CN109020906A - A kind of energy-containing compound and its synthetic method and application - Google Patents
A kind of energy-containing compound and its synthetic method and application Download PDFInfo
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- CN109020906A CN109020906A CN201810615806.XA CN201810615806A CN109020906A CN 109020906 A CN109020906 A CN 109020906A CN 201810615806 A CN201810615806 A CN 201810615806A CN 109020906 A CN109020906 A CN 109020906A
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- 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
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/14—Nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
Abstract
The invention discloses a kind of 5- (nitro bromine methylene diazanyl) -3- nitros -1,2, and 4- triazole compounds, for structural formula as shown in<I>, density is up to 2.2g/cm3, generating heat is 412.6kJ/mol, and calculating explosion velocity is 9112m/s, and detonation pressure 39.2GPa, present invention is mainly used for energetic material fields.
Description
Technical field
The invention belongs to energetic material technical fields, and in particular to a kind of 5- (nitro bromine methylene diazanyl) -3- nitro -
1,2,4- triazole compounds and its synthetic method and application.
Background technique
Energetic material is indispensable one of the material of weapon system, is that conventional-weapons system realizes the energy efficiently injured
Loading gage body and weapon are remotely delivered and the power producer of firearms transmitting.Wherein, energy-containing compound is core component, closely
Nian Laifu nitrogen energy-containing compound has developed into one of the research hotspot in energy-containing compound field.Rich nitrogen energy-containing compound is usually
Refer to the energy-containing compound based on skeletons such as rich azacyclo- such as three (four) azoles, furazan, three (four) piperazines, contains a large amount of N- in molecule
N, N=N, C-N, C=N key make entire molecule have the high positive enthalpy of formation, are the main sources of chemical energy.In addition, rich nitrogen contains
The low-carbon hydrogen of energy compound, high nitrogen-containing characteristic make it easily reach oxygen balance, and its decomposition product is mainly nitrogen, this makes
They become the candidate of environmentally friendly energetic material application.The energy-containing compound of the skeleton containing nitro-triazole has highly dense
Degree, the features such as thermal stability is good, sensitivity is low, by the concern of energetic material worker.
Currently, the comprehensive performance of the energy-containing compound of the skeleton containing nitro-triazole is not yet completely fully up to expectations, have higher quick-fried
The compound of speed and detonation pressure, which is commonly present, generates the lower situation of heat, public in such as Eur.J.Inorg.Chem.2012,3474-3484
Bis- (1,2,4- triazole) compounds of the 5,5 ' of the cloth -3- of dinitro -3 '；It is higher but quick-fried then to there is generation heat in other compounds
It presses, the problem that explosion velocity and density are lower.
In general, generating the energy-containing compound that heat reaches the skeleton containing nitro-triazole of 400kJ/mol, explosion velocity is more difficult
More than 9000m/s, detonation pressure is only 35GPa or so, and single crystal density is more difficult more than 2.0g cm-3。
In conclusion this field need a kind of density, generate heat, detonation pressure and explosion velocity performance it is excellent containing nitro-triazole
The energy-containing compound of skeleton.
Summary of the invention
In view of the shortcomings of the prior art, one of the objects of the present invention is to provide a kind of 5- (nitro bromine methylene diazanyl)-
3- nitro -1,2,4- triazole compounds, the compound monocrystal density are up to 2.2 g cm-3, explosion velocity 9112m/s, detonation pressure is
39.2GPa, generating heat is 412.6kJ/mol, and chemical structural formula is as shown in formula<I>:
Another object of the present invention is that providing above-mentioned 5- (nitro bromine methylene diazanyl) -3- nitro -1,2,4- three
The synthetic method of azole compounds, this method comprises the following steps:
(1) 3- nitro -5- amino-1,2,4-triazole is placed in water, inorganic acid solution is added；
(2) sodium nitrite solution is added dropwise into step (1) gains to be reacted；
(3) nitro bromomethane is added to step (2) gains to be reacted；
(4) after completion of the reaction, it filters, solid phase is washed, dries to obtain solid product A, filtrate is extracted, again
Crystallization obtains solid product B, combining solid product A and solid product B and obtains the compound.
In step (1), the inorganic acid includes hydrochloric acid, nitric acid, sulfuric acid, any one in phosphoric acid.
As the preferred embodiments of the invention, the inorganic acid and 3- nitro -5- amino -1,2, mole of 4- triazole
Than for 6~10:1.
As the preferred embodiments of the invention, when carrying out step (2), carried out in ice bath；Best, temperature is not higher than 5
DEG C, the reaction time is 0.5 hour；More preferably scheme is the molar ratio of sodium nitrite and 3- nitro -5- amino-1,2,4-triazole
For 1.05~1.20:1.
As the preferred embodiments of the invention, in step (3), reaction temperature is 0~25 DEG C, the reaction time is 0.5~
24 hours；Preferably, nitro bromomethane and 3- nitro -5- amino -1,2, the molar ratio of 4- triazole are 1.1~1.3:1.
In step (4), the washing is to be carried out using distilled water.
As the preferred embodiments of the invention, in step (4), the extraction is carries out using ethyl acetate.
As the preferred embodiments of the invention, in step (4), the recrystallization is carries out using n-hexane.
Another object of the present invention is that providing above-mentioned 5- (nitro bromine methylene diazanyl) -3- nitro -1,2,4- three
Application of the azole compounds in terms of preparing energetic material.
Beneficial effects of the present invention: 5- (nitro bromine methylene diazanyl) -3- nitro -1,2,4- triazole monocrystalline of the invention
Density is up to 2.2g cm-3, generation heat is higher, and generating heat is 412.6 kJ/mol；5- (nitro bromine methylene hydrazine of the invention
Base) -3- nitro -1,2,4- triazole compounds energy is higher, and calculating its explosion velocity is 9112m/s, detonation pressure 39.2GPa.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is
For the present invention to be further detailed, it should not be understood as limiting the scope of the invention, the technology in the field is ripe
Practice some nonessential modifications and adaptations that personnel are made according to foregoing invention content, still falls within protection scope of the present invention.
Embodiment 1
1.2g (9.3mmol) 3- nitro -5- amino-1,2,4-triazole is added in 15mL distilled water, is added dropwise thereto
1mL concentrated hydrochloric acid observes that yellow solid gradually all dissolves in reaction flask in course of dissolution.
0.7060g (11.23mmol) sodium nitrite is weighed, is dissolved in 2mL distilled water, is added to ice bath in batches
In cooling reaction system, control temperature is no more than 5 DEG C.After being added dropwise, continuation reacts 0.5h under condition of ice bath.
1.6923g (12.09mmol) nitro bromomethane is dissolved in 2mL acetonitrile, is slowly dropped in reaction system, 5
It is reacted at DEG C for 24 hours, solution colour gradually becomes rufous in reaction process, and red brown solid generates.After completion of the reaction, subtract
It presses through and filters out solid product, distill water washing with 5mL, it is dry.Filtrate is extracted with ethyl acetate, and rotary evaporation removes solvent
Afterwards, obtained solid is recrystallized with n-hexane.Two solid products merge, and obtain yellow solid, yield 60%, purity is
99.8% (HPLC).
Product structure identification:
Infrared spectroscopy: IR (KBr, cm-1),υ:3532,1620,1549,1521,1390,1311, 1638,1056,838
Mass spectrum: MS:ESI pos:m/z=279.9,282.1 [M+H]
Nuclear magnetic spectrum:1H NMR(DMSO-d6,600MHz),δ:3.51(br,NH)；13CNMR (DMSO-d6,150MHz),
δ:162.11,159.23,130.96
Substance obtained by above structure appraising datum confirms is 5- (nitro bromine methylene diazanyl) -3- nitro -1,2,4- three
Azoles.
The performance of product 5- (nitro bromine methylene diazanyl) -3- nitro -1,2,4- triazole:
Appearance: yellow powdery solid；
Decomposition temperature peak value: 219.40 DEG C.
Embodiment 2
1.2g (9.3mmol) 3- nitro -5- amino-1,2,4-triazole is added in 15mL distilled water, is added dropwise thereto
1mL concentrated hydrochloric acid observes that yellow solid gradually all dissolves in reaction flask in course of dissolution.
0.6431g (10.23mmol) sodium nitrite is weighed, is dissolved in 2mL distilled water, is added to ice bath in batches
In cooling reaction system, control temperature is no more than 5 DEG C.After being added dropwise, continuation reacts 0.5h under condition of ice bath.
1.6923g (12.09mmol) nitro bromomethane is dissolved in 2mL acetonitrile, is slowly dropped in reaction system, 0
DEG C reaction for 24 hours.After completion of the reaction, it is filtered under diminished pressure out solid product, with 5mL distillation water washing, is dried to obtain solid product.Filter
Liquid is extracted with ethyl acetate, and after rotary evaporation removes solvent, obtained solid is recrystallized with n-hexane.Two solid products merge,
Yellow solid, yield 65% are obtained, purity is 99.8% (HPLC).
Reacting phenomenon in the present embodiment preparation process is same as Example 1.
Product structure qualification result made from the present embodiment is same as Example 1.
Embodiment 3
1.2g (9.3mmol) 3- nitro -5- amino-1,2,4-triazole is added in 15mL distilled water, is added dropwise thereto
1mL concentrated phosphoric acid observes that yellow solid gradually all dissolves in reaction flask in course of dissolution.
0.7060g (11.23mmol) sodium nitrite is weighed, is dissolved in 2mL distilled water, is added to ice bath in batches
In cooling reaction system, control temperature is no more than 5 DEG C.After being added dropwise, continuation reacts 0.5h under condition of ice bath.
1.5719g (11.23mmol) nitro bromomethane is dissolved in 2mL acetonitrile, is slowly dropped in reaction system,
15 DEG C of reactions are for 24 hours.After completion of the reaction, it is filtered under diminished pressure out solid product, with 5mL distillation water washing, is dried to obtain solid product.
Filtrate is extracted with ethyl acetate, and after rotary evaporation removes solvent, obtained solid is recrystallized with n-hexane.Two solid products merge,
Yellow solid, yield 60% are obtained, purity is 99.8% (HPLC).
Reacting phenomenon in the present embodiment preparation process is same as Example 1.
Product structure qualification result made from the present embodiment is same as Example 1.
Embodiment 4
1.2g (9.3mmol) 3- nitro -5- amino-1,2,4-triazole is added in 15mL distilled water, is added dropwise thereto
The 0.5mL concentrated sulfuric acid observes that yellow solid gradually all dissolves in reaction flask in course of dissolution.
0.6139g (9.765mmol) sodium nitrite is weighed, is dissolved in 2mL distilled water, is added to ice bath in batches
In cooling reaction system, control temperature is no more than 5 DEG C.After being added dropwise, continuation reacts 0.5h under condition of ice bath.
1.6923g (12.09mmol) nitro bromomethane is dissolved in 2mL acetonitrile, is slowly dropped in reaction system,
10 DEG C of reactions are for 24 hours.After completion of the reaction, it is filtered under diminished pressure out solid product.
Claims (10)
1. a kind of 5- (nitro bromine methylene diazanyl) -3- nitro -1,2,4- triazole compounds, which is characterized in that its chemical structure
Formula is as shown in formula<I>:
2. 5- (nitro bromine methylene diazanyl) -3- nitro -1,2 described in claim 1, the synthetic method of 4- triazole compounds,
It is characterized in that, described method includes following steps:
(1) 3- nitro -5- amino-1,2,4-triazole is placed in water, inorganic acid solution is added；
(2) sodium nitrite solution is added dropwise into step (1) gains to be reacted；
(3) nitro bromomethane is added to step (2) gains to be reacted；
(4) after completion of the reaction, it filters, solid phase is washed, dries to obtain solid product A, filtrate is extracted, is recrystallized
The compound is obtained to solid product B, combining solid product A and solid product B.
3. synthetic method according to claim 2, which is characterized in that in step (1), the inorganic acid includes hydrochloric acid, nitre
Acid, sulfuric acid, any one in phosphoric acid.
4. synthetic method according to claim 2 or 3, which is characterized in that the inorganic acid and amino -1 3- nitro -5-,
The molar ratio of 2,4- triazole is 6~10:1.
5. synthetic method according to claim 2, which is characterized in that when carrying out step (2), carried out in ice bath；Preferably,
Temperature is not higher than 5 DEG C, and the reaction time is 0.5 hour；It is furthermore preferred that sodium nitrite and 3- nitro -5- amino-1,2,4-triazole
Molar ratio is 1.05~1.20:1.
6. synthetic method according to claim 2, which is characterized in that in step (3), reaction temperature is 0~25 DEG C, reaction
Time is 0.5~24 hour；Preferably, the molar ratio of nitro bromomethane and 3- nitro -5- amino-1,2,4-triazole be 1.1~
1.3:1。
7. synthetic method according to claim 2, which is characterized in that in step (4), it is described washing for using distilled water into
Row.
8. synthetic method according to claim 2, which is characterized in that in step (4), the extraction is to utilize ethyl acetate
It carries out.
9. synthetic method according to claim 2, which is characterized in that in step (4), the recrystallization is to utilize n-hexane
It carries out.
10. 5- (nitro bromine methylene diazanyl) -3- nitro -1,2,4- triazole compounds described in claim 1 contain energy in preparation
Application in terms of material.
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| CN113968851A (en) * | 2021-11-01 | 2022-01-25 | 西安近代化学研究所 | 3- (3-nitro-1, 2, 4-triazole-5-yl) -azasdeone compound, preparation method and application |
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