A geminal dinitrobitetrazole and its ammonium salt, preparation method and application
By preparing gem-dinitrobistetrazole and its ammonium salt, the problem of low density of high-nitrogen compounds was solved, and the density and detonation performance were improved, making it suitable for high explosives.
Patent Information
- Application Number
- CN202410776080.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-06-17
- Publication Date
- 2025-09-26
- Estimated Expiration
- 2044-06-17
AI Technical Summary
The low density of existing high-nitrogen compounds limits their detonation ability, so how to increase the density of nitrogen-rich skeletons has become a research focus.
The invention adopts the preparation method of gem-dinitrobitetrazole and its ammonium salt, and generates three diacetonylbitetrazole compound isomers by reacting bitetrazole with NaOH and bromoacetone. Then, three different nitration methods are used to obtain stable meta-substituted gem-dinitrobitetrazole, which is finally reacted with ammonia to prepare gem-dinitrobitetrazole diammonium salt.
The density of gem-dinitrobistetrazole and its ammonium salt was increased to above 1.85 g/cm3, with good detonation performance and oxygen balance close to 0. It has green and high-energy characteristics and is suitable for high explosives.
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Abstract
Description
Technical Field
[0001] The invention relates to gem-dinitrobistetrazole and its ammonium salt, a preparation method and application, and belongs to the technical field of energetic materials. Background Art
[0002] In recent years, the development of high-nitrogen compounds has attracted widespread attention due to their excellent detonation properties. High-nitrogen compounds are increasingly becoming a new generation of energetic materials. These compounds, composed of a large number of N=N or N-N bonds, decompose into N2 molecules, releasing a large amount of energy at the same time. Their energy storage and release patterns are also different from those of traditional CHON energetic materials. Theoretical calculations show that total nitrogen compounds have a higher formation enthalpy (8×10 3 ~2×10 4 kJ·kg -1 ), with energy reaching 3 to 8 times that of TNT equivalent, high formation enthalpy, and clean, pollution-free detonation products. However, high-nitrogen compounds currently tend to have low densities, which severely limits their detonation capabilities. Therefore, increasing the density of nitrogen-rich frameworks has become a research priority. Summary of the Invention
[0003] In view of this, the object of the present invention is to provide a gem-dinitrobistetrazole and its ammonium salt, a preparation method and application.
[0004] To achieve the above objectives, the technical solutions of the present invention are as follows.
[0005] A geminal dinitrobiquatetrazol with the molecular formula C4H2N 12 O8, the structural formula is:
[0006]
[0007] A geminal dinitrobistetrazolyl diammonium salt with the molecular formula C4H8N 14 O8, the structural formula is:
[0008]
[0009] A method for preparing gem-dinitrobitetrazole according to the present invention comprises the following steps:
[0010] (1) Dissolve bitetrazole in water, add NaOH and bromoacetone, react at 20-80°C for 8-24 hours, and collect the solid by filtration to obtain a mixture of intermediate products;
[0011] (2) separating the mixture to obtain a first intermediate product, a second intermediate product, and a third intermediate product, respectively;
[0012] Among them, the structural formula of the first intermediate product is:
[0013] The structural formula of the second intermediate product is:
[0014] The structural formula of the third intermediate product is:
[0015] (3) The first intermediate product is added to the nitration system under stirring at -5 to 5°C, and the temperature is raised to 70±5°C within 20 to 30 minutes. The heating is then stopped, the temperature is lowered to 20 to 30°C, the reaction is filtered, the mixture is washed, and the gem-dinitrotetrazole is obtained by crystallization. Preferably, nitric acid with a mass fraction of 63% to 67% is added to sulfuric acid with a mass fraction of 98%, trifluoroacetic acid is added, and the first intermediate product is added in batches under stirring at -5 to 5°C, the temperature is raised to 70±5°C within 20 to 30 minutes, the reaction is then stopped, the temperature is lowered to 20 to 30°C, the reaction is filtered, the mixture is washed, and the gem-dinitrotetrazole is obtained by crystallization. More preferably, the volume ratio of nitric acid, sulfuric acid and trifluoroacetic acid is 1:0.5 to 1.5:1; and the dosage ratio of the first intermediate product to nitric acid is 1g:3 to 6ml.
[0016] The second intermediate product is added to a nitrating agent under stirring at a temperature below -10°C, the temperature is raised to 0-5°C, the reaction is stirred for more than 24 hours, the reaction is filtered, washed, and crystallized to obtain gem-dinitrobiquatrazol; preferably, nitric acid with a mass fraction of 63% to 67% is added to sulfuric acid with a mass fraction of 98%, the second intermediate product is added in batches under stirring at a temperature below -10°C, the temperature is raised to 0-5°C, the reaction is stirred for 24-48 hours, the reaction is filtered, washed, and crystallized to obtain gem-dinitrobiquatrazol; more preferably, the volume ratio of nitric acid to sulfuric acid is 1:1.5-2.5; and the dosage ratio of the second intermediate product to nitric acid is 1g:3-6ml.
[0017] The third intermediate product is added to a nitrating agent under stirring at -5 to 5°C, reacted at 20 to 30°C for more than 4 hours, filtered, washed, and crystallized to obtain gem-dinitrobitetrazole. Preferably, nitric acid having a mass fraction of 63% to 67% is added to sulfuric acid having a mass fraction of 98%, the third intermediate product is added in batches under stirring at -5 to 5°C, reacted at 20 to 30°C for more than 4 hours, filtered, washed, and crystallized to obtain gem-dinitrobitetrazole; more preferably, the volume ratio of nitric acid to sulfuric acid is 1:1 to 1.2; and the dosage ratio of the third intermediate product to nitric acid is 1 g:3 to 6 ml.
[0018] Preferably, in step (1), the tetrazole is prepared by the following method: dissolving tetrazole diammonium salt in water, adding sulfuric acid dropwise for acidification; then extracting with ethyl acetate, and drying by spin drying to obtain tetrazole.
[0019] Preferably, in step (1), the molar ratio of the tetrazole to NaOH is 1:2-3; the molar ratio of the tetrazole to bromoacetone is 1:2-3.
[0020] Preferably, in step (2), the mixture is slurried in acetonitrile, filtered and separated, and the solid is collected to obtain a first intermediate product; the filtrate is collected, evaporated and recrystallized to obtain a second intermediate product; and the residual liquid after recrystallization is spin-dried to obtain a third intermediate product.
[0021] Preferably, during slurrying, the ratio of the mixture to acetonitrile is 1-2 g:10-15 ml.
[0022] A method for preparing the gem-dinitrobistetrazole diammonium salt of the present invention comprises the following steps:
[0023] The gem-dinitrobitetrazole is dissolved in methanol, and aqueous ammonia is added dropwise until precipitation is complete. The precipitate is collected by filtration to obtain the gem-dinitrobitetrazole diammonium salt.
[0024] Preferably, the molar ratio of ammonium ions to gem-dinitrobitetrazole in the ammonia water is 2 to 3.5:1.
[0025] An application of the gem-dinitrobiquatrazol of the present invention, wherein the gem-dinitrobiquatrazol is used as a high explosive.
[0026] An application of the gem-dinitrobistetrazolyl diammonium salt of the present invention, wherein the gem-dinitrobistetrazolyl diammonium salt is used as a high explosive.
[0027] Beneficial effects
[0028] The present invention provides a geminal dinitro tetrazolyl and its ammonium salt, which realizes the introduction of geminal dinitro into the nitrogen-rich skeleton tetrazolyl, successfully improving the density and detonation performance of the nitrogen-rich skeleton. The density of both is 1.85g / cm 3 Above, the oxygen balance is close to 0 oxygen balance, the detonation performance is good, it does not contain halogen, is green, and has high energy characteristics, and is a good high explosive.
[0029] The present invention provides a method for preparing gem-dinitrobitetrazole and its ammonium salt. The diisocyanate reacts with NaOH and bromoacetone to produce three isomers of diacetonylbitetrazole compounds. Three different nitration methods are used to obtain the gem-dinitrobitetrazole. The first and second intermediate products are rearranged and nitrated to form stable meta-substituted gem-dinitrobitetrazoles, and the yield of the gem-dinitrobitetrazole can reach over 80%. The gem-dinitrobitetrazole reacts with aqueous ammonia to produce the gem-dinitrobitetrazole diammonium salt. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 This is the single crystal structure diagram of the first intermediate product in Example 1 by X-ray diffraction.
[0031] Figure 2 This is the single crystal structure diagram of the third intermediate product in Example 1 by X-ray diffraction.
[0032] Figure 3 1 is the single crystal structure diagram of gem-dinitrobitetrazole in Example 1 by X-ray diffraction.
[0033] Figure 4 This is the single crystal structure diagram of the gem-dinitrobistetrazole diammonium salt obtained by X-ray diffraction in Example 2. DETAILED DESCRIPTION
[0034] The present invention will be further described in detail below with reference to specific embodiments.
[0035] In the following examples or comparative examples:
[0036] (1) Single crystal X-ray diffraction: The instrument was Bruker D2 Advance with a Cu Karadiation, and the test temperature was 170K.
[0037] (2) Nuclear magnetic resonance testing: The instrument is a Bruker Ascend 400 MHz nuclear magnetic spectrometer.
[0038] (3) Thermal decomposition temperature test: The instrument is TA-DSC Q2000 differential scanning calorimeter.
[0039] (4) Impact sensitivity test: The instrument is a BAM drop weight sensitivity meter.
[0040] (5) Friction sensitivity test: The instrument is FSKM-10BAM friction sensitivity meter.
[0041] (6) Density, oxygen balance, oxygen content, and nitrogen and oxygen content are all calculated values.
[0042] Example 1
[0043] 5,5'-bistetrazole (4.14g 30mmol) is dissolved in the water containing 2.2eq NaOH. Subsequently, bromoacetone (4.52g 33mmol) dissolved in 15mL acetone is added to the obtained solution at room temperature. The reaction mixture is then heated to 70°C (or at 20°C) and stirred for 16 hours. The solvent is removed under reduced pressure to obtain an intermediate product mixture 5.72g (productive rate 76.24%).
[0044] 5.72 g of the intermediate product mixture was added to 58 ml of acetonitrile, stirred for 15 min, filtered, and dried to obtain 1.27 g of the first intermediate product. The filtrate was naturally evaporated until 10 ml remained, and colorless crystals were precipitated. The second intermediate product was filtered and dried to obtain 3.44 g of the second intermediate product. The remaining filtrate was spin-dried to obtain 1.01 g of the third intermediate product as a white solid. The structural formula of the first intermediate product is: The results of H-NMR and C-NMR are: 1H NMR (dextrin-dimethyl sulfoxide): δ = 2.34 (S, 6H) δ = 6.14 (S, 4H). 13 C NMR (deuterated dimethyl sulfoxide): δ = 199.58, 143.42, 58.67, 27.59. The single crystal structure is shown in Figure 1 shown.
[0045] The structural formula of the second intermediate product is: The results of H-NMR and C-NMR are: 1 HNMR (deuterated acetone): δ = 2.41 (d, 6H), δ = 6.05, 6.02 (d, 4H). 13 C NMR (deuterated acetonitrile): δ = 199.42, 198.81, 154.01, 146.27, 62.35, 58.43, 27.19, 27.09.
[0046] The structural formula of the third intermediate product is: The results of H-NMR and C-NMR are: 1 H NMR (dextrin-dimethyl sulfoxide): δ = 2.39 (S, 6H) δ = 6.04 (S, 4H). 13 C NMR (deuterated dimethyl sulfoxide): δ = 199.58, 143.42, 58.67, 27.59. The single crystal structure is shown in Figure 2 shown.
[0047] HNO3 (67%, 5mL) was added to H2SO4 (98%, 5ml), followed by 5ml of trifluoroacetic acid, stirred at 0°C, and then the first intermediate product (1.0g) was added to the mixed acid in batches, heated to 70°C in 30 minutes, the reaction was immediately stopped, cooled to room temperature, filtered, washed with CF3COOH (10mL), and crystallized from dichloromethane to obtain gem-dinitrotetrazole with a yield of 84% (1.1g).
[0048] HNO3 (67%, 5 mL) was added to H2SO4 (98%, 10 ml) and stirred at -10°C, and then the second intermediate product (1.0 g) was added portionwise to the mixed acid. After 0.5 hours, the reaction mixture was heated to 0°C and stirred for 24 hours, after which the product was isolated by filtration, washed with CF3COOH (10 mL), and crystallized from dichloromethane to give gem-dinitrobistetrazole in 55% yield (720 mg).
[0049] HNO3 (67%, 5mL) was added to H2SO4 (98%, 5ml) and stirred at 0°C. The third intermediate product (1.0g) was then added to the mixed acid in batches and the mixture was heated to room temperature for 4 hours. The product was then separated by filtration, washed with CF3COOH (10mL), and crystallized from dichloromethane to obtain gem-dinitrotetrazole with a yield of 47% (615mg).
[0050] The reaction route is as follows:
[0051]
[0052] The H NMR and C NMR spectra of the geminal dinitrotetrazole are as follows: 1 H NMR (deuterated chloroform): δ = 8.33 (S, 1H). 13 C NMR (deuterated acetonitrile): δ = 157.21, 105.78. The single crystal structure is shown in Figure 3 shown.
[0053] The thermal decomposition temperature, density, impact sensitivity, friction sensitivity, and oxygen balance of the gem-dinitrobistetrazole are shown in Table 1. Calculations show that the compound has a formation enthalpy of 597.1 kJ / mol, a detonation velocity of 9305 m / s, and a detonation pressure of 38.0 GPa.
[0054] In conclusion, gem-dinitrobiquatrazolium can be used as a high explosive due to its excellent detonation velocity and detonation pressure.
[0055] Example 2
[0056] 1 g of gem-dinitrobitetrazole prepared in Example 1 was dissolved in 2 ml of methanol, to which 0.5 ml of 28% ammonia water was added dropwise to precipitate a solid, which was filtered and air-dried to obtain 0.8 g of yellow-white solid gem-dinitrobitetrazole diammonium salt.
[0057] The reaction route is as follows:
[0058]
[0059] The NMR carbon spectrum results of the gem-dinitrobistetrazole diammonium salt are: 13 C NMR (deuterated methanol): δ = 155.73, 131.03. The single crystal structure is as follows Figure 4 shown.
[0060] The thermal decomposition temperature, density, impact sensitivity, friction sensitivity, and oxygen balance results of the gem-dinitrobistetrazolyl diammonium salt are shown in Table 1.
[0061] Table 1
[0062]
[0063] Comparative Example 1
[0064] At room temperature, bitetrazole was dissolved in water, 2.2 molar equivalents of sodium hydroxide were added, and chloroacetone was used instead of bromoacetone at room temperature. No solid precipitation was observed, and the reaction did not occur, and no intermediate product could be obtained.
[0065] Comparative Example 2
[0066] At room temperature, a mixed acid of 67% nitric acid: 98% sulfuric acid = 1:1 (volume ratio) was prepared, and the second intermediate product was added and reacted at room temperature. In the end, no solid precipitation was observed, and the product did not rearrange but decomposed.
[0067] Comparative Example 3
[0068] At 0°C, a mixed acid of 67% nitric acid: 98% sulfuric acid: trifluoroacetic acid = 1:1:1 (volume ratio) was prepared and the second intermediate product was added. The temperature was raised to 70°C within 30 minutes, then the reaction was stopped and the temperature was lowered. Ultimately, no solid precipitation was observed, and the product did not rearrange but decomposed.
[0069] Comparative Example 4
[0070] At room temperature, a mixed acid of 67% nitric acid: 98% sulfuric acid = 1:1 (volume ratio) was prepared, and the first intermediate product was added and reacted at room temperature. In the end, no solid precipitation was observed, and the product did not rearrange but decomposed.
[0071] At -10°C, a mixed acid of 67% nitric acid: 98% sulfuric acid = 1:2 was prepared, and the first intermediate product was added. The reaction was carried out at 0°C. In the end, no solid precipitation was observed, and the product did not undergo rearrangement but decomposed.
[0072] Comparative Example 5
[0073] When the nitration temperature of the first intermediate product was increased to 80°C, the product decomposed; when the nitration temperature of the compound was lowered to 50°C, the product did not completely rearrange and partially decomposed, and no pure product was obtained.
[0074] Comparative Example 6
[0075] In both the examples and comparative examples, 100% nitric acid was used instead of 67% nitric acid for addition and the reaction was carried out at 0° C. Ultimately, no solid precipitation was observed, and the pure compound could not be obtained.
[0076] In summary, the invention includes but is not limited to the above embodiments. Any equivalent replacement or partial improvement made under the spirit and principle of the present invention shall be deemed to be within the scope of protection of the present invention.
Claims
1. A method for preparing gem-dinitrobitetrazole, characterized in that: The method steps include: (1) Dissolve bisectazole in water, add NaOH and bromoacetone, react at 20-80°C for 8-24 hours, and collect the solid by filtration to obtain a mixture of intermediate products; (2) separating the mixture to obtain a first intermediate product, a second intermediate product, and a third intermediate product, respectively; Among them, the structural formula of the first intermediate product is: ; The structural formula of the second intermediate product is: ; The structural formula of the third intermediate product is: ; (3) Add nitric acid (63% to 67% by mass) to sulfuric acid (98% by mass), add trifluoroacetic acid, add the first intermediate product in batches under stirring at -5 to 5°C, raise the temperature to 70±5°C within 20 to 30 minutes, stop the reaction, cool to 20 to 30°C, filter, wash, and crystallize to obtain gem-dinitrobistetrazole; Add 63% to 67% nitric acid to 98% sulfuric acid, add the second intermediate product in batches under stirring at -10°C, raise the temperature to 0-5°C, stir and react for 24-48 hours, filter, wash, and crystallize to obtain gem-dinitrobistetrazole; Add nitric acid (mass fraction: 63% to 67%) to sulfuric acid (mass fraction: 98%), add the third intermediate product in batches under stirring at -5°C to 5°C, react at 20°C to 30°C for more than 4 hours, filter, wash, and crystallize to obtain gem-dinitrobistetrazole; The molecular formula of gem-dinitrobitriazole is C4H2N 12 O8, the structural formula is: 。 2. The method for preparing a gem-dinitrobiquatrazol according to claim 1, wherein: In step (1), the tetrazole is prepared by the following method: dissolving tetrazole diammonium salt in water, adding sulfuric acid dropwise for acidification; then extracting with ethyl acetate, and drying by rotation to obtain tetrazole.
3. A method for preparing gem-dinitrobitetrazole as claimed in claim 2, characterized in that: The molar ratio of the tetrazole to NaOH is 1:2-3; the molar ratio of the tetrazole to bromoacetone is 1:2-3.
4. The method for preparing a gem-dinitrobitetrazole according to claim 1, wherein: In step (2), the mixture is slurried in acetonitrile, filtered and separated, and the solid is collected to obtain a first intermediate product; The filtrate is collected, evaporated and recrystallized to obtain the second intermediate product; The residual liquid after recrystallization is spin-dried to obtain a third intermediate product.
5. A method for preparing gem-dinitrobitetrazole as claimed in claim 4, characterized in that: During slurrying, the ratio of the mixture to acetonitrile is 1-2 g:10-15 ml.
6. The method for preparing gem-dinitrobitetrazole according to claim 1, wherein: In step (3), when the first intermediate product is reacted, the volume ratio of nitric acid, sulfuric acid and trifluoroacetic acid is 1:0.5~1.5:1; the dosage ratio of the first intermediate product to nitric acid is 1g:3~6ml; When the second intermediate product reacts: the volume ratio of nitric acid to sulfuric acid is 1:1.5~2.5; the dosage ratio of the second intermediate product to nitric acid is 1g:3~6ml; When the third intermediate product is reacted, the volume ratio of nitric acid to sulfuric acid is 1:1~1.2; the dosage ratio of the third intermediate product to nitric acid is 1g:3~6ml.
7. A method for preparing a gem-dinitrobistetrazole diammonium salt, characterized in that: The method steps include: The gem-dinitrobi-tetrazolyl prepared by the method according to any one of claims 1 to 6 is dissolved in methanol, and ammonia water is added dropwise until the precipitation is complete. The precipitate is collected by filtration to obtain the gem-dinitrobi-tetrazolyl diammonium salt, the molecular formula of which is C4H8N 14 O8, the structural formula is: 。 8. A method for preparing a gem-dinitrobistetrazole diammonium salt as claimed in claim 7, characterized in that: The molar ratio of ammonium ions to gem-dinitrobitetrazole in the ammonia water is 2-3.5:1.