2-amino-4, 5-bis (fluorine geminal dinitro)-1, 2, 3-triazole and preparation method thereof
By preparing 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole, the problem of low density of nitrogen heterocyclic energetic compounds was solved, and the density and detonation performance of the compounds were improved.
Patent Information
- Application Number
- CN202511771915.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-28
- Publication Date
- 2026-02-10
AI Technical Summary
Existing nitrogen heterocyclic energetic compounds have low densities, which affects their energy density and detonation performance.
The preparation method of 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole involves reacting 4,5-bis(fluorogesyldinitro)-1,2,3-triazole with an organic solvent solution of potassium hydroxide and O-2,4,6-trimethylbenzenesulfonylhydroxylamine at room temperature to generate 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole.
It increased the density and detonation velocity of the compound, with a 7.1% increase in density, a 3.3% increase in detonation velocity, and a 3.3% increase in detonation pressure, but its sensitivity was relatively low.
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Figure CN121494794A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of energetic materials technology, specifically relating to a 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole and its preparation method. Background Technology
[0002] In recent years, nitrogen-containing five-membered aromatic rings (such as pyrazoles, imidazoles, and 1,2,4-triazoles) have attracted much attention both domestically and internationally due to their high nitrogen content, large gas production, and clean detonation products. The nitrogen and oxygen atoms in these compounds are highly electronegative, and the molecules possess a cyclic conjugated structure, thus exhibiting good thermal stability and low sensitivity. Researchers of energetic materials both domestically and internationally have designed and synthesized various nitrogen-containing energetic compounds, such as 4,5-trinitroimidazole, 4-amino-3,5-dinitropyrazole, and 5-amino-3-nitro-1,2,4-triazole, which possess high energy densities. The combination of fluoro-dinitromethyl, a novel high-energy energetic group, with nitrogen-containing five-membered aromatic rings is expected to further improve the energy density and detonation performance of these compounds.
[0003] However, existing technologies produce nitrogen heterocyclic energetic compounds with low density. Summary of the Invention In view of the above-mentioned shortcomings and defects of the prior art, the purpose of the present invention is to provide a 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole, its preparation method and application, to solve the problem of low density of nitrogen heterocyclic energetic compounds in the prior art.
[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: a 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole, the structure of which is shown below:
[0005] This invention also provides a method for preparing 2-amino-4,5-bis(fluorogestigma)-1,2,3-triazole, which specifically includes the following steps: Step 1: At room temperature, add 4,5-bis(fluorogesyldinitro)-1,2,3-triazole and solvent to the reactor in sequence, and stir until completely dissolved.
[0006] Step 2: Under ice-salt cooling, add potassium hydroxide organic solvent solution dropwise, and continue the reaction after the addition is complete.
[0007] Step 3: After the reaction is complete, add dropwise a substance containing [a specific ingredient] to the above reaction solution under ice-salt cooling. OThe organic solvent solution of -2,4,6-trimethylbenzenesulfonylhydroxylamine was reacted at room temperature, filtered, the filtrate was concentrated, washed with ether, and dried to give 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole (pale yellow solid).
[0008] The present invention also has the following technical features: The 4,5-bis(fluorogesyldinitro)-1,2,3-triazole, potassium hydroxide, O The molar ratio of -2,4,6-trimethylbenzenesulfonylhydroxylamine is 1:1 to 1.5:1 to 2.
[0009] In step one, the solvent is methanol or acetonitrile, and the solvent volume is 5 to 20 mL.
[0010] In step two, the temperature of the ice salt is -5 to 5°C.
[0011] In step two, after adding potassium hydroxide, the reaction time is 0.5 to 2 hours.
[0012] In step two, the organic solvent is methanol or acetonitrile.
[0013] In step three, the room temperature reaction temperature range is 15–25°C.
[0014] In step three, the reaction time at room temperature is 12–24 hours.
[0015] The 4,5-bis(fluorogesyldinitro)-1,2,3-triazole, potassium hydroxide, O The molar ratio of -2,4,6-trimethylbenzenesulfonylhydroxylamine is 1:1:1.5.
[0016] In step three, the room temperature reaction temperature is 25°C.
[0017] In step three, the reaction time at room temperature is 20 hours.
[0018] The 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole of the present invention is used as an energetic material.
[0019] Compared with the prior art, the beneficial technical effects of this invention are: (I) The 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole of the present invention has a relatively high calculated density, which is 1.96 g / cm³. 3 The density of 2-amino-4,5-dinitro-1,2,3-2H-triazole in the comparative literature is 1.83 g / cm³. 3 This represents an increase of 7.1%.
[0020] (2) The 4,5-bis(fluorogesyldinitro)-1,2,3-triazole compound of the present invention has high energy, with a calculated detonation velocity of 8878 m / s and a detonation pressure of 37.2 GPa. Compared with the calculated detonation pressure of 36.2 GPa for 2-amino-4,5-dinitro-1,2,3-2H-triazole in the comparative document, this represents an improvement of 3.3%. Attached Figure Description Figure 1 The image shows the infrared spectrum of compound 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole from Example 1 of this invention.
[0021] Figure 2 This is the 1H NMR spectrum of compound 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole in Example 1 of this invention.
[0022] Figure 3 This is the carbon NMR spectrum of compound 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole in Example 1 of this invention.
[0023] Figure 4 This is the NMR fluorine spectrum of compound 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole in Example 1 of this invention.
[0024] Figure 5 This is the DSC diagram of compound 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole in Example 1 of this invention.
[0025] The specific content of the present invention will be further explained in detail below with reference to the embodiments. Detailed Implementation
[0026] It should be noted that, unless otherwise specified, all raw materials used in this invention are those known in the prior art.
[0027] The following are specific embodiments of the present invention. It should be noted that the present invention is not limited to the following specific embodiments. All equivalent modifications made based on the technical solutions of this application fall within the protection scope of the present invention.
[0028] The present invention provides 4,5-bis(fluorogestigma)-1,2,3-triazole and its synthesis method. The molecular structure of 2-amino-4,5-bis(fluorogestigma)-1,2,3-triazole is shown below:
[0029] Using 4,5-bis(fluorogesyldinitro)-1,2,3-triazole as a starting material, its structural formula is shown below:
[0030] Using O-2,4,6-trimethylbenzenesulfonylhydroxylamine (MSH) as the amination reagent, its structural formula is shown below:
[0031] The synthetic route for the 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole compound of the present invention is as follows:
[0032] A method for preparing 2-amino-4,5-bis(fluorogestigma)-1,2,3-triazole, specifically comprising the following steps: Step 1: At room temperature, add 4,5-bis(fluorogesyldinitro)-1,2,3-triazole and solvent to the reactor in sequence, and stir until completely dissolved.
[0033] Step 2: Under ice-salt cooling, add potassium hydroxide organic solvent solution dropwise, and continue the reaction after the addition is complete.
[0034] Step 3: After the reaction is complete, add a mixture containing [a specific ingredient] dropwise to the above reaction solution under ice-salt cooling. O The organic solvent solution of -2,4,6-trimethylbenzenesulfonylhydroxylamine was reacted at room temperature, filtered, the filtrate was concentrated, washed with ether, and dried to give 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole (pale yellow solid).
[0035] The 4,5-bis(fluorogesyldinitro)-1,2,3-triazole, potassium hydroxide, O The molar ratio of -2,4,6-trimethylbenzenesulfonylhydroxylamine is 1:1 to 1.5:1 to 2.
[0036] In step one, the solvent is methanol or acetonitrile, and the solvent volume is 5-20 mL.
[0037] In step two, the temperature of the ice salt is -5 to 5°C.
[0038] In step two, after adding potassium hydroxide, the reaction time is 0.5 to 2 hours.
[0039] In step two, the organic solvent is methanol or acetonitrile.
[0040] In step three, the room temperature reaction temperature range is 15–25°C.
[0041] In step three, the reaction time at room temperature is 12–24 hours.
[0042] The 4,5-bis(fluorogesyldinitro)-1,2,3-triazole, potassium hydroxide, OThe molar ratio of -2,4,6-trimethylbenzenesulfonylhydroxylamine is 1:1:1.5.
[0043] In step three, the room temperature reaction temperature is 25°C. In step three, the reaction time at room temperature is 20 hours.
[0044] Example 1: At room temperature, 0.313 g (1 mmol) of 4,5-bis(fluorogesyldinitro)-1,2,3-triazole and 8.0 mL of methanol were added sequentially to a reaction flask, stirred to dissolve, cooled with ice salt, and at 0 °C, 2.0 mL of a methanol solution containing 0.056 g (1 mmol) of potassium hydroxide was added dropwise. After the addition was complete, the reaction was maintained for 1 h. After the reaction was completed, 13.0 mL of anhydrous acetonitrile was added to the above reaction solution, cooled with ice salt, and at 0 °C, 3.0 mL of an acetonitrile solution containing 0.32 g (1.5 mmol) of MSH was added dropwise. The reaction was maintained at room temperature for 20 h, filtered, the filtrate was concentrated, washed with diethyl ether, and dried to obtain 0.08 g of white solid, with a yield of 46%.
[0045] Structural assessment: IR (KBr, cm -1 ): 3474,3187 (NH), 1452,1186 (-NO2), 1441 (CF), 1093 (CN), 1021,845,582 (triazole ring) 1 H NMR (DMSO, 500 MHz): 6.75 (NH) 13 C NMR (DMSO, 125 MHz): 159.03 (CF), 135.78 (C) 19F NMR (DMSO, 500MHz): -91.99 (CF) Elemental analysis: (%) calculated for C4H3F2N8O8 (313.09): C 14.64; H0.61; N 34.15. Found C 14.58; H 0.64; N 34.18.
[0046] The above structural identification data confirms that the obtained substance is indeed 2-amino-4,5-bis(fluorogesyl)-1,2,3-triazole.
[0047] Example 2: At room temperature, 0.313 g (1 mmol) of 4,5-bis(fluorogesyldinitro)-1,2,3-triazole and 8.0 mL of methanol were added sequentially to a reaction flask, stirred to dissolve, cooled with ice salt, and at 0 °C, 2.0 mL of a methanol solution containing 0.084 g (1.5 mmol) of potassium hydroxide was added dropwise. After the addition was complete, the reaction was maintained for 1 h. After the reaction was completed, 13.0 mL of anhydrous acetonitrile was added to the above reaction solution, cooled with ice salt, and at 0 °C, 3.0 mL of an acetonitrile solution containing 0.32 g (1.5 mmol) of MSH was added dropwise. The reaction was maintained at room temperature for 20 h, filtered, the filtrate was concentrated, washed with diethyl ether, and dried to obtain 0.06 g of white solid, with a yield of 37%.
[0048] Example 3: At room temperature, 0.313 g (1 mmol) of 4,5-bis(fluorogesyldinitro)-1,2,3-triazole and 8.0 mL of methanol were added sequentially to a reaction flask, stirred to dissolve, cooled with ice salt, and at 0 °C, 2.0 mL of a methanol solution containing 0.056 g (1 mmol) of potassium hydroxide was added dropwise. After the addition was complete, the reaction was maintained for 1 h. After the reaction was completed, 13.0 mL of anhydrous acetonitrile was added to the above reaction solution, cooled with ice salt, and at 0 °C, 3.0 mL of an acetonitrile solution containing 0.24 g (1 mmol) of MSH was added dropwise. The reaction was maintained at room temperature for 20 h, filtered, the filtrate was concentrated, washed with diethyl ether, and dried to obtain 0.04 g of white solid, with a yield of 24%.
[0049] Example 4: At room temperature, 0.313 g (1 mmol) of 4,5-bis(fluorogesyldinitro)-1,2,3-triazole and 8.0 mL of methanol were added sequentially to a reaction flask, stirred to dissolve, cooled with ice salt, and at 0 °C, 2.0 mL of methanol solution containing 0.056 g (1 mmol) of potassium hydroxide was added dropwise. After the addition was complete, the reaction was maintained for 1 h. After the reaction was completed, 13.0 mL of anhydrous acetonitrile was added to the above reaction solution, cooled with ice salt, and at 0 °C, 3.0 mL of acetonitrile solution containing 0.47 g (2 mmol) of MSH was added dropwise. The reaction was maintained at room temperature for 20 h, filtered, the filtrate was concentrated, washed with diethyl ether, and dried to obtain 0.07 g of white solid, with a yield of 40%.
[0050] The properties of the 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole of this invention: (1) Physicochemical properties: Appearance: White solid.
[0051] Density: 1.96 g / cm³ 3 , Gaussian 09 program B3LYP method.
[0052] (2) Detonation performance: Detonation velocity: density is 1.96 g / cm³ 3Calculate the detonation velocity as 8878 m / s using the KJ equation.
[0053] Explosion pressure: density is 1.96 g / cm³ 3 The explosion pressure was calculated to be 37.2 GPa using the KJ equation.
[0054] The use of 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole in this invention.
[0055] The 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole compound of this invention has the characteristics of high density, high energy and low sensitivity, and can be used as an energetic material component in the fields of mixed explosives, solid propellants and propellants.
[0056] The 4,5-bis(fluorogesyldinitro)-1,2,3-triazole of this application accounts for approximately 85-90% of the total mass when used as a mixed explosive and propellant, and approximately 5-15% of the total mass when used as an oxidizer in a solid propellant.
[0057] Comparative example: Yanqiang Zhang et al., in their paper "Derivatives of 5-nitro-1,2,3-2H-triazole-high-performance energetiv materials" Journal of Materials Chemistry A ; 2013(3); 585- 593) disclosed the synthetic process of 2-amino-4,5-dinitro-1,2,3-2H-triazole, and the structure of the compound is shown in (I):
[0058] According to the inventor's tests, the density of compound (I) is 1.83 g / cm³. 3 It has a detonation velocity of 8843 m / s, a detonation pressure of 36.2 GPa, and an impact sensitivity of 24 J. However, its density is relatively low. The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions conceived by those skilled in the art within the scope of the technology disclosed in the present invention without creative effort are covered within the scope of protection of the present invention.
Claims
1. A 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole, characterized in that, The structure is as follows: 。 2. A method for preparing 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole as described in claim 1, characterized in that, Specifically, the steps include the following: Step 1: At room temperature, add 4,5-bis(fluorogesyldinitro)-1,2,3-triazole and solvent to the reactor in sequence, and stir until completely dissolved; Step 2: Under ice-salt cooling, add potassium hydroxide organic solvent solution dropwise, and maintain the reaction after the addition is complete; Step 3: After the reaction is complete, add dropwise a substance containing [a specific ingredient] to the above reaction solution under ice-salt cooling. O The organic solvent solution of -2,4,6-trimethylbenzenesulfonylhydroxylamine was reacted at room temperature, filtered, the filtrate was concentrated, washed with ether, and dried to give 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole (pale yellow solid).
3. The method for preparing 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole as described in claim 2, characterized in that, The 4,5-bis(fluorogesyldinitro)-1,2,3-triazole, potassium hydroxide, O The molar ratio of -2,4,6-trimethylbenzenesulfonylhydroxylamine is 1:1 to 1.5:1 to 2.
4. The method for preparing 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole as described in claim 2, characterized in that, In step one, the solvent is methanol or acetonitrile.
5. The method for preparing 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole as described in claim 2, characterized in that, In step two, the temperature of the ice salt is -5 to 5°C; In step two, after adding potassium hydroxide, the reaction time is 0.5 to 2 hours. In step two, the organic solvent is methanol or acetonitrile.
6. The method for preparing 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole as described in claim 2, characterized in that, In step three, the room temperature reaction temperature range is 15–25°C. In step three, the reaction time at room temperature is 12–24 hours.
7. The method for preparing 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole as described in claim 2, characterized in that, The 4,5-bis(fluorogesyldinitro)-1,2,3-triazole, potassium hydroxide, O The molar ratio of -2,4,6-trimethylbenzenesulfonylhydroxylamine is 1:1:1.
5.
8. The method for preparing 2-amino-4,5-bis(fluoroges-dinitro)-1,2,3-triazole as described in claim 2, characterized in that, In step one, the solvent is acetonitrile.
9. The method for preparing 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole as described in claim 2, characterized in that, In step two, the temperature of the ice salt is 0°C; In step two, after adding potassium hydroxide, the reaction time is 1 hour. In step two, the organic solvent is acetonitrile.
10. The method for preparing 2-amino-4,5-bis(fluorogesyldinitro)-1,2,3-triazole as described in claim 2, characterized in that, In step three, the room temperature reaction temperature is 25°C. In step three, the reaction time at room temperature is 20 hours.