CN105669582A - 5,5'-azodi(1-nitriminotetrazolate)bi-potassium compound - Google Patents
5,5'-azodi(1-nitriminotetrazolate)bi-potassium compound Download PDFInfo
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- CN105669582A CN105669582A CN201610133948.3A CN201610133948A CN105669582A CN 105669582 A CN105669582 A CN 105669582A CN 201610133948 A CN201610133948 A CN 201610133948A CN 105669582 A CN105669582 A CN 105669582A
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- double
- tetrazolium
- azo
- nitramino
- potassium salt
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- LUEVJFFKBDOYJI-UHFFFAOYSA-O [N+](=O)([O-])N[N+]=1NN=NC=1 Chemical compound [N+](=O)([O-])N[N+]=1NN=NC=1 LUEVJFFKBDOYJI-UHFFFAOYSA-O 0.000 claims description 18
- 159000000001 potassium salts Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 12
- 125000003831 tetrazolyl group Chemical group 0.000 description 10
- KZRAAPTWXAMZHQ-UHFFFAOYSA-N methoxymethanamine Chemical compound COCN KZRAAPTWXAMZHQ-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000005474 detonation Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 239000000243 solution 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
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- -1 potassium salt compound Chemical class 0.000 description 3
- 230000037452 priming Effects 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
- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 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
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B41/00—Compositions containing a nitrated metallo-organic compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/06—Potassium compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a 5,5'-azodi(1-nitriminotetrazolate)bi-potassium compound.The structural formula of the 5,5'-azodi(1-nitriminotetrazolate)bi-potassium compound is shown in the description.The 5,5'-azodi(1-nitriminotetrazolate) bi-potassium compound is mainly used for the field of energetic materials.
Description
Technical field
The present invention relates to a kind of energetic material, be specifically related to a kind of 5, double; two (1-nitramino tetrazolium) the double; two potassium salt compounds of 5 '-azo.
Background technology
At present, the design of Nitrogen Heterocyclic Energetic Compounds, synthesis and explorative research research are subject to the common concern of various countries' researcher, containing substantial amounts of N-N, N=N key in this compounds, there is the higher positive enthalpy of formation, high nitrogen, low carbohydrate content make it easier to reach oxygen balance, and higher nitrogen content makes its catabolite be mainly nitrogen, and gas production is bigger, cleanliness without any pollution, future has broad application prospects in fields such as composite explosives, solid propellant and gas-forming agents. 1,5-diaminourea tetrazolium and correlative thereof are a kind of important tetrazolium energy-containing compound precursors, amino in its structure can be modified further, derive containing nitramino, azo group etc. containing can the high energy material of group, thus designing, synthesizing multiple detonation property preferably energetic derivative, particularly its nitramino metallic potassium salt compound, traditional lead azide priming can be replaced as a kind of novel green high energy priming, avoid the plumbous heavy metal pollution caused because the latter uses, there is potential application prospect.
LianjieZhai et al. " Agreenhigh-initiation-powerprimaryexplosive:synthesis, 3Dstructureandenergeticpropertiesofdipotassium3,4-bis (3-dinitromethylfurazan-4-oxy) furazan ", RSCAdv., 2015,5,57833 57841 disclose 1,1 '-two nitramino-5, the molecular structure of the double; two potassium salt of 5 '-bis-tetrazoliums and performance data, this compound structure is as follows:
This compound crystal density is 2.11g/cm3, nitrogen content is 50.28%, and calculating explosion velocity is 8055m/s, and detonation pressure is 28.9GPa, and generating heat is 326.4kJ/mol, and quick-fried heat is 4959kJ/kg. But this compound generates, and heat is less, energy is relatively low.
Summary of the invention
The technical problem to be solved is the deficiency and the defect that overcome background technology, it is provided that a kind of generate that heat is relatively big, energy is higher 5, double; two (1-nitramino tetrazolium) the double; two potassium salt compounds of 5 '-azo.
The synthetic route of double; two (1-nitramino tetrazolium) the double; two potassium salt compounds of the 5,5 ' of the present invention-azo is as follows:
With 1-methoxy methyl acyl group-1; 5-diaminourea tetrazolium is raw material; first generation 5 is reacted with the hydrochloric acid solution of potassium permanganate; 5 '-azo double; two (1-methoxymethylamide base tetrazolium); react then through Nitrolysis with Nitrogen Peroxide, potassium hydroxide alkaline hydrolysis etc.; ultimately produce 5, double; two (1-nitramino tetrazolium) the double; two potassium salt of 5 '-azo.
The 5 of the present invention, double; two (1-nitramino tetrazolium) the double; two potassium salt compounds of 5 '-azo, its structural formula is as shown in (I):
The 5 of the present invention, the synthetic method of double; two (1-nitramino tetrazolium) the double; two potassium salt of 5 '-azo, comprise the following steps:
The synthesis of (1) 5,5 '-azo double; two (1-methoxymethylamide base tetrazolium)
Under ice-water bath stirring, successively by 36～38% (quality) concentrated hydrochloric acid, 1-methoxy methyl acyl group-1,5-diaminourea tetrazolium joins in flask, dropping potassium permanganate solution, 50～55 DEG C of reaction 5h it are warming up to after adding, be cooled to 20～25 DEG C, filter, washing, dry 5,5 '-azo double; two (1-methoxymethylamide base tetrazolium);Wherein 1-methoxy methyl acyl group-1,5-diaminourea tetrazolium is 1:1～3 with the mol ratio of potassium permanganate.
The synthesis of double; two (1-nitramino tetrazolium) the double; two potassium salt of (2) 5,5 '-azos
Under ice-water bath stirring, by 5,5 '-azo double; two (1-methoxymethylamide base tetrazolium) is distributed in anhydrous acetonitrile, the acetonitrile solution of dinitrogen pentoxide is added at 0 DEG C, 2h～5h is reacted at 0 DEG C～5 DEG C after adding, it is subsequently adding potassium hydroxide aqueous solution reaction 0.5h～2h, solvent is evaporated off, add methanol, stir 3h～5h at 20～25 DEG C, filter, filter cake is added to the water stirring 10min～60min, filter, filter cake through methanol wash column, dry 5, double; two (1-nitramino tetrazolium) the double; two potassium salt of 5 '-azo; Wherein 5, the mol ratio of 5 '-azo double; two (1-methoxymethylamide base tetrazolium) and dinitrogen pentoxide is 1:2～5, and the mol ratio of dinitrogen pentoxide and potassium hydroxide is 1:1～3.
Advantages of the present invention:
The 5 of the present invention, double; two (1-nitramino tetrazolium) the double; two potassium salt compounds of 5 '-azo calculate and generate heat relatively greatly, and it generates heat is 617.0kJ/mol, the 1 of documents, 1 '-two nitramino-5, it is 326.4kJ/mol that the calculating of the double; two potassium salt of 5 '-bis-tetrazoliums generates heat; The 5 of the present invention, double; two (1-nitramino tetrazolium) the double; two potassium salt compound energy of 5 '-azo are higher, it calculates explosion velocity is 8367m/s, detonation pressure is 31.5GPa, and quick-fried heat is 5358kJ/kg, the 1 of documents, 1 '-two nitramino-5, the calculating explosion velocity of the double; two potassium salt of 5 '-bis-tetrazoliums is 8055m/s, and detonation pressure is 28.9GPa, and quick-fried heat is 4959kJ/kg.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The synthesis of (1) 5,5 '-azo double; two (1-methoxymethylamide base tetrazolium)
Under ice-water bath stirring; successively by concentrated hydrochloric acid that 12.9mL mass percent is 36%～38%, 0.79g (5mmol) 1-methoxy methyl acyl group-1; 5-diaminourea tetrazolium joins in flask; the dropping 14.0mL aqueous solution containing 0.79g (5mmol) potassium permanganate; being warming up to 50～55 DEG C of reaction 5h after adding, reactant liquor is cooled to 20～25 DEG C, filter, washing, dry 5; double; two (the 1-methoxymethylamide base tetrazolium) 0.7g of 5 '-azo, yield is 89.7%.
Structural Identification:
Infrared spectrum: IR (KBr, cm-1), υ: 3242,3024,2968,1767,1638,1536,1504,1467,1437,1309,1248,1 147,1074,1049,964,848,767,751,594
Nuclear magnetic spectrum:1HNMR(DMSO-d6,500MHz),δ:3.808(s,6H,2CH3), 12.843 (s, 2H, 2NH);13CNMR(DMSO-d6,125MHz),δ:54.473,155.24,158.00
Elementary analysis: molecular formula C6H8N12O4
Theoretical value: C23.08, H2.58, N53.84
Measured value: C23.13, H2.52, N53.90
No. CCDC: 1442365.
Said structure appraising datum confirms that obtaining material is strictly 5,5 '-azo double; two (1-methoxymethylamide base tetrazolium).
The synthesis of double; two (1-nitramino tetrazolium) the double; two potassium salt of (2) 5,5 '-azos
Under ice-water bath stirring, by 1.87g (6mmol) 5, 5 '-azo double, two (1-methoxymethylamide base tetrazolium) is distributed in 58.0mL anhydrous acetonitrile, the 32.0mL acetonitrile solution containing 2.59g (24mmol) dinitrogen pentoxide is added at 0 DEG C, 3h is reacted at 0 DEG C～5 DEG C after adding, it is subsequently adding the 24.0mL reactant aqueous solution 1h containing 2.69g (48mmol) potassium hydroxide, solvent is evaporated off, add 35.0mL methanol and stir 4h at 20～25 DEG C, filter, filter cake is added in 20.0mL water and stir 30min at 20～25 DEG C, filter, filter cake is through methanol wash column, dry 5, double, two (1-nitramino tetrazolium) the double, two potassium salt 0.46g of 5 '-azo, yield is 21.2%.
Structural Identification:
Infrared spectrum: IR (KBr, cm-1), υ: 3442,1635,1479,1456,1431,1298,1242,1226,1154,1079,1015,9 27,879,775,753,739,613
Nuclear magnetic spectrum:13CNMR(DMSO-d6,125MHz),δ:157.96
Elementary analysis: molecular formula K2C2N14O4
Theoretical value: C6.63, N54.12
Measured value: C6.71, N54.06
No. CCDC: 1439593.
Said structure appraising datum confirms that obtaining material is strictly double; two (1-nitramino tetrazolium) the double; two potassium salt of 5,5 '-azo.
The performance of double; two (1-nitramino tetrazolium) the double; two potassium salt of the present invention 5,5 '-azo
(1) physical and chemical performance
Outward appearance: Tan solid
Dissolubility: soluble in water; It is slightly soluble in dimethyl sulfoxide, N,N-dimethylformamide, methanol etc.
Crystalline density: 2.11g/cm3X-ray diffraction method
(2) detonation property
The purposes of double; two (1-nitramino tetrazolium) the double; two potassium salt of the 5,5 ' of the present invention-azo
The 5 of the present invention, double; two (1-nitramino tetrazolium) the double; two potassium salt compounds of 5 '-azo have that generation heat is relatively big, energy relatively high, it is possible to be applied to the field such as composite explosives, high energy priming.
Claims (1)
1. one kind 5, double; two (1-nitramino tetrazolium) the double; two potassium salt compounds of 5 '-azo, its structural formula is as shown in (I):
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|---|---|---|---|
| CN201610133948.3A CN105669582B (en) | 2016-03-09 | 2016-03-09 | Double (1- nitre aminotetrazole) the double potassium salt compounds of 5,5 '-azo |
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| CN201610133948.3A CN105669582B (en) | 2016-03-09 | 2016-03-09 | Double (1- nitre aminotetrazole) the double potassium salt compounds of 5,5 '-azo |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892933A (en) * | 2017-03-21 | 2017-06-27 | 中国工程物理研究院化工材料研究所 | A kind of high Energy Density Materials and its synthetic method |
| CN107382891A (en) * | 2017-09-11 | 2017-11-24 | 西安近代化学研究所 | A kind of synthetic method of 5,5 ' azos double (1 nitre aminotetrazoles) |
| CN107698532A (en) * | 2017-10-09 | 2018-02-16 | 西安近代化学研究所 | The diazanyl tetrazine salt compound of 1,5 dinitro aminotetrazole two |
| CN108285435A (en) * | 2018-03-15 | 2018-07-17 | 西安近代化学研究所 | 1,5- dinitro aminotetrazole dicyandiamidines salt compounds |
| CN108424398A (en) * | 2018-03-15 | 2018-08-21 | 西安近代化学研究所 | 1,5- dinitro aminotetrazole 4- amino -1,2,4- triazole salt compounds |
| CN108424397A (en) * | 2018-03-15 | 2018-08-21 | 西安近代化学研究所 | 1,5- dinitro aminotetrazole diamino tetrazolium salt compounds |
-
2016
- 2016-03-09 CN CN201610133948.3A patent/CN105669582B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| DENNIS FISCHER,等: "1,1’-Nitramino-5,5’-bitetrazoles", 《CHEM. EUR. J.》 * |
| FANG LI,等: "1,1’-Diamino-5,5’-azotetrazole: a nitrogen rich compound", 《NEW J. CHEM.》 * |
| ZHIYUE HAN，等: "1,1’-Diisopropylideneamino-5,5"-azotetrozole", 《J THERM ANAL CALORIM》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106892933A (en) * | 2017-03-21 | 2017-06-27 | 中国工程物理研究院化工材料研究所 | A kind of high Energy Density Materials and its synthetic method |
| CN106892933B (en) * | 2017-03-21 | 2018-11-09 | 中国工程物理研究院化工材料研究所 | A kind of high Energy Density Materials and its synthetic method |
| CN107382891A (en) * | 2017-09-11 | 2017-11-24 | 西安近代化学研究所 | A kind of synthetic method of 5,5 ' azos double (1 nitre aminotetrazoles) |
| CN107698532A (en) * | 2017-10-09 | 2018-02-16 | 西安近代化学研究所 | The diazanyl tetrazine salt compound of 1,5 dinitro aminotetrazole two |
| CN107698532B (en) * | 2017-10-09 | 2019-08-27 | 西安近代化学研究所 | Two diazanyl tetrazine salt compound of 1,5- dinitro aminotetrazole |
| CN108285435A (en) * | 2018-03-15 | 2018-07-17 | 西安近代化学研究所 | 1,5- dinitro aminotetrazole dicyandiamidines salt compounds |
| CN108424398A (en) * | 2018-03-15 | 2018-08-21 | 西安近代化学研究所 | 1,5- dinitro aminotetrazole 4- amino -1,2,4- triazole salt compounds |
| CN108424397A (en) * | 2018-03-15 | 2018-08-21 | 西安近代化学研究所 | 1,5- dinitro aminotetrazole diamino tetrazolium salt compounds |
| CN108424398B (en) * | 2018-03-15 | 2019-08-23 | 西安近代化学研究所 | 1,5- dinitro aminotetrazole 4- amino -1,2,4- triazole salt compound |
| CN108285435B (en) * | 2018-03-15 | 2019-08-27 | 西安近代化学研究所 | 1,5- dinitro aminotetrazole dicyandiamidines salt compound |
| CN108424397B (en) * | 2018-03-15 | 2019-08-27 | 西安近代化学研究所 | 1,5- dinitro aminotetrazole diamino tetrazolium salt compound |
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