A triazole-linked bisoxadiazole polynitro energetic compound and its preparation method
Patent Information
- Application Number
- CN202211366265.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-11-02
- Publication Date
- 2025-08-01
- Estimated Expiration
- 2042-11-02
AI Technical Summary
In the prior art, there are few energy-containing compounds with triazole, oxadiazole, and nitrogen imitation structures, and the bromoacetone used in the synthesis route is prone to discoloration, making the reaction process difficult to control.
The 4-step method is used to synthesize triazole bisoxadiazole polynitroenergic compounds. Using common and easy-to-get raw materials and simple equipment, 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazole-3-yl)-2H-1,2,3-triazole is prepared by reactions such as organic solvents, hydroxylamine, diethyl malonic acid and fumigated nitric acid.
The synthetic compounds have high density and low sensitivity, high theoretical explosion speed, meet industrial production requirements, low cost and safe and reliable process.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of explosive synthesis processes, and particularly relates to an energetic compound 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole and a synthesis method thereof. Background Art
[0002] In the field of energetic materials, the triazole ring has a relatively high nitrogen content, and there are nitrogen-hydrogen bonds in the molecule that are prone to form intramolecular or intermolecular hydrogen bonds, thereby increasing the melting point of the compound. The bond lengths and bond angles of the triazole ring tend to be averaged, approaching the theoretical bond angles of a five-membered ring, and the ring strain is significantly reduced. Moreover, in the conjugated system of the triazole parent compound, the lone pair electrons of the nitrogen atom participate in conjugation, which can improve the thermal stability of the molecule. The 1,2,4-oxadiazole ring is relatively insensitive in terms of sensitivity. It can be used as a parent structure and then introduce high-energy chemical groups (such as -NH2, -NO2, -ONO2, -N3, -NHNO2, etc.), thereby increasing the enthalpy of formation of the energetic compound. By effectively combining azole rings to form C,C'-bridged energetic compounds, they not only have the advantages of traditional azole-based energetic materials such as high enthalpy of formation and high nitrogen content, but also have higher density and lower sensitivity, and are a class of energetic compounds with broad application prospects. However, domestic and foreign researchers have rarely reported energetic compounds with both triazole, oxadiazole, and nitroform structures.
[0003] Energetic Materials, 2017, 25(5): 437-440 reported a synthesis route of an energetic compound with a nitroform and triazole parent ring as shown in the following formula. This route uses 3-nitro-1,2,4-triazole as a raw material, and obtains 1-acetonyl-3-nitro-1,2,4-triazole through a C-N coupling reaction, and then prepares 1-trinitromethyl-3-nitro-1,2,4-triazole through a nitration reaction. The bromoacetone used in this method is prone to turn purple when exposed to air, and the reaction process is difficult to control.
[0004] Summary of the Invention
[0005] In view of the above problems, the present invention provides a new energetic compound, which is a triazole-linked bis-oxadiazole polynitro energetic compound, 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, and the structure is as follows:
[0006]
[0007] A preparation method of the above-mentioned triazole-linked bis-oxadiazole polynitro energetic compound is as follows:
[0008] Step 1: Dissolve 4,5-dicyano-1,2,3-triazole in an organic solvent. Generally, a low-boiling solvent is selected, which is beneficial for later treatment. Add hydroxylamine at room temperature, stir for 30 min, heat for a certain period of time, cool to room temperature after the reaction is completed, rotary evaporate the solvent under reduced pressure, extract the remaining mixture with ethyl acetate, wash with saturated brine, and dry with anhydrous sodium sulfate to obtain 4,5-diaminooxime-1,2,3-triazole;
[0009] Step 2: Dissolve 4,5-diaminooxime-1,2,3-triazole in an organic solvent, add diethyl malonate, heat for a certain period of time, cool to room temperature, pour the reaction mixture into ice water, and filter to obtain 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole;
[0010] Step 3: Add 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole to a mixed acid of fuming nitric acid and concentrated sulfuric acid at -10 °C, heat and stir for a certain period of time, pour the reaction solution into ice water, extract with ethyl acetate, wash with saturated brine, rotary evaporate under reduced pressure, and dry to obtain the product 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole.
[0011] Preferably, in the first step, the molar ratio of 4,5-dicyano-1,2,3-triazole to hydroxylamine is 1:3 - 1:5.
[0012] Preferably, the organic solvent in the first step is one or more of acetonitrile, ethyl acetate, tetrahydrofuran, acetone, methanol, and ethanol; preferably one or more of acetonitrile, tetrahydrofuran, and acetone.
[0013] Preferably, the organic solvent in the second step is one or more of dimethyl sulfoxide, N,N-dimethylformamide, sulfolane, and nitrobenzene, and the preferred organic solvent is dimethyl sulfoxide or N,N-dimethylformamide.
[0014] Preferably, in the second step, the molar ratio of 4,5-diaminooxime-1,2,3-triazole to diethyl malonate is 1:3 - 1:5.
[0015] Preferably, the reaction temperature in the second step is 160 - 180 °C, and the reaction time is 8 - 12 h.
[0016] Preferably, in the third step, the volume ratio of fuming nitric acid to concentrated sulfuric acid is 1:2 - 1:3, the reaction temperature of the mixed solution is 10 - 20 °C, and the reaction time is 6 - 8 h.
[0017] For the first time, a triazole-linked bis(oxadiazole) polynitro energetic compound, 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, was synthesized through the above preparation method. This compound combines the structures of triazole, oxadiazole, and nitroform. The theoretically calculated detonation velocity is 8200 m / s, and the density is 2.0 g / cm 3 , and it can be used in the field of energetic materials.
[0018] Referring to the entire reaction process, the raw materials used are common and easily available, and the cost is not high. The equipment required is also relatively simple, without the need for special devices. The reaction steps are generally simple, and the post-treatment in the product is relatively simple, all of which are common operating steps and can meet the basic requirements of industrial scale-up production. Detailed implementation mode
[0019] To deepen the understanding of the present invention, the following will further describe the present invention in detail with reference to the embodiments. These embodiments are only used to explain the present invention and do not limit the scope of protection.
[0020] The molecular formula of 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole is: C8HN 13 O 14 , and the structural formula is:
[0021]
[0022] The synthesis route is:
[0023]
[0024] The specific steps are as follows:
[0025] First step, dissolve 4,5-dicyano-1,2,3-triazole in an organic solvent, add hydroxylamine at room temperature, stir for 30 min, and heat the reaction for 12 h. After the reaction is completed, cool to room temperature, rotary evaporate the solvent under reduced pressure, extract the remaining mixture with ethyl acetate, wash with saturated brine, and dry with anhydrous sodium sulfate to obtain 4,5-diaminooxime-1,2,3-triazole;
[0026] Second step, dissolve 4,5-diaminooxime-1,2,3-triazole in an organic solvent, add diethyl malonate, and heat to 150 - 180 °C. After reacting for 4 h, cool to room temperature, pour the reaction mixture into ice water, and filter to obtain 4,5-bis(5-(ethyl acetate group)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole;
[0027] Step 3: Add 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole to the mixed acid of fuming nitric acid and concentrated sulfuric acid at -10°C, warm up to room temperature, stir for 8 h, pour the reaction solution into ice water, extract with ethyl acetate, wash with saturated brine, rotary evaporate under reduced pressure, and dry to obtain the product 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole.
[0028] Example 1
[0029] Dissolve 1.19 g (10 mmol) of 4,5-dicyano-1,2,3-triazole in 15 mL of acetonitrile, add 1.32 g (40 mmol) of hydroxylamine at room temperature, stir for 30 min, and react at 40°C for 6 h. After the reaction is completed, cool to room temperature, rotary evaporate the solvent under reduced pressure, extract the remaining mixture with ethyl acetate, wash with saturated brine, and dry with anhydrous sodium sulfate to obtain 1.11 g of 4,5-diaminooxime-1,2,3-triazole, with a yield of 60%; 1 H NMR (DMSO-d6, 500 MHz), δ: 10.76 (s, 2H), 7.77 (s, 4H); MS (ESI) m / z: 186.4 (M+H).
[0030] Dissolve 1.85 g (10 mmol) of 4,5-diaminooxime-1,2,3-triazole in 15 mL of dimethyl sulfoxide, add 6.40 g (40 mmol) of diethyl malonate, and heat to 160°C. After reacting for 12 h, cool to room temperature, pour the reaction mixture into ice water, and filter to obtain 2.45 g of 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, with a yield of 65%; 1 H NMR (DMSO-d6, 500 MHz), δ: 4.13 (dd, 2H), 3.51 (s, 2H), 1.21 (t, 3H); MS (ESI) m / z: 378.3 (M+H).
[0031] Add 0.38 g (1 mmol) of 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole to the mixed acid of 4 mL of fuming nitric acid and 8 mL of concentrated sulfuric acid at -10°C, warm up to 10°C, stir for 8 h, pour the reaction solution into ice water, extract with ethyl acetate, wash with saturated brine, rotary evaporate under reduced pressure, and dry to obtain 0.18 g of the product 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, with a yield of 36%. 1313C NMR (DMSO-d6, 125 MHz), δ: 141.5, 158.2, 166.3, 172.6; MS (ESI) m / z: 504.2 (M+H).
[0032] Example 2
[0033] Dissolve 1.19 g (10 mmol) of 4,5-dicyano-1,2,3-triazole in 15 mL of acetonitrile. Add 1.32 g (40 mmol) of hydroxylamine at room temperature and stir for 30 min. Then raise the temperature to 40 °C and react for 6 h. After the reaction is completed, cool to room temperature, rotary evaporate the solvent under reduced pressure. The remaining mixture is extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate to obtain 1.20 g of 4,5-diaminooxime-1,2,3-triazole, with a yield of 65%;
[0034] Dissolve 1.85 g (10 mmol) of 4,5-diaminooxime-1,2,3-triazole in 15 mL of dimethyl sulfoxide, add 6.40 g (40 mmol) of diethyl malonate, and heat to 160 °C. After reacting for 12 h, cool to room temperature. Pour the reaction mixture into ice water and filter to obtain 2.11 g of 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, with a yield of 56%;
[0035] Add 0.38 g (1 mmol) of 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole to a mixed acid of 4 mL of fuming nitric acid and 8 mL of concentrated sulfuric acid at -10 °C. Raise the temperature to 10 °C and stir for 8 h. Pour the reaction solution into ice water, extract with ethyl acetate, wash with saturated brine, rotary evaporate under reduced pressure, and dry to obtain 0.21 g of the product 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, with a yield of 42%.
[0036] Example 3
[0037] Dissolve 1.19 g (10 mmol) of 4,5-dicyano-1,2,3-triazole in 15 mL of tetrahydrofuran. Add 1.32 g (40 mmol) of hydroxylamine at room temperature and stir for 30 min. Then raise the temperature to 50 °C and react for 5 h. After the reaction is completed, cool to room temperature, rotary evaporate the solvent under reduced pressure. The remaining mixture is extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate to obtain 1.02 g of 4,5-diaminooxime-1,2,3-triazole, with a yield of 55%;
[0038] Dissolve 1.85 g (10 mmol) of 4,5-diaminooxime-1,2,3-triazole in 15 mL of dimethyl sulfoxide, add 6.40 g (40 mmol) of diethyl malonate, and heat to 170 °C. After reacting for 10 h, cool to room temperature, pour the reaction mixture into ice water, filter to obtain 2.19 g of 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, with a yield of 58%;
[0039] Add 0.38 g (1 mmol) of 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole to a mixed acid of 4 mL of fuming nitric acid and 12 mL of concentrated sulfuric acid at -10 °C, warm up to 20 °C, stir for 6 h, pour the reaction solution into ice water, extract with ethyl acetate, wash with saturated brine, rotary evaporate under reduced pressure, and dry to obtain 0.22 g of the product 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, with a yield of 44%.
[0040] Example 4
[0041] Dissolve 1.19 g (10 mmol) of 4,5-dicyano-1,2,3-triazole in 15 mL of tetrahydrofuran, add 1.65 g (50 mmol) of hydroxylamine at room temperature, stir for 30 min, and warm up to 50 °C to react for 5 h. After the reaction is completed, cool to room temperature, rotary evaporate the solvent under reduced pressure, extract the remaining mixture with ethyl acetate, wash with saturated brine, and dry with anhydrous sodium sulfate to obtain 1.15 g of 4,5-diaminooxime-1,2,3-triazole, with a yield of 62%;
[0042] Dissolve 1.85 g (10 mmol) of 4,5-diaminooxime-1,2,3-triazole in 15 mL of N,N-dimethylformamide, add 4.80 g (30 mmol) of diethyl malonate, and heat to 170 °C. After reacting for 10 h, cool to room temperature, pour the reaction mixture into ice water, filter to obtain 1.96 g of 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, with a yield of 52%;
[0043] Add 0.38 g (1 mmol) of 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole to a mixed acid of 4 mL of fuming nitric acid and 8 mL of concentrated sulfuric acid at -10 °C, warm up to 20 °C, stir for 6 h, pour the reaction solution into ice water, extract with ethyl acetate, wash with saturated brine, rotary evaporate under reduced pressure, and dry to obtain 0.20 g of the product 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, with a yield of 40%.
[0044] Example 5
[0045] Dissolve 1.19 g (10 mmol) of 4,5-dicyano-1,2,3-triazole in 15 mL of acetone. Add 1.65 g (50 mmol) of hydroxylamine at room temperature and stir for 30 min. Then raise the temperature to 60 °C and react for 4 h. After the reaction is completed, cool to room temperature, rotary evaporate the solvent under reduced pressure. The remaining mixture is extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate to obtain 1.28 g of 4,5-diamidoximino-1,2,3-triazole, with a yield of 69%;
[0046] Dissolve 1.85 g (10 mmol) of 4,5-diamidoximino-1,2,3-triazole in 15 mL of N,N-dimethylformamide. Add 4.80 g (30 mmol) of diethyl malonate and heat to 180 °C. After reacting for 8 h, cool to room temperature. Pour the reaction mixture into ice water and filter to obtain 1.70 g of 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, with a yield of 45%;
[0047] Add 0.38 g (1 mmol) of 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole to a mixed acid of 4 mL of fuming nitric acid and 12 mL of concentrated sulfuric acid at -10 °C. Raise the temperature to 20 °C and stir for 6 h. Pour the reaction solution into ice water, extract with ethyl acetate, wash with saturated brine, rotary evaporate under reduced pressure, and dry to obtain 0.24 g of the product 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, with a yield of 48%.
[0048] Example 6
[0049] Dissolve 1.19 g (10 mmol) of 4,5-dicyano-1,2,3-triazole in 15 mL of acetone. Add 1.65 g (50 mmol) of hydroxylamine at room temperature and stir for 30 min. Then raise the temperature to 60 °C and react for 4 h. After the reaction is completed, cool to room temperature, rotary evaporate the solvent under reduced pressure. The remaining mixture is extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate to obtain 0.93 g of 4,5-diamidoximino-1,2,3-triazole, with a yield of 50%;
[0050] Dissolve 1.85 g (10 mmol) of 4,5-diaminooxime-1,2,3-triazole in 15 mL of N,N-dimethylformamide, add 4.80 g (30 mmol) of diethyl malonate, and heat to 180 °C. After reacting for 8 h, cool to room temperature, pour the reaction mixture into ice water, filter to obtain 1.81 g of 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, with a yield of 48%;
[0051] Add 0.38 g (1 mmol) of 4,5-bis(5-(ethyl acetate)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole to a mixed acid of 4 mL of fuming nitric acid and 12 mL of concentrated sulfuric acid at -10 °C, warm up to 20 °C, stir for 6 h, pour the reaction solution into ice water, extract with ethyl acetate, wash with saturated brine, evaporate under reduced pressure, and dry to obtain 0.18 g of the product 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole, with a yield of 36%.
[0052] Based on the above examples, it can be seen that the steps of the whole process are simple, the raw materials used are extensive and relatively inexpensive, no special equipment is used, the whole production process is relatively safe and reliable, and the post-treatment steps of the product are all conventional steps, which can meet the basic requirements of industrial scale-up production. The obtained product has the structures of triazole, oxadiazole, and nitroform, and can be applied to the field of energetic materials.
Claims
1. A triazole-linked bisoxadiazole polynitro energetic compound, with its structure as follows:
2. A preparation method of the triazole-linked bisoxadiazole polynitro energetic compound as described in Claim 1, with the specific steps as follows: The first step: Dissolve 4,5-dicyano-1,2,3-triazole in an organic solvent, add hydroxylamine at room temperature, stir for 30 min, heat up to 40 - 60 °C, react for 4 - 6 h, cool to room temperature, rotary evaporate the solvent under reduced pressure, extract the remaining mixture with ethyl acetate, wash with saturated brine, and dry with anhydrous sodium sulfate to obtain 4,5-diaminooxime-1,2,3-triazole; The second step: Dissolve 4,5-diaminooxime-1,2,3-triazole in an organic solvent, add diethyl malonate, heat and react for a period of time, then cool to room temperature, pour the reaction mixture into ice water, filter to obtain 4,5-bis(5-(ethyl acetate group)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole; The third step: Add 4,5-bis(5-(ethyl acetate group)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole to a mixed acid of fuming nitric acid and concentrated sulfuric acid at -10 °C, heat up and stir for a period of time, pour the reaction solution into ice water, extract with ethyl acetate, wash with saturated brine, rotary evaporate under reduced pressure, and dry to obtain the product 4,5-bis(5-(trinitromethyl)-1,2,4-oxadiazol-3-yl)-2H-1,2,3-triazole.
3. The preparation method of the triazole-linked bisoxadiazole polynitro energetic compound according to claim 2, characterized in that: In the first step, the molar ratio of 4,5-dicyano-1,2,3-triazole to hydroxylamine is 1:3 - 1:
5.
4. The preparation method of the triazole-linked bisoxadiazole polynitro energetic compound according to claim 2, characterized in that: The organic solvent in the first step is one or more of acetonitrile, ethyl acetate, tetrahydrofuran, acetone, methanol, and ethanol.
5. The preparation method of the triazole-linked bisoxadiazole polynitro energetic compound according to claim 4, characterized in that: The organic solvent in the first step is one or more of acetonitrile, tetrahydrofuran, and acetone.
6. The preparation method of the triazole-linked bisoxadiazole polynitro energetic compound according to claim 2, wherein: The organic solvent in the second step is one or more of dimethyl sulfoxide, N,N-dimethylformamide, sulfolane, and nitrobenzene.
7. The preparation method of the triazole-linked bisoxadiazole polynitro energetic compound according to claim 6, characterized in that: The organic solvent in the second step is dimethyl sulfoxide or N,N-dimethylformamide.
8. The preparation method of the triazole-linked bisoxadiazole polynitro energetic compound according to claim 2, characterized in that: In the second step, the molar ratio of 4,5-diaminooxime-1,2,3-triazole to diethyl malonate is 1:3 - 1:
5.
9. The preparation method of the triazole-linked bisoxadiazole polynitro energetic compound according to claim 2, characterized in that: The reaction temperature in the second step is 160 - 180 °C, and the reaction time is 8 - 12 h.
10. The preparation method of the triazole-linked bisoxadiazole polynitro energetic compound according to claim 2, characterized in that: In the third step, the volume ratio of fuming nitric acid to concentrated sulfuric acid is 1:2 - 1:3, the reaction temperature for heating and stirring the mixed solution is 10 - 20 °C, and the reaction time is 6 - 8 h.