High-density and high-energy azo compound as well as preparation method and application thereof
By preparing 1,2-bis(7-nitrobis([1,2,4]triazole)[1,5-b;5',1'-f][1,2,4,5]tetraazine-2-yl)azo compounds, the problems of low density and low enthalpy of formation of existing high-nitrogen heterocyclic energetic compounds have been solved, achieving high-density and high-energy detonation performance, which is suitable for fields such as safe munitions and aerospace exploration.
Patent Information
- Application Number
- CN202510832722.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-20
- Publication Date
- 2025-11-07
AI Technical Summary
Existing high-nitrogen heterocyclic energetic compounds have low density, low enthalpy of formation, and low energy level, making it difficult to meet the requirements of high-performance energetic materials.
By synthesizing 1,2-bis(7-nitrobis([1,2,4]triazole)[1,5-b;5',1'-f][1,2,4,5]tetraazine-2-yl)azo compounds using specific raw materials and reaction conditions, including a multi-step synthetic route, and finally azotization reaction under the action of trichloroisocyanuric acid, a compound with high density, high enthalpy of formation and high energy was prepared.
It achieves high-performance characteristics with a compound density of 2.04 g/cm3, an enthalpy of formation of 1676.43 kJ/mol, a detonation velocity of 9556.73 m/s, and a detonation pressure of 39.27 GPa, making it suitable for fields such as safe munitions and aerospace exploration.
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Figure CN120904221A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the field of energetic materials, and relates to a high-density high-energy azo compound, a preparation method and application, in particular to a 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl)azo compound. BACKGROUND
[0002] Heat-resistant energetic materials refer to a special type of energetic compounds that can be reliably initiated and maintain appropriate mechanical sensitivity and high energy after being stored in a high-temperature environment for a long time, and have broad application prospects in safe ammunition, space exploration, deep oil wells and other fields, and are valued and concerned by many military powers. High-nitrogen heterocyclic energetic compounds have high-energy chemical bonds and conjugated rings in their structures, and thus exhibit excellent energy performance and good stability. High-nitrogen fused ring compounds constructed by high-nitrogen heterocycles generally have a coplanar molecular structure and a large conjugated system, which is beneficial to improve the molecular stability, density and enthalpy of formation of the compounds, and thus the compounds have more outstanding detonation performance and heat resistance, and have become a research hotspot in the field of energetic materials in recent years.
[0003] Gennady F.Rudakov et al. reported the structure, synthesis route and calculated performance of a bis([1,2,4]triazolo[1,5-b;5',1'-f]-1,2,4,5-tetrazin-2-amine compound in the article "Energetic compounds based on a new fused Bis[1,2,4]Triazolo[1,5-b;5',1'-f]-1,2,4,5-Tetrazine", Chemical Engineering Journal, 2022, 450, 138073, and the structure is shown as (II): The density of the compound is 1.713 g / cm 3 , the enthalpy of formation is 668 kJ / mol, the calculated detonation velocity is 8340 m / s, and the detonation pressure is 29.2 GPa. The compound has low density, small enthalpy of formation and low energy level. SUMMARY
[0004] The technical problem to be solved by the application is to overcome the deficiencies and defects of the background art, and to provide a 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl)azo compound with high density, high enthalpy of formation and high energy, a preparation method and application.
[0005] The specific scheme of the application is as follows:
[0006] A 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl)azo compound, the structural formula of the compound is shown as (I):
[0007]
[0008] Specifically, the physicochemical properties of the compound include:
[0009] Appearance: orange red solid;
[0010] Solubility: insoluble in water or methanol, soluble in acetonitrile or dimethyl sulfoxide;
[0011] Density: 2.044 g / cm 3 ;
[0012] Enthalpy of formation: 1676.43 kJ / mol.
[0013] Specifically, the detonation performance of the compound includes:
[0014] Detonation velocity: 9556.73 m / s;
[0015] Detonation pressure: 39.27 GPa.
[0016] The preparation method of the 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl)azo compound described in any of the present application, the synthesis route is:
[0017]
[0018] Optionally, 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine is used as raw material to substitute 5-amino tetrazole to obtain 3,6-bis(1-hydrogen-1,2,3,4-tetrazole-5-amino)-1,2,4,5-tetrazine;
[0019] 3,6-bis(1-hydrogen-1,2,3,4-tetrazole-5-amino)-1,2,4,5-tetrazine is reacted with polyphosphoric acid to obtain bis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2,7-diamine);
[0020] Bis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2,7-diamine) is oxidized by hydrogen peroxide to obtain 7-nitro-bis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-amine);
[0021] 7-nitro-bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-amine is azotized by trichloroisocyanuric acid to obtain 1,2-bis(7-nitro-bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl) azo.
[0022] Optionally, the synthesis of 3,6-bis(1-hydro-1,2,3,4-tetrazol-5-amino)-1,2,4,5-tetrazine comprises:
[0023] 5-amino-tetrazole is dissolved in sulfolane at a temperature of 15-25℃, 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine is added in batches, and after the addition is completed, the temperature is raised to 135℃ and reacted for 16-20h;
[0024] After the reaction is completed, it is cooled to 50-70℃, ethyl acetate is added, the solvent is removed by filtration, washed, and dried to obtain 3,6-bis(1-hydro-1,2,3,4-tetrazol-5-amino)-1,2,4,5-tetrazine; wherein the molar ratio of 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine to 5-amino-tetrazole is 1:(2-3).
[0025] Optionally, the synthesis of bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2,7-diamine comprises:
[0026] 3,6-bis(1-hydro-1,2,3,4-tetrazol-5-amino)-1,2,4,5-tetrazine is added to polyphosphoric acid under stirring at a temperature of 130-150℃, after the addition is completed, the temperature is raised to 180-200℃ and reacted for 2-5h;
[0027] After the reaction is completed, it is cooled to 50-70℃, diluted with water, and precipitated by standing, filtered and washed with water to obtain bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2,7-diamine, and the mass ratio of 3,6-bis(1-hydro-1,2,3,4-tetrazol-5-amino)-1,2,4,5-tetrazine to polyphosphoric acid is 1:(15-30).
[0028] Optionally, the synthesis of 7-nitro-bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-amine comprises:
[0029] Sodium tungstate is added into hydrogen peroxide solution under stirring at a temperature of 0-5 DEG C, concentrated sulfuric acid is added dropwise, then bis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazine-2,7-diamine) is added into the mixture, after the addition is completed, the temperature is slowly increased to 30-60 DEG C, and the reaction is kept for 4-12 hours;
[0030] After the reaction is completed, filtration, water washing and drying are carried out, and 7-nitro-bis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine) is obtained; wherein the molar ratio of bis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazine-2,7-diamine) to hydrogen peroxide is 1:(100-500).
[0031] Optionally, the synthesis of the 1,2-bis(7-nitro-bis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl) azo compound comprises:
[0032] 7-nitro-bis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine) is added into acetonitrile under stirring at a temperature of 15-25 DEG C, then trichloroisocyanuric acid is added into the mixture, and the reaction is kept for 4-12 hours.
[0033] After the reaction is completed, filtration, water washing and drying are carried out, and 1,2-bis(7-nitro-bis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl) azo) is obtained through silica gel column chromatography separation and purification; wherein the molar ratio of 7-nitro-bis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine) to trichloroisocyanuric acid is 1:(1-5).
[0034] The 1,2-bis(7-nitro-bis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl) azo compound of any of the present application is used for preparing energetic materials.
[0035] The present application has the following advantages:
[0036] The 1,2-bis(7-nitro-bis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl) azo compound of the present application has high density, and the calculated density is 2.04 g / cm 3The 1,2-bis(7-nitrobis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl)azo compound of the present application has a formation enthalpy of 1676.43 kJ / mol; the 1,2-bis(7-nitrobis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl)azo compound of the present application has a high energy, and its detonation velocity is 9557 m / s and its detonation pressure is 39.27 GPa. BRIEF DESCRIPTION OF DRAWINGS
[0037] The accompanying drawings are included to provide a further understanding of the present application, and are incorporated in and constitute a part of this specification, illustrate embodiments of the present application and serve to explain the principles of the present application, but are not intended to limit the present application. In the drawings:
[0038] Figure 1 The infrared spectrum of the 1,2-bis(7-nitrobis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl)azo compound prepared for Example 1;
[0039] Figure 2 The nuclear magnetic resonance spectrum of the 1,2-bis(7-nitrobis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl)azo compound prepared for Example 1. DETAILED DESCRIPTION
[0040] The present application will be further described in detail below in conjunction with the examples.
[0041] The following is an example given by the inventor, it should be noted that this example is a preferred example, mainly for understanding the present application, but the present application is not limited to this example.
[0042] The synthesis route of the 1,2-bis(7-nitrobis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl)azo compound of the present application:
[0043]
[0044] 3,6-bis(1-hydro-1,2,3,4-tetrazol-5-amino)-1,2,4,5-tetrazine (BTATz) is obtained by substituting 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine with 5-aminotetrazole, then 3,6-bis(1-hydro-1,2,3,4-tetrazol-5-amino)-1,2,4,5-tetrazine reacts with polyphosphoric acid (PPA) to obtain bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2,7-diamine (DATC), then bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2,7-diamine is oxidized by hydrogen peroxide to obtain 7-nitro-bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine (ANTC), finally, 7-nitro-bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine is subjected to azo reaction under the action of trichloroisocyanuric acid (TCI) to obtain 1,2-bis(7-nitro-bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-yl) azo.
[0045] The 1,2-bis(7-nitro-bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-yl) azo of the present application has a structural formula as shown in (I):
[0046]
[0047] The synthesis method of the 1,2-bis(7-nitro-bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-yl) azo of the present application comprises the following steps:
[0048] (1) Synthesis of 3,6-bis(1-hydro-1,2,3,4-tetrazol-5-amino)-1,2,4,5-tetrazine (BTATz)
[0049] 5-aminotetrazole is added into sulfolane under stirring at a temperature of 15-25℃, 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine is added in batches, after the addition is completed, the temperature is raised to 135℃ and reacted for 16-20h. After the reaction is completed, the temperature is cooled to 50-70℃, ethyl acetate is added, the solvent is removed by filtration, washed and dried to obtain 3,6-bis(1-hydro-1,2,3,4-tetrazol-5-amino)-1,2,4,5-tetrazine; wherein the molar ratio of 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine to 5-aminotetrazole is 1:(2-3).
[0050] (2) Synthesis of bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2,7-diamine (DATC)
[0051] Under stirring, 3,6-bis(1-hydro-1,2,3,4-tetrazol-5-amino)-1,2,4,5-tetrazine is added into polyphosphoric acid at a temperature of 130-150°C, after the addition is completed, the temperature is raised to 180-200°C, and the reaction is kept for 2-5h. After the reaction is completed, the temperature is cooled to 50-70°C, water is added for dilution, and the product is precipitated, filtered, and washed with water to obtain bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2,7-diamine, and the mass ratio of 3,6-bis(1-hydro-1,2,3,4-tetrazol-5-amino)-1,2,4,5-tetrazine to polyphosphoric acid is 1:(15-30).
[0052] (3) Synthesis of 7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine (ANTC)
[0053] Under stirring, sodium tungstate is added into hydrogen peroxide solution (30%-70%) at a temperature of 0-5°C, concentrated sulfuric acid is added dropwise, and then bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2,7-diamine is added into the mixture, after the addition is completed, the temperature is slowly raised to 30-60°C, and the reaction is kept for 4-12h. After the reaction is completed, the product is filtered, washed with water, and dried to obtain 7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine; wherein the molar ratio of bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2,7-diamine to hydrogen peroxide is 1:(100-500).
[0054] (4) Synthesis of 1,2-bis(7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-yl) azo
[0055] Under stirring, 7-nitro-bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-amine was added into acetonitrile at temperature 15-25℃, then trichloroisocyanuric acid was added into the mixture, and the reaction was kept for 4-12h. After the reaction was completed, filtration, water washing and drying were carried out, and then 1,2-bis(7-nitro-bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl) azo was obtained by silica gel column chromatography separation and purification; wherein the molar ratio of 7-nitro-bis([1,2,4]triazol)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-amine to trichloroisocyanuric acid was 1:(1-5).
[0056] Example 1:
[0057] (1) Synthesis of 3,6-bis(1-hydro-1,2,3,4-tetrazol-5-amino)-1,2,4,5-tetrazine (BTATz)
[0058] Under stirring, 40g 5-aminotetrazole was dissolved in 380mL sulfolane at temperature 25℃, and then 50g 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine was added in batches, after the addition was completed, the temperature was increased to 135℃ and the reaction was kept for 18h. After the reaction was completed, the temperature was cooled to 50℃, 120mL ethyl acetate was added, the solvent was removed by filtration, and then washing and drying were carried out to obtain 3,6-bis(1-hydro-1,2,3,4-tetrazol-5-amino)-1,2,4,5-tetrazine 31.81g, with a yield of 69.30%.
[0059] Structure identification:
[0060] Infrared spectrum: IR (KBr, cm -1 ),υ:3430,3332,1615,1490,1443,1067;
[0061] Nuclear magnetic spectrum: 1 H NMR (DMSO-d6, 500MHz)δ: 12.5 (br-s, 2H, NH) ppm; 13 C NMR (DMSO-d6, 125MHz), δ: 151.4, 158.6 ppm;
[0062] Elemental analysis: molecular formula C4H4N 14 ;
[0063] Theoretical value (%): C, 19.36; H, 1.62; N, 79.02;
[0064] Actual value (%): C, 19.31; H, 1.75; N, 78.94;
[0065] The above structural identification data confirm that the obtained substance is indeed 3,6-bis(l-hydro-l,2,3,4-tetrazol-5-amino)-l,2,4,5-tetrazine (BTATz).
[0066] (2) Synthesis of bis([l,2,4]triazol)[l,5-b;5',l'-f][l,2,4,5]tetrazine-2,7-diamine (DATC)
[0067] Under stirring, 4.5 g of 3,6-bis(l-hydro-l,2,3,4-tetrazol-5-amino)-l,2,4,5-tetrazine was added to 95 g of polyphosphoric acid at a temperature of 145°C, and after the addition was completed, the temperature was raised to 180°C and the reaction was maintained for 4 h. After the reaction was completed, the temperature was cooled to 70°C, 300 mL of water was added for dilution, and the precipitate was allowed to settle, filtered and washed with water to obtain bis([l,2,4]triazol)[l,5-b;5',l'-f][l,2,4,5]tetrazine-2-amine 1.20 g, with a yield of 34.68%.
[0068] Structural identification:
[0069] Infrared spectrum: IR (KBr, cm -1 ), u: 3318, 3134, 1639, 1538, 1365, 1124, 1024, 824;
[0070] Nuclear magnetic spectrum: 1 H NMR (DMSO-d6, 500 MHz) δ: 7.40 (s, 4H, 2NH2) ppm; 13 C NMR (DMSO-d6, 125 MHz) δ: 167.37, 147.42 ppm;
[0071] Elemental analysis: molecular formula C4H4N 10 ;
[0072] Theoretical value: C, 25.00; H, 2.10; N, 72.90;
[0073] Found: C, 24.46; H, 2.10; N, 73.44;
[0074] The above structural identification data confirm that the obtained substance is indeed bis([l,2,4]triazol)[l,5-b;5',l'-f][l,2,4,5]tetrazine-2,7-diamine (DATC).
[0075] (3) 7-nitro-bis([l,2,4]triazol)[l,5-b;5',l'-f][l,2,4,5]tetrazine-2-amine (ANTC)
[0076] Under stirring, 5 g of sodium tungstate was added into 30 mL of hydrogen peroxide solution (50%) at temperature 0-5°C, 9 mL of concentrated sulfuric acid was added dropwise, then 0.5 g of bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2,7-diamine was added into the mixture, after the addition was completed, the temperature was slowly increased to 50°C, and the reaction was kept for 8 h. After the reaction was completed, filtration, water washing and drying were carried out, and 7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine 0.496 g was obtained, with a yield of 85.81%.
[0077] Structure identification:
[0078] Infrared spectrum: IR (KBr, cm -1 ), υ: 3462, 3352, 1687, 1623, 1546, 1479, 1368, 1318, 1165, 847;
[0079] Nuclear magnetic spectrum: 1 H NMR (DMSO-d6, 500 MHz) δ: 11.27 (s, 2H, NH2) ppm; 13 C NMR (DMSO-d6, 125 MHz) δ: 157.65 141.15 ppm;
[0080] Elemental analysis: molecular formula C4H2N 10 O2
[0081] Theoretical value (%): C 21.63, H 0.91, N 63.06
[0082] Actual value (%): C 21.25, H 0.901, N 61.93
[0083] The above structure identification data prove that the obtained substance is indeed 7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine.
[0084] (4) Synthesis of 1,2-bis(7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl) azo
[0085] Under stirring, 0.2 g 7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-amine was added into 10 mL acetonitrile at 25 ℃, then 0.628 g trichloroisocyanuric acid was added into the mixture, and the reaction was kept for 12 h. After the reaction was completed, the product was filtered, washed with water and dried, and then purified by silica gel column chromatography to obtain 1,2-bis(7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl) azo 0.195 g with a yield of 98.4%.
[0086] Structure identification:
[0087] Infrared spectrum: IR (KBr, cm -1 ), υ: 1688, 1626, 1553, 1458, 1369, 1315, 1153, 854, 714, the spectrum is shown in Figure 1 ;
[0088] Nuclear magnetic spectrum: 13 C NMR (DMSO-d6, 125 MHz) δ: 172.03, 159.87, 152.73, 145.35 ppm; the spectrum is shown in Figure 2 ;
[0089] Elemental analysis: molecular formula C8N 20 O4;
[0090] Theoretical value (%): C 21.83, N 63.64, O 14.54
[0091] Actual value (%): C 20.69, N 62.03;
[0092] The above structure identification data prove that the obtained substance is indeed 7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-amine.
[0093] 1,2-bis(7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl) azo
[0094] (1) Physicochemical properties
[0095] Appearance: orange-red solid
[0096] Solubility: insoluble in water and methanol, soluble in acetonitrile, dimethyl sulfoxide, etc.
[0097] Density: 2.044 g / cm 3 , Gaussian 09 program B3LYP / 6-311G(d,p) method
[0098] Enthalpy of formation: 1676.43 kJ / mol, Gaussian 09 program B3LYP / 6-311G(d,p) method
[0099] (2) Detonation performance
[0100] Detonation velocity: density 2.04 g / cm 3 , calculated detonation velocity 9556.73 m / s K-J equation
[0101] Detonation pressure: density 2.04 g / cm 3 , calculated detonation pressure 39.27 GPa K-J equation
[0102] Use of 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl)azo
[0103] The 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl)azo compound of the present application has the characteristics of high density and high energy, and can be used in the fields of melt-cast explosive liquid phase carrier, high-energy propellant, etc.
[0104] The above is only a specific embodiment of the present application, but the present application is not limited to the above embodiment. Various modifications, improvements and changes of the present application should be included in the protection scope of the present application without departing from the design concept and principles of the present application.
Claims
1. A 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5-b;5',1 '-f][1,2,4,5]tetrazin-2-yl)azo compound characterized in that, The compound has a structural formula as shown in (I):
2. The 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl)azo compound according to claim 1, characterized in that, The physical and chemical properties of the compound include: Appearance: orange red solid; Solubility: insoluble in water or methanol, soluble in acetonitrile or dimethyl sulfoxide; Density: 2.044 g / cm 3 ; Enthalpy of formation: 1676.43 kJ / mol.
3. The 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5-b;5',1'-f][1,2,4,5]tetrazin-2-yl)azo compound according to claim 1, characterized in that, The detonation performance of the compound includes: Detonation velocity: 9556.73 m / s; Detonation pressure: 39.27 GPa.
4. Process for the preparation of the 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5- b;5',1 '-f][1,2,4,5]tetrazin-2-yl)azo compound according to any one of claims 1 to 3, characterized in that, It includes: The synthesis route is:
5. Process for the preparation of 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5- b;5',1 '-f][1,2,4,5]tetrazin-2-yl)azo compounds according to claim 4, characterized in that 3,6-bis(1-hydro-1,2,3,4-tetrazole-5-amino)-1,2,4,5-tetrazine is obtained by substitution of 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine with 5-aminotetrazole; 3,6-bis(1-hydro-1,2,3,4-tetrazole-5-amino)-1,2,4,5-tetrazine is reacted with polyphosphoric acid to obtain bis([1,2,4]triazole) [1,5-b; 5',1'-f][1,2,4,5] tetrazine-2,7-diamine; Bis([1,2,4]triazole) [1,5-b; 5',1'-f][1,2,4,5] tetrazine-2,7-diamine is oxidized by hydrogen peroxide to obtain 7-nitro-bis([1,2,4]triazole) [1,5-b; 5',1'-f][1,2,4,5] tetrazine-2-amine; 7-nitro-bis([1,2,4]triazole) [1,5-b; 5',1'-f][1,2,4,5] tetrazine-2-amine is subjected to azo reaction under the action of trichloroisocyanuric acid to obtain 1,2-bis(7-nitro-bis([1,2,4]triazole) [1,5-b; 5',1'-f][1,2,4,5] tetrazine-2-yl) azo.
6. Process for the preparation of 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5-b;5',1 '- f][1,2,4,5]tetrazin-2-yl)azo compounds according to claim 5, characterized in that, The synthesis of 3,6-bis(1-hydro-1,2,3,4-tetrazole-5-amino)-1,2,4,5-tetrazine includes: Under stirring, 5-aminotetrazole is added to sulfolane at a temperature of 15-25°C and dissolved, 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine is added in batches, after the addition is completed, the temperature is raised to 135°C and reacted for 16-20h; After the reaction is completed, it is cooled to 50-70°C, ethyl acetate is added, the solvent is removed by filtration, washed and dried to obtain 3,6-bis(1-hydro-1,2,3,4-tetrazole-5-amino)-1,2,4,5-tetrazine; wherein the molar ratio of 3,6-bis(3,5-dimethylpyrazolyl)-1,2,4,5-tetrazine to 5-aminotetrazole is 1:(2-3).
7. A process for the preparation of 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5-b;5',1 '- f][1,2,4,5]tetrazin-2-yl)azo compounds according to claim 5, characterized in that The synthesis of bis([1,2,4]triazole) [1,5-b; 5',1'-f][1,2,4,5] tetrazine-2,7-diamine includes: Under stirring, 3,6-bis(1-hydro-1,2,3,4-tetrazole-5-amino)-1,2,4,5-tetrazine is added to polyphosphoric acid at a temperature of 130-150°C, after the addition is completed, the temperature is raised to 180-200°C and reacted for 2-5h; After the reaction is completed, cool to 50-70℃, dilute with water, stand to precipitate, filter and wash with water to obtain bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2,7-diamine, 3,6-bis(1-hydro-1,2,3,4-tetrazol-5-amino)-1,2,4,5-tetrazine and polyphosphoric acid with a mass ratio of 1:(15-30).
8. A process for the preparation of 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5-b;5',1 '- f][1,2,4,5]tetrazin-2-yl)azo compounds according to claim 5, characterized in that, The 7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine is synthesized by the following steps: The synthesis of the 7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine comprises: Under stirring, add sodium tungstate into the hydrogen peroxide solution at a temperature of 0-5℃, drop in concentrated sulfuric acid, then add bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2,7-diamine into the mixture, after the addition is completed, slowly warm to 30-60℃, and keep the temperature for 4-12h of reaction; After the reaction is completed, filter, wash with water and dry to obtain 7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine; wherein the molar ratio of bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2,7-diamine to hydrogen peroxide is 1:(100-500).
9. A process for the preparation of 1,2-bis(7-nitrobis([1,2,4]triazolo[1,5- b;5',1 '-f][1,2,4,5]tetrazin-2-yl)azo compounds according to claim 5, characterized in that, The synthesis of the 1,2-bis(7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-yl)azene comprises: Under stirring, add 7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine into acetonitrile at a temperature of 15-25℃, then add trichloroisocyanuric acid into the mixture, and keep the temperature for 4-12h of reaction; After the reaction is completed, filter, wash with water and dry, then separate and purify by silica gel column chromatography to obtain 1,2-bis(7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-yl)azene; wherein the molar ratio of 7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-amine to trichloroisocyanuric acid is 1:(1-5).
10. Use of the 1,2-bis(7-nitro-bis([1,2,4]triazolo)[1,5-b;5',1'-f][1,2,4,5]tetrazine-2-yl)azene compound according to any one of claims 1-3 for the preparation of energetic materials.