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

Abstract

The invention discloses a 1, 2-bis (4-azido-3, 5-dinitro pyrazole) diazene compound, and the structure of the 1, 2-bis (4-azido-3, 5-dinitro pyrazole) diazene compound is as shown in a figure I. A synthesis process of the compound comprises the following steps: (1) carrying out a diazotization reaction on 4-amino-3, 5-dinitropyrazole to obtain 4-azido-3, 5-dinitropyrazole; (2) enabling the 4-azido-3, 5-dinitropyrazole to react with sodium hydroxide and O-2, 4, 6-trinitrobenzene hydroxylamine in sequence to generate 4-azido-3, 5-dinitropyrazole-1-amine, and enabling the 4-azido-3, 5-dinitropyrazole-1-amine to react with the sodium hydroxide and the O-2, 4, 6-trinitrobenzene hydroxylamine in sequence; and (3) carrying out a coupling reaction on the 4-azido-3, 5-dinitropyrazole-1-amine under the action of tert-butyl hypochlorite to generate the 1, 2-bis (4-azido-3, 5-dinitropyrazole) diazene. The 1, 2-bis (4-azido-3, 5-dinitropyrazole) diazene synthesized by the method has excellent detonation performance, and has the potential to be used as a high-energy single-compound explosive. # imgabs0 #

Description

Technical Field

[0001] The invention relates to 1,2-bis(4-azido-3,5-dinitropyrazole)diazene 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] High-energy explosives refer to explosives that can release a large amount of explosive energy, usually with characteristics such as high detonation velocity, high detonation heat and high detonation pressure. They are widely used in many fields, and high-energy explosives play an important role in the military field. They are used to make military weapon systems such as bombs, explosive packs, missiles and rockets. The explosive energy of high-energy explosives can quickly destroy enemy facilities, equipment and personnel, and plays a key role in attack, destruction and defense in war. At the same time, high-energy explosives also play an important role in civilian fields such as civil blasting and oil extraction, generating powerful shock waves and vibrations to achieve the effect of rapid destruction and removal. High explosive pressure can generate huge vibrations and impact forces, causing rocks to break and disintegrate, thereby facilitating mining operations.

[0003] The detonation velocity of traditional high-energy explosives is generally difficult to exceed 9500m / s, such as 8750m / s for RDX and 9100m / s for HMX. With the high-energy performance requirements of modern warfare for single-element explosives, traditional single-element explosives can no longer meet the requirements, and high-energy explosives with higher detonation velocity, higher detonation pressure, and higher detonation heat are needed. CL-20 is an ultra-high detonation velocity explosive, and its detonation velocity can reach about 9520m / s, but its synthesis process is complicated. The present invention discloses for the first time a high-energy explosive 1,2-bis(4-azido-3,5-dinitropyrazole)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 material 1,2-bis(4-azido-3,5-dinitropyrazole)diazene with high detonation velocity, high detonation heat and high detonation pressure, and provide a synthesis method of 1,2-bis(4-azido-3,5-dinitropyrazole)diazene.

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

[0006]

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

[0008]

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

[0010] (1) Synthesis of 4-azido-3,5-dinitropyrazole

[0011] At 20 to 50° C., 4-amino-3,5-dinitropyrazole is dissolved in dilute hydrochloric acid, sodium nitrite is added at 0 to 20° C., and the reaction solution is stirred at 0 to 10° C. for 2 to 10 hours. Sodium azide is added at -5 to 15° C., and the reaction solution is stirred at 10 to 40° C. for 1 to 5 hours, and then the reaction is stopped. The reaction solution is poured into crushed ice, extracted with ethyl acetate, dried and concentrated to obtain 4-azido-3,5-dinitropyrazole, wherein the molar ratio of sodium nitrite to 4-amino-3,5-dinitropyrazole is 1 to 10, and the molar ratio of sodium azide to 4-amino-3,5-dinitropyrazole is 1 to 4.

[0012] (2) Synthesis of 4-azido-3,5-dinitropyrazole-1-amine

[0013] At 10-20°C, sodium hydroxide is added to an anhydrous acetonitrile solution containing 4-azido-3,5-dinitropyrazole, and the reaction solution is stirred at 20-50°C for 1-4 hours. PHA is added at 0-10°C, and the reaction solution is reacted at 0-20°C for 12-48 hours to stop the reaction, filtered, concentrated, and separated by chromatography to obtain 4-azido-3,5-dinitropyrazole-1-amine, wherein the molar ratio of 4-azido-3,5-dinitropyrazole to sodium hydroxide is 1-4, and the molar ratio of PHA to 4-azido-3,5-dinitropyrazole is 1-3.

[0014] (3) Synthesis of 1,2-bis(4-azido-3,5-dinitropyrazole)diazene

[0015] At 0-20°C, add tert-butyl hypochlorite to an acetonitrile solution containing 4-azido-3,5-dinitropyrazole-1-amine, react at -5-15°C for 0.5h-4h, pour into 10-50ml ethyl acetate, wash with water, dry and concentrate to obtain 1,2-bis(4-azido-3,5-dinitropyrazole)diazepine.

[0016] Beneficial Effects

[0017] 1. The 1,2-bis(4-azido-3,5-dinitropyrazole)diazene compound of the present invention has high energy performance, with a detonation velocity of 9800 m / s, a detonation pressure of 43 Gpa, and a detonation heat of 6840 J / g;

[0018] 2. The synthesis method of the 1,2-bis(4-azido-3,5-dinitropyrazole)diazene compound of the present invention is simple and the reaction conditions are mild;

[0019] 3. The 1,2-bis(4-azido-3,5-dinitropyrazole)diazene compound of the present invention can be used in the field of high-energy explosives. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is the molecular structure diagram of 1,2-bis(4-azido-3,5-dinitropyrazole)diazene.

[0021] Figure 2 This is the DSC chart 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 4-azido-3,5-dinitropyrazole

[0025] At room temperature, 4-amino-3,5-dinitropyrazole (6.96 g, 40.00 mmol) was dissolved in dilute hydrochloric acid (20 mL, 20%), sodium nitrite (6.28 g, 90.00 mmol) was added at 10°C, and the reaction solution was stirred at 0°C for 5 h. Sodium azide was added at 0°C, and the reaction solution was stirred at 15°C for 1 h before stopping the reaction. The reaction solution was poured into crushed ice and extracted with ethyl acetate 3 times, 150 mL each time. The extract was dried and concentrated to obtain 5.17 g of white solid, with a yield of 65%.

[0026] Characterization data

[0027] 13 C NMR (400MHz, DMSO-d6): δ = 147.42, 115.91.

[0028] FT-IR(KBr,cm -1 ):3618,3470,2900,2727,2223,2125,1574,1500,1423,1369,1312,1247,1114,1011,834.

[0029] EA: C3HN7O4, theoretical value C18.10, H 0.51, N 49.25; measured value C18.08, H 1.02, N 48.58.

[0030] (2) Synthesis of 4-azido-3,5-dinitropyrazole-1-amine

[0031] At room temperature, 4-azido-3,5-dinitropyrazole (0.398 g, 2 mmol) was dissolved in 20 mL of anhydrous acetonitrile solution, sodium hydroxide (0.10 g, 2.5 mmol) was added, and the reaction solution was stirred at 40°C for 3 h. PHA (0.492 g, 2 mmol) was added at 0°C, and the reaction solution was reacted at 15°C for 48 h to stop the reaction, filtered, and the filtrate was concentrated and separated by chromatography column (ethyl acetate: petroleum ether = 1:6), and vacuum dried to obtain 0.23 g of white needle-like solid with a yield of 53%.

[0032] Characterization data

[0033] 13 C NMR (400MHz, DMSO-d6): δ=165,150,95.

[0034] FT-IR(KBr,cm -1 ):3351,2161,2133,1567,1533,1506,1448,1322,1264,1075,948,872,804,774,755.

[0035] EA: C3HN7O4, theoretical value C16.83, H 0.94, N 52.34; measured value C16.81, H 1.08, N 52.31.

[0036] (3) Synthesis of 1,2-bis(4-azido-3,5-dinitropyrazole)diazene

[0037] At 0°C, 4-azido-3,5-dinitropyrazole-1-amine (1.07 g, 5 mmol) was dissolved in acetonitrile solution, tert-butyl hypochlorite (1.08 g, 10 mmol) was added, and the reaction solution was reacted at -5°C for 1 h, poured into 40 mL of ethyl acetate, washed with saturated brine 3 times, 15 mL each time, dried and concentrated to obtain 0.10 g of yellow solid, with a yield of 48%.

[0038] Characterization data

[0039] 13 C NMR (400MHz, DMSO-d6): δ=161,99.

[0040] FT-IR(KBr,cm -1 ):2161,2143,1567,1533,1448,1312,1244,1175,912,856,804,774,755.

[0041] EA: C3HN7O4, theoretical value C 16.99, N 52.48; measured value C 16.89, N 52.40.

[0042] The above data prove that the structure of the synthesized compound is correct.

[0043] Properties of 1,2-bis(4-azido-3,5-dinitropyrazole)diazene

[0044] 1 Physical and chemical properties

[0045] Solubility: Insoluble in dichloromethane, chloroform, and water, easily soluble in ethyl acetate, ethanol, methanol, acetone, etc.

[0046] Density: 1.89 g / cm 3 , gas density meter.

[0047] 2 Thermal performance

[0048] 1,2-Bis(4-azido-3,5-dinitropyrazole)diazene has no melting point, and the initial decomposition temperature is 165°C. (DSC method, 10°C·min -1 ).

[0049] 3 Detonation performance

[0050] Enthalpy of formation: The calculated enthalpy of formation is 1549 kJ / mol (Gaussian 09 program B3LYP method).

[0051] Detonation velocity: density is 1.89g / cm 3 , the detonation velocity is calculated to be 9800m / s (EXPLO5ν6·04).

[0052] Explosion pressure: density is 1.89g / cm 3 , the detonation velocity is calculated to be 43 Gpa (EXPLO5ν6·04).

[0053] Explosion heat: calculated explosion heat 6893 J / g, (EXPLO5ν6·04).

[0054] Sensitivity: impact sensitivity 3.6J, friction sensitivity 20N.

Claims

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

2. The method for synthesizing a 1,2-bis(4-azido-3,5-dinitropyrazole)diazene compound according to claim 1, characterized in that: The synthetic route is as follows: The specific steps include: (1) Synthesis of 4-azido-3,5-dinitropyrazole At 20 to 50°C, 4-amino-3,5-dinitropyrazole is dissolved in dilute hydrochloric acid, sodium nitrite is added at 0 to 20°C, and the reaction solution is stirred at 0 to 10°C for 2 to 10 hours. At -5 to 15°C, sodium azide is added, and the reaction solution is stirred at 10 to 40°C for 1 to 5 hours, then the reaction is stopped, and the reaction solution is poured into crushed ice, extracted with ethyl acetate, dried and concentrated to obtain 4-azido-3,5-dinitropyrazole, wherein the molar ratio of sodium nitrite to 4-amino-3,5-dinitropyrazole is 1 to 10, and the molar ratio of sodium azide to 4-amino-3,5-dinitropyrazole is 1 to 4; (2) Synthesis of 4-azido-3,5-dinitropyrazole-1-amine At 10-20°C, sodium hydroxide is added to an anhydrous acetonitrile solution containing 4-azido-3,5-dinitropyrazole, and the reaction solution is stirred at 20-50°C for 1-4 hours. PHA is added at 0-10°C, and the reaction solution is reacted at 0-20°C for 12-48 hours to stop the reaction, filtered, concentrated, and separated by chromatography to obtain 4-azido-3,5-dinitropyrazole-1-amine, wherein the molar ratio of 4-azido-3,5-dinitropyrazole to sodium hydroxide is 1-4, and the molar ratio of PHA to 4-azido-3,5-dinitropyrazole is 1-3; (3) Synthesis of 1,2-bis(4-azido-3,5-dinitropyrazole)diazene At 0-20°C, add tert-butyl hypochlorite to an acetonitrile solution containing 4-azido-3,5-dinitropyrazole-1-amine, react at -5-15°C for 0.5h-4h, pour into 10-50ml ethyl acetate, wash with water, dry and concentrate to obtain 1,2-bis(4-azido-3,5-dinitropyrazole)diazepine.

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