CN117903070A - Preparation method of 4, 4-azo-1, 2, 4-triazole - Google Patents
Preparation method of 4, 4-azo-1, 2, 4-triazole Download PDFInfo
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- CN117903070A CN117903070A CN202410069131.9A CN202410069131A CN117903070A CN 117903070 A CN117903070 A CN 117903070A CN 202410069131 A CN202410069131 A CN 202410069131A CN 117903070 A CN117903070 A CN 117903070A
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- triazole
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- calcium hypochlorite
- aqueous solution
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 11
- 238000005691 oxidative coupling reaction Methods 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 238000001953 recrystallisation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- 239000012467 final product Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000004153 Potassium bromate Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- -1 monochloroisonitrile urea Chemical compound 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical group [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 229940094037 potassium bromate Drugs 0.000 description 1
- 235000019396 potassium bromate Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- QVTVDJWJGGEOGX-UHFFFAOYSA-N urea;cyanide Chemical compound N#[C-].NC(N)=O QVTVDJWJGGEOGX-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 4, 4-azo-1, 2, 4-triazole. 4-amino-1, 2, 4-triazole is used as a raw material, calcium hypochlorite is used as an oxidant, 4-azo-1, 2, 4-triazole can be obtained through one-step reaction, and then high-purity 4, 4-azo-1, 2, 4-triazole can be obtained through hot water recrystallization, and the whole reaction process does not need organic solvent for purification, and the method is simple in synthesis, low in cost and environment-friendly.
Description
Technical Field
The invention relates to a preparation method of 4, 4-azo-1, 2, 4-triazole, and belongs to the technical field of energetic materials.
Background
4, 4-Azo-1, 2, 4-triazole is a high-nitrogen energetic material and is also an important energetic intermediate, and various energetic materials with excellent performances, such as lead-free high-energy initiating explosive-4, 4-azo-1, 2, 4-triazole copper and the like, are synthesized by taking 4, 4-azo-1, 2, 4-triazole as an intermediate.
The synthesis methods of 4, 4-azo-1, 2, 4-triazole reported in the current literature mainly comprise three methods: the first method is to prepare 4, 4-azo-1, 2, 4-triazole by using 4-amino-1, 2, 4-triazole as a raw material and sodium dichloroisonitrile urea as an oxidant through oxidative coupling reaction, and the method has the defects that sodium dichloroisonitrile urea can generate indissoluble impurities such as dichloroisonitrile urea acid, monochloroisonitrile urea acid and isonitrile urea acid after the reaction, and the 4, 4-azo-1, 2, 4-triazole has poor water solubility, so that the synthesized product contains a plurality of impurities and cannot meet application requirements, and the subsequent purification method of the product prepared by the method is reported in the literature 'three-dimensional (3D) energetic Metal Organic Frameworks (MOFs)': methanol is used as a solvent, and the product is washed in a Soxhlet extractor for up to 2 days to remove impurities, but the method takes a long time, consumes an organic solvent, and is unfavorable for mass preparation. The second method is to use potassium bromate as an oxidant to prepare 4, 4-azo-1, 2, 4-triazole, which is reported in literature "New iron(II) spin crossover coordination polymers [Fe(atrz)3]X2·2H2O (X=ClO4,BF4) and [Fe(atrz)(μ-pyz)(NCS)2]·4H2O with an interesting solvent effect.[J]. Inorganic Chemistry,2012, 51(8):4663-71.", and has the disadvantage that a large amount of bromine simple substance is generated in the preparation process, so that the post-treatment is very troublesome, is not friendly to the environment, and is not suitable for industrialized large-scale preparation. The third method is reported in the literature "improvement of synthesis process of 4,4' -azo-124-three", which uses sodium hypochlorite as an oxidizing agent, and has disadvantages in that the reaction time is long, 5 hours are required, and the process of separating the product requires distillation under reduced pressure, which is disadvantageous for large-scale preparation.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for producing 4, 4-azo-1, 2, 4-triazole. The method has the advantages of short reaction time, simplicity, easiness in implementation, high environmental friendliness, suitability for large-scale preparation and the like.
In order to achieve the above object, the technical scheme of the present invention is as follows.
A preparation method of 4, 4-azo-1, 2, 4-triazole comprises the following steps:
adding a mixed aqueous solution consisting of calcium hypochlorite and acid into an aqueous solution of 4-amino-1, 2, 4-triazole to perform an oxidative coupling reaction, filtering after the reaction is finished, and recrystallizing a filter cake with water to obtain 4, 4-azo-1, 2, 4-triazole;
Wherein the molar ratio of the calcium hypochlorite to the 4-amino-1, 2, 4-triazole is more than or equal to 0.5:1; the molar ratio of the calcium hypochlorite to the acid is 1:2-2.5;
the temperature of the oxidative coupling reaction is-20-10 ℃, and the reaction time is 30-120 min.
Preferably, the acid mixed with the calcium hypochlorite is one or more of formic acid and acetic acid.
Preferably, the temperature of the oxidative coupling reaction is-10-0 ℃.
Preferably, the oxidative coupling reaction time is 30 min-120 min.
Preferably, the molar ratio of the 4-amino-1, 2, 4-triazole to the calcium hypochlorite is 1:0.5-0.7.
Preferably, the concentration of the aqueous solution of 4-amino-1, 2, 4-triazole is 1-9M.
Preferably, the concentration of calcium hypochlorite in the mixed aqueous solution of calcium hypochlorite and acid is 0.2-1M.
4, 4-Azo-1, 2, 4-triazole is prepared by the method.
Advantageous effects
The invention provides a preparation method of 4, 4-azo-1, 2, 4-triazole, which is carried out in water in the whole reaction process, an oxidant does not produce precipitated impurities after the reaction, the oxidant is filtered after the reaction is finished, and the 4, 4-azo-1, 2, 4-triazole with high purity can be obtained by re-crystallizing by using an aqueous solution.
Drawings
FIG. 1 is a physical diagram of the final product in example 1 of the present invention.
FIG. 2 is a graph showing the morphology of crystals in example 1 of the present invention.
FIG. 3 is an X-ray diffraction (XRD) pattern of the final product of example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
Preparing 100ml of 4-amino-1, 2, 4-triazole aqueous solution with the concentration of 4M as a base solution; 400ml of an aqueous solution of calcium hypochlorite at a concentration of 0.5M was prepared, and 0.4mol of acetic acid was added thereto, and stirred so that the calcium hypochlorite was completely dissolved as a dropping liquid. The reaction temperature is kept at 0 ℃, a mixed aqueous solution of calcium hypochlorite and acetic acid is added into the base solution to react for 1h, then suction filtration is carried out, and the filter cake is recrystallized by water to obtain 28.6g of 4, 4-azo-1, 2, 4-triazole, and the yield is 85%.
The final product is shown in a physical photograph in figure 1, the crystal form is shown in figure 2, the XRD pattern is shown in figure 3, and the result shows that the final product is 4, 4-azo-1, 2, 4-triazole.
Example 2
Preparing 100ml of aqueous solution of 4-amino-1, 2, 4-triazole with the concentration of 6M as a base solution; 500ml of an aqueous solution of calcium hypochlorite at a concentration of 0.65M was prepared, and 0.7mol of acetic acid was added thereto, and stirred so that the calcium hypochlorite was completely dissolved as a dropping liquid. And (3) keeping the reaction temperature at-5 ℃, adding a mixed aqueous solution of calcium hypochlorite and acetic acid into the base solution in batches, reacting for 1.5 hours after the addition, then carrying out suction filtration, and recrystallizing a filter cake by using water to obtain 38.3g of 4, 4-azo-1, 2, 4-triazole, wherein the yield is 76%.
XRD test results show that the final product is 4, 4-azo-1, 2, 4-triazole.
Example 3
200Ml of an aqueous solution of 4-amino-1, 2, 4-triazole having a concentration of 8M was prepared as a base solution; 1000ml of an aqueous solution of calcium hypochlorite at a concentration of 0.8M was prepared, and 1.65mol of acetic acid was added thereto, and stirred so that the calcium hypochlorite was completely dissolved as a dropping liquid. The reaction temperature is kept at minus 10 ℃, a mixed aqueous solution of calcium hypochlorite and acetic acid is added into the base solution, after the addition is finished, the reaction is carried out for 2 hours, then suction filtration is carried out, and the filter cake is recrystallized by water, thus obtaining 36.3g of 4, 4-azo-1, 2, 4-triazole, and the yield is 72%.
XRD test results show that the final product is 4, 4-azo-1, 2, 4-triazole.
Example 4
400Ml of an aqueous solution of 4-amino-1, 2, 4-triazole having a concentration of 8M was prepared as a base solution; 2000ml of an aqueous solution of calcium hypochlorite at a concentration of 0.8M was prepared, and 3.25mol of acetic acid was added thereto, and stirred so that the calcium hypochlorite was completely dissolved as a dropping liquid. The reaction temperature is kept at minus 10 ℃, a mixed aqueous solution of calcium hypochlorite and acetic acid is added into the base solution to react for 2 hours, then suction filtration is carried out, the filter cake is recrystallized by water, and 94.1g of 4, 4-azo-1, 2, 4-triazole is prepared, and the yield is 70%.
XRD test results show that the final product is 4, 4-azo-1, 2, 4-triazole.
In view of the foregoing, it will be appreciated that the invention includes but is not limited to the foregoing embodiments, any equivalent or partial modification made within the spirit and principles of the invention.
Claims (8)
1. A preparation method of 4, 4-azo-1, 2, 4-triazole is characterized by comprising the following steps: the method comprises the following steps:
adding a mixed aqueous solution consisting of calcium hypochlorite and acid into an aqueous solution of 4-amino-1, 2, 4-triazole to perform an oxidative coupling reaction, filtering after the reaction is finished, and recrystallizing a filter cake with water to obtain 4, 4-azo-1, 2, 4-triazole;
Wherein the molar ratio of the calcium hypochlorite to the 4-amino-1, 2, 4-triazole is more than or equal to 0.5:1; the molar ratio of the calcium hypochlorite to the acid is 1:2-2.5;
the temperature of the oxidative coupling reaction is-20-10 ℃, and the reaction time is 30-120 min.
2. The method for preparing 4, 4-azo-1, 2, 4-triazole according to claim 1, wherein: the acid mixed with calcium hypochlorite is more than one of formic acid and acetic acid.
3. The method for preparing 4, 4-azo-1, 2, 4-triazole according to claim 1, wherein: the temperature of the oxidative coupling reaction is-10-0 ℃.
4. A process for the preparation of 4, 4-azo-1, 2, 4-triazole as claimed in claim 1 or 3, characterized in that: the oxidative coupling reaction time is 30-120 min.
5. The method for preparing 4, 4-azo-1, 2, 4-triazole according to claim 1, wherein: the molar ratio of the 4-amino-1, 2, 4-triazole to the calcium hypochlorite is 1:0.5-0.7.
6. A process for the preparation of 4, 4-azo-1, 2, 4-triazole as claimed in claim 1 or 5, characterized in that: the concentration of the aqueous solution of 4-amino-1, 2, 4-triazole is 1-9M.
7. A process for the preparation of 4, 4-azo-1, 2, 4-triazole as claimed in claim 1 or 5, characterized in that: the concentration of calcium hypochlorite in the mixed aqueous solution of calcium hypochlorite and acid is 0.2-1M.
8. A 4, 4-azo-1, 2, 4-triazole, characterized in that: the method according to any one of claims 1 to 7.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410069131.9A CN117903070A (en) | 2024-01-17 | 2024-01-17 | Preparation method of 4, 4-azo-1, 2, 4-triazole |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202410069131.9A CN117903070A (en) | 2024-01-17 | 2024-01-17 | Preparation method of 4, 4-azo-1, 2, 4-triazole |
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