CN105669574B - 3 fluorine are together with the triazole compounds of dinitro methyl 1,2,4 - Google Patents
3 fluorine are together with the triazole compounds of dinitro methyl 1,2,4 Download PDFInfo
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- CN105669574B CN105669574B CN201610019022.1A CN201610019022A CN105669574B CN 105669574 B CN105669574 B CN 105669574B CN 201610019022 A CN201610019022 A CN 201610019022A CN 105669574 B CN105669574 B CN 105669574B
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- Prior art keywords
- isophthalic acid
- methyl isophthalic
- fluorine
- dinitro methyl
- triazoles
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of 3 fluorine together with the triazole compounds of dinitro methyl 1,2,4, 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 3- fluorine is together with dinitro methyl isophthalic acid, 2,4- triazole compounds.
Background technology
In recent years, five yuan of aromatic rings of azepine (such as pyrazoles, imidazoles, 1,2,4- triazoles etc.) compound is with its high nitrogen-containing, aerogenesis
Measure the advantages of big, detonation product is cleaned and enjoy domestic and international concern.Due to nitrogen, the electricity of oxygen atom contained by such high nitrogen compound
Negativity is higher, and whole heterocyclic system forms the big л keys conjugated structure of similar phenyl ring, therefore the features such as with thermally-stabilised good, insensitiveness.
Domestic and international energetic material research worker, designs and synthesizes out a variety of Nitrogen Heterocyclic Energetic Compounds, such as：4,5- trinitro-s
Imidazoles, 4- amino -3,5- binitropyrazoles, 5- amino -3- nitro -1,2,4- triazoles etc.；And fluorine is used as one kind together with dinitro methyl
The higher functional group containing energy of energy density, is introduced into compound structure, can not only improve the energy density of compound,
The detonation property of compound can further be improved.
King tin outstanding person et al.《The improvement in synthesis of 5- amino -3- nitro -1,2,4- triazoles (ANTA)》, 2006,14 (6):
443-445 discloses the molecular structure of 5- Amino-3-nitro-1,2,4-triazoles and the improvement synthesis technique of the compound, has no
Relevant performance data report, the compound structure is as follows：
Calculated through inventor, the solid density of 5- Amino-3-nitro-1,2,4-triazoles is 1.69g/cm3, calculating explosion velocity is
8010.5m/s, detonation pressure is 24.6GPa, and quick-fried heat is 5083.0kJ/kg.But the compound density is smaller, energy is relatively low.
The content of the invention
The technical problems to be solved by the invention be overcome the shortcomings of background technology and defect there is provided a kind of density it is larger,
The higher 3- fluorine of energy is together with dinitro methyl isophthalic acid, 2,4- triazole compounds.
The 3- fluorine of the present invention is together with dinitro methyl isophthalic acid, and the synthetic route of 2,4- triazole compounds is as follows：
With 3- together with chlorine oximido -1,2,4- triazoles are raw material, first with dinitrogen pentoxide reaction generation 3- chlorine together with dinitro methyl -
1,2,4- triazole, then with iodate nak response generation 3- together with dinitro methyl isophthalic acid, 2,4- triazole sylvite finally react with xenon difluoride and given birth to
Into 3- fluorine together with dinitro methyl isophthalic acid, 2,4- triazoles.
The 3- fluorine of the present invention is together with dinitro methyl isophthalic acid, and 2,4- triazole compounds, its structural formula such as (I) is shown：
The 3- fluorine of the present invention is together with dinitro methyl isophthalic acid, and the synthetic method of 2,4- triazoles comprises the following steps：
(1) 3- chlorine is together with dinitro methyl isophthalic acid, the synthesis of 2,4- triazoles
Under stirring, successively by 3- together with chlorine oximido -1,2,4- triazoles, chloroform are added in flask, and five oxygen are added portionwise
Change phenodiazine, 45 DEG C of reaction 45min are warming up to after adding, chloroform is removed under reduced pressure, dry 3- chlorine is together with dinitro methyl isophthalic acid, 2,4-
Triazole；Wherein 3- is 1 together with chlorine oximido -1,2,4- triazoles and the mol ratio of dinitrogen pentoxide:4~10.
(2) 3- is together with dinitro methyl isophthalic acid, the synthesis of 2,4- triazole sylvite
Under stirring, successively by 3- chlorine together with dinitro methyl isophthalic acid, 2,4- triazoles, methanol are added in flask, and KI is added dropwise
Methanol solution, reacts 1h at 25 DEG C after adding, filtering, methanol are washed, dry 3- is together with dinitro methyl isophthalic acid, 2,4- triazole sylvite；Its
Middle 3- chlorine is together with dinitro methyl isophthalic acid, and the mol ratio of 2,4- triazoles and KI is 1:1~4.
(3) 3- fluorine is together with dinitro methyl isophthalic acid, the synthesis of 2,4- triazoles
Under stirring, successively by 3- together with dinitro methyl isophthalic acid, 2,4- triazole sylvite, acetonitrile are added in flask, then in batches to
Xenon difluoride is added in system, reaction 48h are kept after adding at 25 DEG C, filtering, filtrate solvent evaporated, dry 3- fluorine are together with dinitro
Methyl isophthalic acid, 2,4- triazoles；Wherein 3- is together with dinitro methyl isophthalic acid, and the mol ratio of 2,4- triazoles sylvite and xenon difluoride is 1:1.5~3.
Advantages of the present invention：
The 3- fluorine of the present invention is together with dinitro methyl isophthalic acid, and 2,4- triazole compounds calculating density is larger, and its density is 1.81g/
cm3, the calculating density of the 5- Amino-3-nitro-1,2,4-triazoles of documents is 1.69g/cm3；The 3- fluorine of the present invention is together with dinitro
Methyl isophthalic acid, 2,4- triazole compounds energy are higher, calculate its explosion velocity for 8365.0m/s, detonation pressure is 31.1GPa, and quick-fried heat is
5614.4kJ/kg, the calculating explosion velocity of the 5- Amino-3-nitro-1,2,4-triazoles of documents is 8010.5m/s, and detonation pressure is
24.6GPa, quick-fried heat is 5083.0kJ/kg.
Embodiment
The present invention is described in further detail with reference to embodiments.
Embodiment 1
(1) 3- chlorine is together with dinitro methyl isophthalic acid, the synthesis of 2,4- triazoles
Under stirring, successively by 1.5g (0.01mol) 3- together with chlorine oximido -1,2,4- triazoles, 75.0mL chloroforms are added to
In flask, 1.5g (0.053mol) dinitrogen pentoxide is added portionwise, 45 DEG C of reaction 45min are warming up to after adding, three are removed under reduced pressure
Chloromethanes, dry 3- chlorine is together with dinitro methyl isophthalic acid, 2,4- triazole 1.95g, and yield is 91.9%.
Structural Identification：
Infrared spectrum：IR(KBr,cm-1),υ：3152,3103(-NH),3025(-CH),1537,1348,1326(-NO2),
1476,1385,1279,1052 (triazole rings)
Nuclear magnetic spectrum：1HNMR(DMSO-d6,500MHz),δ:8.988(s,1H,CH),9.114(s,1H,NH)；13CNMR
(DMSO-d6,125MHz),δ:144.49,147.49,153.09
Elementary analysis：Molecular formula C3H2N5O4Cl
Theoretical value：C 17.36,H 0.97,N 33.75
Measured value：C 17.33,H 0.92,N 33.80
Mass spectrum：(ESI-)m/z：206、208[M-H]-。
Said structure appraising datum confirms that it is strictly 3- chlorine together with dinitro methyl isophthalic acid, 2,4- triazoles to obtain material.
(2) 3- is together with dinitro methyl isophthalic acid, the synthesis of 2,4- triazole sylvite
Under stirring, successively by 0.5g (2.4mmol) 3- chlorine together with dinitro methyl isophthalic acid, 2,4- triazoles, 10.0mL methanol are added to
In flask, the methanol solution that 10.0mL contains 1.0g (6.0mmol) KI is added dropwise, 1h, filtering, methanol is reacted after adding at 25 DEG C
Wash, dry 3- together with dinitro methyl isophthalic acid, 2,4- triazole sylvite 0.31g, yield is 61.0%.
Structural Identification：
Infrared spectrum：IR(KBr,cm-1),υ：3150(-NH),3097(-CH),1538,1520,1359,1323(-NO2),
2879,1463,1377,1243,1099 (triazole rings)
Nuclear magnetic spectrum：1HNMR(H2O-d2,500MHz),δ:8.503(s,1H,CH)；13CNMR(H2O-d2,125MHz),δ:
126.90,146.17,150.91
Elementary analysis：Molecular formula C3H2N5O4K
Theoretical value：C 17.06,H 0.95,N 33.16
Measured value：C 17.13,H 0.91,N 33.22
Said structure appraising datum confirms that it is strictly 3- together with dinitro methyl isophthalic acid, 2,4- triazole sylvite to obtain material.
(3) 3- fluorine is together with dinitro methyl isophthalic acid, the synthesis of 2,4- triazoles
Under stirring, successively by 0.15g (0.71mmol) 3- together with dinitro methyl isophthalic acid, 2,4- triazole sylvite, 8.0mL acetonitriles are added
Into flask, 0.25g (1.49mmol) xenon difluoride is then added into system in batches, reaction 48h is kept after adding at 25 DEG C,
Filtering, filtrate solvent evaporated, dry 3- fluorine are together with dinitro methyl isophthalic acid, 2,4- triazole 0.077g, and yield is 56.6%.
Structural Identification：
Infrared spectrum：IR(KBr,cm-1),υ：3142(-NH),2908(-CH),1520,1348,1314(-NO2),1463,
1267,1052 (triazole rings)
Nuclear magnetic spectrum：1HNMR(DMSO-d6,500MHz),δ:8.348(s,1H,CH)；13CNMR(DMSO-d6,125MHz),
δ:124.68,147.18,153.09
Elementary analysis：Molecular formula C3H2N5O4F
Theoretical value：C 18.86,H 1.06,N 36.65
Measured value：C 18.83,H 1.11,N 36.72.
Said structure appraising datum confirms that it is strictly 3- fluorine together with dinitro methyl isophthalic acid, 2,4- triazoles to obtain material.
The 3- fluorine of the present invention is together with dinitro methyl isophthalic acid, the performance of 2,4- triazoles
(1) physical and chemical performance
Outward appearance：White powder crystal
Solubility：It is soluble in dimethyl sulfoxide (DMSO), N,N-dimethylformamide, methanol, ethanol etc.；Be slightly soluble in dichloromethane,
Water, ether, petroleum ether, hexamethylene etc.
Density：1.81g/cm3Gaussian 09 program B3LYP methods (2) detonation property
Explosion velocity：Density is 1.81g/cm3, calculating explosion velocity is 8365.0m/s K-J equations
Detonation pressure：Density is 1.81g/cm3, calculating detonation pressure is 31.1GPa K-J equations
Quick-fried heat：Density is 1.81g/cm3, it is 5614.4kJ/kg K-J equations to calculate quick-fried heat
The 3- fluorine of the present invention is together with dinitro methyl isophthalic acid, the purposes of 2,4- triazoles
The 3- fluorine of the present invention is together with dinitro methyl isophthalic acid, and 2,4- triazole compounds have the features such as density is larger, energy is higher, can
To be applied to composite explosives field as energetic material component.
Claims (1)
1. a kind of 3- fluorine is together with dinitro methyl isophthalic acid, 2,4- triazole compounds, its structural formula such as (I) is shown：
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| CN106432196A (en) * | 2016-07-11 | 2017-02-22 | 北京理工大学 | Production method and performances of high-energy and ultrahigh-temperature heatproof explosive K (CPT) structure |
| CN106432192A (en) * | 2016-07-11 | 2017-02-22 | 北京理工大学 | Preparation method and performance of high-energy insensitive N-(3,5-binitro-1H-pyrazol-4-yl)-1H-tetrazole-5-amine ionic salt structure |
| CN109232424B (en) * | 2018-10-31 | 2020-07-17 | 西安近代化学研究所 | 1-nitro-3-trinitromethylpyrazole compounds |
| CN109251174B (en) * | 2018-10-31 | 2020-06-23 | 西安近代化学研究所 | 3-trinitromethylpyrazole compounds |
| CN114436980A (en) * | 2022-01-23 | 2022-05-06 | 中北大学 | Fluoro geminal dinitromethyl substituted triazole and pyrazole, and preparation method and application thereof |
| CN116003333A (en) * | 2022-12-06 | 2023-04-25 | 西安近代化学研究所 | 2-gem dinitropyrazine hydrazine salt compound, preparation method and application |
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| US4311649A (en) * | 1980-11-28 | 1982-01-19 | The United States Of America As Represented By The Secretary Of The Navy | N,N-Bis(2-fluoro-2,2-dinitroethyl)carbamate esters |
| US7745635B1 (en) * | 2003-06-16 | 2010-06-29 | Drake Greg W | Energetic ionic salts |
| US8012277B2 (en) * | 2007-04-13 | 2011-09-06 | Alliant Techsystems Inc. | Ionic liquid and a method of synthesizing an ionic liquid |
| CN103483264A (en) * | 2012-06-12 | 2014-01-01 | 北京理工大学 | Energetic ion salts of 1-nitramine-2, 4-dimetridazloe and preparation method thereof |
| CN104672158B (en) * | 2015-02-12 | 2017-04-12 | 西安近代化学研究所 | 1, 1'-bi(germinal dinitro methyl)-3, 3'-dinitro-5, 5'-co-1, 2, 4-triazole guazatine |
| CN104649984B (en) * | 2015-02-12 | 2018-04-20 | 西安近代化学研究所 | 1,1 ' two (together with dinitro methyl) 3,3 ' dinitros 5,5 ' join the double hydroxylamine salts of 1,2,4 triazoles |
| CN105153053B (en) * | 2015-09-25 | 2018-04-20 | 西安近代化学研究所 | A kind of 3 together with 1,2,4 triazole of dinitro methyl synthetic method |
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