CN109020910B - 2-amino-4-nitramine-6-formazanolamine-1, 3, 5-triazine nitrogen oxide and preparation method thereof - Google Patents
2-amino-4-nitramine-6-formazanolamine-1, 3, 5-triazine nitrogen oxide and preparation method thereof Download PDFInfo
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000005457 ice water Substances 0.000 claims abstract description 31
- 238000010791 quenching Methods 0.000 claims abstract description 31
- 230000000171 quenching effect Effects 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 230000035484 reaction time Effects 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 5
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 125000002950 monocyclic group Chemical group 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 29
- -1 1,3, 5-triazine nitramine compound Chemical class 0.000 description 18
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000003760 magnetic stirring Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 description 5
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005474 detonation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical compound O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 description 1
- HTJMXYRLEDBSLT-UHFFFAOYSA-N 1,2,4,5-tetrazine Chemical compound C1=NN=CN=N1 HTJMXYRLEDBSLT-UHFFFAOYSA-N 0.000 description 1
- HYYSTOVSGMUPTP-UHFFFAOYSA-N 1,3,5-triazine;2h-triazole Chemical compound C=1C=NNN=1.C1=NC=NC=N1 HYYSTOVSGMUPTP-UHFFFAOYSA-N 0.000 description 1
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 description 1
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 1
- SLYVQEOUGKXEAV-UHFFFAOYSA-N 4-azidotriazine Chemical compound [N-]=[N+]=NC1=CC=NN=N1 SLYVQEOUGKXEAV-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical group [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/66—Derivatives of melamine in which a hetero atom is directly attached to a nitrogen atom of melamine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a 2-amino-4-nitramine-6-formacyl nitramine-1, 3, 5-triazine nitrogen oxide and a preparation method thereof, wherein the preparation method comprises the following steps: (1) adding 1,3, 5-triazino-1, 2, 4-triazole into trifluoroacetic acid at 25 ℃, then adding 50% hydrogen peroxide for full reaction at the temperature, then pouring ice water for quenching, and filtering to obtain an intermediate; (2) adding the intermediate into 100 percent of HNO under the condition of low temperature3And then fully reacting at the temperature, pouring ice water for quenching, stirring for a period of time to separate out a solid, filtering, and washing with water to obtain the target product. The preparation method is beneficial to obtaining the monocyclic triazine high-energy material 2-amino-4-nitramine-6-formazanolamine-1, 3, 5-triazine nitrogen oxide.
Description
Technical Field
The invention relates to the technical field of energetic materials, and particularly relates to 2-amino-4-nitramine-6-formazanolamine-1, 3, 5-triazine oxynitride and a preparation method thereof.
Background
In the aromatic heterocyclic skeleton of the six-membered ring, the nitrogen content of 1,3, 5-triazine is as high as 51 percent, which is second only to 1,2,4, 5-tetrazine (68 percent), and triazine-based compounds have the advantages of high density, high positive formation enthalpy, good thermal stability and the like, and are commonly used for constructing chemical raw materials (melamine), gas generants, solid propellants, pyrotechnic agents, initiating explosive (azido triazine) and the like. Triazine ring's ring tension is little, and stability is good, has three modifiable loci, can react with the nucleophile, introduces azido, nitro amino, azo bond and hydrazine bond and other five-membered heterocyclic structure, but introduces the degree of difficulty of nitrogen oxygen group on 1,3, 5-triazine is very big.
Disclosure of Invention
The invention aims to provide a 1,3, 5-triazine nitramine compound 2-amino-4-nitramine-6-formamido nitramine-1, 3, 5-triazine nitrogen oxide and a preparation method thereof, wherein a synthetic strategy of nitrogen oxidation and N-N bond breakage is carried out on 1,3, 5- triazine 1,2, 4-triazole, then nitration is carried out, nitrogen and oxygen are successfully introduced into triazine, and meanwhile, nitroamination structural modification is carried out on the triazine to obtain a brand-new compound 2-amino-4-nitramine-6-formamido nitramine-1, 3, 5-triazine nitrogen oxide.
In order to achieve the technical effects, the invention provides a 1,3, 5-triazine nitramine compound 2-amino-4-nitramine-6-formyl nitramine-1, 3, 5-triazine nitrogen oxide, which has the structural formula as follows:
the invention also provides a preparation method of the 2-amino-4-nitramine-6-formazanolamine-1, 3, 5-triazine nitrogen oxide, which comprises the following steps: (1) 1,3, 5-triazino-1, 2, 4-triazoles at 25 ℃
Adding into trifluoroacetic acid, adding 50% hydrogen peroxide, reacting at the temperature, pouring into ice water for quenching, and filtering to obtain intermediate
(2) Adding the intermediate into 100 percent of HNO under the condition of low temperature3Then fully reacting at the temperature, then pouring ice water for quenching, stirring for a period of time to separate out a solid, filtering and washing to obtain a target product2-amino-4-nitramine-6-formazan-1, 3, 5-triazine nitroxide.
The further technical scheme is that the molar ratio of the 1,3, 5-triazine-1, 2, 4-triazole, 50% hydrogen peroxide and trifluoroacetic acid in the step (1) is 1 (66-166) to 13.4-53.8.
The further technical scheme is that the reaction time of the step (1) is 5-24 h.
The further technical proposal is that the intermediate in the step (2) is mixed with 100 percent of HNO3The molar ratio of (A) to (B) is 1 (48-80).
The further technical scheme is that the low temperature of the step (2) is 2 ℃.
The further technical scheme is that the reaction time of the step (2) is 2-24 h.
The further technical scheme is that the stirring time of the ice water quenching in the step (2) is 0.5-2 h.
Compared with the prior art, the invention has the following advantages:
1. the nitrogen and oxygen are successfully introduced into the triazine by a synthetic strategy of carrying out nitrogen oxidation on the 1,3, 5-triazino-1, 2, 4-triazole, then N-N bond breakage occurs, and then nitration is carried out, and meanwhile, the nitroamination structure modification is carried out on the triazine, so that a brand-new compound 2-amino-4-nitroamine-6-formylnitroamine-1, 3, 5-triazine nitrogen oxide is obtained.
2. The synthesis difficulty of simply introducing the nitramine explosion-causing group on the 1,3, 5-triazine ring is larger, and the synthesis technology of introducing coordinated oxygen on the skeleton of the 1,3, 5-triazine triazole, simultaneously performing ring opening on the triazole and then continuing nitration is favorable for realizing the target compound.
Drawings
FIG. 1 is a synthetic route of a target product 2-amino-4-nitroamine-6-formylnitroamine-1, 3, 5-triazine oxynitride of the invention;
FIG. 2 shows nuclear magnetic hydrogen spectrum of 1,3, 5-triazine oxynitride derivative as an intermediate of the present invention (1H-NMR)；
FIG. 3 shows nuclear magnetic carbon spectra of 1,3, 5-triazine oxynitride derivatives as intermediates of the present invention: (13C-NMR)；
FIG. 4 is an X-ray single crystal diffraction pattern of a target product 2-amino-4-nitroamine-6-formylnitroamine-1, 3, 5-triazine oxynitride and methanol eutectic according to the invention;
FIG. 5 shows the nuclear magnetic hydrogen spectrum of the target product 2-amino-4-nitroamine-6-formylnitroamine-1, 3, 5-triazine nitroxide of the present invention1H-NMR)；
FIG. 6 shows the nuclear magnetic carbon spectrum of the target product 2-amino-4-nitroamine-6-formylnitroamine-1, 3, 5-triazine nitroxide of the present invention13C-NMR)。
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
FIG. 1 shows a process for preparing a 1,3, 5-triazine nitramine compound of the present invention, which comprises a first step of adding 1,3, 5- triazino 1,2, 4-triazole to trifluoroacetic acid at 25 ℃ and then adding 50% hydrogen peroxide dropwise at a temperature not exceeding 40 ℃. Fully reacting at normal temperature, then pouring ice water for quenching, and filtering out an intermediate; secondly, adding the intermediate into 100 percent of HNO in low-temperature bath3Then fully reacting at a specific temperature, then pouring ice water for quenching, stirring for a period of time to separate out a solid, filtering and washing with water to obtain the target product 2-amino-4-nitramine-6-formylnitramine-1, 3, 5-triazine nitrogen oxide. Wherein in the first step, the molar ratio of 1,3, 5- triazino 1,2, 4-triazole, 50% hydrogen peroxide and trifluoroacetic acid is 1 (33.2-66.4): 13.4-53.8, and the reaction time in the first step is 5-24 h; in the second step, the molar ratio of the intermediate 1,3, 5-triazine nitrogen oxide derivative to 100% nitric acid is 1 (48-80), the reaction time is 2-24 h, and the stirring time for ice water quenching is 0.5-2 h.
Example 1
0.83g (5mmol) of 1,3, 5- triazino 1,2, 4-triazole is dissolved in 10mL (0.135mol) of trifluoroacetic acid under magnetic stirring at 25 ℃, after dissolution, 5mL (0.166mol) of 50% hydrogen peroxide is slowly added dropwise, and the adding temperature is not more than 40 ℃. Reacting at 25 deg.C for 5 hr, adding into ice water, quenching, filtering to obtain solid, washing with water, and oven drying to obtain0.39g of intermediate 1,3, 5-triazine nitrogen oxide derivative, and the yield is 42%. 0.19g (1mmol) of the above intermediate was dissolved in 2mL of 100% HNO at-5 deg.C3(48mmol), the reaction is continued for 2h after the temperature is restored to 2 ℃, then ice water is poured for quenching, the stirring is carried out for 0.5h, the precipitate is filtered out, the filter cake is washed by water and dried in vacuum, and white powder 2-amino-4-nitramine-6-formazan-1, 3, 5-triazine nitrogen oxide 53mg is obtained, and the yield is 19%.
Example 2
0.83g (5mmol) of 1,3, 5- triazino 1,2, 4-triazole is dissolved in 20mL (0.269mol) of trifluoroacetic acid at 25 ℃ with magnetic stirring, after dissolution, 5mL (0.166mol) of 50% hydrogen peroxide are slowly added dropwise, the addition temperature not exceeding 40 ℃. After the dripping is finished, the mixture reacts for 5 hours at 25 ℃, is poured into ice water for quenching, solid is filtered out, and the intermediate 1,3, 5-triazine nitrogen oxide derivative is obtained by washing and drying, wherein the yield is 30 percent, and 0.28 g. 0.19g (1mmol) of the above intermediate was dissolved in 2mL of 100% HNO at-5 deg.C3(48mmol), the reaction is continued for 2h after the temperature is restored to 2 ℃, then ice water is poured for quenching, the stirring is carried out for 0.5h, the precipitate is filtered out, the filter cake is washed by water and dried in vacuum, and white powder 2-amino-4-nitramine-6-formazan-1, 3, 5-triazine nitrogen oxide 53mg is obtained, and the yield is 19%.
Example 3
0.83g (5mmol) of 1,3, 5- triazino 1,2, 4-triazole is dissolved in 15mL (0.202mol) of trifluoroacetic acid under magnetic stirring at 25 ℃, after dissolution, 8mL (0.266mol) of 50% hydrogen peroxide is slowly added dropwise, and the adding temperature is not more than 40 ℃. After the dripping is finished, the mixture reacts for 5 hours at 25 ℃, is poured into ice water for quenching, solid is filtered out, and the intermediate 1,3, 5-triazine nitrogen oxide derivative is obtained by washing and drying, wherein the yield is 52 percent, and 0.49 g. 0.57g (3mmol) of the above intermediate was dissolved in 8mL of 100% HNO at-5 deg.C3(0.144mol), the temperature is restored to 2 ℃, the reaction is continued for 2h, then ice water is poured for quenching, the stirring is carried out for 0.5h, the precipitate is filtered out, the filter cake is washed by water and dried in vacuum, and white powder 0.16g of 2-amino-4-nitramine-6-formazanolamine-1, 3, 5-triazine nitrogen oxide is obtained, and the yield is 19 percent.
Example 4
0.83g (5mmol) of 1,3, 5- triazino 1,2, 4-triazole are dissolved in 15mL (0.202mol) of trifluoroacetic acid at 25 ℃ with magnetic stirring, and after dissolution, 10mL (0.332mol) are slowly added dropwise50% hydrogen peroxide, and the feeding temperature is not more than 40 ℃. After finishing dropping, the mixture reacts for 5 hours at 25 ℃, is poured into ice water for quenching, solid is filtered out, and the intermediate 1,3, 5-triazine nitrogen oxide derivative is obtained by washing and drying, wherein the yield is 37 percent, and 0.35 g. 0.57g (3mmol) of the above intermediate was dissolved in 10mL of 100% HNO at-5 deg.C3(0.24mol), the temperature is restored to 2 ℃, the reaction is continued for 2h, then ice water is poured for quenching, the stirring is carried out for 0.5h, the precipitate is filtered out, the filter cake is washed by water and dried in vacuum, and white powder 0.12g of 2-amino-4-nitramine-6-formacylnitramine-1, 3, 5-triazine nitrogen oxide is obtained, and the yield is 15%.
Example 5
0.83g (5mmol) of 1,3, 5- triazino 1,2, 4-triazole is dissolved in 15mL (0.202mol) of trifluoroacetic acid under magnetic stirring at 25 ℃, after dissolution, 8mL (0.266mol) of 50% hydrogen peroxide is slowly added dropwise, and the adding temperature is not more than 40 ℃. After finishing the dripping, the mixture reacts for 12 hours at 25 ℃, is poured into ice water for quenching, solid is filtered out, and the intermediate 1,3, 5-triazine nitrogen oxide derivative is obtained by washing and drying, wherein the yield is 61 percent. 0.57g (3mmol) of the above intermediate was dissolved in 8mL of 100% HNO at-5 deg.C3(0.144mol), the temperature is restored to 2 ℃, the reaction is continued for 2h, then ice water is poured for quenching, the stirring is carried out for 0.5h, the precipitate is filtered out, the filter cake is washed by water and dried in vacuum, and white powder 0.16g of 2-amino-4-nitramine-6-formazanolamine-1, 3, 5-triazine nitrogen oxide is obtained, and the yield is 19 percent.
Example 6
0.83g (5mmol) of 1,3, 5- triazino 1,2, 4-triazole is dissolved in 15mL (0.202mol) of trifluoroacetic acid under magnetic stirring at 25 ℃, after dissolution, 8mL (0.266mol) of 50% hydrogen peroxide is slowly added dropwise, and the adding temperature is not more than 40 ℃. After the dripping is finished, the mixture reacts for 24 hours at 25 ℃, is poured into ice water for quenching, and then solid is filtered out, washed and dried, thus obtaining 0.51g of the intermediate 1,3, 5-triazine nitrogen oxide derivative with the yield of 55 percent. 0.57g (3mmol) of the above intermediate was dissolved in 8mL of 100% HNO at-5 deg.C3(0.144mol), the temperature is restored to 2 ℃, the reaction is continued for 6h, then ice water is poured for quenching, the stirring is carried out for 0.5h, the precipitate is filtered out, the filter cake is washed by water and dried in vacuum, and white powder 0.26g of 2-amino-4-nitramine-6-formacylnitramine-1, 3, 5-triazine nitrogen oxide is obtained, and the yield is 32%.
Example 7
Magnetism at 25 DEG C0.83g (5mmol) of 1,3, 5- triazino 1,2, 4-triazole is dissolved in 15mL (0.202mol) of trifluoroacetic acid with vigorous stirring, after dissolution, 8mL (0.266mol) of 50% hydrogen peroxide are slowly added dropwise, the addition temperature not exceeding 40 ℃. After finishing the dripping, the mixture reacts for 12 hours at 25 ℃, is poured into ice water for quenching, solid is filtered out, and the intermediate 1,3, 5-triazine nitrogen oxide derivative is obtained by washing and drying, wherein the yield is 61 percent. 0.57g (3mmol) of the above intermediate was dissolved in 8mL of 100% HNO at-5 deg.C3(0.144mol), the temperature is restored to 2 ℃, the reaction is continued for 12h, then ice water is poured for quenching, the stirring is carried out for 0.5h, the precipitate is filtered out, the filter cake is washed by water and dried in vacuum, and white powder 0.41g of 2-amino-4-nitramine-6-formazanolamine-1, 3, 5-triazine nitrogen oxide is obtained, and the yield is 50%.
Example 8
0.83g (5mmol) of 1,3, 5- triazino 1,2, 4-triazole is dissolved in 15mL (0.202mol) of trifluoroacetic acid under magnetic stirring at 25 ℃, after dissolution, 8mL (0.266mol) of 50% hydrogen peroxide is slowly added dropwise, and the adding temperature is not more than 40 ℃. After finishing the dripping, the mixture reacts for 12 hours at 25 ℃, is poured into ice water for quenching, solid is filtered out, and the intermediate 1,3, 5-triazine nitrogen oxide derivative is obtained by washing and drying, wherein the yield is 61 percent. 0.57g (3mmol) of the above intermediate was dissolved in 8mL of 100% HNO at-5 deg.C3(0.144mol), the temperature is restored to 2 ℃, the reaction is continued for 24h, then ice water is poured for quenching, the stirring is carried out for 0.5h, the precipitate is filtered out, the filter cake is washed by water and dried in vacuum, and white powder 0.33g of 2-amino-4-nitramine-6-formazanolamine-1, 3, 5-triazine nitrogen oxide is obtained, and the yield is 40%.
Example 9
0.83g (5mmol) of 1,3, 5- triazino 1,2, 4-triazole is dissolved in 15mL (0.202mol) of trifluoroacetic acid under magnetic stirring at 25 ℃, after dissolution, 8mL (0.266mol) of 50% hydrogen peroxide is slowly added dropwise, and the adding temperature is not more than 40 ℃. After finishing the dripping, the mixture reacts for 12 hours at 25 ℃, is poured into ice water for quenching, solid is filtered out, and the intermediate 1,3, 5-triazine nitrogen oxide derivative is obtained by washing and drying, wherein the yield is 61 percent. 0.57g (3mmol) of the above intermediate was dissolved in 8mL of 100% HNO at-5 deg.C3(0.144mol), the temperature is restored to 2 ℃, the reaction is continued for 18h, then ice water is poured for quenching, the stirring is carried out for 1h, the precipitate is filtered out, the filter cake is washed by water and dried in vacuum, and white powder 2-amino-4-nitramine-6-formyl is obtainedThe yield of the nitramine-1, 3, 5-triazine nitroxide is 55 percent, and the amount of the nitramine-1, 3, 5-triazine nitroxide is 0.45 g.
Example 10
0.83g (5mmol) of 1,3, 5- triazino 1,2, 4-triazole is dissolved in 15mL (0.202mol) of trifluoroacetic acid under magnetic stirring at 25 ℃, after dissolution, 8mL (0.266mol) of 50% hydrogen peroxide is slowly added dropwise, and the adding temperature is not more than 40 ℃. After finishing the dripping, the mixture reacts for 12 hours at 25 ℃, is poured into ice water for quenching, solid is filtered out, and the intermediate 1,3, 5-triazine nitrogen oxide derivative is obtained by washing and drying, wherein the yield is 61 percent. 0.57g (3mmol) of the above intermediate was dissolved in 8mL of 100% HNO at-5 deg.C3(0.144mol), the temperature is restored to 2 ℃, the reaction is continued for 18h, then ice water is poured for quenching, the stirring is carried out for 2h, the precipitate is filtered out, the filter cake is washed by water and dried in vacuum, and white powder 0.42g of 2-amino-4-nitramine-6-formazanolamine-1, 3, 5-triazine nitrogen oxide is obtained, and the yield is 51 percent. The 1,3, 5-triazine nitramine compound 2-amino-4-nitramine-6-formyl nitramine-1, 3, 5-triazine nitrogen oxide is cultured to obtain eutectic crystal containing a target product and a molecular methanol solvent by adopting a mixed solution of methanol and acetonitrile, and the crystal size of the eutectic crystal is 0.22 multiplied by 0.15 multiplied by 0.12mm3The X-ray single crystal diffraction pattern is shown in FIG. 4. The single crystal is P21A space group of/c, monoclinic system, cell parameters of
α -90 deg., β -104.39 (2 deg.) deg., and gamma-90 deg., and has a crystal density of 1.740g/cm3. The solvent-free powder was found to have a density of 1.861g/cm3. The nuclear magnetic hydrogen spectrum of the intermediate 1,3, 5-triazine nitrogen oxide derivative is shown in figure 2,1H-NMR(DMSO-d6) δ 9.84,9.01,8.70,8.27,7.40 ppm; the nuclear magnetic carbon spectrum is shown in figure 3,13C-NMR(DMSO-d6) δ 159.16,155.55,154.29 ppm; infrared IR (KBr, cm)-1): 3363,3213,1728,1654,1579,1357,1122,1010,819,769,709,628,576, respectively; the nuclear magnetic hydrogen spectrum of the target product 2-amino-4-nitramine-6-formazanolamine-1, 3, 5-triazine nitrogen oxide is shown in figure 5;1H-NMR(DMSO-d6) δ 7.91,7.58,6.90,6.49 ppm; the nuclear magnetic carbon spectrum is shown in figure 6,13C-NMR(CD3OD-d4) δ 157.64,156.64,155.01,147.17 ppm; infrared rayIR(KBr，cm-1): 3417,3280,3045,2571,1762,1689,1608,1448,1217,1049,969,815,746,684. The calculated detonation velocity is 8736m/s, the actually measured impact sensitivity is 40J, the friction sensitivity is 288N, and the comprehensive performance is superior to that of hexogen (the detonation velocity is 8700m/s, the impact sensitivity is 7.5J, and the friction sensitivity is 120N).
Claims (8)
1. The 2-amino-4-nitramine-6-formacyl nitramine-1, 3, 5-triazine nitrogen oxide is characterized in that the structural formula is as follows:
2. the method of preparing 2-amino-4-nitroamine-6-formylnitroamine-1, 3, 5-triazine nitroxide of claim 1, comprising the steps of: (1) 1,3, 5-triazino-1, 2, 4-triazoles at 25 ℃
Adding into trifluoroacetic acid, adding 50% hydrogen peroxide, reacting at the temperature, pouring into ice water for quenching, and filtering to obtain intermediate
(2) Adding the intermediate into 100 percent of HNO under the condition of low temperature3And then fully reacting at the temperature, then pouring ice water for quenching, stirring for a period of time to separate out a solid, filtering and washing with water to obtain the target product 2-amino-4-nitramine-6-formylnitramine-1, 3, 5-triazine nitrogen oxide.
3. The method for preparing 2-amino-4-nitroamine-6-formylnitroamine-1, 3, 5-triazine oxynitride as claimed in claim 2, wherein the molar ratio of 1,3, 5-triazino-1, 2, 4-triazole, 50% hydrogen peroxide and trifluoroacetic acid in the step (1) is 1 (66-166) to (13.4-53.8).
4. The preparation method of 2-amino-4-nitroamine-6-formylnitroamine-1, 3, 5-triazine nitroxide as claimed in claim 2, wherein the reaction time in step (1) is 5-24 h.
5. The method for preparing 2-amino-4-nitroamine-6-formylnitroamine-1, 3, 5-triazine nitroxide according to claim 2, wherein the intermediate in the step (2) is reacted with 100% HNO3The molar ratio of (A) to (B) is 1 (48-80).
6. The method for preparing 2-amino-4-nitroamine-6-formylnitroamine-1, 3, 5-triazine nitroxide according to claim 2, wherein the low temperature of step (2) is 2 ℃.
7. The method for preparing 2-amino-4-nitroamine-6-formylnitroamine-1, 3, 5-triazine oxynitride as claimed in claim 2, wherein the reaction time in the step (2) is 2-24 h.
8. The preparation method of 2-amino-4-nitroamine-6-formylnitroamine-1, 3, 5-triazine oxynitride as claimed in claim 2, characterized in that the stirring time of the ice water quenching in the step (2) is 0.5-2 h.
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Non-Patent Citations (4)
| Title |
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| Amino-nitramino functionalized triazolotriazines: a good balance between high energy and low sensitivity;Jinchao Ma,等;《Dalton Transactions》;20180823;第47卷;第14483-14490页 * |
| Prediction of structures and properties of 2,4,6-triamino-1,3,5-triazine-1,3,5-trioxide (MTO) and 2,4,6-trinitro-1,3,5-triazine-1,3,5-trioxide (MTO3N) green energetic materials from DFT and ReaxFF molecular modeling;Saber Naserifar，等;《Journal of Materials Chemistry A》;20151109;第4卷;第1264-1276页 * |
| Synthesis of 5,7-Diamino[1,2,4]triazolo[1,2-a][1,3,5]triazines via Annulation of 1,3,5-Triazine Ring onto 3(5)-Amino-1,2,4-triazoles;DOLZHENKO, A. V.，等;《Heterocycles》;20071231;第429-436页 * |
| Synthesis, Characterization and Properties of Ureido-Furazan Derivatives;T. S. Hermann，等;《J. Heterocyclic Chem.》;20180217;第55卷;第852-862页 * |
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