1, 2-bis (5-azido-3-nitro-1, 2, 4-triazole) diazene and synthetic method thereof

Abstract

The invention discloses a 1, 2-bis (5-azido-3-nitro-1, 2, 4-triazole) diazene compound and a synthesis method of the 1, 2-bis (5-azido-3-nitro-1, 2, 4-triazole) diazene compound. A synthesis process of the 5-azido-3-nitro-1, 2, 4-triazole derivative comprises the following steps: (1) sequentially reacting 5-azido-3-nitro-1, 2, 4-triazole with sodium hydroxide, monopotassium phosphate and hydroxylamine-O-sulfonic acid to generate 5-azido-3-nitro-1, 2, 4-triazole-1-amine; and (2) carrying out a coupling reaction on the 5-azido-3-nitro-1, 2, 4-triazole-1-amine under the action of tert-butyl hypochlorite to generate the 1, 2-bis (5-azido-3-nitro-1, 2, 4-triazole) diazene. The 1, 2-bis (5-azido-3-nitro-1, 2, 4-triazole) diazene synthesized by the method has excellent detonation performance, and has an application prospect in the field of energetic materials.

Description

Technical Field

[0001] The invention relates to a 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene compound and a synthesis method thereof. The compound can be used as a high-energy explosive and belongs to the technical field of energetic materials. Background Art

[0002] Polynitrogen compounds have important scientific value in many fields and are widely used in biopharmaceuticals, chemical raw materials, materials science and environmental monitoring. In addition, they occupy a pivotal position in the research and application of energetic materials and are often used as propellants, propellants, high explosives, gas generating agents and other purposes. The energy of high-nitrogen energetic compounds mainly comes from their own extremely high positive heat of formation. The large number of high-energy NN bonds and CN bonds in the molecules determine this unique energy source. In recent decades, in the development of high-energy energetic compounds, the development of high-energy energetic compounds faces a key challenge in weapon systems, that is, how to achieve a balance between higher performance and lower sensitivity. The most ideal properties of new energetic materials include high positive heat of formation, high density, high detonation velocity and pressure, high thermal stability and low sensitivity to external forces (such as impact, shock and friction). Triazole compounds are typical representatives of high-nitrogen energetic compounds. The high nitrogen and low carbon and hydrogen properties in the molecular structure make it easy to achieve oxygen balance, and the decomposition product is environmentally friendly and pollution-free N2.

[0003] In the field of triazole research, the existing structures of long nitrogen chain covalent compounds are very limited. In the process of trying to construct triazole-based full carbon nitration long nitrogen chain compounds, researchers found that chlorination reaction would occur at the nitro substitution position during the oxidative coupling process to generate chlorinated byproducts. In addition, the detonation velocity of triazole energetic compounds is difficult to exceed 9000m·s -1 The present invention discloses for the first time a 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene with a simple synthesis process and a synthesis method thereof. Summary of the invention

[0004] The technical problem to be solved by the present invention is to overcome the defects of the prior art, provide a high energy density energetic compound 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazepine with high detonation velocity, high detonation heat and high detonation pressure, and provide a synthesis method of 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazepine.

[0005] The structural formula of 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene of the present invention is shown as I:

[0006]

[0007] The synthetic route of 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene of the present invention is:

[0008]

[0009] To achieve the above object, the present invention provides a method for synthesizing 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene, comprising the following steps:

[0010] (1) Synthesis of 5-azido-3-nitro-1,2,4-triazole-1-amine

[0011] At 15-25° C., 5-azido-3-nitro-1,2,4-triazole is added to a deionized water solution containing sodium hydroxide and potassium dihydrogen phosphate, the mixed system is heated to 50° C., and then hydroxylamine-O-sulfonic acid is slowly added. The feeding time is not less than 30 minutes. After the addition is completed, the system is heated to 70° C. The reaction progress is detected by TLC plate. After the reaction is completed, the temperature is lowered to room temperature, the solid is collected by filtration, washed with water for purification, and vacuum dried to obtain the target product 5-azido-3-nitro-1,2,4-triazole-1-amine, wherein the molar ratio of sodium hydroxide to 5-azido-3-nitro-1,2,4-triazole is 1-9, the molar ratio of potassium dihydrogen phosphate to 5-azido-3-nitro-1,2,4-triazole is 1-10, and the molar ratio of hydroxylamine sulfonic acid to 5-azido-3-nitro-1,2,4-triazole is 1-3.

[0012] (2) Synthesis of 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene

[0013] At 0 to 20° C., tert-butyl hypochlorite is added to an acetonitrile solution containing 5-azido-3-nitro-1,2,4-triazole-1-amine, the reaction solution is reacted at -5 to 15° C. for 0.5 h to 4 h, poured into 10 to 50 mL of ethyl acetate, washed with water, dried and concentrated to obtain 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazepine, wherein the molar ratio of tert-butyl hypochlorite to 5-azido-3-nitro-1,2,4-triazole-1-amine is 1 to 1.2.

[0014] Beneficial Effects

[0015] 1. The 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene compound of the present invention has excellent detonation performance, and the detonation velocity is 9311m·s -1 , explosion pressure is 38.5GPa, explosion heat is 6080J·g -1 .

[0016] 2. The synthesis method of the 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene compound of the present invention is simple and the reaction conditions are mild.

[0017] 3. The 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene compound of the present invention can be used in the field of energetic materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The molecular structure diagram of 1,2-bis(4-azido-3,5-dinitropyrazole)diazene;

[0019] Figure 2 The DSC graph of 1,2-bis(4-azido-3,5-dinitropyrazole)diazene;

[0020] Figure 3 It is the carbon NMR spectrum of 1,2-bis(4-azido-3,5-dinitropyrazole)diazene;

[0021] Figure 4 This is the infrared spectrum of 1,2-bis(4-azido-3,5-dinitropyrazole)diazene. DETAILED DESCRIPTION

[0022] The present invention is implemented through the following embodiments, but the conditions and results described in the implementation do not limit the content and rights of the invention.

[0023] The infrared characterization was performed using a Nicolet iS20 Fourier transform infrared spectrometer, the nuclear magnetic resonance characterization was performed using a Swiss BRUKERAV500 (400MHz) nuclear magnetic resonance instrument, and the elemental analysis was performed using a German EXEMENTARVARIO-EL-3 elemental analyzer.

[0024] (1) Synthesis of 5-azido-3-nitro-1,2,4-triazole-1-amine

[0025] At room temperature, sodium hydroxide (1.44 g, 36 mmol), potassium dihydrogen phosphate (4.08 g, 34 mmol) and 34 mL of deionized water were added to a 100 mL round-bottom flask and stirred to mix well. Then 5-azido-3-nitro-1,2,4-triazole (0.62 g, 4 mmol) was added. The mixture was heated to 50 ° C. Then hydroxylamine-O-sulfonic acid (1.13 g, 10 mmol) was slowly added. The feeding time was not less than 30 min. After the addition was completed, the system was heated to 70 ° C. The reaction progress was detected by TLC plate. After the reaction was completed, the temperature was lowered to room temperature, the solid was collected by filtration, washed with water for purification, and vacuum dried to obtain 0.46 g of the target product with a yield of 68%.

[0026] Characterization data:

[0027] 13 C NMR (400MHz, DMSO-d6): δ = 155.63, 148.34.

[0028] 1 H NMR (400MHz, DMSO-d6): δ=6.85.

[0029] FT-IR(KBr,cm -1 ):3296,3172,2161,1558,1522,1501,1444,1403,1309,1245,1122,961,877,816,699.

[0030] EA: C2H2N8O2, theoretical value C14.12, H 1.19, N 65.88; measured value C14.11, H 1.20, N 65.99.

[0031] (2) Synthesis of 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene

[0032] Under ice bath condition of 0-5℃, take a 100mL round-bottom flask, add 50mL acetonitrile solution, then put in 5-azido-3-nitro-1,2,4-triazole-1-amine (1.70g, 10mmol), stir evenly with magnetic force, then slowly drop tert-butyl hypochlorite (1.10g, 10mmol) oxidant, and react the mixed system under ice bath condition for 30min. The reaction was monitored by TLC plate. After the reaction was completed, ethyl acetate (30mL×3) was used for extraction. The organic phases were combined and dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The product was separated and purified by silica gel column with the eluent ratio of PE:EA=1:1. Finally, 1.26g of the target product was obtained with a yield of 75%.

[0033] Characterization data

[0034] 13 C NMR (400MHz, DMSO-d6): δ = 158.70, 152.67.

[0035] FT-IR(KBr,cm -1 ):2151,1565,1541,1526,1492,1444,1418,1379,1296,1188,1035,1010,843,793,707,649.

[0036] EA:C4N 16 O4, theoretical value C14.29, N 66.67; measured value C14.26, N 66.68.

[0037] The above data prove that the structure of the synthesized compound is correct.

[0038] Properties of 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene

[0039] (1) Physical and chemical properties

[0040] Solubility: Insoluble in dichloromethane, chloroform, and water, easily soluble in ethyl acetate, ethanol, methanol, acetone, etc.

[0041] Density: 1.85 g cm -3 , gas density meter.

[0042] (2) Thermal decomposition performance

[0043] 1,2-Bis(5-azido-3-nitro-1,2,4-triazole)diazene has no melting point, and the initial decomposition temperature is 161°C. (DSC method, 5°C·min -1 ).

[0044] (3) Detonation performance

[0045] Enthalpy of formation: The calculated enthalpy of formation is 1417.2 kJ·mol -1 (Gaussian 09 program B3LYP method).

[0046] Detonation velocity: Density is 1.82 g·cm -3 , calculated detonation velocity 9311m·s -1 (EXPLO5ν6·04).

[0047] Explosion pressure: density is 1.82g·cm -3 , the detonation velocity is calculated to be 38.5 GPa (EXPLO5ν6·04).

[0048] Explosion heat: Calculated explosion heat 6080J -1 g, (EXPLO5ν6·04).

[0049] Sensitivity: impact sensitivity 5J, friction sensitivity 54N.

Claims

1. A 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene compound, characterized in that: The structural formula is shown in I:

2. The method for synthesizing a 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene compound according to claim 1, characterized in that: The synthetic route is as follows: The specific steps include: (1) Synthesis of 5-azido-3-nitro-1,2,4-triazole-1-amine At 15 to 25° C., 5-azido-3-nitro-1,2,4-triazole is added to a deionized water solution containing sodium hydroxide and potassium dihydrogen phosphate, the mixed system is heated to 50° C., and then hydroxylamine-O-sulfonic acid is slowly added, the feeding time is not less than 30 minutes, the system is heated to 70° C. after the addition is completed, the degree of reaction is detected by TLC plate, the temperature is lowered to room temperature after the reaction is completed, the solid is collected by filtration, washed with water for purification, and vacuum dried to obtain the target product 5-azido-3-nitro-1,2,4-triazole-1-amine, wherein the molar ratio of sodium hydroxide to 5-azido-3-nitro-1,2,4-triazole is 1 to 9, the molar ratio of potassium dihydrogen phosphate to 5-azido-3-nitro-1,2,4-triazole is 1 to 10, and the molar ratio of hydroxylamine sulfonic acid to 5-azido-3-nitro-1,2,4-triazole is 1 to 3; (2) Synthesis of 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene At 0-20°C, tert-butyl hypochlorite is added to an acetonitrile solution containing 5-azido-3-nitro-1,2,4-triazole-1-amine, the reaction solution is reacted at -5-15°C for 0.5h-4h, poured into 10-50mL ethyl acetate, washed with water, dried and concentrated to obtain 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene, wherein The molar ratio of tert-butyl hypochlorite to 5-azido-3-nitro-1,2,4-triazol-1-amine is 1 to 1.

2.

3. Use of the 1,2-bis(5-azido-3-nitro-1,2,4-triazole)diazene compound according to claim 1 in energetic materials.

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