CN115260101B - 1- (diazidomethyl) -3, 4-binitro-1H-pyrazol-5-amine and synthetic method and application thereof - Google Patents
1- (diazidomethyl) -3, 4-binitro-1H-pyrazol-5-amine and synthetic method and application thereof Download PDFInfo
- Publication number
- CN115260101B CN115260101B CN202210989681.3A CN202210989681A CN115260101B CN 115260101 B CN115260101 B CN 115260101B CN 202210989681 A CN202210989681 A CN 202210989681A CN 115260101 B CN115260101 B CN 115260101B
- Authority
- CN
- China
- Prior art keywords
- pyrazol
- amine
- dinitro
- diazidomethyl
- nitromethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 diazidomethyl Chemical group 0.000 title claims abstract description 49
- 238000010189 synthetic method Methods 0.000 title description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- JQVITIDZLJJFBV-UHFFFAOYSA-N [N+](=O)([O-])C1=NN(C(=C1[N+](=O)[O-])[N+](=O)[O-])C[N+](=O)[O-] Chemical compound [N+](=O)([O-])C1=NN(C(=C1[N+](=O)[O-])[N+](=O)[O-])C[N+](=O)[O-] JQVITIDZLJJFBV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- BBFUGBWBYVTGHM-UHFFFAOYSA-N [N+](=O)([O-])C1=NN(C(=C1N)[N+](=O)[O-])C[N+](=O)[O-] Chemical compound [N+](=O)([O-])C1=NN(C(=C1N)[N+](=O)[O-])C[N+](=O)[O-] BBFUGBWBYVTGHM-UHFFFAOYSA-N 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 10
- DNPRVXJGNANVCZ-UHFFFAOYSA-N bromo(nitro)methane Chemical compound [O-][N+](=O)CBr DNPRVXJGNANVCZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 238000005474 detonation Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ZDCGXVZZNAVVFJ-UHFFFAOYSA-N 3,5-dinitro-1h-pyrazol-4-amine Chemical compound NC=1C([N+]([O-])=O)=NNC=1[N+]([O-])=O ZDCGXVZZNAVVFJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- FNYLWPVRPXGIIP-UHFFFAOYSA-N Triamterene Chemical compound NC1=NC2=NC(N)=NC(N)=C2N=C1C1=CC=CC=C1 FNYLWPVRPXGIIP-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- VQXINLNPICQTLR-UHFFFAOYSA-N carbonyl diazide Chemical compound [N-]=[N+]=NC(=O)N=[N+]=[N-] VQXINLNPICQTLR-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/38—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention provides 1- (diazomethyl) -3, 4-binitro-1H-pyrazol-5-amine, which has the structural formula:the 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine is obtained by taking 4-amino-3, 5-dinitropyrazole ammonium salt as a starting material and adding bromonitromethane, and then the 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole is obtained by oxidizing reaction of concentrated sulfuric acid and hydrogen peroxide, and then the 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole is reacted with sodium azide for three-step synthesis. The 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine is used for high-energy energetic materials, and provides good theoretical basis and technical support for subsequent research of the compound in the field of multi-azido energetic materials.
Description
Technical Field
The invention belongs to the technical field of energetic material synthesis, and particularly relates to 1- (diazidomethyl) -3, 4-binitro-1H-pyrazol-5-amine and a synthesis method and application thereof.
Background
The energetic material is one of important components in a weapon system, is an energy carrier for realizing efficient damage of a conventional weapon system, and is also a power source spring for remote delivery of the weapon and firing of the gun. Among them, the energetic compound is a core component, and in recent years, the nitrogen-rich energetic compound has been developed as one of research hotspots in the field of energetic compounds. In contemporary organic chemistry, azide groups are one of the most interesting functional groups for recent decades. In particular, the use of their reactivity with other functional groups has led to a wide range of applications. Cycloaddition with alkynes is therefore commonly used in chemical biology and material science. Organic molecules having one azide group are common and small molecules in which two or more azide groups are attached to the same carbon atom are quite rare. The report on carbonyl diazide is traced back to 1894, and ethyl 2, 2-diazide acetate was described earliest in 1908, however, the danger and explosiveness of diazide may prevent the research work in this field, and the obtained diazide compound with good detonation performance has important significance, thus providing a foundation for the subsequent research of tri-azide and multi-azide energetic compounds.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides 1- (diazidomethyl) -3, 4-binitro-1H-pyrazol-5-amine, and a synthesis method and application thereof, and forms a novel energetic material with high energy.
The invention solves the technical problems by adopting the following technical scheme:
the first aim of the invention is to provide 1- (diazidomethyl) -3, 4-binitro-1H-pyrazol-5-amine, the structural formula of which is shown as follows:
the second object of the present invention is to provide a method for synthesizing 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine, comprising the steps of:
1) Reacting 4-amino-3, 5-dinitropyrazole ammonium salt in bromonitromethane under the action of tetraethylammonium bromide catalyst to obtain 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine;
2) Dissolving the reactant in the step 1) in concentrated sulfuric acid, dropwise adding 30% hydrogen peroxide, and obtaining 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole through oxidation reaction;
3) Adding sodium azide into the reactant in the step 2) to react to obtain 1- (diazomethyl) -3, 4-binitro-1H-pyrazol-5-amine.
Further, N-dimethylformamide is added as a solvent during the reaction of the step 1).
Further, 30% hydrogen peroxide in the step 2) is added dropwise, and the temperature is kept below 20 ℃ in the dropping process.
Further, a synthesis method of 1- (diazomethyl) -3, 4-binitro-1H-pyrazol-5-amine comprises the following steps:
1) Dissolving 4-amino-3, 5-dinitropyrazole ammonium salt in N, N-dimethylformamide, adding tetraethylammonium bromide and bromonitromethane, heating and refluxing the mixture at 70 ℃ for 20 hours, stirring at room temperature for 2 hours after ice addition, filtering to obtain precipitate, drying, and performing column chromatography to obtain bright yellow solid 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine:
2) Dissolving 3, 5-binitro-1- (nitromethyl) -1H-pyrazol-4-amine in concentrated sulfuric acid, dispersing uniformly, cooling to 0-10 ℃, dropwise adding 30% hydrogen peroxide, continuously reacting the mixture system at room temperature for 8 hours after the dropwise addition, pouring the mixture into ice water, stirring for 2 hours, suction filtering to obtain precipitate, washing with ice water, and drying to obtain light yellow solid 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole:
3) Dissolving 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole in methanol, adding sodium azide, reacting for 2 hours at room temperature, removing the solvent, washing with water, filtering to obtain precipitate, and drying in air to obtain yellow brown solid 1- (dinitro methyl) -3, 4-binitro-1H-pyrazol-5-amine.
Further, the molar ratio of 4-amino-3, 5-dinitropyrazole ammonium salt, tetraethylammonium bromide and bromonitromethane in step 1) is 1:2:1.
Further, the ratio of 4-amino-3, 5-dinitropyrazole ammonium salt to N, N-dimethylformamide in step 1) was 0.96mmol:1mL.
Further, the ratio of 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine to concentrated sulfuric acid in step 2) was 1mmol:1.25mL.
Further, in the step 2), the volume ratio of the concentrated sulfuric acid to the 30% hydrogen peroxide is 1:1.2-2.
Further, the molar ratio of 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole to sodium azide in step 3) was 1:1.5.
The third object of the invention is to provide the use of 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine as a high energy energetic material.
Compared with the prior art, the invention has the beneficial technical effects that:
the invention starts from classical compound LLM-116 as a raw material, realizes the synthesis of 1- (diazidomethyl) -3, 4-binitro-1H-pyrazol-5-amine through three steps of reactions, has simple process flow and convenient operation, and provides good theoretical basis and technical support for the subsequent research of the compound in the field of multi-azide energetic materials. The 1- (diazomethyl) -3, 4-binitro-1H-pyrazol-5-amine compound has high nitrogen content, and has good detonation performance when being used as an energetic material.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present invention more readily apparent.
Drawings
FIG. 1 shows the nuclear magnetic resonance hydrogen spectrum of 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine prepared in example 1 of the present invention.
FIG. 2 shows the X-ray single crystal diffraction result of 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine prepared in example 1 of the present invention.
FIG. 3 is a DSC of 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to the attached drawings and specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
In addition, unless otherwise specifically indicated, the various raw materials, reagents, instruments and equipment used in the present invention may be obtained commercially or prepared by existing methods.
Example 1:
the synthesis steps of the 1- (diazidomethyl) -3, 4-binitro-1H-pyrazol-5-amine are as follows:
1) Synthesis of 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine:
weighing 4-amino-3, 5-dinitropyrazole ammonium salt (2.016 g,9.6 mmol), extracting N, N-dimethylformamide (10 ml) in a 100ml three-necked flask by a dropper, adding a magneton, and adding a thermometer with a measuring range of 100 ℃; after uniform dispersion, tetraethylammonium bromide (0.4 g,19.2 mmol) was added, and bromonitromethane (1.36 g,9.6 mmol) was slowly added dropwise with a dropper, heated to 70 ℃ and reacted for 20h; adding 10ml of ice water into a beaker, putting magnetons, pouring the uncooled mixture into the beaker, stirring for 2 hours at room temperature, filtering to obtain a precipitate, drying in air, and carrying out column chromatography to obtain a bright yellow solid, namely 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine. Data for bright yellow solid 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine was characterized as: 1H NMR (400 MHz, D6-DMSO) delta 7.59 (s, 2H), 7.11 (s, 2H).
2) Synthesis of 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole:
5ml of concentrated sulfuric acid is added into a 100ml three-necked flask in a fume hood, 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine (0.92 g,4 mmol) is dissolved in the concentrated sulfuric acid, the concentrated sulfuric acid is uniformly dispersed by ultrasonic waves, and a thermometer with a measuring range of 100 ℃ is added; cooling to 0 ℃, taking 6ml of 30% hydrogen peroxide, dropwise and slowly adding, keeping a thermometer at not more than 20 ℃ in the dropwise adding process, after the dropwise adding is finished, continuously reacting the mixture system for 8 hours at room temperature, then pouring the mixture into 20ml of ice water, stirring for 2 hours at room temperature, suction filtering to obtain precipitate, washing with 10ml of ice water for 3 times, and drying in air to obtain light yellow solid 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole. Data for 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole as a pale yellow solid was characterized as: 1H NMR (400 MHz, D6-DMSO) delta 6.19 (s, 2H).
3) Synthesis of 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine
3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole (0.026 g,0.1 mmol) was dissolved in 1ml methanol and the system was reacted in a plastic tube; sodium azide (0.0098 g,0.15 mmol) was slowly added, reacted at room temperature for 2H, after the disappearance of the spot plate detection raw material, the solvent was dried, washed with 3ml water, suction filtered to obtain precipitate, and dried in air to obtain tan solid 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine. Data for tan solid 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine were characterized as: 1H NMR (400 MHz, D6-DMSO) delta 8.46 (s, 2H), 7.29 (s, 1H).
Specific characterization is shown in figures 1, 2 and 3, DSC analysis is carried out on 1- (diazomethyl) -3, 4-binitro-1H-pyrazol-5-amine by using a differential scanning calorimeter, the test temperature is 40-400 ℃, and the temperature rising rate is 10 ℃/min. It can be seen that the compound starts to decompose exothermically at 107.86℃with a peak exothermic decomposition temperature of 114.05 ℃and an exotherm of 1569.3J/g.
Example 2:
the synthesis steps of the 1- (diazidomethyl) -3, 4-binitro-1H-pyrazol-5-amine are as follows:
1) Synthesis of 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine:
weighing 4-amino-3, 5-dinitropyrazole ammonium salt (2.016 g,9.6 mmol), extracting N, N-dimethylformamide (10 ml) in a 100ml three-necked flask by a dropper, adding a magneton, and adding a thermometer with a measuring range of 100 ℃; after uniform dispersion, tetraethylammonium bromide (0.4 g,19.2 mmol) was added, and bromonitromethane (1.36 g,9.6 mmol) was slowly added dropwise with a dropper, heated to 70 ℃ and reacted for 20h; adding 10ml of ice water into a beaker, putting magnetons, pouring the uncooled mixture into the beaker, stirring for 2 hours at room temperature, filtering to obtain a precipitate, drying in air, and carrying out column chromatography to obtain a bright yellow solid, namely 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine.
2) Synthesis of 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole:
5ml of concentrated sulfuric acid is added into a 100ml three-necked flask in a fume hood, 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine (0.92 g,4 mmol) is dissolved in the concentrated sulfuric acid, the concentrated sulfuric acid is uniformly dispersed by ultrasonic waves, and a thermometer with a measuring range of 100 ℃ is added; cooling to 0 ℃, taking 10ml of 30% hydrogen peroxide, dropwise and slowly adding, keeping a thermometer at not more than 20 ℃ in the dropwise adding process, after the dropwise adding is finished, continuously reacting the mixture system for 8 hours at room temperature, then pouring the mixture into 20ml of ice water, stirring for 2 hours at room temperature, suction filtering to obtain precipitate, washing with 10ml of ice water for 3 times, and drying in air to obtain light yellow solid 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole.
3) Synthesis of 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine
3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole (0.026 g,0.1 mmol) was dissolved in 1ml methanol and the system was reacted in a plastic tube; sodium azide (0.0098 g,0.15 mmol) was slowly added, reacted at room temperature for 2H, after the disappearance of the spot plate detection raw material, the solvent was dried, washed with 3ml water, suction filtered to obtain precipitate, and dried in air to obtain tan solid 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine.
The product structure identification result obtained in this example is the same as that of example 1.
The foregoing embodiment numbers of the present invention are merely for the purpose of description, and do not represent the advantages or disadvantages of the embodiments.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and many forms may be made by those having ordinary skill in the art without departing from the spirit of the present invention and the scope of the claims, which are to be protected by the present invention.
Claims (10)
1. 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine, characterized by the following structural formula:
2. a process for the synthesis of 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine according to claim 1, characterized in that it comprises the following steps:
1) Reacting 4-amino-3, 5-dinitropyrazole ammonium salt in bromonitromethane under the action of tetraethylammonium bromide catalyst to obtain 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine;
2) Dissolving the reactant in the step 1) in concentrated sulfuric acid, dropwise adding 30% hydrogen peroxide, and obtaining 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole through oxidation reaction;
3) Adding sodium azide into the reactant in the step 2) to react to obtain 1- (diazomethyl) -3, 4-binitro-1H-pyrazol-5-amine.
3. A process for the synthesis of 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine according to claim 2, characterized in that: n, N-dimethylformamide is added as a solvent during the reaction of the step 1).
4. A process for the synthesis of 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine according to claim 2, characterized in that: and step 2), dropwise adding 30% hydrogen peroxide, and keeping the temperature below 20 ℃ in the dropwise adding process.
5. A process for the synthesis of 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine according to any one of claims 2 to 4, comprising the following steps:
1) Dissolving 4-amino-3, 5-dinitropyrazole ammonium salt in N, N-dimethylformamide, adding tetraethylammonium bromide and bromonitromethane, heating and refluxing the mixture at 70 ℃ for 20 hours, stirring at room temperature for 2 hours after ice addition, filtering to obtain precipitate, drying, and performing column chromatography to obtain bright yellow solid 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine;
2) Dissolving 3, 5-binitro-1- (nitromethyl) -1H-pyrazol-4-amine in concentrated sulfuric acid, dispersing uniformly, cooling to 0-10 ℃, dropwise adding 30% hydrogen peroxide, continuously reacting at room temperature for 8 hours after the dropwise adding is finished, pouring the mixture into ice water, stirring for 2 hours, filtering to obtain precipitate, washing with ice water, and drying to obtain light yellow solid 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole;
3) Dissolving 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole in methanol, adding sodium azide, reacting for 2 hours at room temperature, removing the solvent, washing with water, filtering to obtain precipitate, and drying in air to obtain yellow brown solid 1- (dinitro methyl) -3, 4-binitro-1H-pyrazol-5-amine.
6. The method for synthesizing 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine according to claim 5, wherein: the molar ratio of 4-amino-3, 5-dinitropyrazole ammonium salt, tetraethylammonium bromide and bromonitromethane in step 1) is 1:2:1.
7. The method for synthesizing 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine according to claim 5, wherein: the ratio of 4-amino-3, 5-dinitropyrazole ammonium salt to N, N-dimethylformamide in step 1) was 0.96mmol:1mL.
8. The method for synthesizing 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine according to claim 5, wherein: the ratio of 3, 5-dinitro-1- (nitromethyl) -1H-pyrazol-4-amine to concentrated sulfuric acid in step 2) was 1mmol:1.25mL.
9. The method for synthesizing 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine according to claim 5, wherein: the molar ratio of 3,4, 5-trinitro-1- (nitromethyl) -1H-pyrazole to sodium azide in step 3) was 1:1.5.
10. Use of 1- (diazidomethyl) -3, 4-dinitro-1H-pyrazol-5-amine according to claim 1 as high energy energetic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210989681.3A CN115260101B (en) | 2022-08-18 | 2022-08-18 | 1- (diazidomethyl) -3, 4-binitro-1H-pyrazol-5-amine and synthetic method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210989681.3A CN115260101B (en) | 2022-08-18 | 2022-08-18 | 1- (diazidomethyl) -3, 4-binitro-1H-pyrazol-5-amine and synthetic method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115260101A CN115260101A (en) | 2022-11-01 |
| CN115260101B true CN115260101B (en) | 2023-12-19 |
Family
ID=83753650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210989681.3A Active CN115260101B (en) | 2022-08-18 | 2022-08-18 | 1- (diazidomethyl) -3, 4-binitro-1H-pyrazol-5-amine and synthetic method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115260101B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017261A (en) * | 2015-08-14 | 2015-11-04 | 西安近代化学研究所 | 1,4-diazidomethyl-3,6-dinitropyrazolo[4,3-c] pyrazole compound |
| CN114149372A (en) * | 2021-11-30 | 2022-03-08 | 湖北航天化学技术研究所 | Nitropyrazole energetic compound and synthesis method thereof |
-
2022
- 2022-08-18 CN CN202210989681.3A patent/CN115260101B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017261A (en) * | 2015-08-14 | 2015-11-04 | 西安近代化学研究所 | 1,4-diazidomethyl-3,6-dinitropyrazolo[4,3-c] pyrazole compound |
| CN114149372A (en) * | 2021-11-30 | 2022-03-08 | 湖北航天化学技术研究所 | Nitropyrazole energetic compound and synthesis method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Tang, Yongxing 等.Versatile functionalization of 3,5-diamino-4-nitropyrazole for promising insensitive energetic compounds.Dalton Transactions.2019,第48卷(第38期),14490-14496. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115260101A (en) | 2022-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103755588A (en) | Synthetic method and application of covalent organic framework (COF) material | |
| CN110372755A (en) | The palladium complex of the ligand of carborane containing meta position of N, N- coordination and its preparation and application | |
| CN113509961B (en) | Application of chitosan/cellulose composite microsphere immobilized copper in preparation of allylsilane compound | |
| CN115260101B (en) | 1- (diazidomethyl) -3, 4-binitro-1H-pyrazol-5-amine and synthetic method and application thereof | |
| CN115160211B (en) | Green synthesis method of isoindolinone compound | |
| CN107501338B (en) | Preparation method of 2, 6-diaminopyridine condensed 4-carboxybenzaldehyde bis-Schiff base cobalt complex | |
| CN113443950B (en) | Method for reducing carbonyl into methylene under illumination | |
| CN109369448A (en) | A kind of method that bimetal composite oxide catalyzes and synthesizes azobenzene compound | |
| CN115108990A (en) | Synthesis method of 3-nitro-amino-4-nitro-2H-pyrazole energetic compound | |
| JP2729272B2 (en) | Preparation of oxalyl- or oxamyl-hydrazide | |
| CN107513078B (en) | Preparation method of 2, 6-diaminopyridine condensed 3-carboxybenzaldehyde bis-Schiff base cobalt complex | |
| CN108264526B (en) | O, O, N coordinated trivalent dicyclic phosphide, synthesis method and catalytic application thereof | |
| CN108623493B (en) | Under mild condition with CO2N-formylation synthesis method for carbon source | |
| CN109289914B (en) | Application of o-methyl aniline lithium in catalyzing imine and borane hydroboration reaction | |
| WO2022155936A1 (en) | Method for synthesizing aryl benzyl ether compound | |
| KR101529507B1 (en) | Di(aminoguanidium) 4,4',5,5'-tetranitro-2,2'-biimidazole, and preparation method thereof | |
| CN113264820B (en) | Method for preparing ketone compound from olefin | |
| CN108912161B (en) | Preparation method of cyanohydrinsiloxane compound | |
| CN114181088B (en) | Ionic liquid [ TEA ] [ TfOH ]2Method for preparing alpha-halogenated acetophenone compound by catalysis | |
| CN114085173B (en) | Preparation method of 2-nitro-4-methylsulfonyl benzaldehyde | |
| CN103254100A (en) | Novel system for coupled reaction of amidine and arylboronic acid | |
| CN115057808B (en) | Synthesis method of Z-3-vinyl substituted isoindolinone compound | |
| CN115286553B (en) | Preparation method of indole compound | |
| CN111925325B (en) | Synthetic method of diaryl ether compound | |
| CN109289913B (en) | Application of 4-methoxyanilino lithium in catalysis of imine and borane hydroboration reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |