CN113185522B - Planar pyrazolo triazine energetic molecule and synthesis method thereof - Google Patents
Planar pyrazolo triazine energetic molecule and synthesis method thereof Download PDFInfo
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Abstract
The invention discloses a planar pyrazolotriazine energetic molecule and a synthesis method thereof, which starts from dinitroaminopyrazole, synthesizes a diazonium salt intermediate under the condition of HCl/tBuONO, closes a ring with propionitrile, and continues to react with NaN under the condition of heating 3 Tetrazole cyclization reaction is carried out to obtain 8-nitro-3- (1H-tetrazole-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-4, 7-diamine is subjected to oxidation reaction, nitrogen oxidation and nitro amination respectively to obtain other planar pyrazolotriazine energetic molecules. The energetic compound synthesized by the method has a series of advantages of simple method, good product planarity, high yield, simple separation and the like.
Description
Technical Field
The invention belongs to the field of synthesis of energetic materials, and particularly relates to planar pyrazolo triazine energetic molecules and a synthesis method thereof.
Background
With the development of military technology, the requirements of weaponry on the heat resistance of energetic material molecules are higher and higher. It is required not only to have a high energy density and a suitable sensitivity but also to have a good heat resistance. To achieve this goal, researchers have synthesized a number of novel energetic molecules based on the pyrazolo [5,1-c ] [1,2,4] triazine backbone, such as PTX (j. Mater. Chem.a,2015,3, 17963-17965) and the like, which exhibit a good overall performance. However, the key reagent 'nitro acetonitrile' in the synthesis process is difficult to be amplified for preparation and long-term storage, so that the novel energetic molecules are difficult to be amplified and evaluated; an energetic molecule with a triazolo [5,1-c ] [1,2,4] triazine skeleton (chem. Commun.,2019,55, 6062-6065) is synthesized by a cyclization reaction of malononitrile by Lumin et al, but the energetic molecule skeleton has low thermal stability and is decomposed at 181 ℃.
Disclosure of Invention
The invention aims to provide planar pyrazolo triazine energetic molecules and a synthesis method thereof, the synthesis method rapidly synthesizes target energetic molecules with a pyrazolo [5,1-c ] [1,2,4] triazine skeleton from 3, 5-diamino-4-nitropyrazole, has the advantages of good chemical stability, long-term storage, commercial availability and the like, and the cyclization reaction process has mild conditions and is beneficial to later-stage amplification preparation. The comprehensive performance of the product is superior to that of active explosive RDX, the synthesis steps are simple, and the reaction conditions are mild.
In order to achieve the technical effects, the invention provides the following technical scheme:
the invention discloses 8-nitro-3- (1H-tetrazole-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-4, 7-diamine having the following structural formula:
the invention discloses 7, 8-dinitro-3- (1H-tetrazole-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-7-amines having the following structural formula:
the invention discloses 4-amino-7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-2-oxy having the following structural formula:
the invention discloses N- (4-amino-8-nitro-3- (1H-tetrazole-5-yl) pyrazolo [5, 1-c)][1,2,4]Triazin-7-yl) nitramines having the following structural formula:
the invention discloses 8-nitro-3- (1H-tetrazole-5-yl) pyrazolo [5,1-c][1,2,4]A method for synthesizing triazine-4, 7-diamine, comprising the following steps: under the ice bath condition, adding hydrogen chloride-1, 4-dioxane solution into methanol solution of 4-nitro-3, 5-diaminopyrazole, continuously stirring for 5-60 min, then adding tert-butyl nitrite into the reaction system, continuously reacting for 0.5-5h, then adding anhydrous ether, stirring, filtering, and washing with the anhydrous ether to obtain yellow solid; the resulting solid was transferred to suspend in 20% H at 0 deg.C 2 SO 4 Then slowly adding a mixed solution prepared from potassium oxalate, water and malononitrile, reacting for 1-6 h, continuing stirring for 1-6 h at room temperature, filtering, washing with water, and drying to obtain 4, 7-diamino-8-nitropyrazolo [5,1-c ]][1,2,4]Triazine-1-cyano; to 4, 7-diamino-8-nitropyrazolo [5,1-c ] at room temperature][1,2,4]Adding DMF into triazine-1-cyano, stirring until the solid is completely dissolved, then adding NaN3 solid into the reaction liquid, stirring for 0.5-3H, continuously stirring and heating the reaction system at the temperature of 40-90 ℃ for 5-20H, stopping heating, cooling to room temperature, pouring the reaction liquid into water, adjusting the pH of the system to about 1 by using HCl solution, filtering, washing with water, naturally drying to obtain 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-4, 7-diamine.
The further technical proposal is that the molar ratio of 4-nitro-3, 5-diaminopyrazole, hydrogen chloride and tert-butyl nitrite in the process of synthesizing the diazonium salt intermediate is 1:1 to 2: the mass volume ratio of 1-5, 4-nitro-3, 5-diaminopyrazole to diethyl ether is 1g: (20-500) mL.
The further technical proposal is that the mol ratio of the 4-nitro-3, 5-diaminopyrazole to the malononitrile in the cyclization reaction is 1: 1-5, 4-nitro-3, 5-diaminopyrazoles with 20％H 2 SO 4 The mass-to-volume ratio of (1 g): (5-50) mL, wherein the mass-volume ratio of potassium oxalate, water and malononitrile is (2-14) g: (10-100) ml:1g of the total weight of the composition.
The further technical proposal is that 4, 7-diamino-8-nitropyrazolo [5,1-c ] is synthesized in tetrazole ring][1,2,4]Triazine-1-cyano, DMF, naN 3 The mass-to-volume ratio of (1 g): (20-200) mL: (0.3-3) g.
The invention discloses a 7, 8-dinitro-3- (1H-tetrazole-5-yl) pyrazolo [5,1-c][1,2,4]A method for synthesizing triazine-7-amine, comprising: adding 30% H to the reaction flask at-30-5 deg.C 2 O 2 Keeping the solution at the temperature for 20min, slowly adding sulfuric acid into hydrogen peroxide solution, keeping the temperature at-10 ℃ for 0.5-2H, and then adding 8-nitro-3- (1H-tetrazole-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-4, 7-diamine is added into the mixed solution in batches to react for 1 to 5 hours, and the reaction is continued for 4 to 12 hours at room temperature. After the reaction is finished, pouring the reaction liquid on crushed ice for quenching to obtain yellow suspension, filtering, washing with water, and naturally airing to obtain 7, 8-dinitro-3- (1H-tetrazole-5-yl) pyrazolo [5,1-c][1,2,4]Triazin-7-amines.
The further technical proposal is that 8-nitro-3- (1H-tetrazole-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-4, 7-diamine, 30% by weight H 2 O 2 Concentrated H 2 SO 4 The mass-to-volume ratio of (1 g): (4-10) mL: (8-20) mL.
The invention discloses a 4-amino-7, 8-dinitro-3- (1H-tetrazole-5-yl) pyrazolo [5,1-c][1,2,4]A method for synthesizing triazine-2-oxygen, comprising: adding 50% H to the reaction flask at-10-5 deg.C 2 O 2 Keeping the temperature of the solution for 10 to 40min, adding trifluoroacetic anhydride at the same temperature, keeping the temperature at 0 ℃ for 0.5 to 2H, and then adding 7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Adding triazine-7-amine into the mixed solution in batches, reacting for 1-4H, continuing to react for 12-48H at room temperature, pouring the reaction solution into crushed ice after the reaction is finished, continuously stirring to obtain light yellow suspension, filtering, washing with water, and naturally drying to obtain 4-amino-7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-2-oxygen.
The further technical proposal is that 7, 8-binitro-3- (1H-tetrazole-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-7-amine, 50% by weight H 2 O 2 The mass-to-volume ratio of TFAA is 1g: (2-8) mL: (6-20) mL.
The invention discloses N- (4-amino-8-nitro-3- (1H-tetrazole-5-yl) pyrazolo [5, 1-c)][1,2,4]A method for synthesizing triazin-7-yl) nitramines, characterized in that the method comprises: at the temperature of-10 to 5 ℃, KNO is added into a reaction bottle 3 And concentrated H 2 SO 4 Stirring until the solid is completely dissolved, and then adding 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Adding triazine-4, 7-diamine into the mixed solution in batches, reacting for 1-4H, then continuing to react for 4-24H at room temperature, pouring the reaction solution into crushed ice after the reaction is finished to obtain yellow suspension, filtering, washing with water, and naturally airing to obtain the N- (4-amino-8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5, 1-c)][1,2,4]Triazin-7-yl) nitramines.
The further technical proposal is that 8-nitro-3- (1H-tetrazole-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-4, 7-diamine, KNO 3 Concentrated H 2 SO 4 The mass-to-volume ratio of (1 g): (2-6) g: (8-20) mL.
The invention is further explained and illustrated below.
The invention starts from a 4-nitro-3, 5-diaminopyrazole compound, and obtains a series of planar energetic compounds through cyclization reaction, nitramine reaction, oxidation and nitrogen oxidation, wherein the specific synthetic route is as follows:
the invention uses malononitrile cyclization reaction strategy for reference, and quickly synthesizes target energetic molecules with pyrazolo [5,1-c ] [1,2,4] triazine skeleton from 3, 5-diamino-4-nitropyrazole. Compared with nitroethyl, the malononitrile used in the synthetic route of the invention has the advantages of good chemical stability, long-term storage, commercial availability and the like, and the cyclization reaction process has mild conditions and is beneficial to later-stage amplification preparation. The initial decomposition temperature of part of target molecules disclosed by the patent is more than 300 ℃, and the thermal stability is excellent. And through introducing tetrazole group, a heat-resistant energetic compound with high energy density is developed, and the heat-resistant energetic compound has certain value and significance for enriching energetic molecular species and improving the comprehensive performance of a weapon system.
Compared with the prior art, the invention has the following beneficial effects:
(1) A class of planar pyrazolotriazines containing the energetic molecules "8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] [1,2,4] triazine-4, 7-diamine", "7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] [1,2,4] triazine-7-amine", "4-amino-7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] [1,2,4] triazine-2-oxo", "N- (4-amino-8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] [1,2,4] triazin-7-yl) nitroamine" was identified and disclosed for the first time in the present invention.
(2) The starting material, 3, 5-diamino-4-nitropyrazole, is a commercial product and is readily available. The synthetic route has simple steps and mild reaction conditions, and the product is easy to separate and purify.
(3) The four energetic molecules provided by the invention are yellow powdery solids, and are transparent flaky or blocky crystals after recrystallization. The density is 1.87-1.92 g/cm 3 The theoretical detonation velocity D = 8820-9070 m/s, and the theoretical detonation pressure P = 29-32 Gpa. The impact sensitivity IS = 9-20J, and the friction sensitivity FS = 136-336N. The decomposition temperature Td = 180-330 ℃. Wherein, the detonation velocity, the sensitivity and the thermal stability of the two compounds are all superior to those of the active RDX explosive, and the two compounds are potential substitutes of the RDX explosive and have good application prospects.
Drawings
FIG. 1 is a scheme for the synthesis of planar pyrazolo triazine energetic molecules of the invention;
FIG. 2 is a single crystal diffraction pattern of a solvate of 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] [1,2,4] triazine-4, 7-diamine;
FIG. 3 is a single crystal diffractogram of a solvate of 7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] [1,2,4] triazin-7-amine;
FIG. 4 is a single crystal diffraction pattern of a solvate of 4-amino-7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] [1,2,4] triazine-2-oxide;
FIG. 5 is a single crystal diffraction pattern of a solvate of N- (4-amino-8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] [1,2,4] triazin-7-yl nitramine ".
Detailed Description
The invention will be further illustrated and described with reference to the following examples of the invention:
example 1: a25 mL single-necked bottle was placed in an ice-water bath and 10mL CH was added 3 OH solution and 0.924g of 4-nitro-3, 5-diaminopyrazole were added to the flask at this temperature and the solution of hydrogen chloride-1, 4-dioxane was stirred for 10min. Subsequently, 1.3mL of a t-butyl nitrite solution was added to the reaction system. The reaction was continued at 0 ℃ for 1h. Then 50mL of anhydrous ether was added, stirred and filtered. Washing with anhydrous ether to obtain a yellow solid; immediately transferring the resulting solid to a 100mL reaction flask, adding 8mL of 20% 2 SO 4 Stirring at 0 deg.C for 10min. A mixed solution of 7g of potassium oxalate, 30ml of water and 0.924g of malononitrile was then slowly added. The reaction was continued at 0 ℃ for 2h, room temperature for 2h. Filtering, washing and drying to obtain brick red solid 4, 7-diamino-8-nitropyrazolo [5,1-c ]][1,2,4]Triazine-1-cyano "1.3g (95%).
Example 2: 1.10g of 4, 7-diamino-8-nitropyrazolo [5,1-c ] are reacted at room temperature][1,2,4]Triazine-1-cyano (5 mmol) was added to a 100mL one-neck flask, followed by 50mL of DMF, stirred until the solid was completely dissolved, and then 0.34g of NaN was weighed out using a balance 3 Solid, added to the reaction solution, stirred for 0.5h, then connected to a reflux apparatus, set at 86.5 ℃. After refluxing at this temperature for 10h, a yellow solid precipitated from the solution and the solution became cloudy. After the reflux was completed, heating was stopped and the mixture was cooled to room temperature. The reaction mixture was poured into a 250mL beaker, 40mL of water was added, and the pH of the solution was adjusted to about 1 with 1N HCl, at which time a large amount of yellow solid precipitated. Filtering, washing with water (3X 15mL), and naturally drying to obtain solid 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-4, 7-diamine "1.24g, yield 94%.
Example 3: setting the low temperature bath at-15 deg.C to reachAfter setting the temperature, 2.8mL of 30% H was added to the reaction flask 2 O 2 The solution was incubated at this temperature for 20min. Thereafter, 5.6mL of concentrated H were charged from a constant pressure dropping funnel 2 SO 4 At this temperature, sulfuric acid was slowly added to the hydrogen peroxide solution at a controlled dropping rate of 8s per drop over about 1.5H, followed by 0.5H incubation at 0 ℃ and then 0.526g of 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] was added][1,2,4]Adding triazine-4, 7-diamine into the mixed solution in batches, reacting at 0 ℃ for 2h, and reacting at 35 ℃ for 8h. After the reaction is finished, pouring the reaction liquid onto 20g of crushed ice for quenching, continuously stirring to obtain a yellow suspension, filtering, washing with water (3X 15mL), and naturally airing to obtain a solid 7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Triazin-7-amine "0.43g, 73% yield.
Example 4: setting the low temperature bath at-5 deg.C, adding 1.5mL of 50% H into the reaction flask 2 O 2 The solution was incubated at this temperature for 20min. Thereafter, 3.5mL of trifluoroacetic anhydride (TFAA) was charged into a constant pressure dropping funnel, TFAA was slowly added to the hydrogen peroxide solution at this temperature for about 20min, followed by 0.5H of incubation at 0 ℃ and 0.526g of 7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] was added][1,2,4]Adding triazine-7-amine into the mixed solution in batches, reacting at 0 ℃ for 2h, and at 30 ℃ for 24h, wherein the solution gradually turns turbid from clear. After the reaction is finished, pouring the reaction liquid onto 20g of crushed ice for quenching, continuously stirring to obtain a light yellow suspension, filtering, washing with water (3X 15mL), and naturally airing to obtain solid 4-amino-7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-2-oxo "0.34g, yield 63%.
Example 5: the low temperature bath was set at-5 ℃ and after reaching the set temperature, 1.3g of KNO was added to the reaction flask 3 Solid, incubate at this temperature for 20min. Thereafter, 4.5mL of concentrated H 2 SO 4 Adding into the reaction solution, stirring until the solid is completely dissolved, and adding 0.40g of 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Adding triazine-4, 7-diamine into the mixed solution in batches, reacting at 0 ℃ for 2h, and reacting at 35 ℃ for 8h. After the reaction, the reaction solution was poured onto 20g of crushed ice and quenched with constant stirringStirring to obtain yellow suspension, filtering, washing with water (3 × 15mL), and naturally air drying to obtain solid "N- (4-amino-8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Triazin-7-yl) nitramine "0.32g, 71% yield.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (10)
- 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] [1,2,4] triazine-4, 7-diamine characterized by the following structural formula:
- a7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] [1,2,4] triazin-7-amine characterized by the following structural formula:
- 4-amino-7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] [1,2,4] triazine-2-oxy characterized by the following structural formula:
- n- (4-amino-8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c ] [1,2,4] triazin-7-yl) nitramine characterized by the following structural formula:
- 5. the 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c as claimed in claim 1][1,2,4]The method for synthesizing the triazine-4, 7-diamine is characterized by comprising the following steps: under the ice bath condition, adding hydrogen chloride-1, 4-dioxane solution into methanol solution of 4-nitro-3, 5-diaminopyrazole, continuously stirring for 5-60 min, then adding tert-butyl nitrite into the reaction system, continuously reacting for 0.5-5h, then adding anhydrous ether, stirring, filtering, and washing with the anhydrous ether to obtain yellow solid; the resulting solid was transferred to suspend in 20% H at 0 deg.C 2 SO 4 Then slowly adding a mixed solution prepared from potassium oxalate, water and malononitrile, reacting for 1-6 h, continuing stirring for 1-6 h at room temperature, filtering, washing with water, and drying to obtain 4, 7-diamino-8-nitropyrazolo [5,1-c ]][1,2,4]Triazine-1-cyano; to 4, 7-diamino-8-nitropyrazolo [5,1-c ] at room temperature][1,2,4]Adding DMF into triazine-1-cyano, stirring until the solid is completely dissolved, and then adding NaN 3 Adding the solid into the reaction solution, stirring for 0.5-3H, continuously stirring and heating the reaction system at the temperature of 40-90 ℃ for 5-20H, stopping heating, cooling to room temperature, pouring the reaction solution into water, adjusting the pH of the system to about 1 by using HCl solution, filtering, washing with water, and naturally drying to obtain 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-4, 7-diamine.
- 6. 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c according to claim 5][1,2,4]The synthesis method of triazine-4, 7-diamine is characterized in that the molar ratio of 4-nitro-3, 5-diaminopyrazole, hydrogen chloride and tert-butyl nitrite is 1:1 to 2: the mass volume ratio of 1-5, 4-nitro-3, 5-diaminopyrazole to diethyl ether is 1g: (20-500) mL; the molar ratio of 4-nitro-3, 5-diaminopyrazole to malononitrile in the cyclization reaction is 1: 1-5, 4-nitro-3, 5-diaminopyrazole with 20% H 2 SO 4 Mass to volume ratio of1g: (5-50) mL, wherein the mass-volume ratio of potassium oxalate, water and malononitrile is (2-14) g: (10-100) ml:1g of the total weight of the composition.
- 7. 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c according to claim 5][1,2,4]A method for synthesizing triazine-4, 7-diamine, which is characterized by comprising the following steps: 4, 7-diamino-8-nitropyrazolo [5,1-c ] in tetrazole ring synthesis][1,2,4]Triazine-1-cyano, DMF, naN 3 The mass-to-volume ratio of (1 g): (20-200) mL: (0.3-3) g.
- 8. The 7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c according to claim 2][1,2,4]The method for synthesizing triazine-7-amine is characterized by comprising the following steps: adding 30% H to the reaction flask at-30-5 deg.C 2 O 2 Keeping the temperature of the solution for 20min, then slowly adding sulfuric acid into hydrogen peroxide solution, keeping the temperature for 0.5 to 2H at the temperature of between 10 ℃ below zero and 10 ℃, and then adding 8-nitro-3- (1H-tetrazole-5-yl) pyrazolo [5,1-c][1,2,4]Adding triazine-4, 7-diamine into the mixed solution in batches, reacting for 1-5H, continuously reacting for 4-12H at room temperature, after the reaction is finished, pouring the reaction solution into crushed ice to quench so as to obtain yellow suspension, filtering, washing with water, and naturally airing to obtain 7, 8-dinitro-3- (1H-tetrazole-5-yl) pyrazolo [5, 1-c)][1,2,4]Triazin-7-amine, 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-4, 7-diamine, 30% by weight H 2 O 2 Concentrated H 2 SO 4 The mass-to-volume ratio of (1 g): (4-10) mL: (8-20) mL.
- 9. 4-amino-7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5, 1-c) as claimed in claim 3][1,2,4]The method for synthesizing triazine-2-oxygen is characterized by comprising the following steps: adding 50% H to the reaction flask at-10-5 deg.C 2 O 2 Keeping the temperature of the solution for 10 to 40min, adding trifluoroacetic anhydride at the same temperature, keeping the temperature at 0 ℃ for 0.5 to 2H, and then adding 7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Adding triazine-7-amine into the mixed solution in batches, reacting for 1-4 h, continuing to react for 12-48 h at room temperature, and pouring the reaction solution into crushed ice after the reaction is finishedStirring continuously to obtain light yellow suspension, filtering, washing with water, and air drying to obtain 4-amino-7, 8-dinitro-3- (1H-tetrazole-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-2-oxo, 7, 8-dinitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-7-amine, 50% by weight H 2 O 2 The mass-to-volume ratio of TFAA is 1g: (2-8) mL: (6-20) mL.
- 10. N- (4-amino-8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5, 1-c) as claimed in claim 4][1,2,4]A method for synthesizing triazin-7-yl) nitramine, which is characterized by comprising the following steps: at the temperature of-10 to 5 ℃, KNO is added into a reaction bottle 3 And concentrated H 2 SO 4 Stirring until the solid is completely dissolved, and then adding 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Adding triazine-4, 7-diamine into the mixed solution in batches, reacting for 1-4H, then continuing to react for 4-24H at room temperature, pouring the reaction solution into crushed ice after the reaction is finished to obtain yellow suspension, filtering, washing with water, and naturally airing to obtain the N- (4-amino-8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5, 1-c)][1,2,4]Triazin-7-yl) nitroamines, 8-nitro-3- (1H-tetrazol-5-yl) pyrazolo [5,1-c][1,2,4]Triazine-4, 7-diamine, KNO 3 Concentrated H 2 SO 4 The mass-to-volume ratio of (1 g): (2-6) g: (8-20) mL.
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