CN117343012A - Methanoamide polynitro nitrogen-rich energy-containing compound and preparation method thereof - Google Patents
Methanoamide polynitro nitrogen-rich energy-containing compound and preparation method thereof Download PDFInfo
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- CN117343012A CN117343012A CN202311156649.8A CN202311156649A CN117343012A CN 117343012 A CN117343012 A CN 117343012A CN 202311156649 A CN202311156649 A CN 202311156649A CN 117343012 A CN117343012 A CN 117343012A
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- formamide
- polynitropyrazole
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 121
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 16
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 109
- 125000000524 functional group Chemical group 0.000 claims abstract description 23
- 150000003948 formamides Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 29
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- 150000003857 carboxamides Chemical class 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- VQFAIAKCILWQPZ-UHFFFAOYSA-N bromoacetone Chemical compound CC(=O)CBr VQFAIAKCILWQPZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002360 explosive Substances 0.000 claims description 9
- 239000013067 intermediate product Substances 0.000 claims description 9
- 238000006396 nitration reaction Methods 0.000 claims description 8
- IXZDIALLLMRYOU-UHFFFAOYSA-N tert-butyl hypochlorite Chemical compound CC(C)(C)OCl IXZDIALLLMRYOU-UHFFFAOYSA-N 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- MZILPZDBVFUXMY-UHFFFAOYSA-N [O-][N+]([S])=O Chemical compound [O-][N+]([S])=O MZILPZDBVFUXMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000003380 propellant Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 4
- -1 pyrazole compound Chemical class 0.000 abstract description 4
- SFDJOSRHYKHMOK-UHFFFAOYSA-N nitramide Chemical group N[N+]([O-])=O SFDJOSRHYKHMOK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 abstract 1
- 150000002830 nitrogen compounds Chemical class 0.000 abstract 1
- 238000005474 detonation Methods 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229940125773 compound 10 Drugs 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- UUKWKUSGGZNXGA-UHFFFAOYSA-N 3,5-dinitrobenzamide Chemical compound NC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UUKWKUSGGZNXGA-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- MZRUFMBFIKGOAL-UHFFFAOYSA-N 5-nitro-1h-pyrazole Chemical class [O-][N+](=O)C1=CC=NN1 MZRUFMBFIKGOAL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- KHKLOEASBOKRLA-UHFFFAOYSA-N 1,1-dinitrourea Chemical compound NC(=O)N([N+]([O-])=O)[N+]([O-])=O KHKLOEASBOKRLA-UHFFFAOYSA-N 0.000 description 2
- FTBBGQKRYUTLMP-UHFFFAOYSA-N 2-nitro-1h-pyrrole Chemical compound [O-][N+](=O)C1=CC=CN1 FTBBGQKRYUTLMP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- YNGRGHODNDCZCC-UHFFFAOYSA-N nitro hydrogen sulfate Chemical compound OS(=O)(=O)O[N+]([O-])=O YNGRGHODNDCZCC-UHFFFAOYSA-N 0.000 description 2
- FAQOZARUOBFXBH-UHFFFAOYSA-N nitroformamide Chemical compound NC(=O)[N+]([O-])=O FAQOZARUOBFXBH-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- ZIHQUWYJSTVYAT-UHFFFAOYSA-N [NH-][N+]([O-])=O Chemical group [NH-][N+]([O-])=O ZIHQUWYJSTVYAT-UHFFFAOYSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 1
- 229960000282 metronidazole Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 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
- C07D231/16—Halogen atoms or nitro radicals
-
- 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
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a nitro-rich nitrogen compound containing multiple formamide, which is characterized by comprising nitro-simulated functional group substituted nitro-rich pyrazole compound containing multiple formamide and azo-bridged nitro-rich pyrazole compound; the structural formula of the nitro-simulated functional group substituted formamide polynitropyrazole energetic compound is shown as a formula I or a formula II, and the structural formula of the azo-bridged formamide polynitropyrazole energetic compound is shown as a formula III or a formula IV. The invention also provides an application and a preparation method of the formamide polynitrogen nitrogen-rich energy-containing compound. The invention combines the nitramide group with the traditional nitro-substituted polynitropyrazole compound and azo bridged polynitropyrazole compound, and is green and high-energy.
Description
Technical Field
The invention belongs to the technical field of energetic material synthesis, and particularly relates to a formamide polynitro nitrogen-rich energetic compound and a preparation method thereof.
Background
In recent decades, the development of new energetic materials has received considerable attention as these materials are widely used for military or civil purposes. Meanwhile, higher requirements are put on the novel energetic materials, including high energy, good safety and environmental friendliness. The energy of the nitroazole energetic compound mainly comes from high-energy chemical bonds such as N-N bonds, C-N bonds, N-O bonds and the like contained in a ring structure and ring tension, has high nitrogen and low carbon hydrogen, higher density, is easier to reach oxygen balance, and most combustion products are environment-friendly N2, so that the nitroazole energetic compound is a novel energetic compound.
Amide groups have been used as functional groups commonly involved in pharmaceutical chemistry and have been rarely studied in energetic materials. The presence of the high molecular weight O atoms and NH2 hydrogen bonds in the amide itself may often allow for the adjustment of the density and sensitivity of the energetic material. At the same time, the amide group may be further nitrated to form a nitramide group. Classical energetic material Dinitrourea (DNU) is obtained by urea nitration, and has the advantages of high density and high detonation performance. It is sufficient to see that the nitroamide is an energetic group with very great energetic derivatization potential. The combination of a nitroamide group with an nitrogen-rich heterocyclic pyrazole to construct a novel nitrogen-rich energetic material with high density and high detonation performance is the focus of research herein.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a formamide polynitro nitrogen-rich energy compound and a preparation method thereof, wherein a nitramide group is combined with a traditional nitro-substituted polynitropyrazole compound and an azo bridged polynitropyrazole compound, so that the compound is green and high-energy.
The invention solves the technical problems by adopting the following technical scheme:
the first object of the invention is to provide a nitro-rich nitrogen-containing compound containing nitro-amide, which is characterized by comprising nitro-imitation functional group substituted nitro-amide, nitro-pyrazole and azo-bridged nitro-amide; the structural formula of the nitro-simulated functional group substituted formamide polynitropyrazole energetic compound is shown as a formula I or a formula II, and the structural formula of the azo-bridged formamide polynitropyrazole energetic compound is shown as a formula III or a formula IV:
a second object of the present invention is to provide the use of the above-described carboxamide polynitro nitrogen-rich energetic compound as an energetic material.
Furthermore, the nitro-simulated functional group substituted formamide polynitropyrazole energetic compound is used as an oxidant in propellant or explosive preparation.
Further, the azo-bridged formamide polynitropyrazole energetic compound is applied as an explosive.
The third object of the present invention is to provide a method for preparing the above-mentioned compound having a polynitrogen effect, wherein the compound having a polynitrogen effect is a nitro-functional group-substituted compound having a polynitropyrazole effect, and the method comprises the following steps:
1) Dissolving a formamide polynitro compound in an organic solvent, then adding an aqueous solution of NaOH into the solution, stirring for 20-60 min, then dropwise adding bromoacetone, reacting at room temperature for 20-30 h, and collecting solids after the reaction is finished to obtain an intermediate product.
2) And (3) performing nitration reaction on the intermediate product and nitro-sulfur mixed acid to obtain the nitro-simulated functional group substituted metronidamide polynitropyrazole energetic compound.
Further, the carboxamide polynitro compound is selected from 5-carboxamide-3, 4-dinitro-1H-pyrazole or 4-carboxamide-3, 5-dinitro-1H-pyrazole.
Further, the organic solvent in the step 1) is methanol or acetonitrile.
Further, the molar ratio of NaOH to carboxamide polynitro compound is 1.2:1.
Further, the molar ratio of bromoacetone to formamide polynitro compound is 1.5:1.
And the nitration reaction is to slowly add the intermediate product into the mixed acid of the nitro-sulfuric acid at the temperature of 0-10 ℃, then slowly raise the temperature to room temperature for reaction for 40-60 hours, and after the reaction is finished, the filtration, solid washing and drying are carried out.
Further, the ratio of the intermediate product to the nitric-sulfuric mixed acid is 1g: 11-15 ml, wherein the nitre sulfur mixed acid is obtained by mixing nitric acid with the mass fraction of 100% and sulfuric acid with the mass fraction of 98% in a volume ratio of 1:1.5.
The preparation method of the azotemic amide polynitrogen-rich energy-containing compound comprises the following steps of:
1) Ammoniation reaction of the formamide polynitro compound and THA to obtain N-NH 2 An intermediate compound;
2) N-NH 2 And (3) dissolving the intermediate compound in acetonitrile, adding saturated sodium carbonate solution to adjust the pH to be neutral after the reaction of tert-butyl hypochlorite is completed after the intermediate compound is completely dissolved, and collecting solids to obtain the azo-bridged formamide polynitropyrazole energetic compound.
3) And (3) performing nitration reaction on the azo-bridged formamide polynitropyrazole energetic compound and nitro-sulfur mixed acid to obtain the azo-bridged formamide polynitropyrazole energetic compound.
Further, the carboxamide polynitro compound is selected from 5-carboxamide-3, 4-dinitro-1H-pyrazole or 4-carboxamide-3, 5-dinitro-1H-pyrazole.
Further, during the ammonification reaction, DBU is added in an equivalent amount to that of the carboxamide polynitro compound, and then THA is added.
Further, in step 2), N-NH 2 The ratio of intermediate compound to t-butyl hypochlorite was 1mmol:1.5mmol.
Further, in step 2), N-NH 2 The temperature condition for the reaction of the intermediate compound and the tert-butyl hypochlorite is-20 to-5 ℃.
And further, the nitration reaction is to add an azo bridged formamide polynitropyrazole energetic compound into a nitrosulfuric mixed acid at 0-10 ℃, then react for 0.5-1.5 h at room temperature, and after the reaction is finished, filter, and solid washing and drying are performed.
Further, the ratio of the azo-bridged carboxamide polynitropyrazole energetic compound to the nitrosulfuric acid mixture is 0.1g: 1.1-1.5 ml, wherein the nitre sulfur mixed acid is prepared from nitric acid with the mass fraction of 100% and sulfuric acid with the mass fraction of 98% in a ratio of 1:1.5 by volume of the mixed acid.
Further, the resulting azo-bridged carboxamide polynitropyrazole energetic compound was washed with trichloroacetic acid.
Compared with the prior art, the invention has the beneficial technical effects that:
the invention selects 5-formamide-3, 4-binitro-1H-pyrazole or 4-formamide-3, 5-binitro-1H-pyrazole as raw materials to obtain the nitro-amide polynitro nitrogen-rich energy-containing compound, and the density of the nitro-imitation functional group substituted nitro-amide polynitro pyrazole energy-containing compound is 1.89g/cm 3 Above, the oxygen balance is greater than 10%; the density of the obtained azo bridged formamide polynitropyrazole energetic compound is 1.93g/cm 3 The detonation velocity is greater than 9400m/s. The preparation process is safe and reliable by further controlling the nitration reaction conditions.
The nitroimitation functional group substituted formamide polynitropyrazole energetic compound is used as an oxidant, has higher density and higher oxygen balance, does not contain halogen atoms and the like which can generate characteristic signals, has the characteristics of green and high energy, and is a good energetic oxidant.
The azo bridged formamide polynitropyrazole energetic compound is used as an explosive, has higher density and detonation performance, and is expected to replace RDX.
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 is a single crystal X-ray diffraction pattern diagram of a nitro-functional group-substituted nitro-pyrazole-containing compound of the present invention.
FIG. 2 is a single crystal X-ray diffraction pattern diagram of a nitro-functional group-substituted nitro-pyrazole-containing compound of the present invention.
FIG. 3 is an X-ray diffraction pattern diagram of an azo-bridged carboxamide polynitropyrazole energetic compound 6 obtained in example 3 of a preparation method of the present invention.
FIG. 4 is a nuclear magnetic resonance spectrum of an azo-bridged nitrocarboxamide polynitropyrazole energetic compound 7 in example 3 of a preparation method of the present invention.
FIG. 5 is an X-ray diffraction pattern diagram of an azo-bridged, metronidazole polynitro-pyrazole energetic compound 7 according to the invention and a process for its preparation, example 3.
FIG. 6 is an X-ray diffraction pattern diagram of an azo-bridged carboxamide polynitropyrazole energetic compound 9 obtained in example 4 of a preparation method of the present invention.
FIG. 7 is a nuclear magnetic resonance spectrum of an azo-bridged nitrocarboxamide polynitropyrazole energetic compound 10 in example 4 of a preparation method of the present invention.
FIG. 8 is an X-ray diffraction pattern diagram of an azo-bridged, carboxamide polynitropyrazole energetic compound 10 according to the invention and a method for preparing the same, example 4.
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: a preparation method of a nitrofunctional group-substituted metronidamide polynitropyrazole energetic compound comprises the following steps:
1) 2mmol 402mg of 5-formamide-3, 4-dinitro-1H-pyrazole was added to 5ml of acetonitrile and completely dissolved, and 6ml of H was added with 96mg of NaOH 2 O aqueous solution, stirring for 30min at normal temperature, adding 3mmol bromoacetone, reacting at room temperature for 24h, collecting solid after the reaction, washing with 10ml deionized water, and drying to obtain intermediate product 1 with yield of 70%.
2) Slowly adding 1g of intermediate product 1 into 11-15 mL of nitric acid with the mass fraction of 100% and nitric acid with the mass fraction of 98% and the volume ratio of sulfuric acid of 1:1.2 at the temperature of 0-10 ℃, slowly heating to 25 ℃, reacting for 48 hours at the temperature, filtering after the reaction, washing the solid with 2mL of trifluoroacetic acid, and drying to obtain the nitro-simulated functional group substituted metronidamide polynitropyrazole energetic compound 2 with the yield of 63%.
The reaction route is as follows:
the nuclear magnetic hydrogen spectrum of intermediate 1 results as follows:
1 H NMR(d6-DMSO):δ8.307,δ8.082(br,2H),δ5.684(s,2H),δ2.336(s,3H).
the structure of the nitroimitation functional group substituted metronidamide polynitropyrazole energetic compound 2 is verified by single crystal X-ray diffraction, and the structure is shown in figure 1.
The structure of the compound was determined from the above results as shown in the reaction scheme.
The thermal decomposition temperature, density, detonation performance, impact sensitivity and friction sensitivity of the nitrofunctional group-substituted metronidamide polynitropyrazole energetic compound 2 are shown in table 1.
The formation enthalpy of the nitro-simulated functional group substituted formamide polynitropyrazole energetic compound 2 is 247.92KJ/mol, the explosion speed is 8757m/s and the explosion pressure is 33.1Gpa.
In conclusion, the nitro-simulated functional group substituted formamide polynitropyrazole energetic compound has high density, high oxygen balance and good detonation performance, and is suitable for being used as an oxidant in the preparation of propellant or explosive.
Example 2: preparation method of nitro-simulated functional group substituted formamide polynitropyrazole energetic compound
The preparation method of the nitrosimulated functional group substituted formamide polynitropyrazole energetic compound comprises the following steps:
1) 2mmol 402mg of 4-formamide-3, 5-dinitro-1H-pyrazole was added to 5ml of acetonitrile and completely dissolved, and 6ml of H was added with 96mg of NaOH 2 O aqueous solution, stirring for 30min at normal temperature, adding 3mmol bromoacetone, reacting at room temperature for 24h, collecting solid after the reaction, washing with 10ml deionized water, and drying to obtain intermediate product 3 with a yield of 72%.
2) Slowly adding 1g of intermediate 3 into 11-15 mL of nitric acid with the mass fraction of 100% and nitric acid with the mass fraction of 98% and the volume ratio of sulfuric acid of 1:1.2 at the temperature of 0-10 ℃, slowly heating to 25 ℃, reacting for 48 hours at the temperature, filtering after the reaction, washing the solid with 2mL of trifluoroacetic acid, and drying to obtain the nitro-simulated functional group substituted metronidamide polynitropyrazole energetic compound 4 with the yield of 68%.
The reaction route is as follows:
the nuclear magnetic hydrogen spectrum of intermediate 3 results as follows:
1H NMR(d6-DMSO):δ7.063,δ6.730(br,2H),δ5.658(s,2H),δ2.234(s,3H).
the nitro-simulated functional group substituted metronidamide polynitropyrazole energetic compound 4 is subjected to structural verification by single crystal X-ray diffraction, and the structure is shown in figure 2.
The structure of the compound was determined from the above results as shown in the reaction scheme.
The thermal decomposition temperature, density, detonation performance, impact sensitivity and friction sensitivity of the nitrofunctional group-substituted metronidamide polynitropyrazole energetic compound 4 are shown in table 1.
The formation enthalpy of the nitro-simulated functional group substituted formamide polynitropyrazole energetic compound 4 is 228.4KJ/mol, the explosion speed is 8817m/s, and the explosion pressure is 33.7Gpa.
In conclusion, the nitro-simulated functional group substituted formamide polynitropyrazole energetic compound has high density, high oxygen balance and good detonation performance, and is suitable for being used as an oxidant in the preparation of propellant or explosive.
Example 3: preparation method of azo-bridged formamide polynitropyrazole energetic compound
The preparation method of the azo-bridged formamide polynitropyrazole energetic compound comprises the following steps:
1) Adding 402mg of 2mmol of 5-formamide-3, 4-dinitro-1H-pyrazole into 5ml of acetonitrile to be completely dissolved, adding equivalent DBU, stirring for 3 hours at normal temperature, adding new THA, continuously stirring for 3 hours, and performing rotary evaporation and vacuum drying to obtain N-NH 2 Intermediate compound 5, 65% yield.
2) 216mg of 1mmol of N-NH 2 Intermediate compound 5 is dissolved in 5ml acetonitrile, after stirring to dissolve completely, 162mg of 1.5mmol of tert-butyl hypochlorite is added and reacted for 3 hours at the temperature of-10 ℃; after the reaction is finished, adding saturated sodium carbonate solution to adjust the PH to be neutral, filtering and collecting solid, washing and drying to obtain azo bridged formamide polynitropyrazole energetic compound 6 with the yield of 60%,
3) At 0-10 ℃, 0.1g of azo bridged formamide polynitropyrazole energetic compound 6 is slowly added into 1.1-1.5 mL of nitric acid with the mass fraction of 100% and nitric acid with the volume ratio of 98% sulfuric acid of 1:1.2, then the temperature is slowly increased to 25 ℃, the reaction is carried out for 1h at the temperature, after the reaction is finished, filtration is carried out, the solid is washed by 2mL of trifluoroacetic acid, and after drying, the azo bridged formamide polynitropyrazole energetic compound 7 is obtained, and the yield is 90%.
The reaction route is as follows:
N-NH 2 the nuclear magnetic pattern of intermediate 5 results as follows:
1H NMR(d6-DMSO):δ8.450(br,2H),δ7.362(s,2H).
13C NMR(d6-DMSO):δ156.2,142.3,135.4,123.3ppm.
the nuclear magnetic pattern of azo-bridged carboxamide polynitropyrazole energetic compound 6 results are as follows:
1H NMR(d6-DMSO):δ8.841(s,2H),δ8.660(s,2H).
13C NMR(d6-DMSO):δ156.2,142.3,135.4,123.3ppm.
the azo-bridged carboxamide polynitropyrazole energetic compound 6 was structurally verified by single crystal X-ray diffraction, the structure is shown in figure 3.
The results of the nuclear magnetic carbon spectrum of the azo-bridged formamide polynitropyrazole energetic compound 7 are shown as follows, and the nuclear magnetic carbon spectrum is shown in figure 4:
13C NMR(d3-CD3CN):δ154.9,150.5,139.5,134.6ppm.
the azo-bridged formamide polynitropyrazole energetic compound 7 is subjected to structural verification by single crystal X-ray diffraction, and the structure is shown in figure 5.
The structure of the compound was determined from the above results as shown in the reaction scheme.
The thermal decomposition temperatures, densities, detonation properties, impact sensitivities, and friction sensitivities of the compounds 6 and 7 are shown in table 1.
The formation enthalpy of the azo-bridged formamide polynitropyrazole energetic compound 7 is 670.65KJ/mol, the detonation velocity is 9405m/s and the detonation pressure is 39.3Gpa.
In conclusion, the azo-bridged formamide polynitropyrazole energetic compound 7 has high density, high oxygen balance and high detonation performance, and is expected to replace RDX to be used as a new generation of high explosive.
Example 4: preparation method of azo-bridged formamide polynitropyrazole energetic compound
The preparation method of the azo-bridged formamide polynitropyrazole energetic compound comprises the following steps:
1) Adding 5ml of acetonitrile into 2mmol 402mg of 4-formamide-3, 5-dinitro-1H-pyrazole to dissolve completely, adding equivalent DBU, stirring at normal temperature for 3H, adding fresh THA, continuously stirring for 3H, steaming, and vacuum drying to obtain N-NH 2 Intermediate 8, 68% yield.
2) 216mg of 1mM ON-NH 2 Intermediate compound 8 is dissolved in 5ml acetonitrile, after stirring to dissolve completely, 162mg of 1.5mmol of tert-butyl hypochlorite is added and reacted for 3 hours at the temperature of-10 ℃; after the reaction is finished, adding saturated sodium carbonate solution to adjust the PH to be neutral, filtering and collecting solid, washing and drying to obtain azo bridged formamide polynitropyrazole energetic compound 9, the yield is 65%,
3) At 0-10 ℃, 0.1g of azo bridged formamide polynitropyrazole energetic compound 9 is slowly added into 1.1-1.5 mL of nitric acid with the mass fraction of 100% and nitric acid with the volume ratio of 98% sulfuric acid of 1:1.2, then the temperature is slowly increased to 25 ℃, the reaction is carried out for 1h, after the reaction is finished, the filtration is carried out, the solid is washed by 2mL of trifluoroacetic acid, and the drying is carried out, thus obtaining azo bridged formamide polynitropyrazole energetic compound 10 with the yield of 88%.
The reaction route is as follows:
N-NH 2 the nuclear magnetic pattern of intermediate compound 8 results as follows:
1H NMR(d6-DMSO):δ7.876(br,2H),δ7.589(s,2H).
13C NMR(d6-DMSO):δ157.2,147.2,137.4,124.6ppm.
the nuclear magnetic pattern of azo-bridged carboxamide polynitropyrazole energetic compound 9 results are as follows:
1H NMR(d6-DMSO):δ7.804(s,2H),δ7.500(s,2H).
13C NMR(d6-DMSO):δ156.5,143.4,135.2,123.8ppm.
the azo bridged formamide polynitropyrazole energetic compound 9 is subjected to structural verification by single crystal X-ray diffraction, and the structure is shown in figure 6.
The results of the nuclear magnetic resonance spectrum of the azo-bridged formamide polynitropyrazole energetic compound 10 are shown as follows, and the nuclear magnetic resonance spectrum is shown in figure 7:
13C NMR(d3-CD3CN):δ155.7,149.7,138.5,131.2ppm.
the azo-bridged formamide polynitropyrazole energetic compound 10 is structurally verified by single crystal X-ray diffraction, and the structure is shown in figure 8.
The structure of the compound was determined from the above results as shown in the reaction scheme.
The thermal decomposition temperatures, densities, detonation properties, impact sensitivities, and friction sensitivities of the compounds 9 and 10 are shown in table 1.
The formation enthalpy of the azo-bridged formamide polynitropyrazole energetic compound 10 is 676.83KJ/mol, the detonation velocity is 9440m/s and the detonation pressure is 39.6Gpa.
In conclusion, the azo-bridged formamide polynitropyrazole energetic compound 10 has high density, high oxygen balance and high detonation performance, and is expected to replace RDX to be used as a new generation of high explosive.
Table 1 shows the properties of the compounds in each example.
Table 1 properties of the compounds in the examples
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. A carboxamide polynitro nitrogen-rich energetic compound characterized in that: comprises nitro-simulated functional group substituted formamide polynitropyrazole energetic compound and azo-bridged formamide polynitropyrazole energetic compound; the structural formula of the nitro-simulated functional group substituted formamide polynitropyrazole energetic compound is shown as a formula I or a formula II, and the structural formula of the azo-bridged formamide polynitropyrazole energetic compound is shown as a formula III or a formula IV:
2. use of a carboxamide polynitro nitrogen-rich energetic compound according to claim 1 as an energetic material.
3. The use according to claim 2, wherein: the application of the nitro-simulated functional group substituted formamide polynitropyrazole energetic compound as an oxidant in propellant or explosive preparation.
4. The use according to claim 2, wherein: the azo-bridged formamide polynitropyrazole energetic compound is applied to high explosive.
5. A process for the preparation of a carboxamide polynitro nitrogen-rich energetic compound according to claim 1, characterized in that the carboxamide polynitro nitrogen-rich compound is a nitro-imitation functional substituted carboxamide polynitropyrazole energetic compound, which comprises the following steps:
1) Dissolving a formamide polynitro compound in an organic solvent, then adding an aqueous solution of NaOH into the solution, stirring for 20-60 min, then dropwise adding bromoacetone, reacting at room temperature for 20-30 h, and collecting solids after the reaction is finished to obtain an intermediate product;
2) And (3) performing nitration reaction on the intermediate product and nitro-sulfur mixed acid to obtain the nitro-simulated functional group substituted metronidamide polynitropyrazole energetic compound.
6. The method for preparing the dinitrate-rich energy-containing compound of formamide polynitro according to claim 5, wherein the method comprises the following steps: the carboxamide polynitro compound is selected from 5-formamide-3, 4-binitro-1H-pyrazole or 4-formamide-3, 5-binitro-1H-pyrazole.
7. The method for preparing the dinitrate-rich energy-containing compound of formamide polynitro according to claim 5, wherein the method comprises the following steps: the mol ratio of NaOH to the carboxamide polynitro compound is 1.2:1, and the mol ratio of bromoacetone to the carboxamide polynitro compound is 1.5:1.
8. A process for the preparation of a carboxamide polynitro nitrogen-rich energetic compound according to claim 1, characterized in that: the preparation method of the azotemic acid amide polynitrogen-rich energetic compound comprises the following steps of:
1) Ammoniation reaction of the formamide polynitro compound and THA to obtain N-NH 2 An intermediate compound;
2) N-NH 2 Dissolving an intermediate compound in acetonitrile, adding tert-butyl hypochlorite after the intermediate compound is completely dissolved, adding a saturated sodium carbonate solution to adjust the pH to be neutral after the reaction is completed, and collecting solids to obtain an azo-bridged formamide polynitropyrazole energetic compound;
3) And (3) performing nitration reaction on the azo-bridged formamide polynitropyrazole energetic compound and nitro-sulfur mixed acid to obtain the azo-bridged formamide polynitropyrazole energetic compound.
9. The method for preparing the dinitrate-rich energy-containing compound of formamide polynitro according to claim 8, wherein the method comprises the following steps: the carboxamide polynitro compound is selected from 5-formamide-3, 4-binitro-1H-pyrazole or 4-formamide-3, 5-binitro-1H-pyrazole.
10. Such as weightThe method for preparing the multi-nitro nitrogen-rich compound of the formamide as claimed in claim 8, which is characterized in that: N-NH in step 2) 2 The ratio of intermediate compound to t-butyl hypochlorite was 1mmol:1.5mmol.
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