CN114573518A - 4-cyano-5-nitro-1, 2, 3-triazole metal salt, and preparation method and application thereof - Google Patents
4-cyano-5-nitro-1, 2, 3-triazole metal salt, and preparation method and application thereof Download PDFInfo
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- CN114573518A CN114573518A CN202210249602.5A CN202210249602A CN114573518A CN 114573518 A CN114573518 A CN 114573518A CN 202210249602 A CN202210249602 A CN 202210249602A CN 114573518 A CN114573518 A CN 114573518A
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- dinitropyrazole
- diamino
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- QOXNULMLMONURJ-UHFFFAOYSA-N 5-nitro-2h-triazole-4-carbonitrile Chemical compound [O-][N+](=O)C1=NNN=C1C#N QOXNULMLMONURJ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 150000003839 salts Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- YXQJEZBWVNVFHZ-UHFFFAOYSA-N 3,5-dinitropyrazole-1,4-diamine Chemical compound NN1N=C(C(N)=C1[N+]([O-])=O)[N+]([O-])=O YXQJEZBWVNVFHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 60
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- 239000011734 sodium Chemical group 0.000 claims description 18
- 239000003208 petroleum Substances 0.000 claims description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 10
- 230000020477 pH reduction Effects 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052788 barium Chemical group 0.000 claims description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Chemical group 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 7
- IXZDIALLLMRYOU-UHFFFAOYSA-N tert-butyl hypochlorite Chemical compound CC(C)(C)OCl IXZDIALLLMRYOU-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical group 0.000 claims description 6
- 229910052784 alkaline earth metal Chemical group 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Chemical group 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Chemical group 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002535 acidifier Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 claims description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- 229950009390 symclosene Drugs 0.000 claims description 2
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 claims 6
- 125000005587 carbonate group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 10
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 21
- 238000003756 stirring Methods 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 239000002360 explosive Substances 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 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 3
- 125000001399 1,2,3-triazolyl group Chemical group N1N=NC(=C1)* 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- -1 alkaline earth metal carbonate Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B41/00—Compositions containing a nitrated metallo-organic compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a 4-cyano-5-nitro-1, 2, 3-triazole metal salt, a preparation method and application thereof. The invention discloses a 4-cyano-5-nitro-1, 2, 3-triazole metal salt shown as a formula I. The invention discloses a preparation method of 4-cyano-5-nitro-1, 2, 3-triazole metal salt, which comprises the following steps: dissolving 1, 4-diamino-3, 5-dinitropyrazole (DADNP) shown in a formula II in a solvent, adding an acidified or non-acidified reagent A for reaction, and adding a pH regulator to regulate the pH value to be more than 7 after the reaction is finished. The compound belongs to the field of energetic materials, and can be applied to energetic materials.
Description
Technical Field
The invention belongs to the field of energetic materials, and particularly relates to 4-cyano-5-nitro-1, 2, 3-triazole metal salt, and a preparation method and application thereof.
Background
Because the high-nitrogen energetic compound has the characteristics of high nitrogen content, clean decomposition products and the like, great attention is paid to the design and synthesis of energetic materials. Wherein, the 1,2, 3-triazole ring contains three adjacent nitrogen atoms, so that the compound has higher enthalpy of formation, and energy-containing groups can be connected to two carbon atoms for energy-containing derivatization, so that the 1,2, 3-triazole ring is very suitable for being used as a heterocyclic skeleton of a high-nitrogen energy-containing compound, and the introduction of the nitro group into the 1,2, 3-triazole can improve the oxygen balance of the compound and improve the energy level of the compound.
The impact sensitivity of the currently used heat-resistant explosive (the thermal decomposition temperature is higher than 300 ℃)2,2 ', 4,4 ', 6,6 ' -Hexanitrostilbene (HNS) is only 5J, which indicates that the safety is poor, is not beneficial to ensuring the safety of weapons and equipment, and has certain limitation on the application.
Disclosure of Invention
The invention provides a 4-cyano-5-nitro-1, 2, 3-triazole metal salt, and a preparation method and application thereof. The metal salt can be used as a insensitive high-nitrogen energetic compound.
The invention provides a 4-cyano-5-nitro-1, 2, 3-triazole metal salt, which has a structure shown in a formula I:
wherein n is 1 or 2;
m is an alkali metal or an alkaline earth metal; preferably lithium, sodium, potassium, cesium, magnesium, calcium, strontium or barium; more preferably lithium, sodium, potassium or barium; sodium is further preferred.
The invention provides a preparation method of 4-cyano-5-nitro-1, 2, 3-triazole or metal salt thereof, which comprises the following steps: in a solvent, 1, 4-diamino-3, 5-dinitropyrazole (DADNP) shown in a formula II and a reagent A react as shown in the specification to obtain 4-cyano-5-nitro-1, 2, 3-triazole, or after the reaction is finished, a pH regulator is added to regulate the pH value to be more than 7 to obtain 4-cyano-5-nitro-1, 2, 3-triazole metal salt,
wherein n is 1 or 2.
In one embodiment, the solvent is a solvent commonly used in such reactions in the art: preferably one or more of water, methanol, ethanol and acetonitrile; more preferably acetonitrile or a mixed solvent of acetonitrile and water.
In a certain embodiment, M is an alkali metal or an alkaline earth metal; preferably lithium, sodium, potassium, cesium, magnesium, calcium, strontium or barium; more preferably lithium, sodium, potassium or barium; sodium is further preferred.
In one embodiment, the reagent A is one or more of acidified sodium hypochlorite, acidified sodium dichloroisocyanurate, trichloroisocyanuric acid and tert-butyl hypochlorite; preferably acidified sodium dichloroisocyanurate or tert-butyl hypochlorite; more preferably acidified sodium dichloroisocyanurate.
In one embodiment, the acidification is the addition of the acidifying agent to a solution of non-acidified agent A and water.
In one embodiment, the temperature of acidification is room temperature.
In a certain scheme, in the acidification, the molar ratio of the acidification reagent to the non-acidified reagent A is 2: 1-8: 1.
In one embodiment, the molar volume ratio of the non-acidified reagent A to water in the acidification is 0.2mol/L to 0.5 mol/L; for example, 0.256 to 0.387 mol/L.
In one embodiment, the preparation method comprises the following steps: and adding the mixture of the reagent A and the solvent into the mixture of the 1, 4-diamino-3, 5-dinitropyrazole and the solvent to carry out the reaction, and adding a pH regulator to adjust the pH value to be more than 7 after the reaction is finished.
In a certain scheme, raw materials in the preparation method are 1, 4-diamino-3, 5-dinitropyrazole, a reagent A and the solvent, or the 1, 4-diamino-3, 5-dinitropyrazole, the reagent A, the solvent and the pH regulator.
In a certain scheme, the reaction is carried out at a temperature of-5 to 5 ℃; preferably at a temperature of 5 ℃.
In one embodiment, the reaction is carried out at atmospheric pressure.
In a certain embodiment, the reaction is carried out in the presence of air;
in a certain embodiment, the acidifying agent is one or more of acetic acid, hydrochloric acid, and trifluoroacetic acid.
In one embodiment, the pH adjusting agent is an alkali metal or alkaline earth metal carbonate, bicarbonate or hydroxide; preferably sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, cesium hydroxide, calcium hydroxide, strontium carbonate or barium hydroxide; more preferably sodium carbonate or sodium bicarbonate.
In one embodiment, the molar ratio of the 1, 4-diamino-3, 5-dinitropyrazole (DADNP) to the reagent a is 1:1 to 1: 1.5.
In one embodiment, the molar volume ratio of the 1, 4-diamino-3, 5-dinitropyrazole (DADNP) to the solvent is 1:8.5 to 1:10.5 mol/L.
In one aspect, the steps are: adding the aqueous solution of the reagent A into the mixture of the 1, 4-diamino-3, 5-dinitropyrazole and the organic solvent at the temperature of between 5 ℃ below zero and 5 ℃ to carry out the reaction; the addition may be dropwise.
In one scheme, the raw materials are the 1, 4-diamino-3, 5-dinitropyrazole (DADNP) shown in the formula III, the reagent A and the solvent.
In a certain scheme, the temperature is-5 ℃, acidified sodium dichloroisocyanurate is dripped into a mixture of 1, 4-diamino-3, 5-dinitropyrazole and acetonitrile to carry out the reaction, and a pH regulator is added to adjust the pH value to be more than 7 after the reaction is finished; wherein the pH regulator is sodium carbonate; m is sodium; the molar ratio of the 1, 4-diamino-3, 5-dinitropyrazole (DADNP) to the reagent A is 1: 1.5; the molar volume ratio of the 1, 4-diamino-3, 5-dinitropyrazole (DADNP) to the solvent is 1:10.5 mol/L.
In a certain scheme, the temperature is 0 ℃, adding acidified sodium dichloroisocyanurate dropwise into a mixture of 1, 4-diamino-3, 5-dinitropyrazole and acetonitrile for reaction, and adding a pH regulator to regulate the pH value to be more than 7 after the reaction is finished; wherein the pH regulator is sodium carbonate; m is sodium; the molar ratio of the 1, 4-diamino-3, 5-dinitropyrazole (DADNP) to the reagent A is 1:1, and the molar volume ratio of the 1, 4-diamino-3, 5-dinitropyrazole (DADNP) to the solvent is 1:10.5 mol/L.
In a certain scheme, the temperature is 5 ℃, acidified sodium dichloroisocyanurate is dripped into a mixture of 1, 4-diamino-3, 5-dinitropyrazole and acetonitrile to carry out the reaction, and a pH regulator is added to adjust the pH value to be more than 7 after the reaction is finished; wherein the pH regulator is sodium bicarbonate; m is sodium; the molar ratio of the 1, 4-diamino-3, 5-dinitropyrazole (DADNP) to the reagent A is 1:1, and the molar volume ratio of the 1, 4-diamino-3, 5-dinitropyrazole (DADNP) to the solvent is 1:10.5 mol/L.
In a certain scheme, the temperature is 0 ℃, tert-butyl hypochlorite is dripped into a mixture of 1, 4-diamino-3, 5-dinitropyrazole and acetonitrile for reaction, and a pH regulator is added after the reaction is finished to regulate the pH value to be more than 7; wherein the pH regulator is sodium carbonate; m is sodium; the molar ratio of the 1, 4-diamino-3, 5-dinitropyrazole (DADNP) to the reagent A is 1: 1; the molar volume ratio of the 1, 4-diamino-3, 5-dinitropyrazole (DADNP) to the solvent is 1:8.5 mol/L.
In a certain embodiment, the preparation method further comprises concentrating the reaction solution and then separating by column chromatography.
In a certain scheme, the eluent of the column chromatography is petroleum ether, petroleum ether and ethyl acetate which are 10:1 to 5:1 to 1:2 in sequence, and ethyl acetate.
The invention also provides the application of the 4-cyano-5-nitro-1, 2, 3-triazole metal salt in the field of high-energy materials.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: provides a novel high-nitrogen energetic compound, the impact sensitivity of which is more than 40J, the friction sensitivity of which is more than 360N, the thermal decomposition temperature of which is more than 300 ℃, and the high-nitrogen energetic compound can be used in the field of high-energy materials.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
1, 4-diamino-3, 5-dinitropyrazole was prepared using literature methods: J.Am.chem.Soc.2015,137, 4778-4786.
Example 1
Sodium dichloroisocyanurate (SDIC,255mg,1.16mmol,1.5eq) was dissolved in water (3mL) at room temperature. 0.35mL of acetic acid (6.19mmol,8.0eq) was added dropwise with stirring, and the mixture was stirred for 0.5 h. 1, 4-diamino-3, 5-dinitropyrazole (DADNP,145mg,0.77mmol) was dissolved in 8mL acetonitrile, cooled to-5 deg.C, SDIC/acetic acid aqueous solution was added dropwise with stirring over 0.5 h. After the DADNP is completely consumed, adding sodium carbonate into the reaction solution until the pH value is more than 7, and concentrating to obtain a crude product. Column chromatography was performed using silica gel eluting with pure petroleum ether, petroleum ether: ethyl acetate 10:1 to 5:1 and 1:1, 1:2, and pure ethyl acetate in sequence to give a pure product as 94mg of an off-white powdery solid in 57% yield.13CNMR(100MHz,DMSO-d6,ppm)δ:155.73,114.81,113.83；IR(cm-1):3432,2927,2856,2465,2262,1545,1504,1400,1354,1315,1170,1158,1065,993,834,766,676,647。
Example 2
Sodium dichloroisocyanurate (SDIC,170mg,0.77mmol,1.0eq) was dissolved in water (3mL) at room temperature. 0.35mL of acetic acid (6.19mmol,8.0eq) was added dropwise with stirring, and the mixture was stirred for 0.5 h. 1, 4-diamino-3, 5-dinitropyrazole (DADNP,145mg,0.77mmol) was dissolved in 8mL of acetonitrile, cooled to 0 deg.C, and SDIC/acetic acid aqueous solution was added dropwise with stirring. After the DADNP is completely consumed, adding sodium carbonate into the reaction solution until the pH value is more than 7, and concentrating to obtain a crude product. Column chromatography was performed using silica gel eluting with pure petroleum ether, petroleum ether: ethyl acetate 10:1 to 5:1 and 1:1, 1:2, and pure ethyl acetate in sequence to give a pure product, 86mg of an off-white powdery solid, yield 52%.
Example 3
Sodium dichloroisocyanurate (SDIC,170mg,0.77mmol,1.0eq) was dissolved in water (3mL) at room temperature. 0.35mL of acetic acid (6.19mmol,8.0eq) was added dropwise with stirring, and the mixture was stirred for 0.5 h. 1, 4-diamino-3, 5-dinitropyrazole (DADNP,145mg,0.77mmol) was dissolved in 8mL of acetonitrile, cooled to 5 ℃ and SDIC/acetic acid aqueous solution was added dropwise with stirring. After the DADNP is completely consumed, adding sodium bicarbonate into the reaction solution until the pH value is more than 7, and concentrating to obtain a crude product. Column chromatography was performed using silica gel eluting with pure petroleum ether, petroleum ether: ethyl acetate 10:1 to 5:1 and 1:1, 1:2, and pure ethyl acetate in sequence to give a pure product, 89mg of an off-white powdery solid, yield 54%.
Example 4
Sodium dichloroisocyanurate (SDIC,170mg,0.77mmol,1.0eq) was dissolved in water (3mL) at room temperature. 0.18mL of acetic acid (3.10mmol,4.0eq) was added dropwise with stirring, and the mixture was stirred for 0.5 h. 1, 4-diamino-3, 5-dinitropyrazole (DADNP,145mg,0.77mmol) was dissolved in 8mL of acetonitrile, cooled to 5 ℃ and SDIC/acetic acid aqueous solution was added dropwise with stirring. After the DADNP is completely consumed, adding sodium bicarbonate into the reaction solution until the pH value is more than 7, and concentrating to obtain a crude product. Column chromatography was performed using silica gel eluting with pure petroleum ether, petroleum ether: ethyl acetate 10:1 to 5:1 and 1:1, 1:2, and pure ethyl acetate in sequence to give a pure product, 89mg of an off-white powdery solid, yield 54%.
Example 5
Sodium dichloroisocyanurate (SDIC,170mg,0.77mmol,1.0eq) was dissolved in water (3mL) at room temperature. 0.04mL of acetic acid (0.77mmol,2.0eq) was added dropwise with stirring, and the mixture was stirred for 0.5 h. 1, 4-diamino-3, 5-dinitropyrazole (DADNP,145mg,0.77mmol) was dissolved in 8mL of acetonitrile, cooled to 5 ℃ and SDIC/acetic acid aqueous solution was added dropwise with stirring. After the DADNP is completely consumed, adding sodium bicarbonate into the reaction solution until the pH value is more than 7, and concentrating to obtain a crude product. Column chromatography was performed using silica gel eluting with pure petroleum ether, petroleum ether: ethyl acetate 10:1 to 5:1 and 1:1, 1:2, and pure ethyl acetate in sequence to give a pure product, 89mg of an off-white powdery solid, yield 54%.
Example 6
1, 4-diamino-3, 5-dinitropyrazole (DADNP,353mg,1.88mmol) was dissolved in 16mL acetonitrile, cooled to 0 deg.C, stirred0.21mL of tert-butyl hypochlorite (t-BuClO,1.86mmol, 1.0eq) was added dropwise to the mixture, the color of the liquid turned from yellow to red, and the addition was completed in 15min (0 ℃). After the DADNP is completely consumed, adding sodium carbonate into the reaction solution until the pH value is more than 7, and concentrating to obtain a crude product. Column chromatography was performed using silica gel eluting with pure petroleum ether, petroleum ether: ethyl acetate 10:1 to 5:1 and 1:1, 1:2, and pure ethyl acetate in sequence to give pure product, 44mg of an off-white powdery solid, yield 11%.13CNMR(100MHz,DMSO-d6,ppm)δ:155.73,114.81,113.83；IR(cm-1):3432,2927,2856,2465,2262,1545,1504,1400,1354,1315,1170,1158,1065,993,834,766,676,647。
Example 7
The impact sensitivity (5kg drop weight), the friction sensitivity and the thermal decomposition temperature (temperature rise rate of 5 Kmin) of the sodium salt and the barium salt of 4-cyano-5-nitro-1, 2, 3-triazole were measured-1) The performance of the explosive material is compared with that of a common explosive material and is shown in a table 1:
table 1: NaCNT and Ba (CNT)2Compared with the performance of the common explosive material
| Compound (I) | Temperature of thermal decomposition (. degree.C.) | Sensitivity to impact (J) | Degree of friction (N) |
| NaCNT | 327 | >40 | >360 |
| Ba(CNT)2 | 310 | >40 | >360 |
| HNS | 320 | 5 | >360 |
| RDX | 210 | 7.5 | 120 |
The sodium salt and barium salt of 4-cyano-5-nitro-1, 2, 3-triazole have impact sensitivity of more than 40J and friction sensitivity of more than 360N, belong to insensitive energetic ionic salts, and have thermal decomposition temperatures of 327 ℃ and 310 ℃ and belong to heat-resistant explosives (the thermal decomposition temperature is higher than 300 ℃).
Claims (10)
1. A4-cyano-5-nitro-1, 2, 3-triazole metal salt has a structure shown in formula I:
wherein n is 1 or 2; and M is alkali metal or alkaline earth metal.
2. The metal 4-cyano-5-nitro-1, 2, 3-triazole salt of claim 1, wherein M is lithium, sodium, potassium, cesium, magnesium, calcium, strontium, or barium.
3. A method for preparing 4-cyano-5-nitro-1, 2, 3-triazole or a metal salt thereof, comprising the steps of: in a solvent, 1, 4-diamino-3, 5-dinitropyrazole shown in a formula II and a reagent A are subjected to a reaction shown in the specification to obtain 4-cyano-5-nitro-1, 2, 3-triazole, or after the reaction is finished, a pH regulator is added to regulate the pH value to be more than 7 to obtain 4-cyano-5-nitro-1, 2, 3-triazole metal salt,
wherein n is 1 or 2; the pH regulator is carbonate, bicarbonate or hydroxide of alkali metal or alkaline earth metal; m is the corresponding alkali metal or alkaline earth metal; the reagent A is one or more of acidified sodium hypochlorite, acidified sodium dichloroisocyanurate, trichloroisocyanuric acid and tert-butyl hypochlorite.
4. The method of claim 3, wherein the method satisfies one or more of the following conditions:
a) the reaction is carried out at a temperature of-5 to 5 ℃;
b) the reaction is carried out at normal pressure;
c) the reaction is carried out in the presence of air;
d) m is lithium, sodium, potassium, cesium, magnesium, calcium, strontium or barium;
e) the solvent is one or more of water, methanol, ethanol and acetonitrile;
f) the acidizing reagent is one or more of acetic acid, hydrochloric acid and trifluoroacetic acid;
g) the molar ratio of the 1, 4-diamino-3, 5-dinitropyrazole to the reagent A is 1: 1-1: 1.5;
h) the molar volume ratio of the 1, 4-diamino-3, 5-dinitropyrazole to the solvent is 1: 8.5-1: 10.5 mol/L.
5. The method of claim 4, wherein the method satisfies one or more of the following conditions:
i) the reaction is carried out at a temperature of 5 ℃;
j) m is lithium, sodium, potassium or barium;
k) the solvent is acetonitrile or a mixed solvent of acetonitrile and water;
l) the reagent A is acidified sodium dichloroisocyanurate or tert-butyl hypochlorite;
m) the pH regulator is sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, cesium hydroxide, calcium hydroxide, strontium carbonate, or barium hydroxide;
n) said acidification is the addition of said acidifying agent to a solution of non-acidified agent A and water.
6. The method of claim 5, wherein the method satisfies one or more of the following conditions:
o) said reagent A is acidified sodium dichloroisocyanurate;
p) said M is sodium;
q) the pH regulator is sodium carbonate or sodium bicarbonate;
r) the acidification temperature is room temperature;
s) in the acidification, the molar ratio of the acidification reagent to the non-acidified reagent A is 2: 1-8: 1;
t) in the acidification, the molar volume ratio of the non-acidified reagent A to water is 0.2-0.5 mol/L;
u) the preparation method comprises the following steps: adding the mixture of the reagent A and the solvent into the mixture of the 1, 4-diamino-3, 5-dinitropyrazole and the solvent to carry out the reaction, and adding a pH regulator to adjust the pH value to be more than 7 after the reaction is finished;
v) the raw materials in the preparation method are 1, 4-diamino-3, 5-dinitropyrazole, a reagent A and the solvent, or 1, 4-diamino-3, 5-dinitropyrazole, a reagent A, the solvent and the pH regulator.
7. The method according to claim 3, wherein the method is any one of the following schemes:
scheme 1, the temperature is-5 ℃, the acidified sodium dichloroisocyanurate is dripped into the mixture of 1, 4-diamino-3, 5-dinitropyrazole and acetonitrile to carry out the reaction, and a pH regulator is added to adjust the pH value to be more than 7 after the reaction is finished; wherein the pH regulator is sodium carbonate; m is sodium; the molar ratio of the 1, 4-diamino-3, 5-dinitropyrazole to the reagent A is 1: 1.5; the molar volume ratio of the 1, 4-diamino-3, 5-dinitropyrazole to the solvent is 1:10.5 mol/L;
scheme 2, the temperature is 0 ℃, the acidified sodium dichloroisocyanurate is dripped into the mixture of 1, 4-diamino-3, 5-dinitropyrazole and acetonitrile to carry out the reaction, and a pH regulator is added to adjust the pH value to be more than 7 after the reaction is finished; wherein the pH regulator is sodium carbonate; m is sodium; the molar ratio of the 1, 4-diamino-3, 5-dinitropyrazole to the reagent A is 1:1, and the molar volume ratio of the 1, 4-diamino-3, 5-dinitropyrazole to the solvent is 1:10.5 mol/L;
scheme 3, the temperature is 5 ℃, the acidified sodium dichloroisocyanurate is dripped into the mixture of the 1, 4-diamino-3, 5-dinitropyrazole and the acetonitrile to carry out the reaction, and a pH regulator is added to adjust the pH value to be more than 7 after the reaction is finished; wherein the pH regulator is sodium bicarbonate; m is sodium; the molar ratio of the 1, 4-diamino-3, 5-dinitropyrazole to the reagent A is 1:1, and the molar volume ratio of the 1, 4-diamino-3, 5-dinitropyrazole to the solvent is 1:10.5 mol/L;
scheme 4, dropwise adding tert-butyl hypochlorite into a mixture of 1, 4-diamino-3, 5-dinitropyrazole and acetonitrile at the temperature of 0 ℃, carrying out the reaction, and adding a pH regulator to regulate the pH value to be more than 7 after the reaction is finished; wherein the pH regulator is sodium carbonate; m is sodium; the molar ratio of the 1, 4-diamino-3, 5-dinitropyrazole to the reagent A is 1: 1; the molar volume ratio of the 1, 4-diamino-3, 5-dinitropyrazole to the solvent is 1:8.5 mol/L.
8. The method according to any one of claims 3 to 7, further comprising purifying the concentrated reaction solution by column chromatography.
9. The preparation method according to claim 8, wherein the eluent for the column chromatography is petroleum ether, petroleum ether-ethyl acetate-10: 1 to 5:1 to 1:2, and ethyl acetate in that order.
10. Use of a metal salt of 4-cyano-5-nitro-1, 2, 3-triazole according to claim 1 or 2 in the field of energetic materials.
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| CN104725328A (en) * | 2015-03-20 | 2015-06-24 | 西安近代化学研究所 | Synthesis method of 1,1'-azo-bis(3,5-dinitro-1,2,4-triazole) |
| CN106432113A (en) * | 2016-09-07 | 2017-02-22 | 西安近代化学研究所 | 1,1'-azo bis(5-chloro-3-nitro-1,2,4-triazole) compound |
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| CN104725328A (en) * | 2015-03-20 | 2015-06-24 | 西安近代化学研究所 | Synthesis method of 1,1'-azo-bis(3,5-dinitro-1,2,4-triazole) |
| CN106432113A (en) * | 2016-09-07 | 2017-02-22 | 西安近代化学研究所 | 1,1'-azo bis(5-chloro-3-nitro-1,2,4-triazole) compound |
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