CN105111156B - 2 amino, 5,5 ' dinitro, 3,3 ' double (1,2,4 triazole) compounds - Google Patents
2 amino, 5,5 ' dinitro, 3,3 ' double (1,2,4 triazole) compounds Download PDFInfo
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- CN105111156B CN105111156B CN201510603835.0A CN201510603835A CN105111156B CN 105111156 B CN105111156 B CN 105111156B CN 201510603835 A CN201510603835 A CN 201510603835A CN 105111156 B CN105111156 B CN 105111156B
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- Prior art keywords
- dinitro
- amino
- bis
- triazole
- triazoles
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- 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 18
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 title claims abstract description 8
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 title 1
- 239000000463 material Substances 0.000 abstract description 7
- OWZPCEFYPSAJFR-UHFFFAOYSA-N 2-(butan-2-yl)-4,6-dinitrophenol Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O OWZPCEFYPSAJFR-UHFFFAOYSA-N 0.000 abstract description 2
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000005474 detonation Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- -1 5, 5’-Dinitro-3,3’-bi-1,2,4-triazol-2-ide Anion Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of dinitro 3 of 2 amino 5,5 ', 3 ' double (1,2,4 triazole) compounds, its structural formula is such as shown in (I)：
Description
Technical field
The present invention relates to a kind of energetic material, and in particular to a kind of 2- amino -5,5 '-dinitro -3, and 3 '-bis- (1,2,4-
Triazole) compound.
Background technology
In recent years, energetic material of the rich nitrogen energy-containing compound as a kind of unique properties, because of the end of its burning or blast
Product is mainly that build environment is friendly, free of contamination nitrogen, and is usually applied to the research fields such as explosive, propellant.It is such
Contain substantial amounts of N-N and N=N keys in molecular structure of compounds, a large amount of nitrogen can be discharged during decomposition, produce higher-energy；It is right
The stimulation such as heat, friction, electric spark is insensitive, and has the characteristics that with higher density, the hot big, better heat stability of positive generation,
Therefore, energetic material researcher in countries in the world generates larger concern to such compound.Part has been filtered out simultaneously contains energy
Compound carries out its explorative research research in fields such as the low sense explosive of high energy, gas-forming agents.Such as Alexander
A.Dippold et al. exists《Insensitive Nitrogen-Rich Energetic Compounds Based on the 5,
5’-Dinitro-3,3’-bi-1,2,4-triazol-2-ide Anion》, Eur.J.Inorg.Chem.2012,3474-3484
One is disclosed herein 5,5 '-dinitro -3, the structure of 3 '-bis- (1,2,4- triazole) compounds and the calculating performance of the compound,
Its structure is such as shown in (II)：
The calculating performance of the compound：Nitrogen content is 49.6%, explosion velocity 8413m/s, detonation pressure 32.0GPa, generation heat
For 285.0kJ/mol.But compound generation heat is smaller, energy is relatively low.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of background technology and defect, there is provided one kind generation heat compared with
2- amino -5,5 '-dinitro -3,3 '-bis- (1,2,4- triazoles) compound high, energy is larger.
The synthetic route of 2- amino -5,5 '-dinitro -3,3 '-bis- (1,2,4- triazoles) compound of the present invention is as follows：
With 5,5 '-dinitro -3,3 '-bis- (1,2,4- triazole) mono-sodium salts are raw material, and aminating reaction occurs with hydroxylamine acid
It is bis- (1,2,4- triazoles) to generate the 2--dinitros -3,3 '-of amino -5,5 '.
2- amino -5 of the present invention, 5 '-dinitro -3,3 '-bis- (1,2,4- triazole) compounds, its structural formula such as (I) institute
Show：
2- amino -5 of the present invention, 5 '-dinitro -3, the synthetic method of 3 '-bis- (1,2,4- triazoles), including following step
Suddenly：
Under 20~25 DEG C of stirrings, successively by 0.5g (2.02mmol) 5,5 '-dinitro -3,3 '-bis- (1,2,4- triazoles)
Mono-sodium salt, 0.4g (3.77mol) sodium carbonate are added in 10.0mL water, are heated to 70 DEG C, and 2.0mL is added dropwise and contains 0.46g
The hydroxylamine acid aqueous solution of (4.03mmol) hydroxylamine acid, after being added dropwise, 0.7g (8.33mol) sodium acid carbonate is added portionwise,
In 70~75 DEG C of reaction 2.5h of temperature, reaction solution is cooled to 20~25 DEG C, pH value is adjusted with 36%~38% (quality) concentrated hydrochloric acid
To 4~5, reacting liquid filtering, filter cake is through washing, dry 2- amino -5,5 '-dinitro -3,3 '-bis- (1,2,4- triazoles).
Advantages of the present invention
2- amino -5 of the present invention, 5 '-dinitro -3,3 '-bis- (1,2,4- triazole) compound generation heat are higher, and it is generated
Heat is 490.7kJ/mol, the 5 of documents, 5 '-dinitro -3, the generation heat of 3 '-bis- (1,2,4- triazoles) is 285.0kJ/
mol；2- amino -5 of the present invention, 5 '-dinitro -3,3 '-bis- (1,2,4- triazole) compound energy are higher, and calculating its explosion velocity is
8900.4m/s, detonation pressure 35.9GPa, quick-fried heat are 5666.9kJ/kg, the 5 of documents, 5 '-dinitro -3,3 '-bis- (1,2,
4- triazoles) calculating explosion velocity be 8413.0m/s, detonation pressure 32.0GPa, quick-fried heat is 4888.0kJ/kg.
Embodiment
The present invention is described in further detail with reference to embodiments.
Embodiment 1
The synthesis of 2- amino -5,5 '-dinitro -3,3 '-bis- (1,2,4- triazoles)
Under 20~25 DEG C of stirrings, successively by 0.5g (2.02mmol) 5,5 '-dinitro -3,3 '-bis- (1,2,4- triazoles)
Mono-sodium salt, 0.4g (3.77mol) sodium carbonate are added in 10.0mL water, are heated to 70 DEG C, and 2.0mL is added dropwise and contains 0.46g
The hydroxylamine acid aqueous solution of (4.03mmol) hydroxylamine acid, after being added dropwise, 0.7g (8.33mol) sodium acid carbonate is added portionwise,
In 70~75 DEG C of reaction 2.5h of temperature, reaction solution is cooled to 20~25 DEG C, pH value is adjusted with 36%~38% (quality) concentrated hydrochloric acid
To 4~5, reacting liquid filtering, filter cake is through washing, dry 2- amino -5,5 '-dinitro -3,3 '-bis- (1,2,4- triazoles)
0.146g, yield 30.1%.
Structural Identification：
Infrared spectrum：IR(KBr,cm-1),υ：3567(-NH),3446,3384(-NH2),1553,1529,1388,1312
(-NO2), 1647,1042,839 (triazole rings)
Nuclear magnetic spectrum：1HNMR(DMSO-d6,500MHz),δ：3.393(s,1H,NH),7.926(s,2H,NH2)；13CNMR
(DMSO-d6,125MHz),δ：144.15,151.76,157.74,166.21
Elementary analysis：Molecular formula C4H3N9O4
Theoretical value：C 19.92,H 1.25,N 52.28
Measured value：C 19.87,H 1.29,N 52.32
Mass spectrum：(APCI)m/z：240[M-H]-。
It is strictly 2- amino -5,5 '-dinitro -3,3 '-bis- (1,2,4- tri- that said structure appraising datum, which confirms to obtain material,
Azoles).
The performance of 2- amino -5,5 '-dinitro -3,3 '-bis- (1,2,4- triazoles)
(1) physical and chemical performance
Outward appearance：Pale pink solid
Solubility：It is soluble in N,N-dimethylformamide, acetone, acetonitrile, methanol, ethanol etc.；It is slightly soluble in dichloromethane, second
Ether, petroleum ether, hexamethylene etc.
Density：1.88g/cm3The program B3LYP methods of Gaussian 09
Nitrogen content：52.3%
(2) detonation property
The purposes of 2- amino -5,5 '-dinitro -3,3 '-bis- (1,2,4- triazoles)
2- amino -5,5 '-dinitro -3,3 '-bis- (1,2,4- triazoles) compound of the present invention has nitrogen content height, generation
The features such as hot big, energy is high, energetic material field can be applied to as high energy material component.
Claims (1)
1. a kind of 2- amino -5,5 '-dinitro -3,3 '-bis- (1,2,4- triazole) compounds, its structural formula is such as shown in (I)：
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510603835.0A CN105111156B (en) | 2015-09-21 | 2015-09-21 | 2 amino, 5,5 ' dinitro, 3,3 ' double (1,2,4 triazole) compounds |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510603835.0A CN105111156B (en) | 2015-09-21 | 2015-09-21 | 2 amino, 5,5 ' dinitro, 3,3 ' double (1,2,4 triazole) compounds |
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| Publication Number | Publication Date |
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| CN105111156A CN105111156A (en) | 2015-12-02 |
| CN105111156B true CN105111156B (en) | 2018-01-23 |
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| CN201510603835.0A Expired - Fee Related CN105111156B (en) | 2015-09-21 | 2015-09-21 | 2 amino, 5,5 ' dinitro, 3,3 ' double (1,2,4 triazole) compounds |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109020906B (en) * | 2018-06-14 | 2020-03-24 | 西南科技大学 | Energetic compound and synthesis method and application thereof |
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