CN116751194A - Energetic compound based on 4-nitro-5-amino isoxazole and preparation method and application thereof - Google Patents
Energetic compound based on 4-nitro-5-amino isoxazole and preparation method and application thereof Download PDFInfo
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- CN116751194A CN116751194A CN202310722727.XA CN202310722727A CN116751194A CN 116751194 A CN116751194 A CN 116751194A CN 202310722727 A CN202310722727 A CN 202310722727A CN 116751194 A CN116751194 A CN 116751194A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 46
- DMGQZHDKTRWLID-UHFFFAOYSA-N 4-nitro-1,2-oxazol-5-amine Chemical compound NC=1ON=CC=1[N+]([O-])=O DMGQZHDKTRWLID-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims description 8
- JKFAIQOWCVVSKC-UHFFFAOYSA-N furazan Chemical class C=1C=NON=1 JKFAIQOWCVVSKC-UHFFFAOYSA-N 0.000 claims abstract description 36
- -1 nitroacetonitrile potassium salt Chemical compound 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 7
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 7
- DWBOSISZPCOPFS-UHFFFAOYSA-N 2-nitroacetonitrile Chemical compound [O-][N+](=O)CC#N DWBOSISZPCOPFS-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 14
- PMYJGTWUVVVOFO-UHFFFAOYSA-N 4-phenyl-3-furoxancarbonitrile Chemical compound N#CC1=[N+]([O-])ON=C1C1=CC=CC=C1 PMYJGTWUVVVOFO-UHFFFAOYSA-N 0.000 abstract description 7
- NOBCEKKTUBFZJO-UHFFFAOYSA-N ClC=1C(NON=1)=NO Chemical compound ClC=1C(NON=1)=NO NOBCEKKTUBFZJO-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 238000005481 NMR spectroscopy Methods 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229940125782 compound 2 Drugs 0.000 description 8
- 229940125904 compound 1 Drugs 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229940126214 compound 3 Drugs 0.000 description 6
- 229940125898 compound 5 Drugs 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000003818 flash chromatography Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005474 detonation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- SGWUZWGHZUNYEL-UHFFFAOYSA-N 1,2,5-oxadiazole Chemical compound C=1C=NON=1.C=1C=NON=1 SGWUZWGHZUNYEL-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- IAIWVQXQOWNYOU-FPYGCLRLSA-N nitrofural Chemical compound NC(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 IAIWVQXQOWNYOU-FPYGCLRLSA-N 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
- 125000005646 oximino group Chemical group 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention discloses an energetic compound based on 4-nitro-5-amino isoxazole, which effectively improves the thermal stability of furazan compounds and reduces sensitivity by introducing 4-nitro-5-amino isoxazole into furazan or furazan compounds, and can well improve the thermal stability and sensitivity, thereby being expected to realize balance of energy level and stability and providing a new thought for synthesizing novel energetic materials meeting practical requirements. The invention also discloses a method for preparing the energetic compound based on the 4-nitro-5-amino isoxazole, which realizes the construction of the energetic skeleton of the 4-nitro-5-amino isoxazole simply and efficiently through the ring closure reaction of the chlorooximino furazan/furoxan and the nitroacetonitrile potassium salt, and designs and synthesizes six novel energetic compounds of the furazan/furoxan and the 4-nitro-5-amino isoxazole with good thermal stability.
Description
Technical Field
The invention relates to the technical field of energetic materials, in particular to an energetic compound based on 4-nitro-5-amino isoxazole, and a preparation method and application thereof.
Background
Since the advent of energetic materials, many nitrogen heterocyclic energetic compounds have been designed and synthesized for decades through the continual efforts of energetic material scientists. The 1,2, 5-oxadiazole (furazan) and 1,2, 5-oxadiazole nitrogen oxide (furazan) compounds have higher density, formation enthalpy and good oxygen balance, are common synthetic building blocks in energetic materials, and still have the problems of slightly high sensitivity, poor thermal stability and the like.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
The invention also aims to provide the energetic compound based on the 4-nitro-5-amino isoxazole, which can effectively improve the thermal stability of the furazan compound and realize the reduction of sensitivity by introducing the 4-nitro-5-amino isoxazole into the furazan or furazan oxide compound, thereby being capable of well improving the thermal stability and the sensitivity, being expected to realize the balance of energy level and stability and providing a new idea for synthesizing novel energetic materials meeting the practical demands.
Still another object of the present invention is to provide a method for preparing an energetic compound based on 4-nitro-5-amino isoxazole, which simply and efficiently realizes the construction of an energetic skeleton of 4-nitro-5-amino isoxazole through the ring closure reaction of chloroximino furazan/furoxan and nitroacetonitrile potassium salt, and designs and synthesizes six novel energetic compounds of furazan/furoxan 4-nitro-5-amino isoxazole with good thermal stability.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided an energetic compound based on 4-nitro-5-aminoisoxazole having the structure of the following formula (I):
wherein R is independently furazan ring or furazan ring.
Preferably, wherein R isWherein R is 1 Independently is a nitro, amino or isoxazole group, R 2 Independently a nitro, amino or isoxazole group.
Preferably, wherein the isoxazole group has the structure
The object of the invention is further achieved by a process for the preparation of an energetic compound based on 4-nitro-5-aminoisoxazole comprising: the method is characterized in that potassium salt of nitroacetonitrile and furazan or furazan derivative are used as raw materials, a ring closure reaction is carried out under the heating of a reaction mixed solution, or furazan ring is further modified to prepare the compound shown in the formula (I).
Preferably, the temperature at which the reaction mixture is heated is 40 to 60 ℃.
Preferably, the molar ratio of the potassium salt of nitroacetonitrile to furazan or furazan derivative is 2:1-1:1.
Preferably, the modification of the furazan or furazan ring comprises: the amino substituent on the furazan or furazan ring is oxidized Cheng Xiaoji.
Preferably, the time of the ring closure reaction is 8-12 h.
The object of the invention is further achieved by the use of energetic compounds based on 4-nitro-5-aminoisoxazole for the preparation of energetic materials.
The invention at least comprises the following beneficial effects:
1. the energetic compound based on 4-nitro-5-amino isoxazole, disclosed by the invention, has the advantages that the 4-nitro-5-amino isoxazole is introduced into the furazan or furazan compound, so that the thermal stability of the furazan compound is effectively improved, the sensitivity is reduced, the thermal stability and the sensitivity can be well improved, the balance between the energy level and the stability is hopefully realized, and a new thought is provided for the synthesis of novel energetic materials meeting the practical demands.
2. The preparation method of the energetic compound based on 4-nitro-5-amino isoxazole, disclosed by the invention, realizes the construction of an energetic skeleton of 4-nitro-5-amino isoxazole simply and efficiently through the ring closure reaction of chlorooximino furazan/furoxan and nitroacetonitrile potassium salt, and designs and synthesizes six novel energetic compounds of furazan/furoxan and 4-nitro-5-amino isoxazole with good thermal stability.
3. According to the preparation method of the energetic compound based on 4-nitro-5-amino isoxazole, disclosed by the invention, the isoxazole skeleton can be constructed in one step and efficiently by taking water as a solvent, and meanwhile, the introduction of ortho-amino nitro functional groups is realized, and the whole reaction process is green and mild.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a single crystal structure diagram of Compound 1 in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of compound 1 in example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance carbon spectrum of compound 1 in example 1 of the present invention;
FIG. 4 is a DSC of Compound 1 of example 1 of the present invention;
FIG. 5 is a single crystal structure of Compound 2 in example 2 of the present invention;
FIG. 6 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 2 in example 2 of the present invention;
FIG. 7 is a nuclear magnetic resonance carbon spectrum of compound 2 in example 2 of the present invention;
FIG. 8 is a DSC of Compound 2 of example 2 of the present invention;
FIG. 9 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 3 in example 3 of the present invention;
FIG. 10 is a nuclear magnetic resonance spectrum of compound 3 in example 3 of the present invention;
FIG. 11 is a DSC of Compound 3 of example 3 of the present invention;
FIG. 12 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 4 in example 4 of the present invention;
FIG. 13 is a nuclear magnetic resonance spectrum of compound 4 in example 4 of the present invention;
FIG. 14 is a DSC of Compound 4 of example 4 of the present invention;
FIG. 15 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 5 in example 4 of the present invention;
FIG. 16 is a nuclear magnetic resonance chromatogram of Compound 5 in example 4 of the present invention;
FIG. 17 is a DSC of Compound 5 of example 4 of the present invention;
FIG. 18 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 6 in example 5 of the present invention;
FIG. 19 is a nuclear magnetic resonance carbon spectrum of compound 6 in example 5 of the present invention;
FIG. 20 is a DSC of Compound 6 of example 5 of the present invention;
FIG. 21 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 7 in example 6 of the present invention;
FIG. 22 is a nuclear magnetic resonance spectrum of compound 7 in example 6 of the present invention;
FIG. 23 is a DSC of compound 7 of example 6 of the present invention.
Detailed Description
The present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The experimental methods described in the following embodiments are conventional methods unless otherwise indicated, and the reagents and materials are commercially available.
Example 1 ]
An energetic compound 1 based on 4-nitro-5-amino isoxazole has the following structural formula:
the specific synthetic route is as follows:
the specific synthesis steps are as follows:
the potassium salt of nitroacetonitrile NANK (1 mmol,124 mg) was dissolved in 10mL of water followed by the addition of aminochlorooximinofurazan (1.0 mmol,163 mg). The reaction mixture is heated to 50 ℃ for reaction for 12 hours until the raw materials disappear, solid precipitate in the system is collected by filtration, and pink solid 1 is obtained after drying, and the yield is 72%.
The single crystal structure diagram of the compound 1 is shown in figure 1, the nuclear magnetic resonance hydrogen spectrogram is shown in figure 2, the nuclear magnetic resonance carbon spectrogram is shown in figure 3, and the DSC chart is shown in figure 4.
Example 2 ]
An energetic compound 2 based on 4-nitro-5-aminoisoxazole has the following structural formula:
the specific synthetic route is as follows:
the specific synthesis steps are as follows:
compound 1 (212 mg,1.0 mmol) was dispersed in 30% H 2 O 2 To (3 mL) was slowly added 98% concentrated sulfuric acid (3.5 mL) dropwise at 0deg.C. Then add Na in portions 2 WO 4 (330 mg,1 mmol) the reaction mixture was slowly warmed to room temperature and stirred for 4 hours. After the completion of the reaction, the reaction mixture was poured into 15mL of ice water, and then the mixture was extracted with ethyl acetate. The organic phases were combined and washed with water, then dried over anhydrous sodium sulfate. After removal of the organic solvent, flash column chromatography on silica gel using petroleum ether/ethyl acetate (3:1) as eluent gave blue solid 2 in 87% yield.
The single crystal structure diagram of the compound 2 is shown in fig. 5, the nuclear magnetic resonance hydrogen spectrogram is shown in fig. 6, the nuclear magnetic resonance carbon spectrogram is shown in fig. 7, and the DSC chart is shown in fig. 8.
Example 3 ]
An energetic compound 3 based on 4-nitro-5-aminoisoxazole has the following structural formula:
the specific synthetic route is as follows:
the specific synthesis steps are as follows:
dichlorooximino furazan (225 mg,1.0 mmol), nitroacetonitrile potassium salt NANK (2 mmol,248 mg) were added to 10mL H 2 In O, the resulting mixture was stirred at 50deg.C for 12h until the substrate disappeared, then cooled to room temperature. The precipitate formed was collected by filtration and air dried to give compound 3 as a yellow solid in 69% yield.
The nuclear magnetic resonance hydrogen spectrum of the compound 3 is shown in figure 9, the nuclear magnetic resonance carbon spectrum is shown in figure 10, and the DSC is shown in figure 11.
Example 4 ]
An energetic compound 5 based on 4-nitro-5-aminoisoxazole having the following structural formula:
the specific synthetic route is as follows:
the specific synthesis steps are as follows:
(1) Synthesis of Compound 4:
the potassium salt of nitroacetonitrile NANK (1 mmol,124 mg) was dissolved in 10mL of water followed by the addition of amino protected chlorooximino furazan (1.0 mmol,233 mg). The reaction mixture was warmed to 50 ℃ and reacted for 12 hours until the raw material disappeared, and then the mixture was extracted with ethyl acetate. The organic phases were combined and then dried over anhydrous sodium sulfate. After removal of the organic solvent, flash column chromatography on silica gel using petroleum ether/ethyl acetate (volume ratio 1:1) as eluent gave 4 as pale yellow solid in 66% yield.
The nuclear magnetic resonance hydrogen spectrum of the compound 4 is shown in figure 12, the nuclear magnetic resonance carbon spectrum is shown in figure 13, and the DSC is shown in figure 14.
(2) Synthesis of Compound 5:
compound 4 (283 mg,1.0 mmol) was added to a mixture of concentrated HCl (4 mL) and water (12 mL), and the suspension was stirred at 25 ℃ for 18h, then the mixture was extracted with ethyl acetate. The organic phases were combined and washed with water, then dried over anhydrous sodium sulfate. After removal of the organic solvent, flash column chromatography on silica gel using petroleum ether/ethyl acetate (volume ratio 2:1) as eluent gave 5 as pale yellow solid in 62% yield.
The nuclear magnetic resonance hydrogen spectrum of the compound 5 is shown in figure 15, the nuclear magnetic resonance carbon spectrum is shown in figure 16, and the DSC is shown in figure 17.
Example 5 ]
An energetic compound 6 based on 4-nitro-5-aminoisoxazole having the following structural formula:
the specific synthetic route is as follows:
the specific synthesis steps are as follows:
compound 5 (228 mg,1.0 mmol) was dispersed in 30% H 2 O 2 To (3 mL) was slowly added 98% concentrated sulfuric acid (3.5 mL) dropwise at 0deg.C. Then add Na in portions 2 WO 4 (330mg,1 mmol), the reaction mixture was slowly warmed to room temperature and stirred for 4 hours. After the completion of the reaction, the reaction mixture was poured into 15mL of ice water, and then the mixture was extracted with ethyl acetate. The organic phases were combined and washed with water, then dried over anhydrous sodium sulfate. After removal of the organic solvent, flash column chromatography on silica gel using petroleum ether/ethyl acetate (3:1) as eluent gave after drying a white solid 6 in 76% yield.
The nuclear magnetic resonance carbon spectrum of the compound 6 is shown in figure 18, the nuclear magnetic resonance carbon spectrum is shown in figure 19, and the DSC is shown in figure 20.
Example 6 ]
An energetic compound 7 based on 4-nitro-5-aminoisoxazole has the following structural formula:
the specific synthetic route is as follows:
the specific synthesis steps are as follows:
dichloro oximino furoxan (241 mg,1.0 mmol), nitroacetonitrile potassium salt NANK (2 mmol,248 mg) was added to 10mL H 2 In O, the resulting mixture was stirred at 50deg.C for 12h until the substrate disappeared, then cooled to room temperature. The precipitate formed was collected by filtration and air dried to give yellow solid 7 in 51% yield.
The nuclear magnetic resonance hydrogen spectrum of the compound 7 is shown in figure 21, the nuclear magnetic resonance carbon spectrum is shown in figure 22, and the DSC is shown in figure 23.
Example 7 ]
The performance of the energetic compound 1-3, 5-7 based on 4-nitro-5-amino isoxazole synthesized in the embodiment of the invention is compared with that of the traditional classical secondary explosive black soxhlet (RDX): table 1 below.
Table 1 comparison of the Properties of Compounds 1 to 3,5 to 7 with classical secondary explosive Heisuojin (RDX)
a A melting temperature; b initial decomposition temperature (heating rate 5 ℃/min); c actual measurement of density; d enthalpy of solid state formation; e detonation velocity; f detonation pressure; g impact sensitivity; h friction sensitivity; i oxygen balance, calculation formula: 1600 (c-a-b/2)/M w (C a H b O c N d CO is used as a standard product, M w =molar mass).
From the above table, the introduction of the 4-nitro-5-amino isoxazole skeleton can effectively improve the thermal stability of furazan compounds and realize the reduction of sensitivity. The thermal decomposition temperatures of the compounds 2,3,7 are all higher than 250 ℃, wherein the double-sided ring-closing products (3, 7) have the highest thermal stability due to the introduction of two o-amino nitroisoxazole skeletons, which are 270.3 ℃,263.4 ℃ respectively. Meanwhile, six novel furazan/furazan 4-nitro-5-amino isoxazole energetic compounds all have lower impact sensitivity (IS:>40J) The problem that the sensitivity of the furazan/furazan compound is slightly high is remarkably improved. Wherein the nitrofurazan compound 2 has optimal combination of properties, decomposition temperature, mechanical sensitivity (T d :254℃；IS:>40J; FS: 192N) is superior to the existing high-performance energetic material RDX. Density and enthalpy of formation of Compound 2 (d: 1.829g cm) -3 ；ΔH f :203.1kJ mol -1 ) Are higher than RDX, and therefore have detonation properties comparable to RDX, while having lower sensitivity and zero oxygen balance than RDX. The 4-nitro-5-amino isoxazole skeleton is introduced into the energetic compound, the stability of the furazan/furazan compound is obviously improved, the balance of energy level and stability is expected to be realized, and the efficient construction of a new energetic skeleton provides a new direction for the design and synthesis of a new energetic material.
Although embodiments of the invention have been disclosed above, they are not limited to the use listed in the specification and embodiments. It can be applied to various fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art. Therefore, the invention is not to be limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (9)
1. An energetic compound based on 4-nitro-5-aminoisoxazole having the structure of formula (I):
wherein R is independently furazan ring or furazan ring.
2. The energetic compound based on 4-nitro-5-aminoisoxazole according to claim 1, wherein R is Wherein R is 1 Independently is a nitro, amino or isoxazole group, R 2 Independently a nitro, amino or isoxazole group.
3. The energetic compound based on 4-nitro-5-aminoisoxazole according to claim 2, the isoxazole group having the structure
4. A process for preparing the 4-nitro-5-aminoisoxazole-based energetic compound according to any one of claims 1 to 3, comprising: the method is characterized in that potassium salt of nitroacetonitrile and furazan or furazan derivative are used as raw materials, a ring closure reaction is carried out under the heating of a reaction mixed solution, or furazan ring is further modified to prepare the compound shown in the formula (I).
5. The process of claim 4, wherein the reaction mixture is heated at a temperature of 40 to 60 ℃.
6. The process according to claim 4, wherein the molar ratio of potassium salt of nitroacetonitrile to furazan or furazan derivative is from 2:1 to 1:1.
7. The method of claim 4, wherein modifying the furazan or furazan ring comprises: the amino substituent on the furazan or furazan ring is oxidized Cheng Xiaoji.
8. The method according to claim 4, wherein the period of the ring closure reaction is 8 to 12 hours.
9. Use of an energetic compound based on 4-nitro-5-aminoisoxazole according to any one of claims 1 to 3 for the preparation of energetic materials.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952124A (en) * | 2011-08-23 | 2013-03-06 | 北京理工大学 | 3,4-bis(1-hydro-5-tetrazolyl)furoxan ionic salt containing energy and preparation method thereof |
| CN103059009A (en) * | 2013-01-24 | 2013-04-24 | 北京理工大学 | 4-nitro-3-(5-tetrazole) furoxan energetic ionic salt and preparation method thereof |
| CN111470924A (en) * | 2020-04-28 | 2020-07-31 | 西安近代化学研究所 | Composite energetic material with embedded structure and preparation method thereof |
| CN112125865A (en) * | 2020-09-30 | 2020-12-25 | 北京理工大学 | Synthesis method of furoxan compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102952124A (en) * | 2011-08-23 | 2013-03-06 | 北京理工大学 | 3,4-bis(1-hydro-5-tetrazolyl)furoxan ionic salt containing energy and preparation method thereof |
| CN103059009A (en) * | 2013-01-24 | 2013-04-24 | 北京理工大学 | 4-nitro-3-(5-tetrazole) furoxan energetic ionic salt and preparation method thereof |
| CN111470924A (en) * | 2020-04-28 | 2020-07-31 | 西安近代化学研究所 | Composite energetic material with embedded structure and preparation method thereof |
| CN112125865A (en) * | 2020-09-30 | 2020-12-25 | 北京理工大学 | Synthesis method of furoxan compound |
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