High-energy-density energetic compound and preparation method thereof

Abstract

The invention discloses a high-energy-density energetic compound and a preparation method thereof.The preparation method comprises the steps that 5-amino-3-nitryl-1H-1, 2, 4-triazole serves as a raw material and reacts with an amination reagent under the alkaline condition, a compound 1, 5-diamino-3-nitryl-1H-1, 2, 4-triazole is formed firstly, and then the compound 1, 5-diamino-3-nitryl-1H-1, 2, 4-triazole reacts with the amination reagent under the alkaline condition; the preparation method comprises the following steps: carrying out N, N '-diazene-1, 2, 4-triazole as a raw material, carrying out N-NH2 protection to obtain a compound 5-amino-3-nitro-1-(propyl-2-subunit amino)-1H-1, 2, 4-triazole, generating an azo compound under the action of an oxidant, and removing a protecting group under an acidic condition to obtain the target compound (E)-5, 5'-(diazene-1, 2-diyl) bis (1-amino-3-nitro-1H-1, 2, 4-triazole). The target compound has the characteristics of high energy, low sensitivity, good thermal stability and the like, and is a high-energy energetic material with potential application value.

Description

Technical Field

[0001] The invention belongs to the field of energetic materials, and in particular relates to energetic organic compounds and preparation methods thereof. Background Art

[0002] High Energy Density Materials (HEDMs) are a class of chemical substances with high energy release rate and storage per unit volume or unit mass. These materials are generally used to make gunpowder, explosives, propellants, etc., and have a wide range of military and civilian applications. The research on high energy density materials aims to increase the energy stored per unit weight or unit volume, and requires stability and controllability during use to ensure safety and reliability.

[0003] Azotriazole is a new type of high energy density material. It has the characteristics of high density, high formation enthalpy and environmental friendliness due to the presence of a large number of CN, NN, C=N and N=N bonds in the molecule. These characteristics make azotriazole a potential candidate material for the preparation of high energy density explosives, propellants, etc., with important application prospects. In recent years, a variety of azotriazole energetic compounds have been reported one after another. For example, in 2011, Shreeve, JM et al. reported (E)-1,2-bis(5-(trinitromethyl)-1H-1,2,4-triazol-3-yl)diazene compound, the measured density of which is 1.83 g cm -3 The thermal decomposition temperature is 150°C and the calculated detonation velocity is 8964 m s -1 , explosion pressure of 36.6 GPa, and impact sensitivity of 1.5 J. In 2021, the research group reported (E)-1,2-bis(3-nitro-1-(trinitromethyl)-1H-1,2,4-triazol-5-yl)diazene compound, the measured density of which is 1.91 g cm -3 The thermal decomposition temperature is 175°C and the detonation velocity is calculated to be 8890 m s -1 , explosion pressure is 33.9 GPa, impact sensitivity is 5 J, and friction sensitivity is 120 N. Although these compounds have excellent performance, they have a difficult balance between energy and safety.

[0004] In current material science research, azotriazole compounds have received extensive attention and are considered to be a class of potential high energy density materials. Therefore, seeking a simple and efficient method to synthesize materials with high energy density while ensuring the stability and safety of the materials, and to apply them to actual production, is a scientific problem that needs to be tackled urgently. Summary of the invention

[0005] In order to solve the above technical problems, the purpose of the present invention is to provide an energetic compound (E)-5,5'-(diazene-1,2-diyl)bis(1-amino-3-nitro-1H-1,2,4-triazole) and a preparation method thereof.

[0006] In the first aspect, the present invention provides a high energy density energetic compound named (E)-5,5'-(diazene-1,2-diyl)bis(1-amino-3-nitro-1H-1,2,4-triazole), having the structural formula:

[0007]

[0008] In a second aspect, the present invention also provides a method for synthesizing a high energy density energetic compound, comprising the following steps:

[0009] (1) reacting 5-amino-3-nitro-1H-1,2,4-triazole (1) with an aminating agent under alkaline conditions to prepare a compound 1,5-diamino-3-nitro-1H-1,2,4-triazole (2);

[0010]

[0011] (2) a step of reacting 1,5-diamino-3-nitro-1H-1,2,4-triazole (2) with acetone under acidic conditions to prepare a compound 5-amino-3-nitro-1-(propan-2-ylideneamino)-1H-1,2,4-triazole (3);

[0012]

[0013] (3) oxidizing 5-amino-3-nitro-1-(propan-2-ylideneamino)-1H-1,2,4-triazole (3) under the action of an oxidant to generate an azo compound and hydrolyzing and removing the protecting group under acidic conditions to obtain the target compound (E)-5,5'-(diazene-1,2-diyl)bis(1-amino-3-nitro-1H-1,2,4-triazole);

[0014]

[0015] Preferably, in step (1), the reaction is carried out in the presence of an organic solvent or water, the organic solvent is acetonitrile or dichloromethane; the amination reagent is any one of hydroxylamine-O-sulfonic acid or O-toluenesulfonylhydroxylamine; the base in the alkaline condition is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, cesium carbonate, potassium tert-butoxide and 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0016] Preferably, in step (1), the reaction temperature is 26 to 50° C. and the reaction time is 2 to 12 hours.

[0017] Preferably, in step (2), the reaction is carried out in the presence of an organic solvent, wherein the organic solvent is acetone; and the acid in the acidic condition is sulfuric acid.

[0018] Preferably, in step (2), the reaction temperature is 26-60° C. and the reaction time is 0.5-12 hours.

[0019] Preferably, in step (3), 5-amino-3-nitro-1-(propan-2-ylideneamino)-1H-1,2,4-triazole (3) is reacted with an oxidant to generate an azo compound, and the reaction is carried out in the presence of an organic solvent or water, wherein the organic solvent is acetonitrile; the oxidant is any one of sodium dichloroisocyanurate, sodium hypochlorite, potassium periodate, hydrogen peroxide, tert-butyl hypochlorite, trichloroisocyanuric acid and bromine water; the oxidation reaction temperature is 0 to 50° C.; and the reaction time is 0.5 to 12 hours.

[0020] Preferably, in step (3), the azo compound is deprotected under acidic conditions to obtain the target compound, the acid in the acidic conditions is a sulfuric acid solution with a mass fraction of 40% to 90%; the hydrolysis reaction temperature is 50 to 100° C., and the reaction time is 0.5 to 12 hours.

[0021] In a third aspect, the present invention further provides the use of the high energy density energetic compound described in the first aspect as a secondary explosive.

[0022] Compared with the prior art, the present invention has the following advantages: (1) the energetic compound (E)-5,5'-(diazene-1,2-diyl)bis(1-amino-3-nitro-1H-1,2,4-triazole) has high energy (detonation velocity: 9293.95 ms) –1 ; explosion pressure: 38.39GPa), low sensitivity (impact sensitivity: >60J, friction sensitivity: >240N), good thermal stability (thermal decomposition temperature: 187℃), etc., making it an energetic material with potential application value. (2) The raw materials for preparing this compound are easily available, and the synthetic route is simple and efficient. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a sample crystal of (E)-5,5'-(diazene-1,2-diyl)bis(1-amino-3-nitro-1H-1,2,4-triazole).

[0024] Figure 2 The crystal structure of (E)-5,5'-(diazene-1,2-diyl)bis(1-amino-3-nitro-1H-1,2,4-triazole).

[0025] Figure 3This is the H NMR spectrum of (E)-5,5'-(diazene-1,2-diyl)bis(1-amino-3-nitro-1H-1,2,4-triazole).

[0026] Figure 4 This is the NMR carbon spectrum of (E)-5,5'-(diazene-1,2-diyl)bis(1-amino-3-nitro-1H-1,2,4-triazole).

[0027] Figure 5 DSC of (E)-5,5'-(diazene-1,2-diyl)bis(1-amino-3-nitro-1H-1,2,4-triazole). DETAILED DESCRIPTION

[0028] In order to make the purpose, technical solution and advantages of the present invention more clear, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0029] The present invention has the following synthetic route:

[0030]

[0031] The specific steps are as follows:

[0032] (1) Synthesis of compound 1,5-diamino-3-nitro-1H-1,2,4-triazole (2)

[0033] 5-amino-3-nitro-1H-1,2,4-triazole (1) is dispersed in an organic solvent, stirred at room temperature, a base is added to the solution, stirred for 30 to 120 minutes, then an aminating agent is added, and then reacted at 26 to 50°C for 2 to 12 hours, filtered, washed, and dried to obtain 1,5-diamino-3-nitro-1H-1,2,4-triazole (referred to as compound 2). The process is carried out in the presence of an organic solvent or water, the organic solvent is acetonitrile or dichloromethane; the aminating agent is any one of hydroxylamine-O-sulfonic acid or O-toluenesulfonylhydroxylamine; the base is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, cesium carbonate, potassium tert-butoxide, and 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0034] (2) Synthesis of compound 5-amino-3-nitro-1-(propan-2-ylideneamino)-1H-1,2,4-triazole (3)

[0035] Compound 2 is dispersed in acetone, sulfuric acid is added dropwise, and the mass fraction of the sulfuric acid used is 99%. The reaction system is then reacted at 26 to 60° C. for 0.5 to 12 hours, and then the reaction system is cooled to room temperature, and the solvent is removed by rotation to obtain a solid product 5-amino-3-nitro-1-(propan-2-ylideneamino)-1H-1,2,4-triazole (3) (referred to as compound 3).

[0036] (3) Synthesis of compound (E)-5,5'-(diazene-1,2-diyl)bis(1-amino-3-nitro-1H-1,2,4-triazole) (4)

[0037] Compound 3 is dispersed in a solvent, the solvent used is an organic solvent or water, and the organic solvent is acetonitrile; then a sufficient amount of an oxidant is added to the reaction system in batches, and the oxidant used is any one of sodium dichloroisocyanurate, sodium hypochlorite, potassium periodate, hydrogen peroxide, tert-butyl hypochlorite, trichloroisocyanuric acid and bromine water. After the addition, the system is heated to 0-50° C. and reacted for 0.5-12 hours. Then, the reaction system is spun to remove the solvent, sulfuric acid is added to the residue, and the mass fraction of the sulfuric acid used is 40%-90%. The reaction system is then heated to 50-100° C. and reacted for 0.5-12 hours. The reaction is cooled to room temperature, the solvent is spun to remove, and the reaction is washed, filtered and dried to obtain the target product (E)-5,5'-(diazene-1,2-diyl)bis(1-amino-3-nitro-1H-1,2,4-triazole) (referred to as target product 4).

[0038] Example 1

[0039] 1.29 g (10.0 mmol) of 5-amino-3-nitro-1H-1,2,4-triazole (prepared by reference to Simpson, RL; Pagoria, PF; Mitchell, AR, et al., Synthesis, Properties and Performance of the High Explosive ANTA [J]. Propellants, Explosives, Pyrotechnics 1994, 19 (4): 174-179) was dispersed in 30 mL of acetonitrile and stirred. Then, 1,8-diazabicyclo[5.4.0]undec-7-ene (2.28 g, 15 mmol) was added to the solution. After the addition was completed, the mixture was stirred at 26° C. for 30 minutes. Then, a solution of O-p-toluenesulfonylhydroxylamine (3.74 g, 20 mmol) in dichloromethane (50 mL) was added to the system (prepared by reference to TM; Piercey, DG; Stierstorfer, J., Amination of energetic anions: high-performing energetic materials [J]. Dalton Transactions 2012, 41 (31): 9451-9459. Preparation), stirred at 26 ° C for 12 hours, filtered, washed and dried to obtain compound 2 (yield: 80%, 1.15 g).

[0040] Compound 2 (0.72 g, 5.0 mmol) was dispersed in 20 mL of acetone, stirred at 26 °C, 5 drops of concentrated sulfuric acid were added, the temperature was raised to 60 °C, and heated for 0.5 hours. After heating, the reaction system was cooled and the solvent was removed to obtain compound 3 (yield: 36%, 0.33 g).

[0041] Compound 3 (0.36 g, 2.0 mmol) was dispersed in 10 mL of acetonitrile, and then tert-butyl hypochlorite (0.65 g, 6.0 mmol) was slowly added dropwise to the reaction solution, and the mixture was stirred at 10° C. for 3 hours. The solvent was then removed by vortexing, and 5 mL of a 90% sulfuric acid aqueous solution was added to the residue. The mixture was heated to 100° C. and heated for 6 hours. After the heating was completed, the reaction system was cooled, the solvent was removed by vortexing, and the mixture was washed, filtered, and dried to obtain the target product 4 (yield: 12%, 0.056 g). The crystal photo is shown in FIG. Figure 1 The crystal structure is shown in Figure 2 shown.

[0042] Example 2

[0043] Disperse 1.29 g (10.0 mmol) of 5-amino-3-nitro-1H-1,2,4-triazole in 30 mL of acetonitrile and stir. Then add sodium carbonate (2.11 g, 20 mmol) to the solution. After the addition is completed, stir at 26°C for 30 minutes. Then add a dichloromethane (50 mL) solution of O-toluenesulfonylhydroxylamine (3.74 g, 20 mmol) to the system and stir at 26°C for 12 hours. Filter, wash and dry to obtain compound 2 (yield: 56%, 0.81 g).

[0044] Compound 2 (0.72 g, 5.0 mmol) was dispersed in 20 mL of acetone, stirred at 26 °C, 4 drops of concentrated sulfuric acid were added, the temperature was raised to 58 °C, and heated for 2 hours. After heating, the reaction system was cooled and the solvent was removed to obtain compound 3 (yield: 41%, 0.38 g).

[0045] Compound 3 (0.36 g, 2.0 mmol) was dispersed in 10 mL of acetonitrile, and then a solution of sodium dichloroisocyanurate (0.87 g, 4.0 mmol) in water (5 mL) was slowly added to the reaction solution, stirred at 50°C for 3 hours, and then filtered, washed and dried. 5 mL of 90% sulfuric acid aqueous solution was added to the obtained compound, the temperature was raised to 100°C, and heated for 3 hours. After the heating was completed, the reaction system was cooled, the solvent was removed by rotation, washed, filtered and dried to obtain the target product 4 (yield: 16%, 0.089 g).

[0046] Example 3

[0047] Disperse 1.29 g (10.0 mmol) of 5-amino-3-nitro-1H-1,2,4-triazole in 30 mL of water and stir. Then add sodium hydroxide (2.39 g, 60 mmol) to the solution. After the addition is completed, heat to 50°C, add hydroxylamine-O-sulfonic acid (3.95 g, 35 mmol) to the system, stir at 50°C for 4 hours, extract with dichloromethane, collect the organic phase, dry, and spin-dry the solvent to obtain compound 2 (yield: 38%, 0.55 g).

[0048] Compound 2 (0.72 g, 5.0 mmol) was dispersed in 20 mL of acetone, stirred at 26 °C, 4 drops of concentrated sulfuric acid were added, the temperature was raised to 58 °C, and heated for 6 hours. After the heating was completed, the reaction system was cooled and the solvent was removed to obtain compound 3 (yield: 46%, 0.42 g).

[0049] Compound 3 (0.36 g, 2.0 mmol) was dispersed in 5 mL of 37% hydrochloric acid, and then potassium permanganate (0.47 g, 3 mmol) in water (5 mL) was slowly added to the reaction solution, stirred at 50°C for 4 hours, and then 30% hydrogen peroxide was added and stirred for 5 minutes, then filtered, washed and dried, 5 mL of 90% sulfuric acid aqueous solution was added to the residue, the temperature was raised to 80°C, and heated for 6 hours. After the heating was completed, the reaction system was cooled, the solvent was removed by rotation, washed, filtered and dried to obtain the target product 4 (yield: 29%, 0.164 g).

[0050] Example 4

[0051] Disperse 1.29 g (10.0 mmol) of 5-amino-3-nitro-1H-1,2,4-triazole in 30 mL of water and stir. Then add potassium tert-butoxide (3.36 g, 30 mmol) to the solution. After the addition is completed, heat to 50°C, add hydroxylamine-O-sulfonic acid (3.95 g, 35 mmol) to the system, stir at 50°C for 4 hours, extract with dichloromethane, collect the organic phase, dry, and spin-dry the solvent to obtain compound 2 (yield: 27%, 0.38 g).

[0052] Compound 2 (0.72 g, 5.0 mmol) was dispersed in 20 mL of acetone, stirred at 26 °C, 4 drops of concentrated sulfuric acid were added, the temperature was raised to 58 °C, and heated for 12 hours. After heating, the reaction system was cooled and the solvent was removed to obtain compound 3 (yield: 52%, 0.48 g).

[0053] Compound 3 (0.36 g, 2.0 mmol) was dispersed in 10 mL of acetonitrile, trichloroisocyanuric acid (0.92 g, 4 mmol) was slowly added dropwise at 0°C, stirred at 0°C for 2 hours, and then the reaction solution was neutralized with saturated sodium carbonate aqueous solution, filtered, washed and dried, 5 mL of 90% sulfuric acid aqueous solution was added to the residue, the temperature was raised to 80°C, and heated for 12 hours. After the heating was completed, the reaction system was cooled, the solvent was removed by rotation, washed, filtered and dried to obtain the target product 4 (yield: 21%, 0.12 g).

[0054] Example 5

[0055] Disperse 1.29 g (10.0 mmol) of 5-amino-3-nitro-1H-1,2,4-triazole in 30 mL of water and stir. Then add cesium carbonate (9.77 g, 30 mmol) to the solution. After the addition is completed, heat to 50°C, add hydroxylamine-O-sulfonic acid (3.95 g, 35 mmol) to the system, stir at 50°C for 4 hours, extract with dichloromethane, collect the organic phase, dry, and spin-dry the solvent to obtain compound 2 (yield: 51%, 0.73 g).

[0056] Compound 2 (0.72 g, 5.0 mmol) was dispersed in 20 mL of acetone, stirred at 26 °C, 3 drops of concentrated sulfuric acid were added, the temperature was raised to 58 °C, and heated for 12 hours. After heating, the reaction system was cooled and the solvent was removed to obtain compound 3 (yield: 55%, 0.51 g).

[0057] Compound 3 (0.36 g, 2.0 mmol) was dispersed in 10 mL of acetonitrile, tert-butyl hypochlorite (0.43 g, 4 mmol) was slowly added dropwise at 0°C, stirred at 0°C for 1 hour, filtered, washed and dried, 5 mL of 60% sulfuric acid aqueous solution was added to the residue, the temperature was raised to 80°C, and heated for 6 hours. After the heating was completed, the reaction system was cooled, the solvent was removed by rotation, washed, filtered and dried to obtain the target product 4 (yield: 28%, 0.159 g).

[0058] Example 6

[0059] Disperse 1.29 g (10.0 mmol) of 5-amino-3-nitro-1H-1,2,4-triazole in 30 mL of acetonitrile and stir. Then add sodium hydroxide (0.59 g, 15 mmol) to the solution. After the addition is completed, stir at 26°C for 30 minutes. Then add O-toluenesulfonylhydroxylamine to the system and stir at 26°C for 12 hours. Filter, wash and dry to obtain compound 2 (yield: 56%, 0.81 g).

[0060] Compound 2 (0.72 g, 5.0 mmol) was dispersed in 20 mL of acetone, stirred at 26 °C, 2 drops of concentrated sulfuric acid were added, the temperature was raised to 58 °C, and heated for 12 hours. After the heating was completed, the reaction system was cooled and the solvent was removed to obtain compound 3 (yield: 58%, 0.53 g).

[0061] Compound 3 (0.36 g, 2.0 mmol) was dispersed in 10 mL of acetonitrile, tert-butyl hypochlorite (0.32 g, 3 mmol) was slowly added dropwise at 0°C, stirred at 10°C for 3 hours, and then the solvent was removed by vortexing. 5 mL of 60% sulfuric acid aqueous solution was added to the residue, the temperature was raised to 60°C, and heated for 6 hours. After the heating was completed, the reaction system was cooled, the solvent was removed by vortexing, washed, filtered, and dried to obtain the target product 4 (yield: 41%, 0.23 g).

[0062] The target product 4 obtained in Example 1 was subjected to spectrum analysis, and the NMR spectrum was as follows Figure 3 and Figure 4 As shown, the test results are as follows: 1 H NMR(DMSO-d6,500MHz)δ:8.24(s,4H). 13 C NMR(DMSO-d6,75MHz)δ:157.2,153.2.IR(KBr,ν / cm –1 ):3322,3189,1617,1552,1497,1416,1367,1313,1170,1042,978,859,784,735,694,645,622,584,570,561,537. Elemental analysis C6H4N8O6: calculated value (%): C16.91, H 1.42, N59.15, O 22.52. Measured value (%): C 16.94, H 1.44, N 59.21. The measured density of the explosive is 1.88 g cm –3 , the thermal decomposition temperature is 187℃ (such as Figure 5 As shown), the theoretical detonation speed is 9293.95ms –1 , explosion pressure is 38.29Gpa, showing excellent detonation performance. Impact sensitivity: >60J, friction sensitivity: >240N. Can be used as a high explosive.

[0063] Although the present invention is described herein with reference to illustrative implementations of the present invention, the above-mentioned embodiments are merely preferred implementations of the present invention, and the implementation methods of the present invention are not limited to the above-mentioned embodiments. It should be understood that those skilled in the art can design many other modifications and implementations, which will fall within the scope and spirit of the principles disclosed in this application.

Claims

1. A high energy density energetic compound, characterized in that: It is named (E)-5,5'-(diazene-1,2-diyl)bis(1-amino-3-nitro-1H-1,2,4-triazole), and its structural formula is:

2. A method for synthesizing a high energy density energetic compound, characterized in that: include: (1) reacting 5-amino-3-nitro-1H-1,2,4-triazole (1) with an aminating agent under alkaline conditions to prepare a compound 1,5-diamino-3-nitro-1H-1,2,4-triazole (2); (2) a step of reacting 1,5-diamino-3-nitro-1H-1,2,4-triazole (2) with acetone under acidic conditions to prepare a compound 5-amino-3-nitro-1-(propan-2-ylideneamino)-1H-1,2,4-triazole (3); (3) oxidizing 5-amino-3-nitro-1-(propan-2-ylideneamino)-1H-1,2,4-triazole (3) under the action of an oxidant to generate an azo compound and hydrolyzing and removing the protecting group under acidic conditions to obtain the target compound (E)-5,5'-(diazene-1,2-diyl)bis(1-amino-3-nitro-1H-1,2,4-triazole); 3. The method according to claim 2, characterized in that In step (1), the reaction is carried out in the presence of an organic solvent or water, the organic solvent is acetonitrile or dichloromethane; the amination reagent is any one of hydroxylamine-O-sulfonic acid or O-toluenesulfonylhydroxylamine; the base in the alkaline condition is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, cesium carbonate, potassium tert-butoxide and 1,8-diazabicyclo[5.4.0]undec-7-ene.

4. The method according to claim 2, characterized in that In step (1), the reaction temperature is 26 to 50° C. and the reaction time is 2 to 12 hours.

5. The method according to claim 2, characterized in that In step (2), the reaction is carried out in the presence of an organic solvent, which is acetone; and the acid in the acidic condition is sulfuric acid.

6. The method according to claim 2, characterized in that In step (2), the reaction temperature is 26 to 60° C. and the reaction time is 0.5 to 12 hours.

7. The method according to claim 2, characterized in that In step (3), 5-amino-3-nitro-1-(propan-2-ylideneamino)-1H-1,2,4-triazole (3) is reacted with an oxidant to generate an azo compound. The reaction is carried out in the presence of an organic solvent or water. The organic solvent is acetonitrile. The oxidant is any one of sodium dichloroisocyanurate, sodium hypochlorite, potassium periodate, hydrogen peroxide, tert-butyl hypochlorite, trichloroisocyanuric acid and bromine water. The oxidation reaction temperature is 0 to 50° C. and the reaction time is 0.5 to 12 hours.

8. The method according to claim 2, characterized in that In step (3), the azo compound is subjected to acidic conditions to remove the protecting group to obtain the target compound, wherein the acid in the acidic conditions is a sulfuric acid solution having a mass fraction of 40% to 90%; The hydrolysis reaction temperature is 50-100°C, and the reaction time is 0.5-12 hours.

9. Use of the high energy density energetic compound as claimed in claim 1 as a secondary explosive.

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