CN104710363B - Energy-containing compound 1（2,2,2 Trinitroethyl amine）3,5 binitropyrazoles and preparation method thereof - Google Patents
Energy-containing compound 1（2,2,2 Trinitroethyl amine）3,5 binitropyrazoles and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of energy-containing compound 1 (2,2,2 Trinitroethyl amine) 3,5 binitropyrazoles and preparation method thereof.With 3,5 dinitro 1H pyrazoles are raw material, act on forming 3 with highly basic, 5 dinitro N ion salts, again with 2,4,6 trimethylbenzenesulfonyl azanols (MSH) carry out nucleophilic substitution and obtain N amino 3 in organic solvent, 5 binitropyrazoles, then carry out Mannich reaction generation target products with trinitro- ethanol in aqueous solvent.Using1HNMR、13CNMR, DSC TG are characterized to the structure and thermal property of target product.Preparation method reaction condition of the present invention is gentle, and reactions steps are few.The detonation energy of target product is higher than RDX (RDX), and specific impulse is higher than RDX and Hexanitrohexaazaisowurtzitane (CL 20), and thermal decomposition peak temperature is up to 332 DEG C, can be used as heat-resistant explosive or high energy oxidizer.
Description
Technical field
Embodiments of the present invention are related to organic chemistry filed, contain more specifically, embodiments of the present invention are related to one kind
Energy compound 1- (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles and preparation method thereof.
Background technology
The features such as nitro azole compounds are due to its generation heat height, good heat stability, in energetic material field, application is wide
It is general, it is used for the multiple fields such as military affairs, Aero-Space, the people are quick-fried frequently as high energy component.In long-term use, this kind of compound is also sudden and violent
Expose some defects, there is active hydrogen on such as 1 nitrogen.A series of problems, such as active hydrogen can bring hygroscopicity, acidity, to space flight
The metal materials such as device, body cause certain corrosion.And active hydrogen can not only be eliminated by introducing amino, while being also new nitro
The design of azole compounds is provided with synthesis may.Azole compounds are mostly short of electricity subsystem, and nitrogen amination reagent is just
Suitable for the nitrogen position amination under this system.Nitrogen amination reagent 2,4,6- trimethylbenzenesulfonyl azanols used in the present invention
(MSH) using Ma Qing et al. in energetic material, 2013,21 (1):Method described in 133-134 is made, and route is as follows：
Further the introducing high-energy unit on nitro azole molecule, is current design and high-energy synthetic metric density material containing energy
One of effective way of material.Trinitroethyl causes quick-fried group as representational high energy, its density, oxygen content and generation heat compared with
Height, but more sensitive is stimulated to machinery and electrostatic spark；And most of nitro azole compounds are to electrostatic, friction and impact sensitivity
All compare insensitiveness.Trinitroethyl is introduced into nitro azole compounds, it is intended in the sensitivity of reduction Trinitroethyl, improves nitre
The energy and density of base azole compounds, while a class formation novel single chmical compound explosive or high energy oxidizer are obtained, it is this at present
Synthetic method is without related report.Raw material 3,5- dinitro -1H- pyrazoles used in the present invention is used
J.W.A.M.Janssen et al. is in The Journal of Organic Chemistry, 1973,38 (10):1777-1782
Described in method be made, its synthetic route is as follows：
The content of the invention
It is an object of the invention to solve energetic material field nitro azole compounds to the corrosivity of metal material, containing energy
Relatively low the problem of there is provided a kind of high energy energy-containing compound 1- (2,2,2- Trinitroethyl amine) -3,5- binitropyrazoles and
Its preparation method.
To solve above-mentioned technical problem, one embodiment of the present invention uses following technical scheme：
The invention provides a kind of energy-containing compound 1- (2,2,2- Trinitroethyl amine) -3,5- binitropyrazoles, it
Structural formula is as follows：
Present invention also offers the system of above-mentioned energy-containing compound 1- (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles
Preparation Method, it comprises the following steps：
Ith, the preparation of intermediate 3,5- binitropyrazoles-N- ion salts
Under normal temperature, 3,5- dinitro -1H- pyrazoles and enough strong base reagents are reacted into 2~3h, solid is filtered out or is spin-dried for molten
Agent, obtains 3,5- binitropyrazole-N- ion salts；
IIth, the preparation of intermediate N amino -3,5- binitropyrazoles
Under the conditions of ice-water bath, intermediate prepared by step I is dissolved in appropriate organic solvent, 2,4,6- trimethyls are added
Benzene sulfonyl hydroxylamine solution, recovers to stirring at normal temperature to react 12~24h, is then spin-dried for solvent, add ethyl acetate dissolving, filter out residual
Slag, obtains yellow oil by filtrate decompression distillation, a small amount of distilled water is added to the yellow oil, separate out yellow solid,
Filter out the yellow solid i.e. N- amino -3,5- binitropyrazoles；
IIIth, the preparation of target compound
Under normal temperature, the intermediate prepared to step II adds appropriate distilled water, 1~2h is stirred at 75~85 DEG C, then
50~55 DEG C are cooled to, trinitro- ethanol is added, 24~72h is reacted at normal temperatures, then stands and separates out dark brown solid, filter out
Solid is target compound 1- (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles.
Further technical scheme is that strong base reagent described in step I is potassium hydroxide, sodium hydroxide or concentrated ammonia liquor；It is described
When strong base reagent is potassium hydroxide or sodium hydroxide, 3,5- dinitro -1H- pyrazoles are dissolved in anti-with strong base reagent again after proper amount of methanol
Should；When the strong base reagent is concentrated ammonia liquor, 3,5- dinitro -1H- pyrazoles directly react with concentrated ammonia liquor.The quality of the concentrated ammonia liquor
Concentration is 22%~25%.
Further technical scheme is, 3, the 5- dinitros -1H- pyrazoles be dissolved in after proper amount of methanol again with strong base reagent
The reaction condition of reaction is that reaction solution is heated into stirring reaction 2h after backflow；3,5- dinitros -1H- the pyrazoles directly with
The reaction condition of concentrated ammonia liquor reaction is stirring reaction 2h under normal temperature.
Further technical scheme is that 3,5- binitropyrazoles-N- ion salts described in step I are 3,5- dinitro pyridines
Azoles-N- sylvite, 3,5- binitropyrazole-N- sodium salts or 3,5- binitropyrazole-N- ammonium salts.
Further technical scheme is, organic solvent described in step II be DMF, acetonitrile or acetonitrile/
Water mixed solvent.
Further technical scheme is, in step II, intermediate and 2 prepared by the step I, 4,6- trimethylbenzenes
The mol ratio of sulphonyl azanol is 1:2.
Further technical scheme is that described 2,4,6- trimethylbenzenesulfonyl hydroxylamine solutions use DMF or dichloromethane
Prepare.
Further technical scheme is, in step III, intermediate prepared by the step II and trinitro- ethanol
Mol ratio is 1:2.
Further technical scheme is that the temperature stirred described in step III is 80 DEG C, and the time is 1h；It is warm after the cooling
Spend for 50 DEG C.
The technical scheme of optimization is that the time of step II stirring reaction is 15~20h；Step III is added after trinitro- ethanol
The normal temperature lower reaction time is 36~72h.
Compared with prior art, one of beneficial effects of the present invention are：1- (2,2,2- Trinitroethyls prepared by the present invention
Amine) -3,5- binitropyrazoles through BKW state equations predict the energy-containing compound detonation energy be higher than RDX (RDX), specific impulse
Higher than RDX and Hexanitrohexaazaisowurtzitane (CL-20), DSC-TG test results show that it thermally decomposes peak temperature and is up to 332 DEG C,
It is heat-resistant explosive and high energy oxidizer with applications well prospect to show the compound, and gained compound is to metallic material corrosion
Property is small；The preparation method of the present invention can prepare energy-containing compound 1- (2,2,2- Trinitroethyls amine) -3,5- using two-step method
Main in binitropyrazole, and preparation method to use DMF, acetonitrile, water as solvent, reaction condition is gentle, reaction
Step is few.
Brief description of the drawings
Fig. 1 is the synthetic route of target compound 1- of the present invention (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles
Realize.
Fig. 2 is the crystal structure of intermediate N amino -3,5- binitropyrazoles of the present invention.
Fig. 3 is target compound 1- of the present invention (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles1H NMR cores
Magnetic hydrogen is composed.
Fig. 4 is target compound 1- of the present invention (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles13C NMR cores
Magnetic carbon is composed.
Fig. 5 is warm for the DSC-TG of target compound 1- of the present invention (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles
Property collection of illustrative plates.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
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 synthetic route of target product 1- of the present invention (2,2,2- Trinitroethyl amine) -3,5- binitropyrazoles, first
First with 3,5- dinitro -1H- pyrazoles for raw material, acid-base neutralization reaction is carried out with strong base reagent, 3,5- binitropyrazoles-N- is obtained
Ion salt, then with 2,4,6- trimethylbenzenesulfonyl azanols carry out nucleophilic substitution and obtain N- amino -3 in organic solvent,
5- binitropyrazoles, then carry out in aqueous solvent with trinitro- ethanol Mannich reaction generation target compounds 1- (2,2,2- tri-
Nitro-ethyl amine) -3,5- binitropyrazoles.
Embodiment 1
3,5- dinitro -1H- pyrazoles (10mmol, 1.58g) is dissolved in methanol (50mL), potassium hydroxide is added
(10mmol, 0.56g), is heated to backflow, and stirring reaction 2h filters out solid, obtains 3,5- binitropyrazole-N- sylvite.Frozen water
Bath, obtained 3,5- binitropyrazole-N- sylvite is dissolved in 30mL DMFs (DMF), then by MSH
(20mmol, 4.3g) is dissolved in DMF (20mL) and is configured to solution, is slowly added dropwise into above-mentioned potassium salt soln, recovers to stirring at normal temperature
React 12h.Solvent is spin-dried for, ethyl acetate is added, white solid is separated out.Filter out, filtrate decompression is distilled, obtain yellow oily
Thing.A small amount of distilled water is added, yellow solid is separated out, filters out and obtain N- amino -3,5- binitropyrazole 1.08g, yield 62.4%.
M.p. 110 DEG C, Td:264 DEG C, MS (EI)：m/z 172.01[M-H]-。
Fig. 2 is the single crystal diffraction figure of intermediate N amino -3,5- binitropyrazole, actual measurement of its crystalline density under 298K
It is worth for 1.796g/cm3。
N- amino -3,5- binitropyrazole (1mmol, 173mg) is added in distilled water (30mL), 80 are heated under stirring
DEG C reaction 1h, is then cooled to 50 DEG C, is slowly added to trinitro- ethanol (2mmol, 362mg), react at room temperature 24h, stand, filter out
Obtain dark brown solid 1- (2,2,2- Trinitroethyl amine) -3,5- binitropyrazole 243mg, yield 72.3%.
Embodiment 2
3,5- dinitro -1H- pyrazoles (10mmol, 1.58g) is dissolved in methanol (50mL), sodium hydroxide is added
(10mmol, 0.40g), is heated to backflow, and stirring reaction 2h filters out solid, obtains 3,5- binitropyrazole-N- sodium salts.Frozen water
Bath, above-mentioned sodium salt is dissolved in DMF (30mL), MSH (20mmol, 4.3g) then is dissolved in into DMF (20mL) is configured to solution,
It is slowly added dropwise into potassium salt soln, recovers to stirring at normal temperature to react 12h.Solvent is spin-dried for, ethyl acetate is added, white is separated out solid
Body.Filter out, filtrate decompression is distilled, obtain yellow oil.A small amount of distilled water is added, yellow solid is separated out, filters out and obtain N-
Amino -3,5- binitropyrazole 1.05g, yield 60.7%.N- amino -3,5- binitropyrazoles (1mmol, 173mg) are added
In distilled water (30mL), 80 DEG C of reaction 1h are heated under stirring, 50 DEG C is then cooled to, is slowly added to trinitro- ethanol
(2mmol, 362mg), reacts at room temperature 24h, stands, filters out and obtain dark brown solid 1- (2,2,2- Trinitroethyl amine) -3,5-
Binitropyrazole 243mg, yield 72.3%.
Embodiment 3
3,5- dinitro -1H- pyrazoles (10mmol, 1.58g) is added into excessive concentrated ammonia (100mL, mass concentration 22%)
In, stirring at normal temperature reaction 2h is spin-dried for solvent, obtains 3,5- binitropyrazole-N- ammonium salts.Ice-water bath, DMF is dissolved in by ammonium salt
In (30mL), MSH (20mmol, 4.3g) is then dissolved in DMF (20mL) and is configured to solution, is slowly added dropwise into potassium salt soln,
Recover to stirring at normal temperature to react 12h.Solvent is spin-dried for, ethyl acetate is added, white solid is separated out.Filter out, filtrate decompression distilled,
Obtain yellow oil.A small amount of distilled water is added, yellow solid is separated out, filters out and obtain N- amino -3,5- binitropyrazoles
1.12g, yield 64.8%.N- amino -3,5- binitropyrazole (1mmol, 173mg) is added in distilled water (30mL), stirring
Under be heated to 80 DEG C reaction 1h, be then cooled to 50 DEG C, be slowly added to trinitro- ethanol (2mmol, 362mg), react at room temperature
24h, stands, filters out and obtain dark brown solid 1- (2,2,2- Trinitroethyl amine) -3,5- binitropyrazole 243mg, yield
72.3%.
Embodiment 4
3,5- dinitro -1H- pyrazoles (10mmol, 1.58g) is dissolved in excessive concentrated ammonia (100mL, mass concentration 22%)
In, stirring at normal temperature reaction 2h is spin-dried for solvent, obtains 3,5- binitropyrazole-N- ammonium salts.Ice-water bath, N, N- second are dissolved in by sylvite
In nitrile (100mL).Then MSH (20mmol, 4.3g) is dissolved in dichloromethane (100mL) and is configured to solution, be slowly added dropwise to ammonium
In salting liquid, recover to stirring at normal temperature to react 12h.Solvent is spin-dried for, ethyl acetate is added, white solid is separated out.Filter out, by filtrate
Vacuum distillation, obtains yellow oil.A small amount of distilled water is added, yellow solid is separated out, filters out and obtain N- amino -3,5- dinitros
Pyrazoles 1.28g, yield 73.9%.N- amino -3,5- binitropyrazole (1mmol, 173mg) is added in distilled water (30mL),
80 DEG C of reaction 1h are heated under stirring, 50 DEG C is then cooled to, is slowly added to trinitro- ethanol (2mmol, 362mg), room temperature is anti-
24h is answered, is stood, is filtered out and obtain dark brown solid 1- (2,2,2- Trinitroethyl amine) -3,5- binitropyrazole 243mg, yield
72.3%.
Embodiment 5
3,5- dinitro -1H- pyrazoles (10mmol, 1.58g) is dissolved in excessive concentrated ammonia (100mL, mass concentration 23%)
In, stirring at normal temperature reaction 2h is spin-dried for solvent, obtains 3,5- binitropyrazole-N- ammonium salts.Ice-water bath, N, N- second are dissolved in by sylvite
The in the mixed solvent of nitrile (100mL) and water (50mL).Then MSH (20mmol, 4.3g) is dissolved in into dichloromethane (100mL) to match somebody with somebody
Solution is set to, is slowly added dropwise into ammonium salt solution, recovers to stirring at normal temperature to react 12h.Solvent is spin-dried for, ethyl acetate, analysis is added
Go out white solid.Filter out, filtrate decompression is distilled, obtain yellow oil.A small amount of distilled water is added, yellow solid, filter is separated out
Go out to obtain N- amino -3,5- binitropyrazoles 1.35g, 78.0%.By N- amino -3,5- binitropyrazoles (1mmol, 173mg)
Add in distilled water (30mL), 80 DEG C of reaction 1h are heated under stirring, 50 DEG C is then cooled to, is slowly added to trinitro- ethanol
(2mmol, 362mg), reacts at room temperature 24h, stands, filters out and obtain dark brown solid 1- (2,2,2- Trinitroethyl amine) -3,5-
Binitropyrazole 243mg, yield 72.3%.
Embodiment 6
3,5- dinitro -1H- pyrazoles (10mmol, 1.58g) is dissolved in excessive concentrated ammonia (100mL, mass concentration 24%)
In, stirring at normal temperature reaction 2h is spin-dried for solvent, obtains 3,5- binitropyrazole-N- ammonium salts.Ice-water bath, N, N- second are dissolved in by sylvite
The in the mixed solvent of nitrile (100mL) and water (50mL).Then MSH (20mmol, 4.3g) is dissolved in into dichloromethane (100mL) to match somebody with somebody
Solution is set to, is slowly added dropwise into ammonium salt solution, recovers to stirring at normal temperature to react 20h.Solvent is spin-dried for, ethyl acetate, analysis is added
Go out white solid.Filter out, filtrate decompression is distilled, obtain yellow oil.A small amount of distilled water is added, yellow solid, filter is separated out
Go out to obtain N- amino -3,5- binitropyrazoles 1.42g, 82.1%.By N- amino -3,5- binitropyrazoles (1mmol, 173mg)
Add in distilled water (30mL), 80 DEG C of reaction 1h are heated under stirring, 50 DEG C is then cooled to, is slowly added to trinitro- ethanol
(2mmol, 362mg), reacts at room temperature 24h, stands, filters out and obtain dark brown solid 1- (2,2,2- Trinitroethyl amine) -3,5-
Binitropyrazole 243mg, yield 72.3%.
Embodiment 7
3,5- dinitro -1H- pyrazoles (10mmol, 1.58g) is dissolved in excessive concentrated ammonia (100mL, mass concentration 25%)
In, stirring at normal temperature reaction 2h is spin-dried for solvent, obtains 3,5- binitropyrazole-N- ammonium salts.Ice-water bath, N, N- second are dissolved in by sylvite
The in the mixed solvent of nitrile (100mL) and water (50mL).Then MSH (20mmol, 4.3g) is dissolved in into dichloromethane (100mL) to match somebody with somebody
Solution is set to, is slowly added dropwise into ammonium salt solution, recovers to stirring at normal temperature to react 24h.Solvent is spin-dried for, ethyl acetate, analysis is added
Go out white solid.Filter out, filtrate decompression is distilled, obtain yellow oil.A small amount of distilled water is added, yellow solid, filter is separated out
Go out to obtain N- amino -3,5- binitropyrazole 1.39g, yield 80.3%.By N- amino -3,5- binitropyrazoles (1mmol,
173mg) add in distilled water (30mL), 80 DEG C of reaction 1h are heated under stirring, 50 DEG C is then cooled to, is slowly added to trinitro-
Ethanol (2mmol, 362mg), react at room temperature 24h, stand, filter out obtain dark brown solid 1- (2,2,2- Trinitroethyl amine)-
3,5- binitropyrazole 243mg, yield 72.3%.
Embodiment 8
3,5- dinitro -1H- pyrazoles (10mmol, 1.58g) is dissolved in excessive concentrated ammonia (100mL, mass concentration 25%)
In, stirring at normal temperature reaction 2h is spin-dried for solvent, obtains 3,5- binitropyrazole-N- ammonium salts.Ice-water bath, N, N- second are dissolved in by sylvite
The in the mixed solvent of nitrile (100mL) and water (50mL).Then MSH (20mmol, 4.3g) is dissolved in into dichloromethane (100mL) to match somebody with somebody
Solution is set to, is slowly added dropwise into ammonium salt solution, recovers to stirring at normal temperature to react 20h.Solvent is spin-dried for, ethyl acetate, analysis is added
Go out white solid.Filter out, filtrate decompression is distilled, obtain yellow oil.A small amount of distilled water is added, yellow solid, filter is separated out
Go out to obtain N- amino -3,5- binitropyrazoles.N- amino -3,5- binitropyrazoles (1mmol, 173mg) are added into distilled water
In (30mL), be heated under stirring 80 DEG C reaction 1h, be then cooled to 50 DEG C, be slowly added to trinitro- ethanol (2mmol,
362mg), 36h is reacted at room temperature, is stood, is filtered out and obtain dark brown solid 1- (2,2,2- Trinitroethyl amine) -3,5- dinitro pyridines
Azoles 257mg, yield 76.5%.
Embodiment 9
3,5- dinitro -1H- pyrazoles (10mmol, 1.58g) is dissolved in excessive concentrated ammonia (100mL, mass concentration 25%)
In, stirring at normal temperature reaction 2h is spin-dried for solvent, obtains 3,5- binitropyrazole-N- ammonium salts.Ice-water bath, N, N- second are dissolved in by sylvite
The in the mixed solvent of nitrile (100mL) and water (50mL).Then MSH (20mmol, 4.3g) is dissolved in into dichloromethane (100mL) to match somebody with somebody
Solution is set to, is slowly added dropwise into ammonium salt solution, recovers to stirring at normal temperature to react 20h.Solvent is spin-dried for, ethyl acetate, analysis is added
Go out white solid.Filter out, filtrate decompression is distilled, obtain yellow oil.A small amount of distilled water is added, yellow solid, filter is separated out
Go out to obtain N- amino -3,5- binitropyrazoles.N- amino -3,5- binitropyrazoles (1mmol, 173mg) are added into distilled water
In (30mL), be heated under stirring 80 DEG C reaction 1h, be then cooled to 50 DEG C, be slowly added to trinitro- ethanol (2mmol,
362mg), 72h is reacted at room temperature, is stood, is filtered out and obtain dark brown solid 1- (2,2,2- Trinitroethyl amine) -3,5- dinitro pyridines
Azoles 255mg, yield 75.9%.
1- (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles1H NMR nucleus magnetic hydrogen spectrums are as shown in Figure 3： [D6]
DMSO, δ=8.16 (s ,-CH-, 1H) ppm, 4.96 (s ,-NH-, 1H) ppm, 4.65 (s ,-CH2-,1H) ppm。
1- (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles13C NMR nuclear-magnetism carbons spectrum is as shown in Figure 4： [D6]
DMSO, δ=150.16 (s, C-NO2,1C)ppm,145.32(s,C-NO2,1C)ppm,101.99(s, C-(NO2)3,1C)ppm,
82.57 (s ,-C=, 1C) ppm, 68.68 (s ,-CH2-,1C)ppm。
Differential thermal analysis-thermal weight loss scanning spectra such as Fig. 5 institutes of 1- (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles
Show：DSC curve display thermal decomposition peak temperature (Td) it is 332 DEG C；TG curves show that thermal weight loss is broadly divided into two stages, first stage
Temperature range is 50~205 DEG C, thermogravimetric 40%；Second stage temperature range is 205~340 DEG C, weightlessness 30%.
Elementary analysis C5H4N8O10(336.13) calculated value：C,17.8；H,1.2；N,33.3；Measured value：C, 17.6；H,
1.2；N,32.6.IR (KBr, cm-1)：3358,3260,3094,3027,1556,1542,1538,1310,1233,977,839,
792,572,419.MS(EI)：m/z 336[M+H]+。
Energy-containing compound 1- (the 2,2,2- Trinitroethyls of the gained of above-described embodiment 1~9 are predicted based on BKW state equations
Amine) -3,5- binitropyrazoles detonation property theoretical value：Explosion velocity is 8987m/s, and detonation pressure is that 36.13GPa RDX explosion velocity is
8500m/s, detonation pressure is 32GPa), show that its detonation energy can be higher than RDX (RDX)；1- (2,2,2- Trinitroethyls amine)-
The specific impulse theoretical value 282.3s (RDX is 258s, and CL-20 is 272s) of 3,5- binitropyrazoles, shows itself or a kind of high energy
Oxidant.
Although reference be made herein to invention has been described for multiple explanatory embodiments of the invention, however, it is to be understood that
Those skilled in the art can be designed that a lot of other modification and embodiment, and these modifications and embodiment will fall in this Shen
Please be within disclosed spirit and spirit.More specifically, can be to theme group in the range of disclosure and accompanying drawing
The building block and/or layout for closing layout carry out a variety of variations and modifications.Except the modification carried out to building block and/or layout
Outer with improving, to those skilled in the art, other purposes also will be apparent.
Claims (6)
1. a kind of preparation method of energy-containing compound 1- (2,2,2- Trinitroethyl amine) -3,5- binitropyrazoles, its feature exists
Comprise the following steps in it：
Ith, the preparation of intermediate 3,5- binitropyrazoles-N- ion salts
3,5- dinitro -1H- pyrazoles and enough strong base reagents are reacted into 2~3h, solid is filtered out or is spin-dried for solvent, obtain 3,5- bis-
Nitropyrazole-N- ion salts；
IIth, the preparation of intermediate N amino -3,5- binitropyrazoles
Under the conditions of ice-water bath, intermediate prepared by step I is dissolved in appropriate organic solvent, 2,4,6- trimethylbenzenesulfonyls are added
Hydroxylamine solution, recovers to stirring at normal temperature to react 12~24h, is then spin-dried for solvent, add ethyl acetate dissolving, filter out residue, will
Filtrate decompression distillation obtains yellow oil, and a small amount of distilled water is added to the yellow oil, separates out yellow solid, filters out institute
State yellow solid i.e. N- amino -3,5- binitropyrazoles；Intermediate prepared by the step I and 2,4,6- trimethylbenzenesulfonyl hydroxyls
The mol ratio of amine is 1:2；The organic solvent is acetonitrile/water mixed solvent；
IIIth, the preparation of target compound
Under normal temperature, the intermediate prepared to step II adds appropriate distilled water, and 1~2h is stirred at 75~85 DEG C, is then cooled
To 50~55 DEG C, trinitro- ethanol is added, 24~72h is reacted at normal temperatures, then stands and separates out dark brown solid, filter out solid
As target compound 1- (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles；Intermediate prepared by the step II with
The mol ratio of trinitro- ethanol is 1:2.
2. the system of energy-containing compound 1- (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles according to claim 1
Preparation Method, it is characterised in that strong base reagent described in step I is potassium hydroxide, sodium hydroxide or concentrated ammonia liquor；The strong base reagent is
When potassium hydroxide or sodium hydroxide, 3,5- dinitro -1H- pyrazoles are dissolved in after proper amount of methanol to react with strong base reagent again；It is described strong
When base reagent is concentrated ammonia liquor, 3,5- dinitro -1H- pyrazoles directly react with concentrated ammonia liquor.
3. the system of energy-containing compound 1- (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles according to claim 2
Preparation Method, it is characterised in that 3, the 5- dinitros -1H- pyrazoles is dissolved in the reaction bar reacted again with strong base reagent after proper amount of methanol
Part is that reaction solution is heated into stirring reaction 2h after backflow；It is anti-that the 3,5- dinitros -1H- pyrazoles directly reacts with concentrated ammonia liquor
It is stirring reaction 2h under normal temperature to answer condition.
4. the system of energy-containing compound 1- (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles according to claim 1
Preparation Method, it is characterised in that 3,5- binitropyrazoles-N- ion salts described in step I are 3,5- binitropyrazole-N- sylvite, 3,5-
Binitropyrazole-N- sodium salts or 3,5- binitropyrazole-N- ammonium salts.
5. the system of energy-containing compound 1- (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles according to claim 1
Preparation Method, it is characterised in that described 2,4,6- trimethylbenzenesulfonyl hydroxylamine solutions are prepared using DMF or dichloromethane.
6. the system of energy-containing compound 1- (2,2,2- Trinitroethyls amine) -3,5- binitropyrazoles according to claim 1
Preparation Method, it is characterised in that the temperature stirred described in step III is 80 DEG C, and the time is 1h；Temperature is 50 DEG C after the cooling.
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