CN109020910A - 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide and preparation method thereof - Google Patents
2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide and preparation method thereof Download PDFInfo
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- CN109020910A CN109020910A CN201811150753.5A CN201811150753A CN109020910A CN 109020910 A CN109020910 A CN 109020910A CN 201811150753 A CN201811150753 A CN 201811150753A CN 109020910 A CN109020910 A CN 109020910A
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- Prior art keywords
- nitramine
- formyl
- amino
- triazinyl
- triazines
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- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 title claims abstract description 75
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 title claims abstract description 75
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000005457 ice water Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 150000000178 1,2,4-triazoles Chemical class 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 125000003363 1,3,5-triazinyl group Chemical class N1=C(N=CN=C1)* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 5
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 150000000182 1,3,5-triazines Chemical class 0.000 description 22
- 230000003647 oxidation Effects 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 11
- 229910017604 nitric acid Inorganic materials 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 206010001497 Agitation Diseases 0.000 description 10
- 238000013019 agitation Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 10
- 230000001376 precipitating effect Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000001228 spectrum Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 5
- 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 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
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- LDTMNNREQORPQM-UHFFFAOYSA-N [N].N1=CN=CN=C1 Chemical compound [N].N1=CN=CN=C1 LDTMNNREQORPQM-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- HTJMXYRLEDBSLT-UHFFFAOYSA-N 1,2,4,5-tetrazine Chemical compound C1=NN=CN=N1 HTJMXYRLEDBSLT-UHFFFAOYSA-N 0.000 description 1
- -1 1,3,5-triazines nitrogen oxides Chemical class 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
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical group [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000005259 measurement 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Catalysts (AREA)
Abstract
The invention discloses 2- amino -4- nitramine -6- formyl nitramines -1,3,5- triazinyl nitroxide and preparation method thereof, comprising the following steps: (1) by 1,3 at 25 DEG C, 5- triazine and 1,2,4- triazoles are added in trifluoroacetic acid, and 50% hydrogen peroxide is then added and is sufficiently reacted at this temperature, it is then poured into ice water to be quenched, intermediate is obtained by filtration；(2) under cryogenic, 100%HNO is added in intermediate3, then sufficiently reaction at such a temperature, is then poured into ice water and is quenched, and solid is precipitated after stirring a period of time, filtering, washing obtain target product.Preparation method of the invention helps to obtain monocycle class triazine high energy material 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide.
Description
Technical field
The present invention relates to energetic material technical fields, and in particular to a kind of 2- amino -4- nitramine -6- formyl nitramine -1,3,
5- triazinyl nitroxide and preparation method thereof.
Background technique
In the aromatic heterocycle skeleton of hexatomic ring, the nitrogen content of 1,3,5-triazines is up to 51%, is only second to 1,2,4,
5- tetrazine (68%), triazine are that the compound of base has many advantages, such as high density, the high positive enthalpy of formation and good thermal stability, are usually used in
Construct industrial chemicals (melamine), gas-forming agent, solid propellant, pyrotechnic compound, priming (azido triazine) etc..Triazine
The ring strain of ring is small, has good stability, and there are three modifiable sites for tool, can react with nucleopilic reagent, introducing azido,
Nitro, nitramine base, azo bond and hydrazine key and other five-ring heterocycles structures, but nitrogen oxygen groups are introduced on 1,3,5-triazines
Difficulty is but very big.
Summary of the invention
The purpose of the present invention is to provide a kind of 1,3,5- triazine nitroamino-compound 2- amino -4- nitramine -6- formyl nitramines -
After carrying out nitrogen oxidation by 1,3,5-triazines and 1,2,4- triazoles N-N occurs for 1,3,5-triazines nitrogen oxides and preparation method thereof
Key fracture, then the synthetic strategy nitrified, success introduces nitrogen oxygen in triazine, while also repairing to its structure for carrying out nitramine
Decorations, obtain completely new compound 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides.
In order to reach above-mentioned technical effect, the present invention provides a kind of 1,3,5-triazines nitroamino-compound 2- amino -4- nitre
The structural formula of amine -6- formyl nitramine -1,3,5- triazinyl nitroxide are as follows:
The present invention also provides a kind of preparation sides of 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide
Method, comprising the following steps: (1) simultaneously 1,2,4- triazoles are added in trifluoroacetic acid by 1,3,5-triazines at 25 DEG C, are then added
50% hydrogen peroxide is sufficiently reacted at this temperature, is then poured into ice water and is quenched, intermediate is obtained by filtration；(2) in low temperature item
Under part, 100%HNO is added in intermediate3, then sufficiently reaction at such a temperature, is then poured into ice water and is quenched, when stirring one section
Between after be precipitated solid, filtering, washing, obtain target product 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxidation
Object.
Further technical solution is, 1,3,5-triazines and 1,2,4- triazoles in the step (1), 50% hydrogen peroxide and
The molar ratio range of trifluoroacetic acid is 1:(66~166): (13.4~53.8).
Further technical solution is, the reaction time of the step (1) is 5~for 24 hours.
Further technical solution is intermediate and 100%HNO in the step (2)3Molar ratio be 1:(48~
80)。
Further technical solution is that the low temperature of the step (2) is 2 DEG C.
Further technical solution is, the reaction time of the step (2) is 2~for 24 hours.
Further technical solution is 0.5~2h of mixing time that the ice water of the step (2) is quenched.
Compared with prior art, the invention has the following advantages that
1, the fracture of N-N key, then the conjunction nitrified occurs after carrying out nitrogen oxidation by 1,3,5-triazines and 1,2,4- triazoles
At strategy, success introduces nitrogen oxygen in triazine, while the structural modification of nitramine is also carried out to it, obtains completely new compound
2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide.
2, nitramine is introduced on 1,3,5-triazines ring merely causes the synthesis difficulty of quick-fried group larger, the present invention by 1,3,
The synthetic technology for introducing coordination oxygen on the skeleton of 5- triazine and triazole, carrying out open loop in triazole simultaneously, being then further continued for nitrification
Be conducive to target compound of the invention to realize.
Detailed description of the invention
Fig. 1 is the synthesis of target product 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide of the present invention
Route；
Fig. 2 be intermediate 1,3,5- triazine nitrogen oxidation derivative of the present invention nucleus magnetic hydrogen spectrum (1H-NMR)；
Fig. 3 be intermediate 1,3,5- triazine nitrogen oxidation derivative of the present invention nuclear-magnetism carbon compose (13C-NMR)；
Fig. 4 is target product 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide of the present invention and methanol
The X-ray single crystal diffraction figure of eutectic；
Fig. 5 is the nuclear-magnetism of target product 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide of the present invention
Hydrogen spectrum (1H-NMR)；
Fig. 6 is the nuclear-magnetism of target product 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide of the present invention
Carbon spectrum (13C-NMR)。
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Fig. 1 is the preparation method of 1,3,5-triazines nitroamino-compound of the present invention, the first step, 25 DEG C by 1,3,5-triazines and 1,
2,4- triazoles are added in trifluoroacetic acid, and 50% hydrogen peroxide is then added dropwise, and charge temperature is no more than 40 DEG C.It is filled at normal temperature
Divide reaction, is then poured into ice water and is quenched, filter out intermediate；Under low temperature bath 100%HNO is added in intermediate by second step3, with
Sufficiently reaction at a certain temperature afterwards, is then poured into ice water and is quenched, and solid is precipitated after stirring a period of time, filtering, washing obtain
Target product 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide.Wherein, in the first step, 1,3,5-triazines
And 1, the molar ratio range of 2,4- triazoles, 50% hydrogen peroxide and trifluoroacetic acid is 1:(33.2~66.4): (13.4~53.8),
The reaction time of the first step be 5~for 24 hours,；In second step, intermediate 1,3,5-triazines nitrogen oxidation derivative and 100% nitric acid
Molar ratio be 1:(48~80), the reaction time be 2~for 24 hours, 0.5~2h of mixing time that ice water is quenched.
Embodiment 1
Under 25 DEG C of magnetic agitations, by the 1,3,5-triazines of 0.83g (5mmol) and 1,2,4- triazoles are dissolved in 10mL
In the trifluoroacetic acid of (0.135mol), after to be dissolved, 50% hydrogen peroxide of 5mL (0.166mol) is slowly added dropwise, charge temperature does not surpass
Cross 40 DEG C.Drop finishes in 25 DEG C of reaction 5h, pours into ice water and is quenched, and filters out solid, and washing, drying obtain intermediate 1,3,5- tri-
Piperazine nitrogen oxidation derivative 0.39g, yield 42%.At -5 DEG C, above-mentioned intermediate 0.19g (1mmol) is dissolved in 2mL 100%HNO3
(48mmol) restores to 2 DEG C of the reaction was continued 2h, is then poured into ice water and is quenched, stir 0.5h, filters out precipitating, filter cake is washed with water,
White powder 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides 53mg, yield are obtained after vacuum drying
19%.
Embodiment 2
Under 25 DEG C of magnetic agitations, by the 1,3,5-triazines of 0.83g (5mmol) and 1,2,4- triazoles are dissolved in 20mL
In the trifluoroacetic acid of (0.269mol), after to be dissolved, 50% hydrogen peroxide of 5mL (0.166mol) is slowly added dropwise, charge temperature does not surpass
Cross 40 DEG C.Drop finishes in 25 DEG C of reaction 5h, pours into ice water and is quenched, and filters out solid, and washing, drying obtain intermediate 1,3,5- tri-
Piperazine nitrogen oxidation derivative 0.28g, yield 30%.At -5 DEG C, above-mentioned intermediate 0.19g (1mmol) is dissolved in 2mL 100%HNO3
(48mmol) restores to 2 DEG C of the reaction was continued 2h, is then poured into ice water and is quenched, stir 0.5h, filters out precipitating, filter cake is washed with water,
White powder 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides 53mg, yield are obtained after vacuum drying
19%.
Embodiment 3
Under 25 DEG C of magnetic agitations, by the 1,3,5-triazines of 0.83g (5mmol) and 1,2,4- triazoles are dissolved in 15mL
In the trifluoroacetic acid of (0.202mol), after to be dissolved, 50% hydrogen peroxide of 8mL (0.266mol) is slowly added dropwise, charge temperature does not surpass
Cross 40 DEG C.Drop finishes in 25 DEG C of reaction 5h, pours into ice water and is quenched, and filters out solid, and washing, drying obtain intermediate 1,3,5- tri-
Piperazine nitrogen oxidation derivative 0.49g, yield 52%.At -5 DEG C, above-mentioned intermediate 0.57g (3mmol) is dissolved in 8mL 100%HNO3
(0.144mol) restores to 2 DEG C of the reaction was continued 2h, is then poured into ice water and is quenched, stir 0.5h, filter out precipitating, filter cake is washed with water
Wash, be dried in vacuo after obtain white powder 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides 0.16g, obtain
Rate 19%.
Embodiment 4
Under 25 DEG C of magnetic agitations, by the 1,3,5-triazines of 0.83g (5mmol) and 1,2,4- triazoles are dissolved in 15mL
In the trifluoroacetic acid of (0.202mol), after to be dissolved, 50% hydrogen peroxide of 10mL (0.332mol) is slowly added dropwise, charge temperature does not surpass
Cross 40 DEG C.Drop finishes in 25 DEG C of reaction 5h, pours into ice water and is quenched, and filters out solid, and washing, drying obtain intermediate 1,3,5- tri-
Piperazine nitrogen oxidation derivative 0.35g, yield 37%.At -5 DEG C, above-mentioned intermediate 0.57g (3mmol) is dissolved in 10mL 100%
HNO3(0.24mol) restores to 2 DEG C of the reaction was continued 2h, is then poured into ice water and is quenched, stir 0.5h, filter out precipitating, filter cake water
White powder 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides 0.12g is obtained after washing, vacuum drying,
Yield 15%.
Embodiment 5
Under 25 DEG C of magnetic agitations, by the 1,3,5-triazines of 0.83g (5mmol) and 1,2,4- triazoles are dissolved in 15mL
In the trifluoroacetic acid of (0.202mol), after to be dissolved, 50% hydrogen peroxide of 8mL (0.266mol) is slowly added dropwise, charge temperature does not surpass
Cross 40 DEG C.Drop finishes in 25 DEG C of reaction 12h, pours into ice water and is quenched, and filters out solid, and washing, drying obtain intermediate 1,3,5- tri-
Piperazine nitrogen oxidation derivative 0.57g, yield 61%.At -5 DEG C, above-mentioned intermediate 0.57g (3mmol) is dissolved in 8mL 100%HNO3
(0.144mol) restores to 2 DEG C of the reaction was continued 2h, is then poured into ice water and is quenched, stir 0.5h, filter out precipitating, filter cake is washed with water
Wash, be dried in vacuo after obtain white powder 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides 0.16g, obtain
Rate 19%.
Embodiment 6
Under 25 DEG C of magnetic agitations, by the 1,3,5-triazines of 0.83g (5mmol) and 1,2,4- triazoles are dissolved in 15mL
In the trifluoroacetic acid of (0.202mol), after to be dissolved, 50% hydrogen peroxide of 8mL (0.266mol) is slowly added dropwise, charge temperature does not surpass
Cross 40 DEG C.Drop finishes reacts for 24 hours at 25 DEG C, pours into ice water and is quenched, and filters out solid, and washing, drying obtain intermediate 1,3,5- tri-
Piperazine nitrogen oxidation derivative 0.51g, yield 55%.At -5 DEG C, above-mentioned intermediate 0.57g (3mmol) is dissolved in 8mL 100%HNO3
(0.144mol) restores to 2 DEG C of the reaction was continued 6h, is then poured into ice water and is quenched, stir 0.5h, filter out precipitating, filter cake is washed with water
Wash, be dried in vacuo after obtain white powder 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides 0.26g, obtain
Rate 32%.
Embodiment 7
Under 25 DEG C of magnetic agitations, by the 1,3,5-triazines of 0.83g (5mmol) and 1,2,4- triazoles are dissolved in 15mL
In the trifluoroacetic acid of (0.202mol), after to be dissolved, 50% hydrogen peroxide of 8mL (0.266mol) is slowly added dropwise, charge temperature does not surpass
Cross 40 DEG C.Drop finishes in 25 DEG C of reaction 12h, pours into ice water and is quenched, and filters out solid, and washing, drying obtain intermediate 1,3,5- tri-
Piperazine nitrogen oxidation derivative 0.57g, yield 61%.At -5 DEG C, above-mentioned intermediate 0.57g (3mmol) is dissolved in 8mL 100%HNO3
(0.144mol) restores to 2 DEG C of the reaction was continued 12h, is then poured into ice water and is quenched, stir 0.5h, filter out precipitating, filter cake is washed with water
Wash, be dried in vacuo after obtain white powder 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides 0.41g, obtain
Rate 50%.
Embodiment 8
Under 25 DEG C of magnetic agitations, by the 1,3,5-triazines of 0.83g (5mmol) and 1,2,4- triazoles are dissolved in 15mL
In the trifluoroacetic acid of (0.202mol), after to be dissolved, 50% hydrogen peroxide of 8mL (0.266mol) is slowly added dropwise, charge temperature does not surpass
Cross 40 DEG C.Drop finishes in 25 DEG C of reaction 12h, pours into ice water and is quenched, and filters out solid, and washing, drying obtain intermediate 1,3,5- tri-
Piperazine nitrogen oxidation derivative 0.57g, yield 61%.At -5 DEG C, above-mentioned intermediate 0.57g (3mmol) is dissolved in 8mL 100%HNO3
(0.144mol), restore to 2 DEG C the reaction was continued for 24 hours, be then poured into ice water and be quenched, stir 0.5h, filter out precipitating, filter cake is washed with water
Wash, be dried in vacuo after obtain white powder 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides 0.33g, obtain
Rate 40%.
Embodiment 9
Under 25 DEG C of magnetic agitations, by the 1,3,5-triazines of 0.83g (5mmol) and 1,2,4- triazoles are dissolved in 15mL
In the trifluoroacetic acid of (0.202mol), after to be dissolved, 50% hydrogen peroxide of 8mL (0.266mol) is slowly added dropwise, charge temperature does not surpass
Cross 40 DEG C.Drop finishes in 25 DEG C of reaction 12h, pours into ice water and is quenched, and filters out solid, and washing, drying obtain intermediate 1,3,5- tri-
Piperazine nitrogen oxidation derivative 0.57g, yield 61%.At -5 DEG C, above-mentioned intermediate 0.57g (3mmol) is dissolved in 8mL 100%HNO3
(0.144mol) restores to 2 DEG C of the reaction was continued 18h, is then poured into ice water and is quenched, stir 1h, filter out precipitating, filter cake is washed with water
Wash, be dried in vacuo after obtain white powder 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides 0.45g, obtain
Rate 55%.
Embodiment 10
Under 25 DEG C of magnetic agitations, by the 1,3,5-triazines of 0.83g (5mmol) and 1,2,4- triazoles are dissolved in 15mL
In the trifluoroacetic acid of (0.202mol), after to be dissolved, 50% hydrogen peroxide of 8mL (0.266mol) is slowly added dropwise, charge temperature does not surpass
Cross 40 DEG C.Drop finishes in 25 DEG C of reaction 12h, pours into ice water and is quenched, and filters out solid, and washing, drying obtain intermediate 1,3,5- tri-
Piperazine nitrogen oxidation derivative 0.57g, yield 61%.At -5 DEG C, above-mentioned intermediate 0.57g (3mmol) is dissolved in 8mL 100%HNO3
(0.144mol) restores to 2 DEG C of the reaction was continued 18h, is then poured into ice water and is quenched, stir 2h, filter out precipitating, filter cake is washed with water
Wash, be dried in vacuo after obtain white powder 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides 0.42g, obtain
Rate 51%.
1,3,5- triazine nitroamino-compound 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide of the present invention
Eutectic containing target product and a molecule methanol solvate is turned out using the mixed solution of methanol and acetonitrile, crystalline size is
0.22×0.15×0.12mm3, X-ray single crystal diffraction map is as shown in Figure 2.The monocrystalline is P21/ c space group, monoclinic system,
Cell parameter isα=90 °, β=104.39 (2) °, γ
=90 °；The crystalline density of its methanol eutectic is 1.740g/cm3.Surveying solvent-free powder density is 1.861g/cm3.Intermediate
The nucleus magnetic hydrogen spectrum of 1,3,5-triazines nitrogen oxidation derivative as shown in Fig. 2,1H-NMR(DMSO-d6): δ=9.84,9.01,8.70,
8.27,7.40ppm；Nuclear-magnetism carbon spectrum as shown in figure 3,13C-NMR(DMSO-d6): δ=159.16,155.55,154.29ppm；It is red
Outer IR (KBr, cm-1): 3363,3213,1728,1654,1579,1357,1122,1010,819,769,709,628,576；Mesh
The nucleus magnetic hydrogen spectrum for marking product 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide is as shown in Figure 5；1H-NMR
(DMSO-d6): δ=7.91,7.58,6.90,6.49ppm；Nuclear-magnetism carbon spectrum as shown in fig. 6,13C-NMR(CD3OD-d4): δ=
157.64,156.64,155.01,147.17ppm；Infrared IR (KBr, cm-1): 3417,3280,3045,2571,1762,1689,
1608,1448,1217,1049,969,815,746,684.It is 8736m/s that it, which calculates explosion velocity, and actual measurement impact sensitivity is 40J, is rubbed
Rubbing feeling degree 288N, comprehensive performance are better than hexogen (explosion velocity 8700m/s, impact sensitivity 7.5J, friction sensitivity 120N).
Claims (8)
1. a kind of 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides, which is characterized in that its structural formula is such as
Under:
2. a kind of preparation method of 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides, which is characterized in that packet
Include following steps: (1) by 1,3,5-triazines, simultaneously 1,2,4- triazoles are added in trifluoroacetic acid at 25 DEG C, are then added 50% pair
Oxygen water is sufficiently reacted at this temperature, is then poured into ice water and is quenched, intermediate is obtained by filtration；(2) under cryogenic, will
100%HNO is added in intermediate3, then sufficiently reaction at such a temperature, is then poured into ice water and is quenched, analyse after stirring a period of time
Solid out, filtering, washing, obtains target product 2- amino -4- nitramine -6- formyl nitramine -1,3,5-triazines nitrogen oxides.
3. the preparation side of 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide according to claim 2
Method, which is characterized in that 1,3,5-triazines and mole of 1,2,4- triazoles, 50% hydrogen peroxide and trifluoroacetic acid in the step (1)
It is 1:(66~166 than range): (13.4~53.8).
4. the preparation side of 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide according to claim 2
Method, which is characterized in that the reaction time of the step (1) be 5~for 24 hours.
5. the preparation side of 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide according to claim 2
Method, which is characterized in that intermediate and 100%HNO in the step (2)3Molar ratio be 1:(48~80).
6. the preparation side of 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide according to claim 2
Method, which is characterized in that the low temperature of the step (2) is 2 DEG C.
7. the preparation side of 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide according to claim 2
Method, which is characterized in that the reaction time of the step (2) be 2~for 24 hours.
8. the preparation side of 2- amino -4- nitramine -6- formyl nitramine -1,3,5- triazinyl nitroxide according to claim 2
Method, which is characterized in that 0.5~2h of mixing time that the ice water of the step (2) is quenched.
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