CN116621840A - 6-nitro-7-amino- [1,2,4] triazole [1,5-a ] pyrimidine, synthesis method and application - Google Patents
6-nitro-7-amino- [1,2,4] triazole [1,5-a ] pyrimidine, synthesis method and application Download PDFInfo
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- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000001308 synthesis method Methods 0.000 title abstract description 8
- 239000002360 explosive Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 29
- GGJAOVLAQCQAFT-UHFFFAOYSA-N 6-nitro-[1,2,4]triazolo[1,5-a]pyrimidin-7-amine Chemical compound Nc1c(cnc2ncnn12)[N+]([O-])=O GGJAOVLAQCQAFT-UHFFFAOYSA-N 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 150000003852 triazoles Chemical class 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 230000035945 sensitivity Effects 0.000 abstract description 15
- 238000005474 detonation Methods 0.000 abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- -1 pyrimidine compound Chemical class 0.000 description 10
- YWBFPKPWMSWWEA-UHFFFAOYSA-O triazolopyrimidine Chemical compound BrC1=CC=CC(C=2N=C3N=CN[N+]3=C(NCC=3C=CN=CC=3)C=2)=C1 YWBFPKPWMSWWEA-UHFFFAOYSA-O 0.000 description 10
- 238000011160 research Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 150000002391 heterocyclic compounds Chemical class 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- JZLUWZPEJDRDEO-UHFFFAOYSA-N [N].C1=CN=CN=C1 Chemical compound [N].C1=CN=CN=C1 JZLUWZPEJDRDEO-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- YSIBQULRFXITSW-OWOJBTEDSA-N 1,3,5-trinitro-2-[(e)-2-(2,4,6-trinitrophenyl)ethenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1\C=C\C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O YSIBQULRFXITSW-OWOJBTEDSA-N 0.000 description 1
- MNUJHDPQSAMAAM-UHFFFAOYSA-N 1,3,7,9-tetranitrobenzotriazolo[2,1-a]benzotriazol-5-ium-6-ide Chemical compound C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=NN(C=3C(=C([N+]([O-])=O)C=C(C=3)[N+](=O)[O-])[N-]3)[N+]3=C21 MNUJHDPQSAMAAM-UHFFFAOYSA-N 0.000 description 1
- QNZDCKBBTJYQDT-UHFFFAOYSA-N 3,5-dinitropyridin-2-amine Chemical compound NC1=NC=C([N+]([O-])=O)C=C1[N+]([O-])=O QNZDCKBBTJYQDT-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- UATJOMSPNYCXIX-UHFFFAOYSA-N Trinitrobenzene Chemical group [O-][N+](=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 UATJOMSPNYCXIX-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000005284 basis set Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005421 electrostatic potential Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- JDFUJAMTCCQARF-UHFFFAOYSA-N tatb Chemical compound NC1=C([N+]([O-])=O)C(N)=C([N+]([O-])=O)C(N)=C1[N+]([O-])=O JDFUJAMTCCQARF-UHFFFAOYSA-N 0.000 description 1
- 239000000015 trinitrotoluene Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B49/00—Use of single substances as explosives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The application provides a 6-nitro-7-amino- [1,2,4]Triazole [1,5-a ]]Pyrimidine, a synthesis method and application, the structure of which is shown as follows:as a first synthesized compound used as an elementary explosive, the compound provided by the application has excellent detonation performance and heat resistance. The sensitivity of the compounds of the application is low: friction Sensitivity (FS)>360N, impact Sensitivity (IS)>40J。
Description
Technical Field
The application belongs to the technical field of energetic materials, relates to an elementary substance explosive, and in particular relates to 6-nitro-7-amino- [1,2,4] triazole [1,5-a ] pyrimidine, a synthesis method and application.
Background
The energetic material is a power source and a power source of the weapon system, and has the characteristics of diversity, complexity, uncertainty and the like of future war modes and war environments, and more stringent and special requirements are put on the battlefield adaptability of the novel weapon system. In recent years, with the increasingly severe use environment of weapon ammunition, safety accidents of global army fire base frequently occur, and the important role of insensitive explosive as an improvement of the survival capability of weapon systems in battlefields becomes one of the important points of research in industry, and the insensitive explosive is a novel high-energy insensitive material (explosion velocity>8000m/s, impact sensitivity>15J) Is increasingly urgent. However, there is an inherent conflict in energy and sensitivity for energetic compound molecules: generally, the energetic compound molecules need to introduce more explosive groups (such as nitro groups) to improve the formation enthalpy and oxygen balance value, and the strong electron withdrawing groups can lead to the separation of charges in the molecules, so that the higher the charge separation degree is, the C-NO in the molecules is 2 /N-NO 2 The weaker the bond, the more labile the molecule.
Disclosure of Invention
Aiming at the defects existing in the prior art, the application aims to provide 6-nitro-7-amino- [1,2,4] triazole [1,5-a ] pyrimidine, a synthesis method and application thereof, and solves the technical problem that the heat resistance and insensitivity of the small-molecule elementary substance explosive containing energy in the prior art are to be further improved.
In order to solve the technical problems, the application adopts the following technical scheme:
a 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine having the structure shown below:
the present application also provides a first synthetic method of 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine as described above, comprising the steps of:
under the condition of ice water bath at 0 ℃, fuming HNO is added 3 And concentration H 2 SO 4 Adding 7-amino- [1,2,4 under stirring]Triazole [1,5-a ]]After the pyrimidine is added, the reaction solution is gradually heated to 80 ℃ and kept for 4.0 hours, then cooled to room temperature, ice is poured into the reaction solution, the pH is adjusted to 7, and white solid is separated out; suction filtering to obtain white solid, washing and drying to obtain white solid product, namely 6-nitro-7-amino- [1,2,4]Triazole [1,5-a ]]Pyrimidine.
The present application also provides a second synthetic method of 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine as described above, comprising the steps of:
adding concentrated H under the condition of ice water bath at 0 DEG C 2 SO 4 Adding 7-amino- [1,2,4 under stirring]Triazole [1,5-a ]]Pyrimidine, followed by KNO 3 Adding the mixture into a reaction solution, gradually heating the reaction solution to 140 ℃, pouring the reaction solution into crushed ice after the reaction is finished, and separating out white solid; suction filtering to obtain white solid product, namely 6-nitro-7-amino- [1,2,4]Triazole [1,5-a ]]Pyrimidine.
The present application also provides a third synthetic method of 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine as described above, comprising the steps of:
under the condition of ice water bath at 0 ℃, 10.0mL of concentrated HNO is added 3 Adding 7-amino- [1,2,4 under stirring]Triazole [1,5-a ]]Pyrimidine, then gradually heating the reaction solution to 25 ℃, stirring the reaction solution at 25 ℃ for 4.0h, and finally gradually heating the reaction solution to 115 ℃; pouring the reaction solution into crushed ice after the reaction is finished, and separating out white solid; suction filtering to obtain white solid product, namely 6-nitro-7-amino- [1,2,4]Triazole [1,5-a ]]Pyrimidine.
The application also protects the use of 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine as described above as an elemental explosive.
The application also protects the application of the 6-nitro-7-amino- [1,2,4] triazole [1,5-a ] pyrimidine synthesized by the synthesis method of the 6-nitro-7-amino- [1,2,4] triazole [1,5-a ] pyrimidine as an elementary explosive.
Compared with the prior art, the application has the following technical effects:
the 6-nitro-7-amino- [1,2,4] triazole [1,5-a ] pyrimidine compound has excellent detonation performance and heat resistance.
(II) the sensitivity of the 6-nitro-7-amino- [1,2,4] triazole [1,5-a ] pyrimidine compound of the present application is low: friction Sensitivity (FS) >360N, impact Sensitivity (IS) >40J.
(III) the raw materials of the synthesis method of the application are cheap and easy to obtain: 7-amino- [1,2,4]]Triazole [1,5-a ]]Pyrimidine, fuming HNO 3 Concentrated H 2 SO 4 、KNO 3 And concentrated HNO 3 Are all commercial reagents.
The synthesis method is simple, the synthesis condition is very mild, and the yield is high.
Drawings
FIG. 1 is a single crystal structure of 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine.
The following examples illustrate the application in further detail.
Detailed Description
All the raw materials in the present application, unless otherwise specified, are known in the art.
The design, synthesis and use of a large number of azaaromatic ring-containing compounds as components of high explosive and propellant formulations have been widely reported. The triazole pyrimidine nitrogen-rich heterocyclic compound is clearly the most attractive star molecule in recent years, and has the characteristics of high formation enthalpy and high nitrogen content, high energy generation during decomposition, high nitrogen release, low hydrocarbon content, low characteristic signals, environment friendliness, easiness in realizing oxygen balance and the like because the molecular structure of the star molecule contains a large number of N-N, C-N, N=N and C=N bonds. In addition, the whole molecular structure of the triazolopyrimidine nitrogen-rich heterocyclic compound can form a large pi bond system similar to a benzene ring structure, so that the degree of molecular charge separation caused by an explosion-causing group can be effectively reduced, and the triazolopyrimidine nitrogen-rich heterocyclic compound is one of the most effective ways for obtaining high-energy insensitive energy-containing compounds. And the triazole pyrimidine nitrogen-rich heterocyclic compound has made great research progress in the civil pharmaceutical field, but has been freshly reported in the field of energetic materials. Therefore, the introduction of the triazolopyrimidine nitrogen-rich heterocyclic structure into the field of energetic materials is of great military value.
The conception of the application is as follows:
recently, azaaromatic ring compounds become hot spots in the field of research and development of energetic materials, and the compounds can often form a conjugated delocalization system with a benzene-like structure, so that the compound is a simple substance energetic material with low impact and friction sensitivity, high thermal decomposition temperature and good detonation performance. And energetic materials containing triazolopyrimidine structures therein have attracted high attention from various countries. The triazolopyrimidine ring is a very effective building block for the design of the C, H, O, N high energy density compound of choice. The triazolopyrimidine ring has several advantages:
(1) the pyrimidine ring has a planar structure, six electrons on the ring form a conjugated large pi bond, and the pyrimidine ring has certain aromaticity. The triazole ring has a 'latent nitro' inner ring structure, one ring contains 3 nitrogen atoms, and the nitrogen content and the crystallization density of molecules are higher. The triazolopyrimidine ring energetic derivative has the advantages of high energy density, high standard formation enthalpy, high nitrogen content and the like, and becomes one of the research directions which are paid attention to in the field of energetic material research. (2) The triazolopyrimidine aza-condensed ring has a compact structure, has a near-plane structure beneficial to molecular accumulation, on one hand, makes the density higher, and on the other hand, effectively improves the energy level of the energetic compound, thereby having better detonation performance. (3) Meanwhile, delocalized pi electrons significantly increase the stability of the condensed ring skeleton, and thus the condensed ring aromaticity of triazolopyrimidines increases the thermal decomposition temperature of the compound by increasing the stability of the condensed ring skeleton. (4) The aromaticity enables atoms in the condensed rings to be in the same plane as much as possible, and reduces torsion angles of nitro, amino and parent rings outside the rings through a conjugate effect, so that the triazolopyrimidine has a plane-like structure, which is beneficial to improving the density of molecular close packing and reducing the sensitivity. In addition, the high nitrogen compound molecule has high electronegativity of nitrogen and oxygen atoms and mostly has unused lone electron pairs, so that the whole heterocyclic ring system is easy to form a large pi-bond conjugated structure similar to a benzene ring. Therefore, the material has the advantages of good thermal stability, insensitive to friction and impact stimulus and the like. And the triazole pyrimidine nitrogen-rich heterocyclic compound has made great research progress in the civil pharmaceutical field, but has been freshly reported in the field of energetic materials. Therefore, the introduction of the triazolopyrimidine nitrogen-rich heterocyclic structure into the field of energetic materials is of great military value.
Based on the structural basis of the triazole pyrimidine aza condensed ring structure molecular skeleton, the application designs a 6-nitro-7-amino- [1,2,4] triazole [1,5-a ] pyrimidine compound with high energy groups, adopts quantum chemical density functional theory to research the influence of a parent structure and an energetic group on the compound structure and detonation performance (formation enthalpy and detonation pressure), expects to obtain the energetic compound molecular structure with excellent performance, and simultaneously provides theoretical basis for the follow-up development of related research work.
The 6-nitro-7-amino- [1,2,4] triazole [1,5-a ] pyrimidine is synthesized for the first time, and the structure is shown as follows:
the following specific embodiments of the present application are provided, and it should be noted that the present application is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical scheme of the present application fall within the protection scope of the present application.
Example 1:
this example shows a process for the synthesis of 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine comprising the steps of:
under the ice water bath condition of 0 ℃, 1.25mL of fuming HNO is added into a 50mL three-neck flask 3 (96% by mass) and 9.60mL of concentrated H 2 SO 4 (98% by mass) 1.35g (10 mmol) of 7-amino- [1,2,4] are added with stirring]Triazole [1,5-a ]]After the pyrimidine addition, the reaction mixture was gradually heated to 80℃and maintained for 4.0 hours, then cooled to room temperature, 30.0g of ice was poured into the reaction mixture, the pH was adjusted to 7 with ammonia water, and a white solid was precipitated. Suction filtration gave a white solid, which was used with 15mLThe distilled water was repeatedly washed 3 times. The white solid obtained was dried. The product was obtained as a white solid in 87% yield.
And (3) structural identification:
(1) infrared spectrum testing:
infrared spectrum (KBr, cm) -1 ): 3418 (-NH. Stretching vibration), 3206 (-CH. Stretching vibration), 1509 (O-N. Stretching vibration), 1363 (O-N. Stretching vibration), 1196 (C-N. Stretching vibration), 736 (-NH. Out-of-plane deformation vibration).
(2) Nuclear magnetism 1 H NMR 13 C NMR：
1 H NMR(DMSO-d 6 ,400MHz):δ8.70(s,1H),9.36(s,1H),9.48(br s,2H).
13 C NMR(DMSO-d 6 ,101MHz):δ119.1,145.8,151.9,156.0,156.4.
(3) Elemental analysis:
Anal.calcd for C 5 H 4 N 6 O 2 :C,33.34；H,2.24；N,46.66.
Found:C,33.24；H,2.06；N,46.53.
(4) single crystal structure testing:
the single crystal structure is shown in FIG. 1.
The above data confirm that the product of the above reaction is a 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine compound.
Example 2:
this example shows a process for the synthesis of 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine comprising the steps of:
13.3mL of concentrated H is added into a 50mL three-neck flask under the condition of ice water bath at 0 DEG C 2 SO 4 (98% by mass) 1.35g (10 mmol) of 7-amino- [1,2,4] are added with stirring]Triazole [1,5-a ]]Pyrimidine, then 1.0g KNO 3 The reaction mixture was added thereto, and the temperature of the reaction mixture was gradually raised to 140 ℃. After the reaction, the reaction mixture was poured into 30.0g of crushed ice and was whiteThe solid is separated out, and the white solid product is obtained by suction filtration, and the yield is 81%.
The structure identification result of this example was the same as that of example 1.
The thermal performance test results of this example are the same as those of example 1.
Example 3:
this example shows a process for the synthesis of 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine comprising the steps of:
10.0mL of concentrated HNO is added into a 50mL three-neck flask under the condition of ice water bath at the temperature of 0 DEG C 3 (mass concentration: 68%) was added 1.35g (10 mmol) of 7-amino- [1,2,4] with stirring]Triazole [1,5-a ]]Pyrimidine, then the reaction solution was gradually warmed to 25 ℃, the reaction solution was stirred at 25 ℃ for 4.0h, and finally the reaction solution was gradually warmed to 115 ℃. After the reaction, the reaction solution was poured into 30.0g of crushed ice, and a white solid was precipitated, followed by suction filtration to obtain a white solid product in a yield of 78%.
The structure identification result of this example was the same as that of example 1.
The thermal performance test results of this example are the same as those of example 1.
Example 4:
this example shows the use of 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine as an elemental explosive.
6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine the 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine synthesized in example 1, example 2 or example 3 above was used.
Thermal performance test:
thermal performance was tested by DSC (differential scanning calorimetry) in a nitrogen atmosphere at a heating rate=10 ℃/min, giving a decomposition temperature of 350 ℃ for the 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine compound.
Sensitivity performance test:
according to GJB772A-97 method, WL-1 type is utilizedThe impact sensitivity instrument and WM-1 type friction sensitivity instrument of the explosives and powders respectively measure the impact explosion probability P I (10 kg drop hammer, 25cm drop height), characteristic drop height H 50 (5 kg drop hammer) probability of friction explosion P F (3.92 MPa gauge pressure, 90 degree swing angle).
Tested: the 6-nitro-7-amino- [1,2,4] triazole [1,5-a ] pyrimidine compound has an Impact Sensitivity (IS) of >40J and a Friction Sensitivity (FS) of > 360N.
Detonation performance test:
in order to study the detonation performance of the synthesized 6-nitro-7-amino- [1,2,4] triazole [1,5-a ] pyrimidine compound derivative, the structure of the three derivatives is fully optimized at the level of 6-31G-based groups by using a Gaussian09 program according to the B3LYP method l of the density functional theory, and no virtual frequency is found through vibration analysis, so that the optimized structure is a very small point on a potential energy plane. Their theoretical volumes were calculated using Monte-Carlo to determine the theoretical density. The method comprises the steps of calculating vapor phase formation enthalpy of molecules by using a complete basis set method (CBS-4M) by adopting an atomization scheme, carrying out statistical calculation on electrostatic potential parameters of the molecules, calculating sublimation enthalpy of the molecules by adopting a formula proposed by Politzer and the like, and obtaining solid phase formation enthalpy. The detonation velocity and detonation pressure of the pellets were calculated by using the Kamlet-Jacobs formula, and the results are shown in Table 1.
In Table 1, the remaining elemental explosive compounds are known elemental explosives, except for the compounds of the present application. TNT represents 2,4, 6-trinitrotoluene; TATB represents trinitrobenzene; HNS represents hexanitrodiethylstilbestrol, also known as 6,6' -hexanitrostilbene; TACOT represents tetranitrodiphenyl tetranitrene; LLM-126 represents 2, 6-di-bitter amino-3, 5-dinitropyridine.
Table 1 6 detonation Performance parameters of nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine Compounds
Claims (6)
1. A 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine, characterized by the structure shown below:
2. a process for the synthesis of 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine according to claim 1, comprising the steps of:
under the condition of ice water bath at 0 ℃, fuming HNO is added 3 And concentration H 2 SO 4 Adding 7-amino- [1,2,4 under stirring]Triazole [1,5-a ]]After the pyrimidine is added, the reaction solution is gradually heated to 80 ℃ and kept for 4.0 hours, then cooled to room temperature, ice is poured into the reaction solution, the pH is adjusted to 7, and white solid is separated out; suction filtering to obtain white solid, washing and drying to obtain white solid product, namely 6-nitro-7-amino- [1,2,4]Triazole [1,5-a ]]Pyrimidine.
3. A process for the synthesis of 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine according to claim 1, comprising the steps of:
adding concentrated H under the condition of ice water bath at 0 DEG C 2 SO 4 Adding 7-amino- [1,2,4 under stirring]Triazole [1,5-a ]]Pyrimidine, followed by KNO 3 Adding the mixture into a reaction solution, gradually heating the reaction solution to 140 ℃, pouring the reaction solution into crushed ice after the reaction is finished, and separating out white solid; suction filtering to obtain white solid product, namely 6-nitro-7-amino- [1,2,4]Triazole [1,5-a ]]Pyrimidine.
4. A process for the synthesis of 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine according to claim 1, comprising the steps of:
under the condition of ice water bath at 0 ℃, 10.0mL of concentrated HNO is added 3 Adding 7-amino- [1,2,4 under stirring]Triazole [1,5-a ]]Pyrimidine, then gradually heating the reaction solution to 25 ℃, stirring the reaction solution at 25 ℃ for 4.0h, and finally gradually heating the reaction solution to 115 ℃; after the reaction is finished, the reaction solution is poured into crushed ice with white solidSeparating out a body; suction filtering to obtain white solid product, namely 6-nitro-7-amino- [1,2,4]Triazole [1,5-a ]]Pyrimidine.
5. Use of 6-nitro-7-amino- [1,2,4] triazolo [1,5-a ] pyrimidine as claimed in claim 1 as an elemental explosive.
6. Use of 6-nitro-7-amino- [1,2,4] triazol [1,5-a ] pyrimidine synthesized by the synthesis of 6-nitro-7-amino- [1,2,4] triazol [1,5-a ] pyrimidine as claimed in claim 2, 3 or 4 as an elemental explosive.
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