CN109020906A - A kind of energy-containing compound and its synthetic method and application - Google Patents

Abstract

The invention discloses a 5‑(nitrobromomethylenehydrazino)‑3‑nitro‑1,2,4‑triazole compound, the structural formula of which is shown in <I>, and its density is as high as 2.2 g/cm ^3. The heat of formation is 412.6kJ/mol, the calculated detonation velocity is 9112m/s, and the detonation pressure is 39.2GPa. The invention is mainly used in the field of energetic materials.

Description

A kind of energetic compound and its synthesis method and application

technical field

The invention belongs to the technical field of energetic materials, and in particular relates to a 5-(nitrobromomethylenehydrazino)-3-nitro-1,2,4-triazole compound and its synthesis method and application.

Background technique

Energetic materials are one of the indispensable materials for weapon systems, they are the energy carriers for conventional weapon systems to achieve efficient damage, and they are also the source of power for long-range weapon delivery and gun launch. Among them, energetic compounds are the core components. In recent years, nitrogen-rich energetic compounds have become one of the research hotspots in the field of energetic compounds. Nitrogen-rich energetic compounds usually refer to energetic compounds based on nitrogen-rich heterocyclic rings such as tri(tetra)azole, furazan, tri(tetra)azine, etc., containing a large number of N-N in the molecule, N=N, C-N, C= The N bond makes the whole molecule have a high positive enthalpy of formation and is the main source of chemical energy. In addition, the low carbon hydrogen and high nitrogen content of nitrogen-rich energetic compounds make them easy to reach oxygen balance, and their decomposition products are mainly nitrogen, which makes them candidates for the application of environmentally friendly energetic materials. Energetic compounds containing nitrotriazole skeletons have the characteristics of high density, good thermal stability, and low sensitivity, and have attracted the attention of energetic material workers.

At present, the comprehensive properties of energetic compounds containing nitrotriazole skeletons are not completely satisfactory, and compounds with higher detonation velocity and pressure often have lower heat of formation, such as Eur.J.Inorg.Chem.2012, 5,5'-dinitro-3'3-bis(1,2,4-triazole) compounds announced in 3474-3484; other compounds have higher heat of formation, but lower detonation pressure, detonation velocity and density low problem.

Generally speaking, for an energetic compound containing a nitrotriazole skeleton with a heat of formation of 400kJ/mol, it is difficult for the detonation velocity to exceed 9000m/s, the detonation pressure is only about 35GPa, and the single crystal density is difficult to exceed 2.0g cm ^-3 .

In summary, there is an urgent need in this area for an energetic compound containing a nitrotriazole skeleton that is excellent in density, heat of formation, detonation pressure and detonation velocity.

Contents of the invention

Aiming at the shortcomings of the prior art, one of the objects of the present invention is to provide a 5-(nitrobromomethylenehydrazino)-3-nitro-1,2,4-triazole compound, the compound single crystal density As high as 2.2 g cm ^-3 , the detonation velocity is 9112m/s, the detonation pressure is 39.2GPa, and the heat of formation is 412.6kJ/mol. Its chemical structure is shown in the formula <Ⅰ>:

Another object of the present invention is to provide a synthetic method of the above-mentioned 5-(nitrobromomethylenehydrazino)-3-nitro-1,2,4-triazole compound, the method comprising the following steps:

(1) Put 3-nitro-5-amino-1,2,4-triazole in water, add mineral acid to dissolve;

(2) dropwise adding sodium nitrite solution in the step (1) garment to react;

(3) add nitrobromomethane to step (2) gain and react;

(4) After the reaction is completed, filter, wash and dry the solid phase to obtain a solid product A, extract and recrystallize the filtrate to obtain a solid product B, and combine the solid product A and solid product B to obtain the compound.

In step (1), described inorganic acid comprises any one in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid.

As a preferred embodiment of the present invention, the molar ratio of the inorganic acid to 3-nitro-5-amino-1,2,4-triazole is 6˜10:1.

As a preferred embodiment of the present invention, when carrying out step (2), it is carried out in an ice bath; the best, the temperature is not higher than 5°C, and the reaction time is 0.5 hours; a more preferable solution is that sodium nitrite and 3-nitrate The molar ratio of base-5-amino-1,2,4-triazole is 1.05～1.20:1.

As a preferred embodiment of the present invention, in step (3), the reaction temperature is 0-25°C, and the reaction time is 0.5-24 hours; preferably, nitrobromomethane and 3-nitro-5-amino-1,2, The molar ratio of 4-triazole is 1.1～1.3:1.

In step (4), the washing is performed with distilled water.

As a preferred embodiment of the present invention, in step (4), the extraction is performed using ethyl acetate.

As a preferred embodiment of the present invention, in step (4), the recrystallization is carried out utilizing n-hexane.

Another object of the present invention is to provide the application of the above-mentioned 5-(nitrobromomethylenehydrazino)-3-nitro-1,2,4-triazole compound in the preparation of energetic materials.

Beneficial effects of the present invention: the 5-(nitrobromomethylenehydrazino)-3-nitro-1,2,4-triazole single crystal density of the present invention is as high as 2.2 g cm ^-3 , and the heat of formation is relatively high. Its heat of formation is 412.6 kJ/mol; the energy of the 5-(nitrobromomethylenehydrazino)-3-nitro-1,2,4-triazole compound of the present invention is relatively high, and its detonation velocity is calculated to be 9112m/s , the burst pressure is 39.2GPa.

Detailed ways

The present invention is described in detail by the following examples, it is necessary to point out that the following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the scope of the present invention, those skilled in the art according to the content of the above invention Some non-essential improvements and adjustments still belong to the protection scope of the present invention.

Example 1

Add 1.2g (9.3mmol) 3-nitro-5-amino-1,2,4-triazole into 15mL distilled water, add 1mL concentrated hydrochloric acid dropwise, during the dissolution process, the yellow solid in the reaction bottle is gradually dissolved .

Weigh 0.7060g (11.23mmol) of sodium nitrite, dissolve it in 2mL of distilled water, and add it in batches to the ice-cooled reaction system, controlling the temperature not to exceed 5°C. After the dropwise addition was completed, the reaction was continued for 0.5 h under ice-bath conditions.

1.6923g (12.09mmol) of nitrobromomethane was dissolved in 2mL of acetonitrile, slowly added dropwise to the reaction system, and reacted at 5°C for 24h. During the reaction, the color of the solution gradually changed to reddish brown, and a reddish brown solid was formed. After completion of the reaction, the solid product was filtered out under reduced pressure, washed with 5 mL of distilled water, and dried. The filtrate was extracted with ethyl acetate, and after the solvent was removed by rotary evaporation, the obtained solid was recrystallized from n-hexane. The two solid products were combined to give a yellow solid in 60% yield and 99.8% purity (HPLC).

Product structure identification:

Infrared Spectrum: IR(KBr,cm ^-1 ),υ:3532,1620,1549,1521,1390,1311, 1638,1056,838

Mass Spectrum: MS:ESI pos:m/z=279.9,282.1[M+H]

NMR spectrum: ¹ H NMR(DMSO-d ₆ ,600MHz),δ:3.51(br,NH); ¹³ CNMR (DMSO-d ₆ ,150MHz),δ:162.11,159.23,130.96

The above structural identification data confirmed that the obtained substance was 5-(nitrobromomethylenehydrazino)-3-nitro-1,2,4-triazole.

The properties of product 5-(nitrobromomethylenehydrazino)-3-nitro-1,2,4-triazole:

Appearance: yellow powdery solid;

Decomposition temperature peak: 219.40℃.

Example 2

Add 1.2g (9.3mmol) of 3-nitro-5-amino-1,2,4-triazole into 15mL of distilled water, and add 1mL of concentrated hydrochloric acid dropwise, during the dissolution process, the yellow solid in the reaction bottle is gradually dissolved. .

Weigh 0.6431g (10.23mmol) of sodium nitrite, dissolve it in 2mL of distilled water, add it in batches to the reaction system cooled in an ice bath, and control the temperature not to exceed 5°C. After the dropwise addition was completed, the reaction was continued for 0.5 h under ice-bath conditions.

Dissolve 1.6923g (12.09mmol) of nitrobromomethane in 2mL of acetonitrile, slowly drop it into the reaction system, and react at 0°C for 24h. After completion of the reaction, the solid product was filtered out under reduced pressure, washed with 5 mL of distilled water, and dried to obtain a solid product. The filtrate was extracted with ethyl acetate, and the solvent was removed by rotary evaporation, and the obtained solid was recrystallized from n-hexane. The two solid products were combined to give a yellow solid in 65% yield and 99.8% purity (HPLC).

The reaction phenomenon in the preparation process of this embodiment is the same as that of Example 1.

The structure identification result of the product obtained in this embodiment is the same as that in Example 1.

Example 3

Add 1.2g (9.3mmol) 3-nitro-5-amino-1,2,4-triazole to 15mL distilled water, add 1mL concentrated phosphoric acid dropwise, during the dissolution process, the yellow solid in the reaction bottle is gradually dissolved .

Weigh 0.7060g (11.23mmol) of sodium nitrite, dissolve it in 2mL of distilled water, and add it in batches to the ice-cooled reaction system, controlling the temperature not to exceed 5°C. After the dropwise addition was completed, the reaction was continued for 0.5 h under ice-bath conditions.

Dissolve 1.5719g (11.23mmol) of nitrobromomethane in 2mL of acetonitrile, slowly drop it into the reaction system, and react at 15°C for 24h. After completion of the reaction, the solid product was filtered out under reduced pressure, washed with 5 mL of distilled water, and dried to obtain a solid product. The filtrate was extracted with ethyl acetate, and the solvent was removed by rotary evaporation, and the obtained solid was recrystallized from n-hexane. The two solid products were combined to give a yellow solid in 60% yield and 99.8% purity (HPLC).

The reaction phenomenon in the preparation process of this embodiment is the same as that of Example 1.

The structure identification result of the product obtained in this embodiment is the same as that in Example 1.

Example 4

Add 1.2g (9.3mmol) of 3-nitro-5-amino-1,2,4-triazole into 15mL of distilled water, add 0.5mL of concentrated sulfuric acid dropwise, during the dissolution process, the yellow solid in the reaction bottle is gradually dissolve.

Weigh 0.6139g (9.765mmol) of sodium nitrite, dissolve it in 2mL of distilled water, add it in batches to the ice-cooled reaction system, and control the temperature not to exceed 5°C. After the dropwise addition was completed, the reaction was continued for 0.5 h under ice-bath conditions.

Dissolve 1.6923g (12.09mmol) of nitrobromomethane in 2mL of acetonitrile, slowly drop it into the reaction system, and react at 10°C for 24h. After the reaction was complete, the solid product was filtered out under reduced pressure.

Claims (10)

1. A 5-(nitrobromomethylene hydrazino)-3-nitro-1,2,4-triazole compound is characterized in that its chemical structural formula is as shown in formula <I>: 2. the synthetic method of 5-(nitro bromomethylene hydrazino)-3-nitro-1,2,4-triazole compound as claimed in claim 1, is characterized in that, described method comprises the steps: (1) Put 3-nitro-5-amino-1,2,4-triazole in water, add mineral acid to dissolve; (2) dropwise adding sodium nitrite solution in the step (1) garment to react; (3) add nitrobromomethane to step (2) gain and react; (4) After the reaction is completed, filter, wash and dry the solid phase to obtain solid product A, extract and recrystallize the filtrate to obtain solid product B, and combine solid product A and solid product B to obtain the compound. 3. synthetic method according to claim 2, is characterized in that, in step (1), described mineral acid comprises any one in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid. 4. The synthesis method according to claim 2 or 3, characterized in that the molar ratio of the inorganic acid to 3-nitro-5-amino-1,2,4-triazole is 6-10:1. 5. The synthetic method according to claim 2, characterized in that, when carrying out step (2), it is carried out in an ice bath; preferably, the temperature is not higher than 5° C., and the reaction time is 0.5 hour; more preferably, nitrous acid The molar ratio of sodium to 3-nitro-5-amino-1,2,4-triazole is 1.05-1.20:1. 6. The synthetic method according to claim 2, characterized in that, in step (3), the reaction temperature is 0 to 25°C, and the reaction time is 0.5 to 24 hours; preferably, nitrobromomethane and 3-nitro- The molar ratio of 5-amino-1,2,4-triazole is 1.1～1.3:1. 7. The synthetic method according to claim 2, characterized in that, in step (4), the washing is carried out using distilled water. 8. synthetic method according to claim 2, is characterized in that, in step (4), described extraction is to utilize ethyl acetate to carry out. 9. The synthetic method according to claim 2, characterized in that, in step (4), the recrystallization is carried out by utilizing n-hexane. 10. The application of the 5-(nitrobromomethylenehydrazino)-3-nitro-1,2,4-triazole compound as claimed in claim 1 in the preparation of energetic materials.