Process for the preparation of amino acid configured amphoteric energetic compounds
By designing amphoteric energetic compounds with amino acid configurations, replacing the carboxyl group with a nitroamino group and introducing a hydrazine configuration to enhance intermolecular hydrogen bonding, the problem of insufficient density in neutral high-energy materials was solved, and energetic compounds with amino acid configurations and high density and excellent detonation performance were realized.
Patent Information
- Application Number
- CN202410235517.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-03-01
- Publication Date
- 2025-12-09
- Estimated Expiration
- 2044-03-01
AI Technical Summary
Existing neutral high-energy materials have long intermolecular hydrogen bond lengths, resulting in insufficient density and affecting detonation performance. It is difficult to further improve density and detonation performance through structural optimization.
A high-density amphoteric energetic compound with an amino acid configuration was designed by replacing the carboxyl group in the amino acid molecule with a nitroamino group and introducing a hydrazine configuration to enhance intermolecular hydrogen bonding.
Energetic compounds with amino acid configurations that achieve high density and excellent detonation performance have shorter hydrogen bond lengths and more compact molecular packing, achieving the highest density and detonation velocity, making them suitable for high-energy-density materials.
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Figure CN118108638B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application relates to a preparation method of an amino acid-structured energetic compound with amphotericity, in particular to a preparation method of an amino acid-structured energetic compound with both acidity and alkalinity, and belongs to the technical field of energetic materials. BACKGROUND
[0002] Amphoteric compounds are compounds that can react with both acids and bases to generate salts and water. Common inorganic oxides and hydroxides of aluminum, gallium, zinc, copper, chromium, etc. are amphoteric compounds, and inorganic amino acids (H2NCH2COOH), peptides, proteins, etc. are also amphoteric compounds. Amphoteric compounds can be applied to probe molecules and have catalytic effects. Energetic materials refer to a class of compounds containing a large amount of chemical energy and capable of releasing heat and pressure under certain stimulation. With the development of science and technology, high-energy density materials (HEDM) are widely used in energy, explosives or propellants, and therefore are paid more and more attention. Traditional HEDM includes 2,4,6-trinitrotoluene (TNT), triaminotrinitrobenzene (TATB), and hexanitrohexaazaisowurtzitane (CL-20) and the like.
[0003] The parameters for measuring the performance of HEDM include density, melting point, decomposition temperature, heat of formation, detonation velocity, detonation pressure, oxygen balance, impact sensitivity and friction sensitivity, etc. The density is one of the most important characteristics of high-energy materials, because it significantly affects the detonation velocity, and more importantly, the detonation pressure increases with the square of the density. Therefore, considerable efforts have been made to develop strategies to increase the density of high-energy materials and improve their detonation performance. Enhanced intermolecular interactions can make molecules have denser packing and smaller volume, thereby increasing the density. In the past few decades, many high-energy materials with enhanced density and interesting structures have been developed using this strategy. By introducing different energetic groups (—NO2, —NH2, —NHNO2, —N3, etc.), the intermolecular interactions, including hydrogen bonds and π-π interactions between adjacent molecules, can be enhanced, which is one of the commonly used strategies. A typical example is 2,4,6-triamino-1,3,5-trinitrobenzene (TATB). The density of TATB (1.937 g cm -3 ) is much higher than that of 1,3,5-trinitrobenzene (1.676 g cm -3 ), which is mainly due to the enhanced intermolecular interactions caused by the introduction of additional amino groups.
[0004] Despite these achievements, most neutral high-energy materials have weak intermolecular interactions. The density of energetic materials is mainly related to the molecular composition and hydrogen bond, especially the hydrogen bond. We found that according to the CCDC database, the current neutral energetic material intermolecular shortest hydrogen bond length (H…A) is generally in the range of Less than Energetic materials, which is possible that most of the existing high-energy material structure is not suitable for the formation of the intermolecular interaction. For example, the shortest intermolecular hydrogen bond length in TATB is And the shortest intermolecular hydrogen bond length in 1,1-diamino-2,2-dinitroethylene (FOX-7) is Further shorten the hydrogen bond length can make the molecular structure more compact, thereby improving the density. Considering the amino acid in the amphoteric compound, the amino acid is a very common amphoteric compound, which itself has a very short hydrogen bond, about Between, for example, D-aspartic acid And D, L-leucine Therefore, we want to design an amphoteric energetic compound containing an amino acid configuration, so as to have a shorter hydrogen bond. We want to enhance the intermolecular interaction by structure optimization, thereby further improving the density and corresponding detonation performance of the energetic material. SUMMARY
[0005] The purpose of the present application is to provide a preparation method of an energetic compound with amino acid configuration having both acidic and basic properties. The present application first realizes an amphoteric energetic compound with amino acid configuration. Since the carboxyl group in the amino acid type molecule is not energetic, it is replaced by a nitro amino group, which can increase the energy of the molecule while maintaining the acidic hydrogen. The methylene is changed to the configuration of the hydrazine, which can introduce hydrogen bonds, enhance intermolecular interactions, and also increase the energy of the molecule. In the designed high-density amphoteric energetic compound structure with amino acid configuration, the hydrogen bond donor amino group and the N-H group can form a strong intermolecular hydrogen bond (N-H…O) with the acceptor (-NO2), which can make the compound have stronger intermolecular interactions, make the molecule have a more compact packing and a smaller molecular volume, thereby resulting in a higher density and a higher detonation, which can make it more advantageous in the application of energetic materials. The present application successfully synthesizes a high-density amphoteric energetic compound with high yield through one-step reaction from known available raw materials. The compound has the potential to be used as a high-energy insensitive energetic material, and provides a new idea for synthesizing new high-energy energetic compounds in the synthesis of energetic materials.
[0006] The purpose of the present application is realized by the following technical scheme.
[0007] A preparation method of an amphoteric energetic compound with amino acid configuration, comprising the following steps:
[0008] Step one, dissolve urea in nitro-sulfur mixed acid, then react for 2-3 hours at -10-0℃, after the reaction, collect the solid to obtain intermediate product I;
[0009]
[0010] Step two, disperse the intermediate product I in aqueous solution, slowly add carbonic acid dihydrazide at 0-5℃, then react completely for 2-3 hours at 30-40℃, after the reaction, collect the solid to obtain the energetic compound II with amino acid structure having both acid and base;
[0011]
[0012] In step (1), the nitro-sulfur mixed acid is nitric acid with a mass fraction of 100% and sulfuric acid with a mass fraction of 98%.
[0013] In step (1), the use amount ratio of urea, nitric acid and sulfuric acid is 25mmol:4mL:3ml.
[0014] In step (2), the use amount ratio of intermediate product I and water is 5mmol:2mL.
[0015] In step (2), the use amount ratio of intermediate product I and carbonic acid dihydrazide is 5mol:3-5mol.
[0016] Preferably, in step (2), the use amount ratio of intermediate product I and carbonic acid dihydrazide is 5mol:3mol.
[0017] In step (2), react completely for 2.5 hours at 35℃, after the reaction, cool the mixed solution to 0℃, form a large amount of precipitate and filter, wash with a small amount of water, and naturally dry the product II.
[0018] Beneficial effects:
[0019] 1. The application provides an energetic compound with amino acid structure having both acid and base, the carboxyl group in the amino acid type molecule does not contain energy, and is replaced by nitro amino group, which can improve the energy of the molecule while maintaining the acidic hydrogen. The methylene is replaced by a continuous amine configuration, which can introduce hydrogen bonds, enhance intermolecular interaction, and also improve the energy of the molecule. The energetic compound with amino acid structure is synthesized for the first time in experiments, and the compound can react with acid and base to generate corresponding anion salt and water. The density of the compound is the highest among all amphoteric energetic compounds, and the detonation velocity is also the highest. It has better detonation performance, is competitive as a high energy density material, and is an ideal insensitive high-energy molecule with good application prospect.
[0020] 2. The application provides an energetic compound with amino acid structure of both acid and base, and the compound can be prepared safely and reliably by further controlling the nitration reaction conditions.
[0021] 3. The application shows that the compound has stronger intermolecular hydrogen bond interaction, resulting in more compact molecular structure and smaller cell volume, and thus higher density, by preparing the energetic compound with amino acid structure of both acid and base.
[0022] 4. The application provides a preparation method of the energetic compound with amino acid structure of both acid and base, which successfully synthesizes the target product in high yield by one-step reaction from known available raw materials, and the compound has potential as high-energy insensitive material.
[0023] 5. The application has a series of advantages such as simple preparation, high yield, high density, high thermal stability, insensitivity, excellent detonation performance, and is close to ideal insensitive high-energy molecules. BRIEF DESCRIPTION OF DRAWINGS
[0024] Figure 1 NMR hydrogen spectrum of the energetic compound with amino acid structure of both acid and base;
[0025] Figure 2 NMR carbon spectrum of the energetic compound with amino acid structure of both acid and base, ppm=159.15, 155.02;
[0026] Figure 3 Infrared spectrum of the energetic compound with amino acid structure of both acid and base;
[0027] Figure 4 Crystal structure diagram of the energetic compound with amino acid structure of both acid and base;
[0028] Figure 5 Infrared spectrum of the hydrochloride salt of the energetic compound with amino acid structure of both acid and base;
[0029] Figure 6 Crystal structure diagram of the hydrochloride salt of the energetic compound with amino acid structure of both acid and base;
[0030] Figure 7 Infrared spectrum of the perchlorate salt of the energetic compound with amino acid structure of both acid and base;
[0031] Figure 8Crystal structure of perchlorate salt of energetic compound with amino acid structure having both acidic and basic properties;
[0032] Figure 9 Infrared spectrum of hydroxylamine salt of energetic compound with amino acid structure having both acidic and basic properties;
[0033] Figure 10 Crystal structure of hydroxylamine salt of energetic compound with amino acid structure having both acidic and basic properties. DETAILED DESCRIPTION
[0034] The application will be further described in conjunction with specific examples.
[0035] Example 1
[0036] The method for preparing the energetic compound with amino acid structure having both acidic and basic properties comprises the following steps:
[0037] (1) 8 ml fuming nitric acid was slowly added to 6 ml concentrated sulfuric acid with mass fraction of 98%, and 3.0 g (50 mmol) of urea was added to the nitric-sulfuric acid mixture, and the reaction was carried out for 2.5 h. The intermediate product I was obtained by filtration, and the yield was 90%.
[0038] (2) 1.5 g (10 mmol) of the intermediate product I was added to 5 ml of water, and 0.9 g (10 mmol) of carbonic acid dihydrazide was slowly added. The reaction was carried out at 30°C for 2 h, and then the mixture was cooled to 0°C. The product II was obtained by filtration and drying, and the yield was 88%. As shown in Figure 1 NMR hydrogen spectrum of the energetic compound with amino acid structure having both acidic and basic properties, Figure 2 NMR carbon spectrum of the energetic compound with amino acid structure having both acidic and basic properties, in carbon spectrum ppm = 159.15, 155.02, Figure 3 Infrared spectrum of the energetic compound with amino acid structure having both acidic and basic properties, Figure 4 Crystal structure of the energetic compound with amino acid structure having both acidic and basic properties.
[0039] (3) 0.2 g (1 mmol) of the product II was dissolved in 5 ml of methanol solution, and hydrochloric acid solution with mass fraction of 37% (1 mmol) was added dropwise at 0-5°C. The reaction was carried out for 30 min. After the reaction was completed, the solid was collected to obtain the hydrochloride salt of the energetic compound with amino acid structure, and the yield was 88%. As shown in Figure 5 Infrared spectrum of the hydrochloride salt of the energetic compound with amino acid structure, Figure 6 Crystal structure of the hydrochloride salt of the energetic compound with amino acid structure.
[0040] Example 2
[0041] The preparation method of the energetic compound with amino acid structure having both acid and base properties comprises the following steps:
[0042] (1) Under ice bath condition, 8 ml fuming nitric acid was slowly added into 6 ml concentrated sulfuric acid with mass fraction of 98%, and 3.0 g (50 mmol) of urea was added into the nitric-sulfur mixed acid, and reacted for 2.5 h, and then the intermediate product I was obtained by filtration, with a yield of 90%.
[0043] (2) 1.5 g (13.3 mmol) of the intermediate product I was added into 5 ml water, and 0.9 g (10 mmol) of dihydrazide carbonate was slowly added, and reacted for 3 h at 35 ℃, and then the mixture was cooled to 0 ℃, and then filtered and dried to obtain the product II, with a yield of 90%.
[0044] (3) 0.2 g (1 mmol) of the product II was dissolved in 5 ml methanol solution, and perchloric acid solution (1 mmol) was added dropwise at 0-5 ℃, and reacted for 30 min, and then the solid was collected to obtain the perchlorate salt of the energetic compound with amino acid structure, with a yield of 85%, as shown in the infrared spectrum of the perchlorate salt of the energetic compound with amino acid structure, Figure 7 Figure 8 the crystal structure diagram of the perchlorate salt of the energetic compound with amino acid structure.
[0045] Example 3
[0046] The preparation method of the energetic compound with amino acid structure having both acid and base properties comprises the following steps:
[0047] (1) Under ice bath condition, 8 ml fuming nitric acid was slowly added into 6 ml concentrated sulfuric acid with mass fraction of 98%, and 3.0 g (50 mmol) of urea was added into the nitric-sulfur mixed acid, and reacted for 2.5 h, and then the intermediate product I was obtained by filtration, with a yield of 90%.
[0048] (2) 1.5 g (10 mmol) of the intermediate product I was added into 5 ml water, and 0.6 g (6.67 mmol) of dihydrazide carbonate was slowly added, and reacted for 3 h at 40 ℃, and then the mixture was cooled to 0 ℃, and then filtered and dried to obtain the product II, with a yield of 89%.
[0049] (3) 0.2 g (1 mmol) of the product II was dissolved in 5 ml methanol solution, and hydroxylamine solution with mass fraction of 85% (1 mmol) was added dropwise at 0-5 ℃, and reacted for 30 min, and then the solid was collected to obtain the hydroxylamine salt of the energetic compound with amino acid structure, with a yield of 86%, as shown in the infrared spectrum of the hydroxylamine salt of the energetic compound with amino acid structure, Figure 9 Figure 10 Crystal structure of hydroxylamine salt of energetic compound with amino acid configuration.
[0050] Comparative Example 1
[0051] (1) 8 ml fuming nitric acid was slowly added into 6 ml concentrated sulfuric acid with mass fraction of 98% under ice-bath condition, 3.0 g (50 mmol) of urea was added into the nitric-sulfuric mixed acid, and reacted for 2.5 h, and then the intermediate product I was obtained by filtration with a yield of 90%.
[0052] (2) 1.5 g (10 mmol) of the intermediate product I was added into 5 ml water, 0.9 g (10 mmol) of carbonic dihydrazide was slowly added, and reacted for 2.5 h at 50°C, and then the mixture was cooled to 0°C, no solid was precipitated, and the yield of the product II was 0%.
[0053] Comparative Example 2
[0054] (1) 8 ml fuming nitric acid was slowly added into 6 ml concentrated sulfuric acid with mass fraction of 98% under ice-bath condition, 3.0 g (50 mmol) of urea was added into the nitric-sulfuric mixed acid, and reacted for 2.5 h, and then the intermediate product I was obtained by filtration with a yield of 90%.
[0055] (2) 1.5 g (10 mmol) of the intermediate product I was added into 5 ml water, 0.9 g (10 mmol) of carbonic dihydrazide was slowly added, and reacted for 6 h at 35°C, and then the mixture was cooled to 0°C, no solid was precipitated, and the yield of the product II was 0%.
[0056] Comparative Example 3
[0057] (1) 8 ml fuming nitric acid was slowly added into 6 ml concentrated sulfuric acid with mass fraction of 98% under ice-bath condition, 3.0 g (50 mmol) of urea was added into the nitric-sulfuric mixed acid, and reacted for 2.5 h, and then the intermediate product I was obtained by filtration with a yield of 90%.
[0058] (2) 1.5 g (10 mmol) of the intermediate product I was added into 5 ml water, 0.6 g (6.67 mmol) of carbonic dihydrazide was slowly added, and reacted for 6 h at 100°C, and then the mixture was cooled to 0°C, no solid was precipitated, and the yield of the product II was 0%.
[0059] Comparison of the yield of the product II in step two with different reaction time and temperature between the intermediate product I and carbonic dihydrazide
[0060] Reaction temperature (°C) Reaction time (h) Yield of product II (%) 1 30 2 88 2 35 3 90 3 40 3 89 4 35 2.5 93 5 50 2.5 0 6 35 6 0 7 100 6 0
[0061] In summary, the use amount ratio of intermediate product I to carbonic dihydrazide in the present application is 5mol:3-5mol, preferably the use amount ratio of intermediate product I to carbonic dihydrazide is 5mol:3mol. In the present application, the intermediate product I is dispersed in aqueous solution, carbonic dihydrazide is slowly added at 0-5℃, then the reaction is completed at 30-40℃ for 2-3h, after the reaction is completed, the solid is collected to obtain the energetic compound II with amino acid structure having both acidity and alkalinity, the optimal condition is that the intermediate product I is dispersed in aqueous solution, carbonic dihydrazide is slowly added at 0-5℃, then the reaction is completed at 35℃ for 2.5h, after the reaction is completed, the solid is collected to obtain the energetic compound II with amino acid structure having both acidity and alkalinity, and the highest yield is 93%. The energetic compound II with amino acid structure having both acidity and alkalinity cannot be obtained outside the specified time and temperature.
[0062] The above detailed description further describes the purpose, technical scheme and beneficial effects of the present application, and it should be understood that the above description is only a specific embodiment of the present application and is not used to limit the protection scope of the present application, and any modification, equivalent replacement, improvement, etc. within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims
1. A process for the preparation of an amino acid configured amphoteric energetic compound, characterized by: The method comprises the following steps: Step one, dissolving urea in nitro-sulfur mixed acid, then reacting completely at -10-0 ℃ for 2-3 h, collecting the solid to obtain intermediate product I; Step two, dispersing intermediate product I in aqueous solution, slowly adding carbonic dihydrazide at 0-5 ℃, then reacting completely at 30-40 ℃ for 2-3 h, after the reaction, collecting the solid to obtain the energetic compound II with amino acid structure having both acid and base properties.
2. The method of claim 1, wherein: In step one, the nitro-sulfur mixed acid is a mixed solution of nitric acid with a mass fraction of 100% and sulfuric acid with a mass fraction of 98%; The dosage ratio of urea, nitric acid and sulfuric acid is 25 mmol:4 mL:3 mL.
3. The method of claim 1, wherein: In step two, The dosage ratio of intermediate product I and water is 5 mmol:2 mL; The dosage ratio of intermediate product I and carbonic dihydrazide is 5 mol:3-5 mol.
4. The method of claim 1, wherein: The dosage ratio of intermediate product I and carbonic dihydrazide is 5 mol:3 mol.