was subjected to reduced pressure rotary evaporation. The concentrated reaction solution was poured into a saturated sodium acetate solution (5 mL), stirred for 0.5 h, filtered, and the filter cake was washed with deionized water. The obtained filter cake was dissolved in hydrazine hydrate (3.3 mL), the reaction system was heated to 70°C for 2 h, then the pH was adjusted to 5, filtered, the filter cake was washed with deionized water, and the filter cake was dried at room temperature to obtain a white solid product compound 5 (0.56 g) with a yield of 79%.

[0044] (3) Synthesis of Compound 6: 5-(3-amino-1H-1,2,4-triazol-5-yl)-1,3,4-oxadiazol-2-amine

[0045]

[0046] Potassium hydroxide (0.62 g, 11 mmol) was added to a water (30 mL) solution containing compound 5 (1.42 g, 10 mmol), and the reaction system temperature was cooled to 0°C. Hydrogen bromide (1.06 g, 10 mmol) was slowly added, and the system temperature was slowly raised to room temperature. Stirring was continued for 24 h, filtered, and the filter cake was washed with deionized water and dried at room temperature to obtain yellow solid compound 6 (1.46 g) with a yield of 87%.

[0047] Characterization of compound 6:

[0048] 1 H NMR (600MHz, DMSO-d6): δ 12.55 (s, 1H NH), 7.26 (s, 2H NH2), 6.31 (s, 2H NH2) ppm.13 C NMR (151 MHz, DMSO-d6): δ 164.03, 158.00, 152.81, 147.98 ppm. Elemental analysis C4H5N7O (167.15) calculated: C 28.75, H 3.02, N 58.67%, found: C 28.73, H 3.05, N 58.66%.

[0049] (4) Synthesis of Compound 7: 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one

[0050]

[0051] At room temperature, compound 6 (0.84 g, 5 mmol) was added to an aqueous solution (2 mL) containing sodium hydroxide (0.20 g, 5 mmol) and stirred. A solution of bromoacetone (0.75 g, 5.5 mmol) in acetone (10 mL) was then slowly added dropwise to the system. The resulting solution was then heated to 70°C and reacted at this temperature in the dark for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, the acetone was removed, and the filter cake was dried at room temperature to obtain compound 7 (0.72 g) as a yellow solid with a yield of 65%.

[0052] Characterization of compound 7:

[0053] 1 H NMR (600MHz, DMSO-d6): δ7.24 (s, 2H NH2), 6.53 (s, 2H NH2), 4.95 (s, 2H CH2), 2.13 (s, 3H CH3)ppm. 13 C NMR (151 MHz, DMSO-d6): δ 201.84, 164.10, 157.45, 152.50, 147.03, 56.27, 27.34 ppm. Elemental analysis C7H9N7O2 (223.20) calculated: C 37.67, H 4.06, N 43.93%, found: C 37.68, H 4.05, N 41.91%.

[0054] (5) Synthesis of the compound N-(3-(5-amino-1,3,4-oxadiazol-2-yl)-1-trinitromethyl-1H-1,2,4-triazol-5-yl)nitramide (TNDATO)

[0055]

[0056] At 0°C, concentrated sulfuric acid (4 mL) was slowly added to the reaction flask. Then, while maintaining the reaction system temperature at 0°C, compound 7 (335 mg, 1.5 mmol) and fuming nitric acid (4 mL) were slowly added dropwise to the concentrated sulfuric acid. The reaction system temperature was then slowly raised to room temperature and allowed to react for 24 h. After the reaction, the reaction solution was poured into 50 mL of ice water and extracted with ether (three times, 10 mL each). The organic phase was washed twice with water, dried over anhydrous sodium sulfate, filtered, and the filtrate was dried to obtain a light yellow compound, TNDATO (326 mg), with a yield of 60%.

[0057] N-(3-(5-amino-1,3,4-oxadiazol-2-yl)-1-trinitromethyl-1H-1,2,4-triazol-5-yl)nitramide (TNDATO) was obtained in a total yield of 20% after five steps of conversion.

[0058] Characterization of compound TNDATO:

[0059] The crystal structure diagram of compound TNDATO is shown in Figure 1 , hydrogen spectrum see Figure 2 , carbon spectrum see Figure 3 , differential scanning calorimetry diagram is shown in Figure 4 , X-ray diffraction (XRD) pattern is shown in Figure 5 , crystallographic data are shown in Table 1.

[0060] Decomposition temperature (T d ):134℃. 1 H NMR (600MHz, DMSO-d6): δ 8.27 (br, 1H NH), 6.32 (br, 2HNH2) ppm. 13 C NMR (151MHz, DMSO-d6): δ163.51, 161.25, 152.37, 150.37, 119.91ppm. IR (KBrpellet): υ3502, 3451, 2984, 2653, 2233, 1716, 1639, 1615, 1597, 1540, 1458, 1386, 1358 , 1290, 1249, 1177, 1092, 1024, 989, 946, 887, 837, 793, 764, 725, 704, 678, 594, 536, 464, 430cm -1 Elemental analysis: C5H3N 11 Calcd. for O9 (361.15): C 16.63, H 0.84, N 42.66%, found: C 16.62, H 0.85, N 42.64%.

[0061] After testing, the density of the compound TNDATO is 1.89 g·cm-3 The measured detonation velocity is 9326m / s, the explosion pressure is 38.9GPa, the impact sensitivity is 12J, and the friction sensitivity is 180N.

[0062] Table 1 Crystallographic data of compound TNDATO

[0063]

[0064]

[0065] Example 2

[0066] (1) Synthesis of compound 4

[0067]

[0068] At room temperature, oxalic acid dihydrate (1.26 g, 10 mmol) was added to a water (6 mL) solution containing aminoguanidine hydrochloride (1.11 g, 10 mol). The reaction system was heated to reflux for 3 h, then cooled to room temperature, filtered, and the filter cake was washed with deionized water. The filter cake was dissolved in an aqueous solution (8 mL), and sodium hydroxide was added portionwise to adjust the pH to 10. The reaction system was heated to reflux for 2 h, and then the pH was adjusted to 1 with 35% sulfuric acid. The solution was filtered and the filter cake was dried at room temperature to obtain a white solid product 4 (0.88 g) with a yield of 70%.

[0069] (2) Synthesis of compound 3-amino-1H-1,2,4-triazole-5-carbohydrazide 5

[0070]

[0071] At 0°C, thionyl chloride (0.5 mL) was slowly added to an anhydrous ethanol solution (6.5 mL) containing compound 4 (0.64 g, 5 mmol), and the reaction system was heated to 80°C and refluxed for 2 h. After the reaction was completed, the temperature of the reaction system was lowered to room temperature, and the reaction solution was subjected to reduced pressure rotary evaporation. The concentrated reaction solution was poured into a saturated sodium acetate solution (5 mL), stirred for 0.5 h, filtered, and the filter cake was washed with deionized water. The obtained filter cake was dissolved in hydrazine hydrate (3.3 mL), the reaction system was heated to 65°C for 2 h, then the pH was adjusted to 5, filtered, the filter cake was washed with deionized water, and the filter cake was dried at room temperature to obtain a white solid product compound 5 (0.55 g) with a yield of 78%.

[0072] (3) Synthesis of Compound 6

[0073]

[0074] Potassium hydroxide (0.56 g, 10 mmol) was added to a water (30 mL) solution containing compound 5 (1.42 g, 10 mmol), and the reaction system temperature was cooled to -5°C. Hydrogen bromide (1.06 g, 10 mmol) was slowly added, and the system temperature was slowly raised to room temperature. Stirring was continued for 16 h, filtered, and the filter cake was washed with deionized water and dried at room temperature to obtain yellow solid compound 6 (1.36 g) with a yield of 84%.

[0075] (4) Synthesis of Compound 7

[0076]

[0077] At room temperature, compound 6 (0.84 g, 5 mmol) was added to an aqueous solution (2 mL) containing sodium hydroxide (0.20 g, 5 mmol) and stirred. A solution of bromoacetone (0.68 g, 5 mmol) in acetone (10 mL) was then slowly added dropwise to the system. The resulting solution was then heated to 25°C and reacted at this temperature in the dark for 16 hours. After the reaction was completed, the reaction solution was cooled to room temperature, the acetone was removed, and the filter cake was dried at room temperature to obtain compound 7 (0.68 g) as a yellow solid with a yield of 61%.

[0078] (5) Synthesis of compound TNDATO

[0079]

[0080] At 0°C, concentrated sulfuric acid (4 mL) was slowly added to the reaction flask. Then, while maintaining the reaction system temperature at -5°C, compound 7 (335 mg, 1.5 mmol) and fuming nitric acid (4 mL) were slowly added dropwise to the concentrated sulfuric acid. The reaction system temperature was then slowly raised to room temperature and allowed to react for 18 h. After the reaction, the reaction solution was poured into 50 mL of ice water and extracted with ether (three times, 10 mL each). The organic phase was washed twice with water, dried over anhydrous sodium sulfate, filtered, and the filtrate was dried to obtain a light yellow compound, TNDATO (303 mg), with a yield of 56%.

[0081] Characterization of compound TNDATO:

[0082] 1 H NMR (600MHz, DMSO-d6): δ8.26, 6.32ppm. 13 C NMR (151MHz, DMSO-d6): δ163.52, 161.25, 152.36, 150.36, 119.90ppm.

[0083] N-(3-(5-amino-1,3,4-oxadiazol-2-yl)-1-trinitromethyl-1H-1,2,4-triazol-5-yl)nitramide (TNDATO) was obtained in a total yield of 16% after five steps of conversion.

[0084] Example 3

[0085] (1) Synthesis of compound 4

[0086]

[0087] At room temperature, oxalic acid dihydrate (1.64 g, 13 mmol) was added to a water (6 mL) solution containing aminoguanidine hydrochloride (1.11 g, 10 mol). The reaction system was heated to reflux for 6 h, then cooled to room temperature, filtered, and the filter cake was washed with deionized water. The filter cake was dissolved in an aqueous solution (8 mL), and sodium hydroxide was added portionwise to adjust the pH to 11. The reaction system was heated to reflux for 2 h, and then the pH was adjusted to 2 with 55% sulfuric acid. The filter cake was filtered and dried at room temperature to obtain a white solid product 4 (0.93 g) with a yield of 73%.

[0088] (2) Synthesis of compound 5

[0089]

[0090] At 0°C, thionyl chloride (0.5 mL) was slowly added to an anhydrous ethanol solution (6.5 mL) containing compound 4 (0.64 g, 5 mmol), and the reaction system was heated to 100°C and refluxed for 4 h. After the reaction was completed, the temperature of the reaction system was reduced to room temperature, and the reaction solution was subjected to reduced pressure rotary evaporation. The concentrated reaction solution was poured into a saturated solution of sodium acetate (5 mL), stirred for 0.5 h, filtered, and the filter cake was washed with deionized water. The obtained filter cake was dissolved in hydrazine hydrate (3.3 mL), the reaction system was heated to 75°C for 4 h, then the pH was adjusted to 6, filtered, the filter cake was washed with deionized water, and the filter cake was dried at room temperature to obtain a white solid product compound 5 (0.54 g) with a yield of 76%.

[0091] (3) Synthesis of compound 5-(3-amino-1H-1,2,4-triazol-5-yl)-1,3,4-oxadiazol-2-amine 6

[0092]

[0093] Potassium hydroxide (0.67 g, 12 mmol) was added to a water (30 mL) solution containing compound 5 (1.42 g, 10 mmol), and the reaction system temperature was cooled to 5°C. Hydrogen bromide (1.06 g, 10 mmol) was slowly added, and the system temperature was slowly raised to room temperature. Stirring was continued for 24 h, filtered, and the filter cake was washed with deionized water and dried at room temperature to obtain yellow solid compound 6 (1.39 g) with a yield of 86%.

[0094] (4) Synthesis of Compound 7

[0095]

[0096] At room temperature, compound 6 (0.84 g, 5 mmol) was added to an aqueous solution (2 mL) containing sodium hydroxide (0.20 g, 5 mmol) and stirred. A solution of bromoacetone (0.75 g, 5.5 mmol) in acetone (10 mL) was then slowly added dropwise to the system. The resulting solution was then heated to 90°C and reacted at this temperature in the dark for 24 hours. After the reaction was completed, the reaction solution was cooled to room temperature, the acetone was removed, and the filter cake was dried at room temperature to obtain compound 7 (0.72 g) as a yellow solid with a yield of 65%.

[0097] (5) Synthesis of compound TNDATO

[0098]

[0099] At 0°C, concentrated sulfuric acid (4 mL) was slowly added to the reaction flask. Then, while maintaining the reaction system temperature at 5°C, compound 7 (335 mg, 1.5 mmol) and fuming nitric acid (6 mL) were slowly added dropwise to the concentrated sulfuric acid. The reaction system temperature was then slowly raised to room temperature and allowed to react for 24 h. After the reaction, the reaction solution was poured into 50 mL of ice water and extracted with ether (three times, 10 mL each). The organic phase was washed twice with water, dried over anhydrous sodium sulfate, filtered, and the filtrate was dried to obtain a light yellow compound, TNDATO (314 mg), with a yield of 58%.

[0100] Characterization of compound TNDATO:

[0101] 1 H NMR (600MHz, DMSO-d6): δ8.27, 6.32ppm. 13 C NMR (151MHz, DMSO-d6): δ163.49, 161.24, 152.35, 150.36, 119.89ppm.

[0102] N-(3-(5-amino-1,3,4-oxadiazol-2-yl)-1-trinitromethyl-1H-1,2,4-triazol-5-yl)nitramide (TNDATO) was obtained in a total yield of 18% in five steps.

[0103] Example 4

[0104] Amplification experiment: The synthetic process of Example 1 was also subjected to a proportional amplification experiment. The experimental results were reproducible and the yield was stable. Specifically, the amplification of 10 times was used as an example. The specific operation was as follows:

[0105] (2) Synthesis of compound 4

[0106]

[0107] At room temperature, oxalic acid dihydrate (16.38 g, 0.13 mol) was added to a water (60 mL) solution containing aminoguanidine hydrochloride (11.05 g, 0.1 mol). The reaction system was heated to reflux for 4 h, then cooled to room temperature, filtered, and the filter cake was washed with deionized water. The filter cake was dissolved in an aqueous solution (80 mL), and sodium hydroxide was added in batches to adjust the pH to 10.5. The reaction system was heated to reflux for 2 h, and then the pH was adjusted to 2 with 45% sulfuric acid. The filter cake was filtered and dried at room temperature to obtain compound 4 (9.34 g) as a white solid product with a yield of 73%.

[0108] (2) Synthesis of compound 5

[0109]

[0110] At 0°C, thionyl chloride (5 mL) was slowly added to an anhydrous ethanol solution (65 mL) containing compound 4 (6.40 g, 50 mmol), and the reaction system was heated to 90°C and refluxed for 2 h. After the reaction was completed, the temperature of the reaction system was reduced to room temperature, and the reaction solution was subjected to reduced pressure rotary evaporation. The concentrated reaction solution was poured into a saturated sodium acetate solution (50 mL), stirred for 0.5 h, filtered, and the filter cake was washed with deionized water. The obtained filter cake was dissolved in hydrazine hydrate (33 mL), the reaction system was heated to 70°C for 2 h, then the pH was adjusted to 5-6, filtered, the filter cake was washed with deionized water, and the filter cake was dried at room temperature to obtain a white solid product compound 5 (5.40 g) with a yield of 76%.

[0111] (3) Synthesis of Compound 6

[0112]

[0113] Potassium hydroxide (6.16 g, 0.11 mol) was added to a water (250 mL) solution containing compound 5 (14.2 g, 0.1 mol), and the reaction system temperature was cooled to below 0°C. Hydrogen bromide (10.6 g, 0.1 mol) was slowly added, and the system temperature was slowly raised to room temperature. Stirring was continued for 24 h, filtered, and the filter cake was washed with deionized water and dried at room temperature to obtain yellow solid compound 6 (14.36 g) with a yield of 86%.

[0114] Characterization of compound 6:

[0115] 1 H NMR (600MHz, DMSO-d6): δ 12.58 (s, 1H NH), 7.27 (s, 2H NH2), 6.33 (s, 2H NH2) ppm. 13 C NMR (151MHz, DMSO-d6): δ164.02, 157.98, 152.80, 147.96ppm.

[0116] (4) Synthesis of Compound 7

[0117]

[0118] At room temperature, compound 6 (8.35 g, 50 mmol) was added to an aqueous solution (20 mL) containing sodium hydroxide (2.00 g, 50 mmol) and stirred. A solution of bromoacetone (7.54 g, 55 mmol) in acetone (100 mL) was slowly added dropwise to the system. The resulting solution was then heated to 70°C and reacted at this temperature in the dark for 12 hours. After the reaction was completed, the reaction solution was cooled to room temperature, the acetone was removed, and the filter cake was dried at room temperature to obtain compound 7 (6.92 g) as a yellow solid with a yield of 62%.

[0119] Characterization of compound 7:

[0120] 1 H NMR (600MHz, DMSO-d6): δ7.23 (s, 2H NH2), 6.52 (s, 2H NH2), 4.94 (s, 2H CH2), 2.12 (s, 3H CH3)ppm. 13 C NMR (151MHz, DMSO-d6): δ201.86, 164.12, 157.46, 152.51, 147.05, 56.28, 27.35ppm.

[0121] (5) Synthesis of compound TNDATO

[0122]

[0123] At 0°C, concentrated sulfuric acid (40 mL) was slowly added to the reaction flask. Then, while maintaining the reaction system temperature at 0°C, compound 7 (3.35 g, 15 mmol) and fuming nitric acid (40 mL) were slowly added dropwise to the concentrated sulfuric acid. The reaction system temperature was then slowly raised to room temperature and allowed to react for 24 h. After the reaction, the reaction solution was poured into 500 mL of ice water and extracted with ether (three times, 50 mL each). The organic phase was washed twice with water, dried over anhydrous sodium sulfate, filtered, and the filtrate was dried to obtain a light yellow compound, TNDATO (3.14 g), with a yield of 58%.

[0124] Characterization of compound TNDATO:

[0125] 1 H NMR (600MHz, DMSO-d6): δ 8.26 (br, 1H NH), 6.31 (br, 2H NH2) ppm. 13 C NMR (151MHz, DMSO-d6): δ163.52, 161.26, 152.39, 150.38, 119.93ppm.

[0126] N-(3-(5-amino-1,3,4-oxadiazol-2-yl)-1-trinitromethyl-1H-1,2,4-triazol-5-yl)nitramide (TNDATO) was obtained in a total yield of 17% in five steps.

[0127] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. An energetic compound TNDATO, characterized in that The energetic compound TNDATO is N-(3-(5-amino-1,3,4-oxadiazol-2-yl)-1-trinitromethyl-1H-1,2,4-triazol-5-yl) nitramide, and its chemical structure is as follows:

2. A method for synthesizing the energetic compound TNDATO according to claim 1, characterized in that: The following steps are involved: 5-(3-amino-1H-1,2,4-triazol-5-yl)-1,3,4-oxadiazol-2-amine was synthesized using aminoguanidine hydrochloride and oxalic acid dihydrate as starting compounds; Under alkaline conditions, reacting the 5-(3-amino-1H-1,2,4-triazol-5-yl)-1,3,4-oxadiazol-2-amine with bromoacetone to obtain 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one; nitrating the 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one to obtain the energetic compound TNDATO; The synthesis method of the 5-(3-amino-1H-1,2,4-triazol-5-yl)-1,3,4-oxadiazole-2-amine comprises the following steps: Add oxalic acid dihydrate to an aqueous solution containing aminoguanidine hydrochloride, heat and reflux for 3 to 6 hours, cool to room temperature, filter to obtain a first filter cake, wash with deionized water, and then dissolve in an aqueous solution. Then, add sodium hydroxide in batches to adjust the pH to 10 to 11, heat and reflux again, adjust the pH to 1 to 2 with dilute sulfuric acid, filter, and dry to obtain 3-amino-1H-1,2,4-triazole-5-carboxylic acid. Slowly adding thionyl chloride to an anhydrous ethanol solution containing the 3-amino-1H-1,2,4-triazole-5-carboxylic acid, heating and reflux for reaction for 2 to 4 hours, cooling to room temperature, and concentrating to obtain a reaction solution. The reaction solution is added to a saturated sodium acetate solution, stirred, and filtered to obtain a second filter cake, which is washed with water and dissolved in hydrazine hydrate. After heating and reaction, the pH is adjusted to 5 to 6, filtered, and dried to obtain 3-amino-1H-1,2,4-triazole-5-carbohydrazide; Potassium hydroxide is added to an aqueous solution containing the 3-amino-1H-1,2,4-triazole-5-carbohydrazide, and the solution is cooled to a temperature of -5 to 5°C, followed by slow addition of hydrogen bromide. The temperature is then raised to room temperature, and the reaction is followed by filtration to obtain a third filter cake, which is then washed with water and dried to obtain the 5-(3-amino-1H-1,2,4-triazole-5-yl)-1,3,4-oxadiazole-2-amine.

3. The synthesis method according to claim 2, characterized in that The molar ratio of the oxalic acid dihydrate to the aminoguanidine hydrochloride is (1-1.3):1; The molar ratio of the potassium hydroxide, the 3-amino-1H-1,2,4-triazole-5-carbohydrazide and the hydrogen bromide is (1.0-1.2):1:

1.

4. The synthesis method according to claim 2, characterized in that The synthesis steps of the 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one include: adding the 5-(3-amino-1H-1,2,4-triazol-5-yl)-1,3,4-oxadiazol-2-amine to an aqueous solution containing sodium hydroxide, then dropwise adding an acetone solution containing bromoacetone to react, filtering after the reaction, and drying to obtain the 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one.

5. The synthesis method according to claim 4, characterized in that The molar ratio of the 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one, the sodium hydroxide and the bromoacetone is 1:1:(1 to 1.1); the reaction temperature is 25 to 90° C., and the reaction time is 16 to 24 hours.

6. The synthesis method according to claim 2, characterized in that The nitration reaction step includes: slowly adding the 1-(5-amino-3-(5-amino-1,3,4-oxadiazol-2-yl)-1H-1,2,4-triazol-1-yl)propan-2-one and fuming nitric acid dropwise into concentrated sulfuric acid in sequence, reacting at -5 to 5° C. for 18 to 24 hours, and then separating to obtain the energetic compound TNDATO.

7. The synthesis method according to claim 6, characterized in that The volume ratio of the concentrated sulfuric acid to the fuming nitric acid is 1:(1-1.5).

8. Use of the energetic compound TNDATO as claimed in claim 1 in preparing high energy density materials.

9. A high energy density material, characterized in that The active ingredient comprises the energy-containing compound TNDATO according to claim 1.

10. Use of the energetic compound TNDATO according to claim 1 or the high energy density material according to claim 9 in the preparation of explosives or pyrotechnics.

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