CN115340501A - Energetic ionic salt based on bitriazole compound and synthetic method thereof - Google Patents

Abstract

The invention discloses an energetic ionic salt based on a bitriazole compound and a synthesis method thereof. The method comprises the following steps: (1) 5-nitro-2H-1, 2, 3-triazole-4-carboxylic acid and 1, 3-diaminoguanidine hydrochloride are subjected to cyclization reaction to prepare 5- (5-nitro-2H-1, 2, 3-triazole-4-yl) -4H-1,2, 4-triazole-3, 4-diamine; (2) Ammonia water, hydrazine hydrate and hydroxylamine aqueous solution with high nitrogen content are selected to respectively undergo salt forming reaction to prepare corresponding energetic ionic salt. The energetic ionic salt synthesized by the method has good detonation performance and positive formation enthalpy; (3) The 5- (5-nitro-2H-1, 2, 3-triazole-4-yl) -4H-1,2, 4-triazole-3, 4-diamine is subjected to nitration reaction to prepare the N- (3-amino-5- (5-nitro-2H-1, 2, 3-triazole-4-yl) -4H-1,2, 4-triazole-4-yl) nitramide. The method has the advantages of simple synthetic process, mild reaction conditions, high safety, economic and easily-obtained raw materials, high product yield, realization of large-scale production and wide application in the field of energetic materials.

Description

Energetic ion salt based on bitriazole compound and its synthesis method

technical field

The invention belongs to the field of energetic materials, and relates to an energetic ion salt based on bitriazole compounds and a synthesis method thereof.

Background technique

The design and study of new energetic materials with great potential value in fields such as explosives, propellants and pyrotechnics has been the focus of many research groups around the world. In the past two centuries, the development of high-energy materials has gone through three stages. The first-generation energetic materials such as TNT and TATB are designed based on benzene skeleton and have low knock performance. Second-generation energetic materials derived from cyclic and aliphatic nitramine structures, such as RDX and HMX, exhibited decreased stability despite enhanced detonation properties of the compounds. The third-generation compounds have high detonation performance and high sensitivity based on the caged nitramine structure, such as CL-20. Obviously, the arrival of each generation has greatly promoted the rapid development of high-energy materials. However, during the research process, there has always been a serious contradiction between high energy and low sensitivity. To develop a new generation of high-energy compounds, many properties should be considered, including high energy, low sensitivity, good thermal stability, environmental friendliness, and transportation safety. Therefore, research on new energy molecular frameworks must be considered. Studies have found that nitrogen-rich heterocyclic frameworks play a key role in new high-energy-density materials because they store huge energy in the N-N and N=N bonds of heterocyclic frameworks and have positive heat of formation.

Nitrogen-rich heterocyclic compounds have attracted great attention in the development of new high-energy compounds. Among them, the triazole molecular skeleton exhibits high nitrogen content, high density, and high enthalpy of formation, and thus is often selected as a possible building block for the structure of nitrogen-rich heterocycles. The triazole molecular skeleton includes 1,2,3-triazole and 1,2,4-triazole, and 1,2,3-triazole is due to the NNN(N3) structure ratio of 1,2,4-triazole (Δ _f H _m = 182kJ mol ^-1 ) has a higher heat of formation. This method of introducing 1,2,3-triazole into energetic molecules can improve the detonation performance of energetic compounds, besides the efficient contribution to the heat of formation of the heterocyclic skeleton, the amino group attached to the main chain Groups are also important to the properties of the compound. And the introduction of amino groups can promote the formation of intramolecular and intermolecular hydrogen bonds, thereby improving the density and stability of the compound, thereby improving the problem of low sensitivity of the compound.

The literature (From N-nitro to N-nitroamino: preparation of high-performance energetic materials by introducing nitrogen-containing ions [J]. Angew. Chem. Int. Ed. 2015, 54, 14513-14517) reported a compound 2, 2'-Dinitroamino-5,5'-dinitro-3,3'-bi-1,2,4 triazole, the thermal decomposition temperature of this compound is 121°C, the impact sensitivity is 3J, and the friction sensitivity is 40N. The low thermal stability and sensitivity of this compound lead to great difficulties in storage and transportation, and there are great safety hazards in the actual production process, which limits the practical application.

Contents of the invention

In order to improve the existing stability problems of bitriazole compounds, the purpose of the present invention is to provide an energetic ion salt based on bitriazole compounds.

The technical solution for realizing the object of the present invention is: a kind of 5-(5-nitro-2H-1,2,3-triazole-4-yl)-4H-1,2,4-triazole-3,4 -Diamine energy-containing ion salt (formula 1,2,3), its structure is as follows:

A kind of N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl)nitroamide Energetic ion salt (formula 4,5), its structure is as follows:

The above-mentioned 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine energetic ion salt (formula 1, 2,3) the synthetic method, comprises:

(1) 5-nitro-2H-1,2,3-triazole-4-carboxylic acid (a) and 1,3-diaminoguanidine hydrochloride (b) are related in polyphosphoric acid reaction system ring reaction to prepare 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine (c),

(2) 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine (c) and ammonia , hydrazine hydrate or hydroxylamine aqueous solution respectively produce the step of salt-forming reaction to prepare target product,

Preferably, in step (1), the polyphosphoric acid reaction system is a mixed system of phosphorus pentoxide and orthophosphoric acid in a ratio of 1.5g:0.5-5.5ml.

Preferably, in step (1), the molar ratio of 5-nitro-2H-1,2,3-triazole-4-carboxylic acid to 1,3-diaminoguanidine hydrochloride is 1:0.8-5.0.

Preferably, in step (1), the reaction temperature is 100-150°C.

Preferably, in step (2), the solvent of the reaction system is any one of anhydrous methanol, water, anhydrous ethanol and acetonitrile; the reaction temperature is 20°C to 100°C.

The above-mentioned N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl)nitroamide contains The synthetic method of energy ion salt (formula 4,5), comprises the following steps:

(1) 5-nitro-2H-1,2,3-triazole-4-carboxylic acid (a) and 1,3-diaminoguanidine hydrochloride (b) are related in polyphosphoric acid reaction system ring reaction to prepare 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine (c),

(2) 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine (c) and nitrated Preparation of N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl by nitration reaction ) the step of nitroamide (d),

(3) N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl) Nitramide (d) and hydrazine hydrate or hydroxylamine aqueous solution generate the step of salt-forming reaction respectively to prepare target product,

Preferably, in step (1), the polyphosphoric acid reaction system is a mixed system of phosphorus pentoxide and orthophosphoric acid in a ratio of 1.5g:0.5-5.5ml.

Preferably, in step (1), the molar ratio of 5-nitro-2H-1,2,3-triazole-4-carboxylic acid to 1,3-diaminoguanidine hydrochloride is 1:0.8-5.0.

Preferably, in step (1), the reaction temperature is 100-150°C.

Preferably, in step (2), the nitrating reagent is any one of 100% HNO ₃ , 98% H ₂ SO ₄ /HNO ₃ and 98% HNO ₃ ; 5-(5-nitro-2H-1,2, The feeding ratio of 3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine to nitrating reagent is 1g:5~25ml; the reaction temperature is -15°C~-5°C.

Preferably, in step (3), the solvent of the reaction system is any one of anhydrous methanol, water, anhydrous ethanol and acetonitrile; the reaction temperature is 20°C to 100°C.

Compared with the prior art, the innovation of the present invention is:

(1) The present invention synthesizes new high-energy and low-sensitivity energetic compounds based on the combination of 1,2,3-triazole and 1,2,4-triazole molecular skeletons. Compared with the reported bi-1,2,4-triazole compounds, the thermal stability, impact sensitivity and friction sensitivity are all improved.

(2) The synthesis of the energetic ion salt in the present invention further improves the detonation performance of the compound.

(3) In the present invention, by comparing different nitrating reagents and feeding amounts, the optimal nitrating reagent is determined, and the productive rate of the target compound is maximized.

Description of drawings

Figure 1 is the single crystal diagram of 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine hydrazine salt .

Detailed ways

The synthetic route of the energetic ion salt of the present invention is as follows:

Example 1

Polyphosphoric acid reaction system: slowly melt phosphorus pentoxide (5.0 g, 35.0 mmol) in phosphoric acid (15.0 g, 153.0 mmol), and heat the solution to 50°C.

5-nitro-2H-1,2,3-triazole-4-carboxylic acid (1.57g, 10.0mmol, 1.0 times equivalent) and diaminoguanidine monohydrochloride (1.88g, 15.0mmol, 1.5 times equivalent ) The mixture is slowly added to the polyphosphoric acid reaction system. The viscous mixture was then gradually raised to 120°C. The mixture was stirred at 120 °C for 10 h, then cooled to room temperature. The reaction solution was poured into ice water (20.0 mL), and then adjusted to pH=2 with concentrated sodium hydroxide solution. The precipitate was filtered, washed with copious amounts of water and dried under vacuum to give 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3, 4-Diamine (c) is a white powder with a yield of 61.9%.

¹ H NMR (500MHz, DMSO-d ₆ ): δ＝8.19(s, 2H), 5.86 (s, 2H) ppm. ¹³ C NMR (125MHz, DMSO-d ₆ ): δ＝152.80, 151.57, 144.75, 125.87 ppm.IR(KBr): v=3431,3318,3218,1683,1633,1504,1380,1251,1196,1132,996,908,809,776,680,649cm ^-1 ; elemental analysiscalcd(%)for C ₄ H ₅ N ₉ O ₂ (211 ): C 22.75, H 2.39, N 59.70; found: C 22.72, H 2.38, N 59.70.

Example 2

0.21g (1.0mmol) 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4- Slowly add ammonia water, hydrazine hydrate, and hydroxylamine aqueous solution dropwise to the suspended aqueous solution of diamine (c) under stirring. The reaction solution was slowly raised to 75°C and maintained at 75°C for 2 hours, then cooled to room temperature, a large amount of solid precipitated out, the precipitate was filtered, washed with a small amount of water, and dried in air for 48 hours. Related energetic ion salts (1-3) were obtained sequentially. Among them, 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diaminehydrazine salt (2) Recrystallization, the resulting crystal structure is shown in Figure 1.

5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine ammonium salt (1):

¹ H NMR (d ₆ -DMSO, 25°C): δ = 7.20(s), 5.73 (s, 2H), 5.30 (s, 2H) ppm. ¹³ C NMR (d ₆ -DMSO, 25°C): δ = 155.22,152.04,143.79,129.65ppm.IR(KBr):v＝3405,2395,2017,1740,1583,1313,1276,1162,1214,1121,1065,1028,973,849,776,739,712,641,502,458cm ^-1 ；elemental analysis calcd(％ ) for C ₄ H ₈ N ₁₀ O ₂ (228): C 21.06, H 3.53, N 63.39; found: C 21.04, H 3.55, N 63.39.

5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diaminehydrazine salt (2):

¹ H NMR (500MHz, DMSO-d ₆ ): δ=7.10(s), 5.73(s, 2H), 5.30(s, 2H) ppm. ¹³ C NMR (125MHz, DMSO-d ₆ ): δ=155.06, 152.00,143.76,129.60ppm.IR(KBr):v=3405,3266,3192,1654,1614,1553,1494,1448,1357,1257,1193,1126,1024,967,826,762,703cm ^-1 ; ) for C ₄ H ₉ N ₁₁ O ₂ (243): C 19.76, H 3.73, N 63.36; found: C 19.75, H 3.72, N 63.36.

5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine hydroxylamine salt (3):

¹ H NMR (500MHz, DMSO-d ₆ ): δ=9.11(s), 6.20(s, 2H), 5.41(s, 2H) ppm. ¹³ C NMR (125MHz, DMSO-d ₆ ): δ=154.22, 152.13,143.93,128.69ppm.IR(KBr):v=3426,3321,3119,1671,1626,1502,1454,1362,1239,1186,1101,1030,987,814,791,697cm ^-1 .elemental analysis for Ccd(%) ₄ H ₈ N ₁₀ O ₃ (244): C 19.68, H 3.30, N 57.36; found: C 19.66, H 3.73, N 57.35.

Example 3

To 15 mL of 100 wt% nitric acid was slowly added 1.57 g of 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4 - Diamine (c), reacted at -15°C for 20 hours. 100mL of ice water quenched the reaction solution, a large amount of solids precipitated, and filtered to obtain N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H -1,2,4-triazol-4-yl)nitramide (d), yield 1.98 g (yield: 89%).

¹ H NMR (500MHz, DMSO-d ₆ ): δ = 8.39 (s, 2H) ppm. ¹³ C NMR (125 MHz, DMSO-d ₆ ): δ = 151.68, 149.46, 140.31, 126.35 ppm. IR (KBr): v=3433,3327,3239,1684,1544,1514,1436,1351,1289,1253,1148,1072,975,897,825,769,714cm ^-1 ; elemental analysis calcd(%)for C ₄ H ₄ N ₁₀ O ₄ (256): C 18.76, H 1.57, N 54.68; found: C 18.73, H 1.56, N 54.68.

Example 4

This example is basically the same as Example 3, the only difference is that the nitrating reagent is 98wt% H ₂ SO ₄ /HNO ₃ , and the target product (d) is obtained with a yield of 72%.

Example 5

This example is basically the same as Example 3, the only difference is that the nitrating reagent is 98wt% HNO ₃ , and the target product (d) is obtained with a yield of 63%.

Example 6

At 25°C, hydrazine hydrate and hydroxylamine aqueous solution were slowly added dropwise to 0.26 g (1.0 mmol) of the compound (d) suspended in methanol solution while stirring. The reaction solution was stirred at room temperature for 2 hours, and the precipitate was filtered, washed with a small amount of water, and dried in air for 48 hours. Sequentially obtain related energetic ion salts (4,5)

N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl)nitramide dihydrazine salt (4)

¹ H NMR (500MHz, DMSO-d ₆ ): δ = 6.75(s) ppm. ¹³ C NMR (125 MHz, DMSO-d ₆ ): δ = 157.09, 152.35, 143.48, 128.36 ppm. IR (KBr): v = 3310,3232,2809,1573,1455,1420,1355,1207,1168,1133,1024,991,960,919,858,782,740cm ^-1 ; elemental analysis calcd(%)forC ₄ H ₁₂ N ₁₄ O ₄ (320):C H 15.0 , N 61.24; found: C 15.03, H 3.75, N 61.25.

N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl)nitramide dihydroxylamine salt (5)

¹ H NMR (500MHz, DMSO-d ₆ ): δ=9.13(s) ppm. ¹³ C NMR (125 MHz, DMSO-d ₆ ): δ=152.66, 149.90, 143.87, 126.42 ppm.IR(KBr): v= 3520,3356,3024,2808,1447,1363,1312,1174,1129,1034,932,882,789,741cm ^-1 ; elemental analysis calcd(%)for C ₄ H ₁₀ N ₁₂ O ₆ (322):C14.91,H 3.13 , N 52.17; found: C 14.93, H 3.14, N 52.18.

Table 1 below gives the properties of each energetic ion salt.

Table 1. Properties of Compounds

^a thermal decomposition rate: 5℃min ^-1 ; ^b formation enthalpy; ^c impact sensitivity; ^d friction sensitivity; ^e detonation velocity; ^f detonation pressure; ^g density.

In summary, the present invention provides a synthetic method based on the combination of 1,2,3-triazole and 1,2,4-triazole compound energetic ion salt, and the reaction conditions are optimized, and at the same time Different nitrating reagents were used in the nitration process, and the nitration conditions were optimized to maximize the yield of the target product.

Claims (10)

1. An energetic ion salt based on a triazole compound, characterized in that it is named 5-(5-nitro-2H-1,2,3-triazole-4-yl)-4H-1, 2,4-triazole-3,4-diamine energetic ion salt, its structure is as follows:

2. An energetic ionic salt based on triazole compounds, characterized in that it is named N-(3-amino-5-(5-nitro-2H-1,2,3-triazole-4- Base)-4H-1,2,4-triazol-4-yl)nitramide energetic ion salt, its structure is as follows:

3. the synthetic method of energetic ion salt as claimed in claim 1, is characterized in that, comprises at least: (1) 5-nitro-2H-1,2,3-triazole-4-carboxylic acid a and 1,3-diaminoguanidine hydrochloride b were subjected to a ring-closing reaction in a polyphosphoric acid reaction system to prepare 5 - the step of (5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine c,

(2) hydrate 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine c with ammonia water and hydration Hydrazine or hydroxylamine aqueous solution takes place the step of salt formation reaction respectively to prepare target product,

4. The method according to claim 3, characterized in that, in step (1), the polyphosphoric acid reaction system is a mixed system of 1.5g: 0.5～5.5ml of phosphorus pentoxide and orthophosphoric acid; The molar ratio of nitro-2H-1,2,3-triazole-4-carboxylic acid to 1,3-diaminoguanidine hydrochloride is 1:0.8～5.0. 5. The method according to claim 3, characterized in that, in step (1), the reaction temperature is 100-150°C. 6. The method according to claim 3, characterized in that, in step (2), the reaction system solvent is any one of anhydrous methanol, water, absolute ethanol and acetonitrile; the reaction temperature is 20°C to 100°C. 7. the synthetic method of energetic ion salt as claimed in claim 2, is characterized in that, comprises at least: (1) 5-nitro-2H-1,2,3-triazole-4-carboxylic acid a and 1,3-diaminoguanidine hydrochloride b were subjected to a ring-closing reaction in a polyphosphoric acid reaction system to prepare 5 - the step of (5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine c,

(2) Generating 5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazole-3,4-diamine c with a nitrating reagent Preparation of N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl)nitrate by nitration reaction Amide d steps,

(3) N-(3-amino-5-(5-nitro-2H-1,2,3-triazol-4-yl)-4H-1,2,4-triazol-4-yl) The step of preparing the target product through a salt-forming reaction between nitramide d and hydrazine hydrate or hydroxylamine aqueous solution respectively,

8. The method according to claim 7, characterized in that, in step (1), the polyphosphoric acid reaction system is a mixed system of 1.5g: 0.5-5.5ml of phosphorus pentoxide and orthophosphoric acid; The molar ratio of nitro-2H-1,2,3-triazole-4-carboxylic acid to 1,3-diaminoguanidine hydrochloride is 1:0.8~5.0; the reaction temperature is 100~150°C. 9. The method of claim 7, wherein 5-(5-nitro-2H-1,2,3-triazole-4-yl)-4H-1,2,4-triazole- The feeding ratio of 3,4-diamine and nitrating reagent is 1g:5~25ml; the reaction temperature is -15℃~-5℃. 10. The method according to claim 7, characterized in that, in step (3), the reaction system solvent is any one of anhydrous methanol, water, absolute ethanol and acetonitrile; the reaction temperature is 20°C to 100°C.

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