2-fluoro-4,6-dinitro-n1,n3-bis(1h-tetrazol-5-yl)phenyl-1,3-diamine energetic compound and method of preparation thereof

Abstract

The application belongs to the field of chemical industry, and particularly relates to a 2-fluoro-4,6-dinitro-N1, N3-di(1H-tetrazol-5-yl) phenyl-1, 3-diamine energetic compound (ZXC-91) and a preparation method thereof, and the structure of the energetic compound is shown in the following formula: The 2-fluoro-4,6-dinitro-N1, N3-di(1H-tetrazol-5-yl) phenyl-1, 3-diamine energetic compound provided by the application is a kind of energetic material with novel structure and reliable initiation, the compound is a novel energetic material with the characteristics of high energy density, high stability and environmental friendliness, and through the carefully designed molecular structure and the optimized synthesis route, the comprehensive performance of the energetic material is improved, and the energetic material has important scientific value and practical application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of chemical industry, and particularly relates to a 2-fluoro-4,6-dinitro-N1, N3-di(1H-tetrazol-5-yl) phenyl-1, 3-diamine energetic compound and a preparation method thereof. BACKGROUND

[0002] A novel energetic material generally refers to a novel energetic compound with high energy density, high safety and environmental friendliness. High-nitrogen compounds contain a large number of N=N bonds and N=C bonds, and the explosion products are mainly clean gases such as nitrogen and carbon dioxide, and often have a high positive heat of formation. Multi-nitrogen azole compounds are a typical class of high-nitrogen heterocyclic compounds. With the increase of the number of nitrogen atoms in the azole ring, they are classified into pyrrole, pyrazole, imidazole, triazole, oxadiazole, tetrazole and pentazole. Pyrazole has good stability but low energy, and pentazole ring has high energy but is extremely unstable due to its ring strain. The introduction of a tetrazole ring or an oxadiazole ring into the molecule can well balance the contradiction between 'energy and stability', and thus the tetrazole ring or the oxadiazole ring is considered to be a good molecular skeleton for designing and synthesizing novel high-energy low-sensitivity high-nitrogen compounds. SUMMARY

[0003] The present application provides a 2-fluoro-4,6-dinitro-N1, N3-di(1H-tetrazol-5-yl) phenyl-1, 3-diamine energetic compound, and a preparation method thereof is another object of the present application. In order to achieve the above object, the present application adopts the following technical scheme:

[0004] A 2-fluoro-4,6-dinitro-N1, N3-di(1H-tetrazol-5-yl) phenyl-1, 3-diamine energetic compound has the following structural formula:

[0005]

[0006] A preparation method of a 2-fluoro-4,6-dinitro-N1, N3-di(1H-tetrazol-5-yl) phenyl-1, 3-diamine energetic compound has the following synthesis route:

[0007]

[0008] Further, the method comprises the following steps: at room temperature, 2, 3, 4-trifluoro-m-dinitrobenzene, THF and 5-amino-1H-tetrazole are sequentially added into a single-necked flask, and after 20 minutes of reaction under magnetic stirring, the temperature of the reaction system is increased to 60 DEG C, and after 24h-25h, the reaction is completed, the reaction system is cooled to room temperature, and then the reaction system is subjected to suction filtration and drying to obtain a grayish white powder, thereby obtaining the product.

[0009] After 24h-25h, the reaction is completed, the reaction system is cooled to room temperature, and then the reaction system is subjected to suction filtration and drying to obtain a grayish white powder, thereby obtaining the product.

[0010] Further, the reaction is complete after 24-25 hours, which is detected by thin layer chromatography analysis.

[0011] Further, the preparation method of 2,3,4-trifluoro-m-dinitrobenzene comprises the following steps:

[0012] At 0℃, KNO3 is slowly added to concentrated sulfuric acid under magnetic stirring, and after the addition of KNO3 is completed, the stirring in the ice water bath is continued for 15-20 minutes; 2,3,4-trifluoronitrobenzene is slowly added dropwise into the mixture, after the dropwise addition is completed, the temperature of the system is increased to 85℃, and the reaction is complete after 48-50 hours; the reaction mixture is slowly poured into an ice water mixture and stirred vigorously until the ice water is completely melted, during which it is observed that flaky solids are continuously precipitated, and the reaction system is filtered again after the temperature returns to room temperature; the solid is repeatedly washed with deionized water until the filtrate obtained is neutral as detected by pH paper, and then dried to obtain a yellowish powder, which is 2,3,4-trifluoro-m-dinitrobenzene.

[0013] Further, the reaction is complete after 48-50 hours, which is detected by thin layer chromatography analysis.

[0014] The beneficial effects of the present application are as follows:

[0015] The energetic compound 2-fluoro-4,6-dinitro-N1,N3-di(1H-tetrazol-5-yl)phenyl-1,3-diamine provided by the present application is a novel energetic material with reliable initiation, and the beneficial effects of the novel energetic compound proposed by the present application mainly lie in the following aspects:

[0016] 1. Combination of high energy density and stability: By skillfully introducing a tetrazole ring into the molecular structure, a good balance between energy density and compound stability is achieved. This kind of molecule not only maintains the unique high energy density characteristics of high-nitrogen compounds, but also improves the safety and reduces the sensitivity of the compound due to the stability of the tetrazole ring, thereby being suitable for the field of novel energetic materials.

[0017] 2. Environmental friendliness: The explosion products of the compound are mainly non-toxic or low-toxic clean gases such as nitrogen and carbon dioxide, which reduces the emission of harmful substances and meets the modern environmental protection concept, being friendly to the environment.

[0018] 3. Optimized molecular design: By introducing a tetrazole ring into the molecular structure, the contradiction between the energy and stability of energetic materials is skillfully balanced. The tetrazole ring not only provides the necessary energy density, but also endows the compound with good stability and low sensitivity, reducing the risk of accidental detonation and improving the safety during use. The tetrazole ring as a molecular skeleton not only helps to improve the energy performance of the compound, but also may enhance the rigidity and heat resistance of the structure.

[0019] 4. Synthesis process controllability: The present application provides a clear synthesis process, which is beneficial to industrial scale-up production, and improves the yield and purity of the product.

[0020] 5. Application value: The compound has application potential in other fields besides explosives due to its unique structure, such as catalysts, drug precursors or functional materials, etc., further expanding its application range. As a high-performance energetic material, the compound can be used as an energy carrier in the military field (such as rocket propellants, explosives), the civilian blasting industry, and certain special chemical reactions, improving the performance of related systems and reducing environmental pollution. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is a crystal structure diagram of 2-fluoro-4,6-dinitro-N1,N3-bis(1H-tetrazol-5-yl)benzene-1,3-diamine;

[0022] Figure 2 is a hydrogen spectrum of intermediate 2,3,4-trifluoro-1,5-dinitrobenzene;

[0023] Figure 3 is a carbon spectrum of intermediate 2,3,4-trifluoro-1,5-dinitrobenzene;

[0024] Figure 4 is a hydrogen spectrum of product 2-fluoro-4,6-dinitro-N1,N3-bis(1H-tetrazol-5-yl)benzene-1,3-diamine;

[0025] Figure 5 is a carbon spectrum of product 2-fluoro-4,6-dinitro-N1,N3-bis(1H-tetrazol-5-yl)benzene-1,3-diamine. DETAILED DESCRIPTION

[0026] The present application proposes an energetic compound 2-fluoro-4,6-dinitro-N1,N3-bis(1H-tetrazol-5-yl)phenyl-1,3-diamine (ZXC-91), whose crystal structure is as shown in Figure 1 , and its structural formula is as follows:

[0027]

[0028] The synthesis route of the energetic compound is as follows:

[0029]

[0030] Example 1

[0031] Synthesis of intermediate (I) 2,3,4-trifluoro-1,5-dinitrobenzene

[0032]

[0033] KNO3(46.102 g, 0.456 mol) was slowly added to a 500 mL flask containing 325 mL of concentrated sulfuric acid under magnetic stirring at 0 °C. After the addition of KNO3was completed, the stirring was continued in an ice-water bath for 15 minutes. 2,3,4- Trifluoronitrobenzene (65.215 g, 0.368 mol) was slowly added dropwise to the above mixture. After the addition was completed, the temperature of the system was increased to 85 °C. The reaction was complete after 48 h (monitored by thin layer chromatography).

[0034] The reaction mixture was slowly poured into an ice-water mixture and stirred vigorously until the ice-water was completely melted. During this period, it was observed that flaky solid was continuously precipitating. The reaction system was filtered until the filtrate was neutral as detected by pH paper. Subsequently, it was dried to obtain a beige powder, 69.93 g, which was the intermediate (I) with a yield of 85.60%.

[0035] The NMR data of the intermediate 2,3,4-trifluoro-1,5-dinitrobenzene are shown in Figures 2-3

[0036] Hydrogen spectrum: 1 HNMR (600 MHz, CDC13-d1) δ: 8.80 (m, 1H).

[0037] Carbon spectrum: 13 CNMR (125 MHz, CDC13-d1) δ: 150.47-148.56 (d), 143.06-141.29 (d), 133.13, 117.91.

[0038] Example 2

[0039] Synthesis of product 2-fluoro-4,6-dinitro-N1,N3-di(lH-tetrazol-5-yl)benzene-1,3-diamine (ZXC-91)

[0040]

[0041] To a 100 mL single necked flask, 2,3,4-trifluoro-m-dinitrobenzene (2.232 g, 0.010 mol), THF (30 mL), 5-amino-lH-tetrazole (1.979 g, 0.023 mol) were added sequentially at room temperature. The reaction was complete after 24 h (monitored by thin layer chromatography) after the temperature of the reaction system was increased to 60 °C under magnetic stirring for 20 minutes.

[0042] ​The reaction system was cooled to room temperature, then it was suction filtered, and dried, the product was off-white powder (3.243 g, 0.009 mol, yield 92.13%)

[0043] The nuclear magnetic data of the product 2-fluoro-4,6-dinitro-N1,N3-di(1H-tetrazol-5-yl)benzene-1,3-diamine is shown as follows: Figures 4-5

[0044] The hydrogen spectrum is: 1 HNMR (600 MHz, DMSO) δ: 10.50 (s, 1H), 8.57 (s, 1H).

[0045] The carbon spectrum is: 13 CNMR (125 MHz, DMSO) δ: 56.33, 148.43-146.14 (d), 134.16, 129.84, 120.54.

[0046] The crystal structure of the product 2-fluoro-4,6-dinitro-N1,N3-di(1H-tetrazol-5-yl)benzene-1,3-diamine is shown as follows: Figure 1

[0047]

[0048] The performance test data of the compound are shown in Table One

[0049] Table One:

[0050]

[0051] The 2-fluoro-4,6-dinitro-N1,N3-di(1H-tetrazol-5-yl)phenyl-1,3-diamine energetic compound provided by the present application is a novel structure, reliable initiation of a class of energetic materials, the beneficial effects of the new energetic compound proposed by the present application mainly reflect in the following aspects:

[0052] 1. High energy density and stability: By skillfully introducing a tetrazole ring in the molecular structure, a good balance between energy density and compound stability is achieved. This kind of molecule not only maintains the unique high energy density characteristics of high nitrogen compounds, but also improves the safety of the compound and reduces its sensitivity because of the stability of the tetrazole ring, so it is suitable for the field of new energetic materials.

[0053] 2. Environmental friendliness: The explosion products of the compound are mainly non-toxic or low-toxic clean gases such as nitrogen and carbon dioxide, which reduces the emission of harmful substances and meets the modern environmental protection concept, which is friendly to the environment.

[0054] ​​3. Optimized molecular design: By introducing a tetrazole ring into the molecular structure, the contradiction between the energy and stability of the energetic material is skillfully balanced. The tetrazole ring not only provides the necessary energy density, but also endows the compound with better stability and lower sensitivity, reducing the risk of accidental detonation and improving safety during use. As a molecular skeleton, the tetrazole ring not only helps to improve the energy performance of the compound, but also may enhance the rigidity and heat resistance of its structure.

[0055] 4. Controllability of synthesis process: The present application provides a clear synthesis process, which is beneficial to industrial scale-up production and improves the yield and purity of the product.

[0056] 5. Application value: The compound, due to its unique structure, shows application potential in other fields besides explosives, such as catalysts, drug precursors or functional materials, further broadening its application range. As a high-performance energetic material, the compound can be used as an energy carrier in the military field (such as rocket propellants, explosives), the civilian blasting industry and certain special chemical reactions, improving the efficiency of related systems and reducing environmental pollution.

[0057] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. An energetic compound of 2-fluoro-4,6-dinitro-N1,N3-di(1 H-tetrazol-5-yl)phenyl-1,3-diamine, characterized by, The structural formula is as follows (ZXC-91):

2. A process for the preparation of the energetic compound 2-fluoro-4,6-dinitro- N1,N3-di(lH-tetrazol-5-yl)phenyl-1,3-diamine according to claim 1, characterized in that, The synthesis route of the energetic compound is:

3. The method for preparing the energetic compound 2-fluoro-4,6-dinitro-N1,N3-bis(1H-tetrazol-5-yl)phenyl-1,3-diamine as described in claim 2, characterized in that, The method comprises the following steps: at room temperature, 2, 3, 4-trifluoro-m-dinitrobenzene, THF, 5-amino-1H-tetrazole are sequentially added into a single-neck flask, and the reaction is carried out under magnetic stirring for 20 minutes; then the temperature of the reaction system is increased to 60 DEG C, and the reaction is completed after 24-25 hours; the reaction system is cooled to room temperature, and then is subjected to suction filtration and drying to obtain a grayish white powder, thereby obtaining the product.

4. A process for the preparation of the 2-fluoro-4,6-dinitro-N1,N3-di(lH-tetrazol-5-yl)phenyl- 1,3-diamine energetic compound as claimed in claim 3, characterized in that, The reaction is completed after 24-25 hours, and thin layer chromatography is used to detect whether the reaction is completed.

5. The method for preparing the energetic compound 2-fluoro-4,6-dinitro-N1,N3-bis(1H-tetrazol-5-yl)phenyl-1,3-diamine as described in claim 3, characterized in that, The method for preparing 2, 3, 4-trifluoro-m-dinitrobenzene comprises the following steps: KNO3 is slowly added into concentrated sulfuric acid under magnetic stirring at 0 DEG C, and after the addition of KNO3 is completed, the stirring in the ice water bath is continued for 15-20 minutes; 2, 3, 4-trifluoro-nitrobenzene is slowly added into the mixture, and after the addition is completed, the temperature of the system is increased to 85 DEG C, and the reaction is completed after 48-50 hours; the reaction mixture is slowly poured into an ice water mixture and is stirred until the ice water is completely melted; during this period, flaky solids are continuously precipitated, and the reaction system is filtered until room temperature is restored; the solids are repeatedly washed with deionized water until the obtained filtrate is neutralized by using a pH test paper; and then the solids are dried to obtain a yellowish brown powder, which is 2, 3, 4-trifluoro-m-dinitrobenzene.

6. The method for preparing the energetic compound 2-fluoro-4,6-dinitro-N1,N3-bis(1H-tetrazol-5-yl)phenyl-1,3-diamine as described in claim 5, characterized in that, The reaction is completed after 48-50 hours, and thin layer chromatography is used to detect whether the reaction is completed.

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