Linearly arranged dinitramine tetracondensed ring high energy density material and its synthesis method

Abstract

The present invention discloses a kind of dinitramine tetracondensed ring high energy density material of linear structure arrangement and its synthesis method. The method is based on 6 (3 amino 1H 1,2,4 triazole 5 bases) 7H [1,2,4] triazole [4,3 b] [1,2,4] triazole 3,7 diamino as raw material, and carries out ring-closure reaction with cyanogen bromide in dilute hydrochloric acid solution to obtain tetracondensed ring compound [1,2,4] triazole [4 ',3 ':1,5] [1,2,4] triazole [3,4 f] [1,2,4] triazole [1,5 d] [1,2,4] triazine 2,5,10 triamino, and then carries out nitration reaction in pure nitric acid to obtain target product DNATT. The synthetic method of the present invention has the characteristics of simple operation, high safety and high yield, and DNATT has higher density and energy, and density is 1.956g / cm 3 The detonation speed reaches 9297m / s, which is higher than that of traditional high-energy explosive Octogen.

Description

Technical Field

[0001] The present invention belongs to the field of energetic materials and relates to a linearly arranged dinitramine tetracondensed ring high energy density material and a synthesis method thereof. Background Art

[0002] In recent years, nitrogen-containing fused ring compounds have become a hot topic in the design of energetic materials due to the large ring tension and conjugated system of the fused ring skeleton, which gives them good thermal stability, detonation performance and low mechanical sensitivity.

[0003] Currently, there are few reports on the research of tetra-fused ring compounds in the field of energetic materials. The structural formula of tetra-fused ring energetic compound I is shown below, and its detonation velocity D = 8376 m s -1 , density ρ = 1.82 g cm -3 (Angew. Chem. Int. Ed., 2012, 51, 9881-9885); the detonation velocity of energetic compound II is D = 9010 m s+, and the density is ρ = 1.892 g cm -3 (Asian J. Org. Chem., 2016, 5, 1388-1397). However, both of the aforementioned four-ring condensed ring compounds have fan-shaped condensed ring arrangements. Compared to fan-shaped condensed ring compounds, linear condensed ring compounds may have better energetic properties.

[0004] Summary of the Invention

[0005] The purpose of the present invention is to provide a dinitramine-based four-fused-ring high-energy density material with a linear structural arrangement and a synthesis method thereof.

[0006] The technical solutions for achieving the purpose of the present invention are as follows:

[0007] The linearly arranged dinitramine tetracondensed ring high energy density material is N,N'-(5-amino-[1,2,4]triazole[4',3':1,5][1,2,4]triazole[3,4-f][1,2,4]triazole[1,5-d][1,2,4]triazine-2,10-diyl)dinitramine (DNATT), and its structural formula is as follows:

[0008]

[0009] The synthesis method of the above-mentioned linearly arranged dinitramine tetracondensed ring high energy density material uses 6-(3-amino-1H-1,2,4-triazol-5-yl)-7H-[1,2,4]triazole[4,3-b][1,2,4]triazole-3,7-diamino as a raw material, undergoes a ring-closure reaction with cyanogen bromide to generate a tetracondensed ring intermediate, and the intermediate is then nitrated with pure nitric acid to synthesize the target product DNATT. The synthesis route is as follows:

[0010]

[0011] The specific steps are as follows:

[0012] Step 1: slowly add 6-(3-amino-1H-1,2,4-triazol-5-yl)-7H-[1,2,4]triazole[4,3-b][1,2,4]triazole-3,7-diamino to a dilute hydrochloric acid solution under stirring at room temperature, then slowly add cyanogen bromide, heat to reflux and react with stirring. After the reaction is completed, cool the mixture, filter the precipitate, and then dissolve it in deionized water. Sodium bicarbonate is added to adjust the pH of the solution to neutral, filter the mixture, wash with ethanol and water, and vacuum dry to obtain the intermediate [1,2,4]triazole[4',3':1,5][1,2,4]triazole[3,4-f][1,2,4]triazole[1,5-d][1,2,4]triazine-2,5,10-triamino;

[0013] Step 2: Add [1,2,4]triazole[4',3':1,5][1,2,4]triazole[3,4-f][1,2,4]triazole[1,5-d][1,2,4]triazine-2,5,10-triamino to the nitration system and react at 0°C. After the reaction is completed, pour into ice water to quench, filter the precipitate, wash with water and vacuum dry to obtain the target product DNATT.

[0014] Preferably, in step 1, the concentration of the dilute hydrochloric acid solution is 2 to 4 mol / L.

[0015] Preferably, in step 1, the molar ratio of cyanogen bromide to 6-(3-amino-1H-1,2,4-triazol-5-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamino is 1 to 4:1, more preferably 2:1.

[0016] Preferably, in step 1, the reaction time is more than 12 hours.

[0017] Preferably, in step 2, the nitration system is selected from pure nitric acid or a nitric acid / sulfuric acid solution with a volume ratio of 1:1.

[0018] Preferably, in step 2, the reaction time is 2±0.5 hours.

[0019] Compared with the prior art, the present invention has the following advantages:

[0020] The present invention uses a high-nitrogen-content triazole ring as the basic skeleton to introduce a triazine ring, and further introduces a high-energy explosive group, the nitramine group, to increase the energy of the four-ring fused skeleton. Compared with the reported compounds with fan-shaped structures, the linear structure of the present invention, DNATT, has higher density and energy, with a density of 1.956g / cm 3 The detonation speed reaches 9297m / s, which is higher than that of traditional high-energy explosive Octogen. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 is the H NMR spectrum of DNATT;

[0022] Figure 2 This is the carbon NMR spectrum of DNATT. DETAILED DESCRIPTION

[0023] The present invention will be further described below with reference to the embodiments and accompanying drawings.

[0024] Example 1

[0025] Dissolve 6-(3-amino-1H-1,2,4-triazol-5-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diaminobenzyl (2.21 g, 10.0 mmol) in dilute hydrochloric acid (50 mL, 2 mol / L) and add cyanogen bromide (2.12 g, 20.0 mmol). Stir and heat under reflux for 12 hours, then cool in a refrigerator to form a yellow precipitate, which is collected by filtration. The yellow solid was dissolved in distilled water (15 mL), and sodium bicarbonate (0.84 g, 10.0 mmol) was added to adjust the pH to neutral. The mixture was then stirred at 25°C for 30 minutes. The precipitate was filtered, washed, and air-dried to obtain the intermediate [1,2,4]triazole[4',3':1,5][1,2,4]triazole[3,4-f][1,2,4]triazole[1,5-d][1,2,4]triazine-2,5,10-triamino in a yield of 61.4%.

[0026] 0.492 g (2.0 mmol) of the intermediate was added to 2 ml of pure nitric acid, the reaction was maintained at 0°C for 2 hours, and then quenched with ice water. The precipitate was filtered, washed with water, and vacuum-dried to obtain 0.393 g of the target tetra-fused ring product DNATT with a yield of 58.6%. The measured density of this high-energy-density material was 1.956 g / cm 3 The thermal decomposition temperature is 171°C, the measured impact sensitivity is 15J, the friction sensitivity is 240N, the theoretically calculated detonation velocity is as high as 9297m / s, and the detonation pressure is 37.9GPa.

[0027] 1 H NMR (500MHz, DMSO-d6): δ = 7.83 (s, 2H), 8.00 (s, 2H) ppm; 13 C NMR (125MHz, DMSO-d6): δ = 166.3, 153.5, 149.1, 142.4, 139.8, 136.3ppm; IR (KBr): Elemental analysis for C6H4N14O4(336.19): C 21.44, H 1.20, N 58.33%; found: C 21.40, H 1.23, N 58.35%.

[0028] Example 2

[0029] Dissolve 6-(3-amino-1H-1,2,4-triazol-5-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diaminobenzyl (2.21 g, 10.0 mmol) in dilute hydrochloric acid (50 mL, 1 mol / L) and add cyanogen bromide (2.12 g, 20.0 mmol). Stir and heat under reflux for 12 hours, then cool in a refrigerator to form a yellow precipitate, which is collected by filtration. Dissolve the yellow solid in distilled water (15 mL). Adjust the pH to neutral by adding sodium bicarbonate (0.84 g, 10.0 mmol), and stir at 25°C for 30 minutes. The precipitate was filtered, washed, and dried in air to obtain the intermediate [1,2,4]triazole[4',3':1,5][1,2,4]triazole[3,4-f][1,2,4]triazole[1,5-d][1,2,4]triazine-2,5,10-triamino in a yield of 30.2%.

[0030] 0.492 g (2.0 mmol) of the intermediate was added to 2 ml of pure nitric acid, and the reaction was controlled at 0°C for 2 hours. The mixture was then poured into ice water for quenching. The precipitate was filtered, washed with water, and dried in vacuo to obtain 0.385 g of the target tetra-fused-ring product DNATT with a yield of 57.4%.

[0031] Example 3

[0032] Dissolve 6-(3-amino-1H-1,2,4-triazol-5-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diaminobenzyl (2.21 g, 10.0 mmol) in dilute hydrochloric acid (50 mL, 2 mol / L) and add cyanogen bromide (3.18 g, 30.0 mmol). Stir and heat under reflux for 12 hours, then cool in a refrigerator to form a yellow precipitate, which is collected by filtration. Dissolve the yellow solid in distilled water (15 mL). Add sodium bicarbonate (0.84 g, 10.0 mmol) to adjust the pH to neutral, then stir at 25°C for 30 minutes. The precipitate was filtered, washed, and dried in air to obtain the intermediate [1,2,4]triazole[4',3':1,5][1,2,4]triazole[3,4-f][1,2,4]triazole[1,5-d][1,2,4]triazine-2,5,10-triamino in a yield of 25.3%.

[0033] 0.492 g (2.0 mmol) of the intermediate was added to 2 ml of pure nitric acid, and the reaction was controlled at 0°C for 2 hours. The mixture was then poured into ice water for quenching. The precipitate was filtered, washed with water, and dried in vacuo to obtain 0.365 g of the target tetra-fused-ring product DNATT with a yield of 54.4%.

[0034] Example 4

[0035] Dissolve 6-(3-amino-1H-1,2,4-triazol-5-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diaminobenzyl (2.21 g, 10.0 mmol) in dilute hydrochloric acid (50 mL, 4 mol / L) and add cyanogen bromide (2.12 g, 20.0 mmol). Stir and heat under reflux for 12 hours, then cool in the refrigerator for 3 hours. A yellow precipitate forms and is collected by filtration. Dissolve the yellow solid in distilled water (15 mL). Adjust the pH to neutral by adding sodium bicarbonate (0.84 g, 10.0 mmol), then stir at 25°C for 30 minutes. The precipitate was filtered, washed, and dried in air to obtain the intermediate [1,2,4]triazole[4',3':1,5][1,2,4]triazole[3,4-f][1,2,4]triazole[1,5-d][1,2,4]triazine-2,5,10-triamino in 18.2% yield.

[0036] 0.492 g (2.0 mmol) of the intermediate was added to 2 ml of a nitric-sulfuric acid mixture (nitric acid / sulfuric acid solution with a volume ratio of 1:1). The reaction was controlled at 0°C for 2 hours and then poured into ice water for quenching. The precipitate was filtered, washed with water, and dried in vacuo to obtain 0.103 g of the target tetra-fused-ring product DNATT with a yield of 14.9%.

[0037] Example 5

[0038] Dissolve 6-(3-amino-1H-1,2,4-triazol-5-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diaminobenzyl (2.21 g, 10.0 mmol) in dilute hydrochloric acid (50 mL, 2 mol / L) and add cyanogen bromide (4.84 g, 40.0 mmol). Stir and heat under reflux for 12 hours, then cool in a refrigerator to form a yellow precipitate, which is collected by filtration. Dissolve the yellow solid in distilled water (15 mL). Add sodium bicarbonate (0.84 g, 10.0 mmol) to adjust the pH to neutral, then stir at 25°C for 30 minutes. The precipitate was filtered, washed, and dried in air to obtain the intermediate [1,2,4]triazole[4',3':1,5][1,2,4]triazole[3,4-f][1,2,4]triazole[1,5-d][1,2,4]triazine-2,5,10-triamino in a yield of 9.5%.

[0039] 0.492 g (2.0 mmol) of the intermediate was added to 2 ml of pure nitric acid, and the reaction was controlled at 0°C for 3 hours. The mixture was then poured into ice water for quenching. The precipitate was filtered, washed with water, and dried in vacuo to obtain 0.091 g of the target tetra-fused-ring product DNATT with a yield of 13.5%.

[0040] Example 6

[0041] Dissolve 6-(3-amino-1H-1,2,4-triazol-5-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diaminobenzyl (2.21 g, 10.0 mmol) in dilute hydrochloric acid (50 mL, 3 mol / L) and add cyanogen bromide (2.12 g, 20.0 mmol). Stir and heat under reflux for 12 hours, then cool in a refrigerator to form a yellow precipitate, which is collected by filtration. Dissolve the yellow solid in distilled water (15 mL). Add sodium bicarbonate (0.84 g, 10.0 mmol) to adjust the pH to neutral, then stir at 25°C for 30 minutes. The precipitate was filtered, washed, and dried in air to obtain the intermediate [1,2,4]triazole[4',3':1,5][1,2,4]triazole[3,4-f][1,2,4]triazole[1,5-d][1,2,4]triazine-2,5,10-triamino in a yield of 5.6%.

[0042] 0.492 g (2.0 mmol) of the intermediate was added to 2 ml of pure nitric acid, and the reaction was controlled at 0°C for 4 hours. The mixture was then poured into ice water for quenching. The precipitate was filtered, washed with water, and dried in vacuo to obtain 0.056 g of the target tetra-fused-ring product DNATT with a yield of 8.3%.

Claims

1. A linearly arranged dinitramine tetracondensed ring high energy density material, characterized in that: It is N,N'-(5-amino-[1,2,4]triazolo[4',3':1,5][1,2,4]triazolo[3,4-f][1,2,4]triazolo[1,5-d][1,2,4]triazine-2,10-diyl)dinitramine, and its structural formula is as follows: 。 2. The method for synthesizing the linearly arranged dinitramine tetracondensed ring high energy density material according to claim 1, characterized in that: The synthetic route is as follows: ， The specific steps are as follows: Step 1: slowly add 6-(3-amino-1H-1,2,4-triazol-5-yl)-7H-[1,2,4]triazole[4,3-b][1,2,4]triazole-3,7-diamino to a dilute hydrochloric acid solution under stirring at room temperature, then slowly add cyanogen bromide, heat to reflux and react with stirring. After the reaction is completed, cool the mixture, filter the precipitate, and then dissolve it in deionized water. Sodium bicarbonate is added to adjust the pH of the solution to neutral, filter the mixture, wash with ethanol and water, and vacuum dry to obtain the intermediate [1,2,4]triazole[4',3':1,5][1,2,4]triazole[3,4-f][1,2,4]triazole[1,5-d][1,2,4]triazine-2,5,10-triamino; Step 2: Add [1,2,4]triazole[4',3':1,5][1,2,4]triazole[3,4-f][1,2,4]triazole[1,5-d][1,2,4]triazine-2,5,10-triamino to the nitration system and react at 0°C. After the reaction is completed, pour into ice water to quench. Filter the precipitate, wash with water and vacuum dry to obtain the target product N,N'-(5-amino-[1,2,4]triazole[4',3':1,5][1,2,4]triazole[3,4-f][1,2,4]triazole[1,5-d][1,2,4]triazine-2,10-diyl)dinitramine.

3. The synthesis method according to claim 2, wherein In step 1, the concentration of the dilute hydrochloric acid solution is 2-4 mol / L.

4. The synthesis method according to claim 2, characterized in that In step 1, the molar ratio of cyanogen bromide to 6-(3-amino-1H-1,2,4-triazol-5-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamino is 1-4:

1.

5. The synthesis method according to claim 2, characterized in that In step 1, the molar ratio of cyanogen bromide to 6-(3-amino-1H-1,2,4-triazol-5-yl)-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazole-3,7-diamino is 2:

1.

6. The synthesis method according to claim 2, characterized in that In step 1, the reaction time is more than 12 hours.

7. The synthesis method according to claim 2, characterized in that In step 2, the nitration system is selected from pure nitric acid or a nitric acid / sulfuric acid solution with a volume ratio of 1:

1.

8. The synthesis method according to claim 2, characterized in that In step 2, the reaction time is 2±0.5 hours.

Images