CN108285435B - 1,5- dinitro aminotetrazole dicyandiamidines salt compound - Google Patents
1,5- dinitro aminotetrazole dicyandiamidines salt compound Download PDFInfo
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- CN108285435B CN108285435B CN201810213799.0A CN201810213799A CN108285435B CN 108285435 B CN108285435 B CN 108285435B CN 201810213799 A CN201810213799 A CN 201810213799A CN 108285435 B CN108285435 B CN 108285435B
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- dicyandiamidines
- salt
- dinitro aminotetrazole
- dinitro
- aminotetrazole
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- YWVHJAFUGSRCQB-UHFFFAOYSA-N [N+](=O)([O-])N1N(NN=C1[N+](=O)[O-])N Chemical compound [N+](=O)([O-])N1N(NN=C1[N+](=O)[O-])N YWVHJAFUGSRCQB-UHFFFAOYSA-N 0.000 title claims abstract description 27
- -1 salt compound Chemical class 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 8
- 238000005474 detonation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004880 explosion Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 239000002360 explosive Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003380 propellant Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- XMVJITFPVVRMHC-UHFFFAOYSA-N roxarsone Chemical group OC1=CC=C([As](O)(O)=O)C=C1[N+]([O-])=O XMVJITFPVVRMHC-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- KUEFXPHXHHANKS-UHFFFAOYSA-N 5-nitro-1h-1,2,4-triazole Chemical compound [O-][N+](=O)C1=NC=NN1 KUEFXPHXHHANKS-UHFFFAOYSA-N 0.000 description 1
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002024 ethyl acetate extract Substances 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000005500 uronium group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
- C07D257/06—Five-membered rings with nitrogen atoms directly attached to the ring carbon atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses one kind 1,5- dinitro aminotetrazole dicyandiamidines salt compounds, and structural formula is such as shown in (I):
Description
Technical field
The present invention relates to a kind of energetic materials, and in particular to one kind 1,5- dinitro aminotetrazole dicyandiamidines salt compound.
Background technique
Rich nitrogen energetic material is because containing a large amount of C-N, N-N and C=N key in its molecular structure, with high positive generation heat, height
Therefore thermal stability and excellent detonation property are shown well in high energy material, high energy composite explosives and propellant field
Prospect, can be applied to high-energy insensitive explosive, small-sized propulsion system solid fuel, smokeless pyrotechnic compound, gas-forming agent, smokeless low
Warm extinguishing chemical.Compared with traditional molecule-type energy-containing compound, azole richness nitrogen ion salt containing energy in its molecular structure due to introducing
Nitrogenous anion or cation and cause it with higher generation heat and higher density, while it is female to remain rich azacyclo- again
The high-tension of body structure becomes a kind of unique high nitrogen-containing energy-containing compound.The ion salt containing energy and molecule-type contain and can change
Close object to compare, there is lower vapour pressure, to friction, the stimulation insensitiveness such as hit, and rich nitrogen containing can salt decomposition product it is predominantly big
The nitrogen for measuring cleanliness without any pollution is conducive to the acting ability or specific impulse that improve composite explosives and propellant, environmentally friendly, makees
All there is more broad application prospect in industry and military aspect for novel high-energy material.Wherein, nitrogen content is higher (55%)
Amidino groups uronium be usually utilized to design, synthesizing new richness azacyclo- containing can salt compound.
" 3- nitro -1,2, the synthesis and characterization of 4- triazole -5- ketone dicyandiamidines salt ", energetic material, 2014,22 (2): 192-
196 1 texts disclose a kind of 3- nitro -1,2, and the structure and performance of 4- triazole -5- ketone dicyandiamidines salt, structure is such as shown in (II):
It is calculated through inventor, the nitrogen content of the compound is 48.3%, and calculating explosion velocity is 6683m/s, and detonation pressure is
19.3GPa.But the compound nitrogen content is lower, energy is smaller.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of background technique and defect, provide a kind of nitrogen content compared with
High, the biggish 1,5- dinitro aminotetrazole dicyandiamidines salt compound of energy.
The synthetic route of 1,5- dinitro aminotetrazole dicyandiamidines salt compound of the invention is as follows:
With 1- methoxy methyl acyl group -1,5- diamino tetrazolium be raw material, first with dinitrogen pentoxide, potassium hydroxide, hydrochloric acid
Reactant aqueous solution generates 1,5- dinitro aminotetrazole, and neutralization reaction then occurs with potassium hydroxide, dicyandiamidines nitrate and generates 1,
5- dinitro aminotetrazole dicyandiamidines salt.
1,5- dinitro aminotetrazole dicyandiamidines salt compound of the invention, structural formula is such as shown in (I):
The synthetic method of 1,5- dinitro aminotetrazole dicyandiamidines salt of the invention, comprising the following steps:
(1) synthesis of 1,5- dinitro aminotetrazole
At room temperature, 1- methoxy methyl acyl group -1,5- diamino tetrazolium being added in acetonitrile, ice-water bath is cooled to 0~5 DEG C,
The acetonitrile solution of dinitrogen pentoxide is added dropwise, in 0~5 DEG C of reaction 1h, continuously adds potassium hydroxide aqueous solution, reacts 0.5h, be evaporated off
Solvent obtains faint yellow solid, and methanol is added and stirs 2h, filtering, dry white solid；2mol/ is added into above-mentioned white solid
The hydrochloric acid of L stirs 0.5h, and ethyl acetate extraction, anhydrous magnesium sulfate is dry, and solvent, dry white solid 1, bis- nitramine of 5- is evaporated off
Base tetrazolium；Wherein the molar ratio of 1- methoxy methyl acyl group -1,5- diamino tetrazolium, dinitrogen pentoxide and potassium hydroxide be 1:2~
4:4~8.
(2) synthesis of 1,5- dinitro aminotetrazole dicyandiamidines salt
At room temperature, dicyandiamidines nitrate, methanol, water are added in reaction flask, after stirring and dissolving, the first of potassium hydroxide is added dropwise
Alcoholic solution stirs 10min after adding, and continuously adds 1,5- dinitro aminotetrazole, is warming up to 35 DEG C of reaction 1.5h, and ice-water bath is cold
But, filtering, dry yellowish solid 1,5- dinitro aminotetrazole dicyandiamidines salt；Wherein 1,5- dinitro aminotetrazole and dicyandiamidines
The molar ratio of nitrate is 1:2.0~2.2.
Advantages of the present invention:
1,5- dinitro aminotetrazole dicyandiamidines salt compound nitrogen content of the invention is higher, and nitrogen content 56.8% is right
Nitrogen content than the 3- nitro -1,2,4- triazole -5- ketone dicyandiamidines salt of file is 48.3%；1,5- dinitro amido four of the invention
Azoles dicyandiamidines salt compound energy is larger, and calculating explosion velocity is 7858m/s, detonation pressure 26.9GPa, the 3- nitro-of documents
The calculating explosion velocity of 1,2,4- triazole -5- ketone dicyandiamidines salt is 6683m/s, detonation pressure 19.3GPa.
Specific embodiment
Invention is further described in detail with reference to embodiments.
Embodiment 1
(1) synthesis of 1,5- dinitro aminotetrazole
At room temperature, 2.21g (14mmol) 1- methoxy methyl acyl group -1,5- diamino tetrazolium is added in 42.0mL acetonitrile,
Ice-water bath is cooled to 0~5 DEG C, and the acetonitrile solution that 42.0mL contains 4.54g (42mmol) dinitrogen pentoxide is added dropwise, reacts at 0~5 DEG C
1h continuously adds 42.0mL containing 4.70g (84mmol) potassium hydroxide aqueous solution, reacts 0.5h, solvent is evaporated off and obtains faint yellow solid,
70.0mL methanol is added and stirs 2h, filtering, dry white solid；It is added 44.0mL 2mol/L's into above-mentioned white solid
Hydrochloric acid stirs 0.5h, and ethyl acetate extracts (40.0mL × 4), and anhydrous magnesium sulfate is dry, and solvent, dry 2.11g white is evaporated off
Solid 1,5- dinitro aminotetrazole, yield 79.3%.
Structural Identification:
Infrared spectroscopy: IR (KBr, cm-1), υ: 3205,3144,1596,1579,1508,1476,1453,1413,1332,
1287,1245,1058,1037,987
Nuclear magnetic spectrum:1H NMR(DMSO-d6, 500MHz), δ: 12.22 (s, 2H, 2NH)
13C NMR(DMSO-d6, 125MHz), δ: 147.60
Elemental analysis: molecular formula CH2N8O4
Theoretical value: C 6.32, H 1.06, N 58.95
Measured value: C 6.44, H 1.16, N 59.09.
Above structure appraising datum confirms to obtain substance to be strictly 1,5- dinitro aminotetrazole.
(2) synthesis of 1,5- dinitro aminotetrazole dicyandiamidines salt
At room temperature, 0.35g (2.1mmol) dicyandiamidines nitrate, 2.5mL methanol, 4.5mL water are added in reaction flask, are stirred
After mixing dissolution, the methanol solution that 2.0mL contains 0.118g (2.1mmol) potassium hydroxide is added dropwise, stirs 10min after adding, continues to add
Enter 0.19g (1mmol) 1,5- dinitro aminotetrazole, be warming up to 35 DEG C of reaction 1.5h, ice-water bath is cooling, filtering, dry 0.32g
Yellowish solid 1,5- dinitro aminotetrazole dicyandiamidines salt, yield 81.2%.
Structural Identification:
Infrared spectroscopy: IR (KBr, cm-1), υ: 3416,3192,1765,1753,1703,1685,1641,1594,1506,
1438,1329,1284,1091,1027,922
Nuclear magnetic spectrum:1H NMR(DMSO-d6, 500MHz), δ: 7.20 (s, 4H, 2NH2 +),8.13(s,8H,4NH2),9.76
(s,2H,2NH)
13C NMR(DMSO-d6, 125MHz), δ: 154.08,154.85,155.86
Elemental analysis: molecular formula C5H14N16O6
Theoretical value: C 15.23, H 3.58, N 56.84
Measured value: C 15.31, H 3.52, N 56.91.
Above structure appraising datum confirms to obtain substance to be strictly 1,5- dinitro aminotetrazole dicyandiamidines salt.
The performance of 1,5- dinitro aminotetrazole dicyandiamidines salt of the present invention
(1) physical and chemical performance
Appearance: yellowish solid
Solubility: dimethyl sulfoxide, N,N-dimethylformamide, water etc. are soluble in；Insoluble in petroleum ether, n-hexane, second
Ether, methanol etc.
Nitrogen content: 56.8%
(2) detonation property
Explosion velocity: density 1.69g/cm3, calculating explosion velocity is 7858m/s K-J equation
Detonation pressure: density 1.69g/cm3, calculating detonation pressure is 26.9GPa K-J equation
Generate heat: density 1.69g/cm3, calculating and generating heat is 343.6kJ/mol K-J equation
The purposes of 1,5- dinitro aminotetrazole dicyandiamidines salt of the invention
1,5- dinitro aminotetrazole dicyandiamidines salt of the invention has nitrogen content is high, energy is high, combustion product residue is few etc.
Advantage can be widely used for composite explosives and propellant technical field, can also be applied in air bag.
Claims (1)
1. one kind 1,5- dinitro aminotetrazole dicyandiamidines salt compound, structural formula is such as shown in (I):
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669582A (en) * | 2016-03-09 | 2016-06-15 | 西安近代化学研究所 | 5,5'-azodi(1-nitriminotetrazolate)bi-potassium compound |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669582A (en) * | 2016-03-09 | 2016-06-15 | 西安近代化学研究所 | 5,5'-azodi(1-nitriminotetrazolate)bi-potassium compound |
Non-Patent Citations (2)
| Title |
|---|
| 3,6-二硝基吡唑[4,3-c]并吡唑（DNPP）有机双胺盐的合成及热性能;李亚南，等;《固体火箭技术》;20150630;第38卷(第3期);引言，第397页1.2 * |
| Theoretical studies of energetic nitrogen-rich ionic salts composed of substituted 5-nitroiminotetrazolate anions and various cations;Fang Xiang，等;《Journal of Molecular Modeling》;20130420;第19卷(第8期);第3106页化学结构，第3107页table1 * |
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