CN108727336A - 4- amino -3,5- the di nitryl pyridines and preparation method thereof of amino azoles substitution - Google Patents

4- amino -3,5- the di nitryl pyridines and preparation method thereof of amino azoles substitution Download PDF

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CN108727336A
CN108727336A CN201710251606.6A CN201710251606A CN108727336A CN 108727336 A CN108727336 A CN 108727336A CN 201710251606 A CN201710251606 A CN 201710251606A CN 108727336 A CN108727336 A CN 108727336A
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amino
azoles
nitryl
bis
pyridines
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马丛明
刘祖亮
姚其正
周九九
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings

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Abstract

The invention discloses a kind of 4- amino -3,5- di nitryl pyridines and preparation method thereof of amino azoles substitution, and in particular to general formula（I）The substitution of amino azoles 4- amino -3,5- di nitryl pyridines, wherein R represents 3- amino-1,2,4-triazoles or 5- Aminotetrazoles；This method is to realize that amino azoles and 2, the reaction of bis- chloro- 4- amino -3,5- di nitryl pyridines of 6- are cooled to room temperature filtering after reaction under suitable temperature condition, and methanol is washed, and washing, drying can be obtained.The energy-containing compound structure novel that the present invention synthesizes, reaction condition is mild, does not need that special device, technique and operating process are simple, production safety is reliable, product postprocessing is convenient, environmental pollution is small, meets the basic demand of industry's enlarging production.

Description

4- amino -3,5- the di nitryl pyridines and preparation method thereof of amino azoles substitution
Technical field
The invention belongs to Shattering rate technology fields, more particularly to a kind of novel high-energy insensitive explosive amino azoles Substituted 4- amino -3,5- di nitryl pyridine energy-containing compounds and preparation method thereof.
Background technology
Compared with homocyclic aromatic energy-containing compound, azepine (virtue) ring nitro compound has higher density and explosion velocity etc. special Property.Wherein, polynitropyridine derivative is exactly a kind of potentially precursor containing energy, can be used as parent nucleus and is used to prepare novel high-energy insensitiveness Energy-containing compound.It is wanted although introducing multiple nitros or azido etc. simultaneously on pyridine ring and can meet the energy of energy-containing compound The problem asked, but molecular structure can be brought unstable.For this purpose, the amino and nitro base at the introducing ortho position on pyridine ring can be passed through Group, its security performance and crystalline density are improved to form intramolecular and intermolecular hydrogen bonding；Nitrogen-enriched compounds can also be introduced to carry Its high energy.However, researcher both domestic and external is but rarely reported the synthesis of such compound.
Energetic material, 2015,23 (11):The synthetic route such as following formula institute of two kinds of analogue compounds of 1099-1102 reports Show.
It is original that the route, which is with the chloro- 4- amino -3,5- di nitryl pyridines of 2- or the chloro- 3,5- di nitryl pyridines of 2- amino -6-, Material, reacts with 5- Aminotetrazoles respectively obtain 2- (5- Aminotetrazole -1- bases) -4- amino -3,5- dinitros under alkaline condition Pyridine or 6- (5- Aminotetrazole -1- bases) -2- amino -3,5- di nitryl pyridines, and use Kamlet-Jacobs prediction equations two The explosion velocity of a compound is all 8.18km/s, and detonation pressure is all 30.7GPa.But both compounds are to pyridine ring substituents utilization rate Not high, prediction explosion velocity is also not up to desirable level, is unable to give full play the detonation property of pyridine ring series energy-containing compound.
Invention content
The object of the present invention is to provide a kind of amino azoles substitution 4- amino -3,5- di nitryl pyridines energy-containing compound and its Preparation method.
In order to solve the above technical problems, one aspect of the present invention is：
The following general formula (I) compound：
Wherein, R represents 3- amino-1,2,4-triazoles or 5- Aminotetrazoles.
The preparation method of above compound, includes the following steps：
Amino azoles is dissolved in ethyl alcohol, alkali and tetrabutylammonium bromide, stirring and dissolving are added at room temperature；2,6- bis- is chloro- 4- amino -3,5- di nitryl pyridines are added in above-mentioned reaction solution, are reacted at 40~60 DEG C, after reaction, will be mixed It closes liquid to be cooled to room temperature, filter, methanol is washed, and is washed, and drying can be obtained target compound.
Further, amino azoles is 3- amino-1,2,4-triazoles or 5- Aminotetrazoles.
Further, alkali selects KHCO3、K2CO3Or any one in KOH or combinations thereof.
Further, the molar ratio of amino azoles and alkali is 1:1.
Further, the molar ratio of amino azoles and tetrabutylammonium bromide is 10:1-20:1.
Further, the molar ratio of amino azoles and 2, bis- chloro- 4- amino -3,5- di nitryl pyridines of 6- is 1:1-1:1.2.
Further, reaction time 1-3h.
Compared with prior art, the present invention its remarkable advantage is：The present invention synthesizes the 4- amino-of amino azoles substitution for the first time 3,5- di nitryl pyridine energy-containing compounds, the synthetic reaction step of the energy-containing compound is simple, mild condition, need not especially fill Set, production safety is reliable, product postprocessing is simple, small to environmental hazard, meet the basic demand of industry's enlarging production；Suchization The structure that object has both three/tetrazolium of amino and amino nitropyridine is closed, high-energy insensitive energetic material field is possibly used for, wherein 2, Bis- (1,2,4- the triazol-1-yls) -4- amino -3,5- di nitryl pyridines of 6- and bis- (5- Aminotetrazole -1- the bases) -4- amino-of 2,6- The theoretical calculation explosion velocity of 3,5- di nitryl pyridines is respectively 7536m/s and 8660m/s.
Present invention is further described in detail below in conjunction with the accompanying drawings.
Description of the drawings
Fig. 1 is the matter of bis- (1,2,4- the triazol-1-yls) -4- amino -3,5- di nitryl pyridines of target product 2,6- of the present invention Spectrogram.
Fig. 2 is the matter of bis- (5- Aminotetrazole -1- the bases) -4- amino -3,5- di nitryl pyridines of target product 2,6- of the present invention Spectrogram.
Specific implementation mode
The preferred embodiments of the present invention will be described in detail below so that advantages and features of the invention can be easier to by It will be appreciated by those skilled in the art that so as to make a clearer definition of the protection scope of the present invention.
The general structure of the 4- amino -3,5- di nitryl pyridine energy-containing compounds of amino azoles of the present invention substitution is：
Including bis- (1,2,4- triazol-1-yl) -4- amino -3, the 5- di nitryl pyridines (a) of 2,6-, molecular formula C9H8N12O4, Structural formula is：
2,6- bis- (5- Aminotetrazole -1- bases) -4- amino -3,5- di nitryl pyridines (b), molecular formula C7H6N14O4, structure Formula is：
The synthetic route of the 4- amino -3,5- di nitryl pyridine energy-containing compounds of amino azoles of the present invention substitution is：
The preparation method of 4- amino -3,5- di nitryl pyridines of amino azoles substitution of the present invention, includes the following steps：
Amino azoles is dissolved in ethyl alcohol, alkali and tetrabutylammonium bromide, stirring and dissolving are added at room temperature.2,6- bis- is chloro- 4- amino -3,5- di nitryl pyridines are added in above-mentioned reaction solution, are reacted at 40~60 DEG C, after reaction, will be mixed It closes liquid to be cooled to room temperature, filter, methanol is washed, and is washed, and drying can be obtained compound (I).
Wherein, the molar ratio of amino azoles and alkali is 1:1, the molar ratio of amino azoles and tetrabutylammonium bromide is 10:1-20:1, Wherein, alkali selects KHCO3、K2CO3Or any one in KOH or combinations thereof.Amino azoles is 3- amino -1,2,4- triazoles or 5- ammonia Base tetrazolium；The molar ratio of bis- chloro- 4- amino -3,5- di nitryl pyridines of amino azoles and 2,6- is 1:1-1:1.2, reaction temperature 40 ~60 DEG C, reaction time 1-3h.
One, the preparation of bis- (1,2,4- the triazol-1-yls) -4- amino -3,5- di nitryl pyridines of 2,6-
Embodiment 1
0.42g (5mmol) 3- amino-1,2,4-triazoles are dissolved in 30mL ethyl alcohol, are added under the conditions of being stirred at room temperature 0.50g (5mmol) saleratus and 0.16g (0.5mmol) tetrabutylammonium bromide stir 30min.By 1.26g (5mmol) 2,6- Two chloro- 4- amino -3,5- di nitryl pyridines are added in above-mentioned reaction solution, are warming up to 40 DEG C of reaction 3h.After reaction, it will mix It closes liquid to be cooled to room temperature, filter, methanol is washed, and is washed, and drying can be obtained yellow solid 2,6- bis- (1,2,4- triazol-1-yls)- 4- amino -3,5- di nitryl pyridine 1.06g, yield 61%, characterization structure are as shown in Figure 1.
Compound has the structure of polynitropyridine and amino azoles simultaneously, has potentially in high-energy insensitive energetic material field Using theoretical calculation explosion velocity is 7536m/s.
Embodiment 2
0.42g (5mmol) 3- amino-1,2,4-triazoles are dissolved in 30mL ethyl alcohol, are added under the conditions of being stirred at room temperature 0.50g (5mmol) saleratus and 0.08g (0.25mmol) tetrabutylammonium bromide stir 30min.By 1.39g (5.5mmol) 2,6- bis- chloro- 4- amino -3,5- di nitryl pyridines are added in above-mentioned reaction solution, are warming up to 50 DEG C of reaction 2.5h.Reaction terminates Afterwards, mixed liquor is cooled to room temperature, is filtered, methanol is washed, and is washed, and drying can be obtained yellow solid 2, bis- (1,2, the 4- triazoles-of 6- 1- yls) -4- amino -3,5- di nitryl pyridine 0.97g, yield 56%.
Embodiment 3
0.42g (5mmol) 3- amino-1,2,4-triazoles are dissolved in 30mL ethyl alcohol, are added under the conditions of being stirred at room temperature 0.69g (5mmol) potassium carbonate and 0.10g (0.31mmol) tetrabutylammonium bromide stir 30min.By 1.39g (5.5mmol) 2, Bis- chloro- 4- amino -3,5- di nitryl pyridines of 6- are added in above-mentioned reaction solution, are warming up to 60 DEG C of reaction 2h.After reaction, will Mixed liquor is cooled to room temperature, and filtering, methanol is washed, and is washed, and drying can be obtained yellow solid 2, bis- (1,2, the 4- triazole -1- of 6- Base) -4- amino -3,5- di nitryl pyridine 0.78g, yield 45%.
Embodiment 4
0.42g (5mmol) 3- amino-1,2,4-triazoles are dissolved in 30mL ethyl alcohol, are added under the conditions of being stirred at room temperature 0.28g (5mmol) potassium hydroxide and 0.13g (0.40mmol) tetrabutylammonium bromide stir 30min.By 1.26g (5mmol) 2, Bis- chloro- 4- amino -3,5- di nitryl pyridines of 6- are added in above-mentioned reaction solution, are warming up to 45 DEG C of reaction 2.5h.After reaction, Mixed liquor is cooled to room temperature, is filtered, methanol is washed, and is washed, and drying can be obtained yellow solid 2, bis- (1,2, the 4- triazole -1- of 6- Base) -4- amino -3,5- di nitryl pyridine 0.66g, yield 38%.
Two, the preparation of bis- (5- Aminotetrazole -1- the bases) -4- amino -3,5- di nitryl pyridines of 2,6-
Embodiment 5
0.43g (5mmol) 5- Aminotetrazoles are dissolved in 30mL ethyl alcohol, 0.50g is added under the conditions of being stirred at room temperature (5mmol) saleratus and 0.16g (0.5mmol) tetrabutylammonium bromide stir 30min.1.26g (5mmol) 2,6- bis- is chloro- 4- amino -3,5- di nitryl pyridines are added in above-mentioned reaction solution, are warming up to 40 DEG C of reaction 3h.After reaction, by mixed liquor It is cooled to room temperature, filters, methanol is washed, and is washed, and drying can be obtained yellow solid 2, bis- (5- Aminotetrazole -1- the bases) -4- ammonia of 6- Base -3,5- di nitryl pyridine 0.93g, yield 53%, characterization structure are as shown in Figure 2.
Compound has the structure of polynitropyridine and amino azoles simultaneously, has potentially in high-energy insensitive energetic material field Using theoretical calculation explosion velocity is 8660m/s.
Embodiment 6
0.43g (5mmol) 3- amino-1,2,4-triazoles are dissolved in 30mL ethyl alcohol, are added under the conditions of being stirred at room temperature 0.50g (5mmol) saleratus and 0.08g (0.25mmol) tetrabutylammonium bromide stir 30min.By 1.39g (5.5mmol) 2,6- bis- chloro- 4- amino -3,5- di nitryl pyridines are added in above-mentioned reaction solution, are warming up to 50 DEG C of reaction 2.5h.Reaction terminates Afterwards, mixed liquor is cooled to room temperature, is filtered, methanol is washed, and is washed, and drying can be obtained yellow solid 2, bis- (1,2, the 4- triazoles-of 6- 1- yls) -4- amino -3,5- di nitryl pyridine 0.77g, yield 44%.
Embodiment 7
0.43g (5mmol) 3- amino-1,2,4-triazoles are dissolved in 30mL ethyl alcohol, are added under the conditions of being stirred at room temperature 0.69g (5mmol) potassium carbonate and 0.10g (0.31mmol) tetrabutylammonium bromide stir 30min.By 1.39g (5.5mmol) 2, Bis- chloro- 4- amino -3,5- di nitryl pyridines of 6- are added in above-mentioned reaction solution, are warming up to 60 DEG C of reaction 2h.After reaction, will Mixed liquor is cooled to room temperature, and filtering, methanol is washed, and is washed, and drying can be obtained yellow solid 2, bis- (1,2, the 4- triazole -1- of 6- Base) -4- amino -3,5- di nitryl pyridine 0.71g, yield 41%.
Embodiment 8
0.43g (5mmol) 3- amino-1,2,4-triazoles are dissolved in 30mL ethyl alcohol, are added under the conditions of being stirred at room temperature 0.28g (5mmol) potassium hydroxide and 0.13g (0.40mmol) tetrabutylammonium bromide stir 30min.By 1.26g (5mmol) 2, Bis- chloro- 4- amino -3,5- di nitryl pyridines of 6- are added in above-mentioned reaction solution, are warming up to 45 DEG C of reaction 2.5h.After reaction, Mixed liquor is cooled to room temperature, is filtered, methanol is washed, and is washed, and drying can be obtained yellow solid 2, bis- (1,2, the 4- triazole -1- of 6- Base) -4- amino -3,5- di nitryl pyridine 0.44g, yield 25%.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair Equivalent structure or equivalent flow shift made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant skills Art field, is included within the scope of the present invention.

Claims (8)

  1. The following general formula 1. (I) compound：
    Wherein, R represents 3- amino-1,2,4-triazoles or 5- Aminotetrazoles.
  2. 2. the preparation method of compound according to claim 1, which is characterized in that include the following steps：
    Amino azoles is dissolved in ethyl alcohol, alkali and tetrabutylammonium bromide, stirring and dissolving are added at room temperature；By bis- chloro- 4- ammonia of 2,6- Base -3,5- di nitryl pyridine is added in above-mentioned reaction solution, is reacted at 40~60 DEG C, after reaction, by mixed liquor It is cooled to room temperature, filters, methanol is washed, and is washed, and drying can be obtained target compound.
  3. 3. method as claimed in claim 2, which is characterized in that amino azoles is 3- amino-1,2,4-triazoles or 5- Aminotetrazoles.
  4. 4. method as claimed in claim 2, which is characterized in that alkali selects KHCO3、K2CO3Or any one in KOH or its group It closes.
  5. 5. method as claimed in claim 2, which is characterized in that the molar ratio of amino azoles and alkali is 1:1.
  6. 6. method as claimed in claim 2, which is characterized in that the molar ratio of amino azoles and tetrabutylammonium bromide is 10:1-20: 1。
  7. 7. method as claimed in claim 2, which is characterized in that amino azoles and 2, bis- chloro- 4- amino -3,5- di nitryl pyridines of 6- Molar ratio be 1:1~1:1.2.
  8. 8. method as claimed in claim 2, which is characterized in that the reaction time is 1~3h.
CN201710251606.6A 2017-04-18 2017-04-18 4- amino -3,5- the di nitryl pyridines and preparation method thereof of amino azoles substitution Pending CN108727336A (en)

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CN101735146A (en) * 2008-11-05 2010-06-16 南京理工大学 Composite method of high-energy insensitive explosive 2,6-diamino-3,5-dinitro pyridine-1-oxide
CN103059009A (en) * 2013-01-24 2013-04-24 北京理工大学 4-nitro-3-(5-tetrazole) furoxan energetic ionic salt and preparation method thereof
CN103304482A (en) * 2013-06-13 2013-09-18 南京理工大学 Multi-nitrobenzene substituted nitroimidazole energetic compound and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008102092A1 (en) * 2007-01-16 2008-08-28 Snpe Materiaux Energetiques Furazane derivatives, preparation thereof and energetic compositions containing them
CN101735146A (en) * 2008-11-05 2010-06-16 南京理工大学 Composite method of high-energy insensitive explosive 2,6-diamino-3,5-dinitro pyridine-1-oxide
CN103059009A (en) * 2013-01-24 2013-04-24 北京理工大学 4-nitro-3-(5-tetrazole) furoxan energetic ionic salt and preparation method thereof
CN103304482A (en) * 2013-06-13 2013-09-18 南京理工大学 Multi-nitrobenzene substituted nitroimidazole energetic compound and preparation method thereof

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Application publication date: 20181102