5,6,5-s-triazine ternary fused ring energetic compound and preparation method thereof

Abstract

The present invention discloses a 5,6,5-s-triazine ternary fused-ring energetic compound and a preparation method thereof. The energetic compound has the following structural formula: #imgabs0# (I), #imgabs1# (II). The preparation method of the 5,6,5-s-triazine ternary fused-ring energetic compound comprises the following steps: A1, preparing 1,3-dinitro-1,2,4-triazole and using the 1,3-dinitro-1,2,4-triazole to prepare compound 1; A2, dissolving compound 1 in water, adding cyanogen bromide, and stirring at room temperature for 24 hours. Filtering the precipitate and washing it with water to obtain an energetic compound having structural formula (I). The present invention utilizes two C‒N-linked bisazole compounds as raw materials, water as a solvent, and ring-closing with cyanogen bromide to obtain two 5,6,5-s-triazine ternary fused-ring energetic compounds having high thermal decomposition temperatures, low mechanical sensitivity, and exhibiting high energy and stability.

Description

Technical Field

[0001] The present invention relates to the technical field of energetic materials, and more specifically, to a 5,6,5-s-triazine ternary fused ring energetic compound and a preparation method thereof. Background Art

[0002] High energy and high stability are eternal themes in the development of energetic materials. The design and synthesis of new high-energy and high-stability energetic compounds holds significant strategic significance for future weapon development. However, the inherent contradiction between high energy and high stability has always been a key research challenge, leading to an urgent need for a high-energy and high-stability energetic compound. Summary of the Invention

[0003] An object of the present invention is to solve at least the above problems and to provide at least the advantages which will be described hereinafter.

[0004] Another object of the present invention is to provide a 5,6,5-s-triazine ternary fused ring energetic compound, which is prepared by using two C‒N bonded bisazole compounds as raw materials, water as solvent, and cyclizing with cyanogen bromide to obtain two 5,6,5-s-triazine ternary fused ring energetic compounds with high thermal decomposition temperature, low mechanical sensitivity, and high energy and stability.

[0005] In order to achieve these objects and other advantages of the present invention, a 5,6,5-s-triazine three-membered fused ring energetic compound is provided. The energetic compound has the following structural formula:

[0006] (I) (II).

[0007] In order to achieve these objects and other advantages of the present invention, a method for preparing a 5,6,5-s-triazine ternary fused ring energetic compound is also provided. The method for preparing the energetic compound of structural formula (I) comprises the following steps:

[0008] A1. preparing 1,3-dinitro-1,2,4-triazole, and using 1,3-dinitro-1,2,4-triazole to prepare compound 1;

[0009] A2. Dissolve compound 1 in water, add cyanogen bromide and stir at room temperature for 24 hours, filter the precipitate and wash it with water to obtain an energetic compound of formula (I);

[0010] Among them, the structural formula of compound 1 is: .

[0011] Preferably, in step A1, the preparation method of 1,3-dinitro-1,2,4-triazole is specifically as follows: trifluoroacetic anhydride and dichloromethane are mixed to obtain a mixed solution, which is set aside; 3-nitro-1,2,4-triazole is dissolved in dichloromethane, ammonium nitrate is added to the system, and the mixed solution is added dropwise to the system. After the addition is completed, the mixture is reacted for 10 hours. After the reaction is completed, the mixture is purified to obtain a light yellow oily product, namely 1,3-dinitro-1,2,4-triazole.

[0012] Preferably, the molar ratio of 3-nitro-1,2,4-triazole to ammonium nitrate is 1:1.

[0013] Preferably, in step A1, the specific method for preparing compound one using 1,3-dinitro-1,2,4-triazole is as follows: dispersing 3,4-dinitro-5-aminopyrazole in anhydrous methanol; dissolving 1,3-dinitro-1,2,4-triazole in anhydrous methanol, and adding the methanol solution of 1,3-dinitro-1,2,4-triazole to 3,4-dinitro-5-aminopyrazole, then adding anhydrous potassium carbonate to the system, heating to 80°C and reacting for 8 hours. After the reaction is completed, filtering and collecting the filter cake to obtain compound one.

[0014] Preferably, the molar ratio of 3,4-dinitro-5-aminopyrazole to 1,3-dinitro-1,2,4-triazole is 1:1.

[0015] In order to achieve these objects and other advantages of the present invention, a method for preparing a 5,6,5-s-triazine ternary fused ring energetic compound is also provided. The method for preparing the energetic compound of structural formula (II) comprises the following steps:

[0016] B1. preparing 1,3,4-trinitro-pyrazole and using 1,3,4-trinitro-pyrazole to prepare compound 2;

[0017] B2. Dissolve compound II in water, add cyanogen bromide and stir at room temperature for 24 hours, filter the precipitate and wash it with water to obtain energetic compounds of structural formula (I) and (II);

[0018] Among them, the structural formula of compound 2 is: .

[0019] Preferably, in step B1, the preparation method of 1,3,4-trinitro-pyrazole is specifically as follows: 3,4-dinitro-pyrazole is dissolved in trifluoroacetic anhydride at 0°C, and then fuming nitric acid is added dropwise. After the addition is completed, the mixture is allowed to react at room temperature for 10 hours. After the reaction is completed, the reaction is quenched and purified to obtain a light yellow oily product, namely 1,3,4-trinitro-pyrazole.

[0020] Preferably, in step B2, the specific method for preparing compound II using 1,3,4-trinitro-pyrazole is as follows: dispersing 3,4-dinitro-5-aminopyrazole in anhydrous methanol; dissolving 1,3,4-trinitro-pyrazole in anhydrous methanol, and adding the methanol solution of 1,3,4-trinitro-pyrazole to 3,4-dinitro-5-aminopyrazole, then adding anhydrous potassium carbonate to the system, heating to 80°C and reacting for 8h. After the reaction is completed, filtering and collecting the filter cake to obtain compound II.

[0021] Preferably, the molar ratio of 3,4-dinitro-5-aminopyrazole to 1,3,4-trinitro-pyrazole is 1:1.

[0022] The present invention has at least the following beneficial effects:

[0023] The present invention uses two C‒N-linked bisazole compounds as raw materials, water as solvent, and cyanogen bromide to react with them to produce two 5,6,5-s-triazine ternary fused ring energetic compounds, TTP and TBP. Both compounds have high thermal decomposition temperatures (285.6°C and 264.8°C) and low mechanical sensitivity (IS = 60 J, FS = 324 N), as well as excellent detonation performance (TBP: vD = 8355 m / s, P = 29.1 GPa; TTP: vD =8859 m / s, P = 34.5 GPa), showing the characteristics of high energy and high stability.

[0024] Other advantages, objectives and features of the present invention will be reflected in part from the following description and will be understood by those skilled in the art through study and practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 A single crystal image of the energetic compound TTP prepared in one embodiment of the present invention;

[0026] Figure 2 A single crystal image of the energetic compound TBP prepared in one embodiment of the present invention;

[0027] Figure 3 This is a hydrogen spectrum of the energetic compound TTP prepared in one embodiment of the present invention;

[0028] Figure 4 This is a hydrogen spectrum of the energetic compound TBP prepared in one embodiment of the present invention;

[0029] Figure 5 This is a carbon spectrum of the energetic compound TTP prepared in one embodiment of the present invention;

[0030] Figure 6 This is a carbon spectrum of the energetic compound TBP prepared in one embodiment of the present invention;

[0031] Figure 7 This is a DSC graph of the energetic compound TTP prepared in one embodiment of the present invention;

[0032] Figure 8 This is the DSC graph of the energetic compound TBP prepared in one example of the present invention. DETAILED DESCRIPTION

[0033] The present invention is further described in detail below with reference to the embodiments so that those skilled in the art can implement the invention with reference to the description.

[0034] In this application, the route for preparing 5,6,5-s-triazine three-membered fused ring energetic compound using Compound 1 and Compound 2 is as follows (the energetic compound of structural formula (I) is named TTP, and the energetic compound of structural formula (II) is named TBP):

[0035]

[0036] <Example 1>

[0037] 5,6,5-s-triazine three-membered fused ring energetic compound, the structural formula of the energetic compound is as follows:

[0038] (I) (II).

[0039] <Example 2>

[0040] 5,6,5-s-triazine three-membered fused ring energetic compound, the structural formula of the energetic compound is as follows:

[0041] (I).

[0042] The preparation method of the energetic compound of structural formula (I) comprises the following steps:

[0043] A1. preparing 1,3-dinitro-1,2,4-triazole, and using 1,3-dinitro-1,2,4-triazole to prepare compound 1;

[0044] A2. Compound 1 was dissolved in water, cyanogen bromide was added, and the mixture was stirred at room temperature for 24 h. The precipitate was filtered and washed with water. The yield of TTP was 69%, that is, the energetic compound of formula (I) was obtained.

[0045] Among them, the structural formula of compound 1 is: .

[0046] In step A1, the preparation method of 1,3-dinitro-1,2,4-triazole is specifically as follows: trifluoroacetic anhydride (10 mL) and dichloromethane (10 mL) are mixed to obtain a mixed solution, which is set aside; 3-nitro-1,2,4-triazole (20 mmol) is dissolved in dichloromethane (20 mL) in an eggplant-shaped flask at room temperature, and ammonium nitrate (20 mmol) is added to the system. The mixed solution is then added dropwise to the system (the temperature is maintained at no more than 30° C. during the addition). After the addition is completed, the mixture is reacted at room temperature for 10 hours. After the reaction is completed (the reaction of the raw material is monitored by TLC), the system is poured into 200 g of crushed ice to quench the reaction. After the quenching is completed, the mixture is extracted three times with dichloromethane, and the dichloromethane layer is retained. The dichloromethane layers after the three extractions are mixed and washed three times with a saturated sodium chloride solution, and then dried over anhydrous sodium sulfate. The solvent is removed by rotary evaporation under reduced pressure to obtain a light yellow oily product, namely 1,3-dinitro-1,2,4-triazole.

[0047] The molar ratio of 3-nitro-1,2,4-triazole and ammonium nitrate is 1:1.

[0048] In step A1, the specific method for preparing compound 1 using 1,3-dinitro-1,2,4-triazole is as follows: 3,4-dinitro-5-aminopyrazole (2 mmol) is dispersed in anhydrous methanol (10 mL); 1,3-dinitro-1,2,4-triazole (2 mmol) is added and dissolved in anhydrous methanol to obtain a methanol solution of 1,3-dinitro-1,2,4-triazole; the methanol solution of 1,3-dinitro-1,2,4-triazole is added to 3,4-dinitro-5-aminopyrazole (dispersed in anhydrous methanol); anhydrous potassium carbonate (2 mmol) is added to the system, the temperature is raised to 80°C, and the reaction is carried out for 8 hours. After the reaction is completed (TLC spot plate monitoring indicates the reaction of the raw materials is complete), the system is cooled to room temperature, filtered, and the filter cake is collected to obtain compound 1. The reaction route is as follows:

[0049] .

[0050] The molar ratio of 3,4-dinitro-5-aminopyrazole to 1,3-dinitro-1,2,4-triazole is 1:1.

[0051] <Example 3>

[0052] 5,6,5-s-triazine three-membered fused ring energetic compound, the structural formula of the energetic compound is as follows:

[0053] (II).

[0054] The preparation method of the energetic compound of structural formula (II) comprises the following steps:

[0055] B1. preparing 1,3,4-trinitro-pyrazole and using 1,3,4-trinitro-pyrazole to prepare compound 2;

[0056] B2. First, compound II was dissolved in water, cyanogen bromide was added, and the mixture was stirred at room temperature for 24 h. The precipitate was filtered and washed with water to obtain an energetic compound of structural formula (II). The yield of TBP was 83%;

[0057] Among them, the structural formula of compound 2 is: .

[0058] In step B1, the preparation method of 1,3,4-trinitro-pyrazole is specifically as follows: 3,4-dinitro-pyrazole (20 mmol) is dissolved in trifluoroacetic anhydride (15 mL) in an eggplant-shaped flask at 0°C, and fuming nitric acid (4.2 mL) is added dropwise. During the dropwise addition, the temperature of the reaction system is maintained at no more than 5°C. After the dropwise addition is completed, the reaction is allowed to react at room temperature for 10 hours. After the reaction is completed (the reaction of the raw materials is monitored by TLC to ensure complete reaction), the reaction is quenched (the system is poured into 200 g of crushed ice to quench the reaction). After quenching the reaction, the product is extracted three times with dichloromethane, and the dichloromethane layer is retained. The dichloromethane layers after the three extractions are mixed and washed three times with a saturated sodium chloride solution, and then dried over anhydrous sodium sulfate. The solvent is removed by rotary evaporation under reduced pressure to obtain a light yellow oily product, namely 1,3,4-trinitro-pyrazole.

[0059] In step B2, the specific method for preparing compound II using 1,3,4-trinitro-pyrazole is as follows: 3,4-dinitro-5-aminopyrazole (2 mmol) is dispersed in anhydrous methanol (10 mL); 1,3,4-trinitro-pyrazole (2 mmol) is dissolved in anhydrous methanol to obtain a methanol solution of 1,3,4-trinitro-pyrazole, the methanol solution of 1,3,4-trinitro-pyrazole is added to 3,4-dinitro-5-aminopyrazole (dispersed in anhydrous ethanol), and anhydrous potassium carbonate (2 mmol) is added to the system. The temperature is raised to 80° C. and the reaction is carried out for 8 hours. After the reaction is completed (TLC spot plate monitoring indicates that the reaction of the raw materials is complete), the mixture is cooled to room temperature and filtered, and the filter cake is collected to obtain compound II. The reaction route is as follows:

[0060] .

[0061] The molar ratio of 3,4-dinitro-5-aminopyrazole to 1,3,4-trinitro-pyrazole is 1:1.

[0062] <Data Representation>

[0063] 1. Single crystal diagrams of TTP and TBP, such as Figure 1 and Figure 2 As shown;

[0064] 2. Hydrogen spectra of TTP and TBP, such as Figure 3 and Figure 4 As shown;

[0065] 3. Carbon spectra of TTP and TBP, such as Figure 5 and Figure 6 As shown;

[0066] 4. DSC diagrams of TTP and TBP, such as Figure 7 and Figure 8 As shown;

[0067] 5. The physical properties and energy data of TTP and TBP are shown in Table 1;

[0068] Table 1 Physical properties and energy data of TTP and TBP

[0069]

[0070] Remark: a Decomposition temperature (heating rate 5 °C min -1 ). b Density, measured with a density meter (25 °C). c Calculation of formation enthalpy - calculation software Gaussian 09 (Revision E.01). d Detonation velocity-EXPLO5 V6.01. e Detonation Pressure - EXPL O5 V6.05. f Impact sensitivity. g Friction sensitivity. h CaHbOcNd oxygen balance, 1600 (cab / 2) / Mw; Mw = molecular weight minus oxygen balance (calculated with CO as the product). RDX: 1,3,5-trinitro-1,3,5-triazacyclohexane; HMX: 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane; TATB: 1,3,5-triamino-2,4,6-trinitrobenzene. The structural formulas of RDX, HMX, and TATB are as follows:

[0071] .

[0072] As can be seen from Table 1, compared with RDX, HMX, and TATB, the two compounds TTP and TBP prepared in this application have higher thermal decomposition temperatures (285.6 °C; 264.8 °C) and lower mechanical sensitivity (IS = 60 J, FS = 324 N), and have excellent detonation performance (TBP: vD= 8355 m / s, P = 29.1 GPa; TTP: vD =8859 m / s, P = 34.5 GPa), showing the characteristics of high energy and high stability.

[0073] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the description and implementation methods. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and embodiments shown and described herein.

Claims

1. 5,6,5-s-triazine three-membered fused ring energetic compound, characterized in that: The structural formula of the energetic compound is as follows: (AND), (II)。 2. The method for preparing a 5,6,5-s-triazine ternary fused ring energetic compound according to claim 1, wherein: The preparation method of the energetic compound of structural formula (I) comprises the following steps: A1. preparing 1,3-dinitro-1,2,4-triazole, and using 1,3-dinitro-1,2,4-triazole to prepare compound 1; A2. Dissolve compound 1 in water, add cyanogen bromide and stir at room temperature for 24 hours, filter the precipitate and wash it with water to obtain an energetic compound of formula (I); Among them, the structural formula of compound 1 is: .

3. The method for preparing a 5,6,5-s-triazine ternary fused ring energetic compound according to claim 2, wherein: In step A1, the preparation method of 1,3-dinitro-1,2,4-triazole is specifically as follows: trifluoroacetic anhydride and dichloromethane are mixed to obtain a mixed solution, which is set aside; 3-nitro-1,2,4-triazole is dissolved in dichloromethane, ammonium nitrate is added to the system, and the mixed solution is added dropwise to the system. After the addition is completed, the mixture is reacted for 10 hours. After the reaction is completed, the mixture is purified to obtain a light yellow oily product, namely 1,3-dinitro-1,2,4-triazole.

4. The method for preparing a 5,6,5-s-triazine ternary fused ring energetic compound according to claim 3, wherein: The molar ratio of 3-nitro-1,2,4-triazole and ammonium nitrate is 1:

1.

5. The method for preparing the 5,6,5-s-triazine ternary fused ring energetic compound according to claim 2, wherein: In step A1, the specific method for preparing compound one using 1,3-dinitro-1,2,4-triazole is as follows: 3,4-dinitro-5-aminopyrazole is dispersed in anhydrous methanol; 1,3-dinitro-1,2,4-triazole is dissolved in anhydrous methanol, and the methanol solution of 1,3-dinitro-1,2,4-triazole is added to 3,4-dinitro-5-aminopyrazole, and then anhydrous potassium carbonate is added to the system, the temperature is raised to 80°C, and the reaction is carried out for 8 hours. After the reaction is completed, it is filtered and the filter cake is collected to obtain compound one.

6. The method for preparing a 5,6,5-s-triazine ternary fused ring energetic compound according to claim 5, wherein: The molar ratio of 3,4-dinitro-5-aminopyrazole to 1,3-dinitro-1,2,4-triazole is 1:

1.

7. The method for preparing a 5,6,5-s-triazine ternary fused ring energetic compound according to claim 1, wherein: The preparation method of the energetic compound of structural formula (II) comprises the following steps: B1. preparing 1,3,4-trinitro-pyrazole and using 1,3,4-trinitro-pyrazole to prepare compound 2; B2. Dissolve compound II in water, add cyanogen bromide and stir at room temperature for 24 hours, filter the precipitate and wash it with water to obtain energetic compounds of structural formula (I) and (II); Among them, the structural formula of compound 2 is: .

8. The method for preparing a 5,6,5-s-triazine ternary fused ring energetic compound according to claim 7, wherein: In step B1, the preparation method of 1,3,4-trinitro-pyrazole is specifically as follows: 3,4-dinitro-pyrazole is dissolved in trifluoroacetic anhydride at 0°C, and fuming nitric acid is added dropwise. After the addition is completed, the mixture is allowed to react at room temperature for 10 hours. After the reaction is completed, the reaction is quenched and purified to obtain a light yellow oily product, namely 1,3,4-trinitro-pyrazole.

9. The method for preparing a 5,6,5-s-triazine ternary fused ring energetic compound according to claim 7, wherein: In step B2, the specific method for preparing compound II using 1,3,4-trinitro-pyrazole is as follows: dispersing 3,4-dinitro-5-aminopyrazole in anhydrous methanol; dissolving 1,3,4-trinitro-pyrazole in anhydrous methanol, and adding the methanol solution of 1,3,4-trinitro-pyrazole to 3,4-dinitro-5-aminopyrazole, and then adding anhydrous potassium carbonate to the system, heating to 80°C and reacting for 8 hours. After the reaction is completed, filtering and collecting the filter cake to obtain compound II.

10. The method for preparing a 5,6,5-s-triazine ternary fused ring energetic compound according to claim 9, wherein: The molar ratio of 3,4-dinitro-5-aminopyrazole to 1,3,4-trinitro-pyrazole is 1:1.

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