CN108727408A - A kind of pyrido furoxan energy-containing compound and preparation method thereof - Google Patents
A kind of pyrido furoxan energy-containing compound and preparation method thereof Download PDFInfo
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- CN108727408A CN108727408A CN201710251607.0A CN201710251607A CN108727408A CN 108727408 A CN108727408 A CN 108727408A CN 201710251607 A CN201710251607 A CN 201710251607A CN 108727408 A CN108727408 A CN 108727408A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 24
- PMYJGTWUVVVOFO-UHFFFAOYSA-N 4-phenyl-3-furoxancarbonitrile Chemical compound N#CC1=[N+]([O-])ON=C1C1=CC=CC=C1 PMYJGTWUVVVOFO-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- FMDQMILDRPQMFU-UHFFFAOYSA-N 2,6-dichloro-3,5-dinitropyridine Chemical class [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Cl)N=C1Cl FMDQMILDRPQMFU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012074 organic phase Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 150000001540 azides Chemical class 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 7
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- QLHVJBXAQWPEDI-UHFFFAOYSA-N 2-chloro-3,5-dinitropyridine Chemical class [O-][N+](=O)C1=CN=C(Cl)C([N+]([O-])=O)=C1 QLHVJBXAQWPEDI-UHFFFAOYSA-N 0.000 claims description 2
- -1 Hydrogen furans Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 125000003831 tetrazolyl group Chemical group 0.000 abstract description 17
- 238000004880 explosion Methods 0.000 abstract description 6
- 230000006837 decompression Effects 0.000 abstract description 5
- 239000000706 filtrate Substances 0.000 abstract description 5
- 238000004364 calculation method Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- GZBKVUGZEAJYHH-UHFFFAOYSA-N 2-nitropyridin-3-amine Chemical compound NC1=CC=CN=C1[N+]([O-])=O GZBKVUGZEAJYHH-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- 150000004866 oxadiazoles Chemical class 0.000 description 12
- LENLQGBLVGGAMF-UHFFFAOYSA-N tributyl([1,2,4]triazolo[1,5-a]pyridin-6-yl)stannane Chemical compound C1=C([Sn](CCCC)(CCCC)CCCC)C=CC2=NC=NN21 LENLQGBLVGGAMF-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 125000003838 furazanyl group Chemical group 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical class [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 2
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XRCUWARAHBODRE-UHFFFAOYSA-N 2,3-dinitropyridin-4-amine Chemical compound NC1=CC=NC([N+]([O-])=O)=C1[N+]([O-])=O XRCUWARAHBODRE-UHFFFAOYSA-N 0.000 description 1
- IBTGEEMBZJBBSH-UHFFFAOYSA-N 2,6-dimethoxypyridine Chemical class COC1=CC=CC(OC)=N1 IBTGEEMBZJBBSH-UHFFFAOYSA-N 0.000 description 1
- HLTDBMHJSBSAOM-UHFFFAOYSA-N 2-nitropyridine Chemical compound [O-][N+](=O)C1=CC=CC=N1 HLTDBMHJSBSAOM-UHFFFAOYSA-N 0.000 description 1
- BLBDTBCGPHPIJK-UHFFFAOYSA-N 4-Amino-2-chloropyridine Chemical class NC1=CC=NC(Cl)=C1 BLBDTBCGPHPIJK-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004774 atomic orbital Methods 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- JKFAIQOWCVVSKC-UHFFFAOYSA-N furazan Chemical compound C=1C=NON=1 JKFAIQOWCVVSKC-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D498/14—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a kind of pyrido furoxan energy-containing compounds and preparation method thereof.This method is Azide and the denitrogenation ring-closure reaction realized at a certain temperature to bis- chloro- 3,5- di nitryl pyridines of 4- amino -2,6-, it after reaction by mixture vacuum rotary steam, is dissolved in water, organic phase is dried with anhydrous sodium sulfate after extraction, filtering, filtrate decompression revolving.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；The compound has both the structure of tetrazolium, furoxan and amino nitropyridine, has potential application, theoretical calculation explosion velocity to reach 8754 m/s in energetic material field.
Description
Technical field
The invention belongs to Shattering rate technology fields, more particularly to a kind of energy-containing compound 4- amino -5- nitros -
[the synthetic method of 1,2,5] oxadiazoles [3,4-e] tetrazolium [1,5-a] pyridine -3- oxides.
Background technology
In energetic material field, there are following features with the energetic derivative that furoxan base is explosion group：1) it aoxidizes
Furazanyl can provide relatively higher energy density；2) its effective oxygen is high, and furoxan derivative is as energetic additive
The oxygen balance of system can be improved；3) furoxan base can assign its derivative ring strain and the high standard enthalpy of formation.If with an oxygen
Changing furazanyl replaces a nitro, density that 0.06~0.08g/cm can be improved3, 300m/s can be improved in explosion velocity.In addition, heterocyclic system
Introducing, the combination of its atomic orbital can be made to be significantly better than carbocyclic ring system due to the perturbation of intramolecular, this is because miscellaneous
Atom plays an important role in minimum molecular orbital energy level.And explosive often can be improved in the static stabilization that additional charge band of density comes
Heat resistance, reduce the mechanical sensitivity of explosive.The amino and nitryl group that ortho position is introduced on pyridine ring, to form intramolecular
The security performance and crystalline density of energy-containing compound can be improved with intermolecular hydrogen bonding；It introduces nitrogen-enriched compounds and then can be improved and contain and can change
Close the energy of object.However, researcher both domestic and external is fresh to having both tetrazolium, furoxan, the compound of amino nitropyridine structure
It has been reported that.
J Energ Mater,2005,23(2):99-106 reports a kind of chemical combination containing energy with tetrazolium, furoxan base
The synthetic route of object is shown below.The route be with 2,6- dimethoxy-pyridines be raw material, through nitrification, hydrazine substitution, Azide,
Pyrolysis denitrogenation synthesizes 7- nitros tetrazole radical [1,5-f] furazano [4,5-b] pyridine -1- oxides (NFP), and decomposition point is about
160℃.The method synthetic route is longer, and not high to the substituent group utilization rate of pyridine ring.
Chin J Chem,2013,31:1299-1304 reports are a kind of to have furoxan ring and amino nitropyridine structure
The synthetic route of energy-containing compound be shown below.The route is made with ethanol/water using the chloro- 4-aminopyridines of 2- as raw material
Solvent, through room temperature complete azido reaction, then in acid condition carry out pyrolysis denitrogenation closed loop obtain 7- amino -6- nitros-[1,
2,5] oxadiazoles simultaneously [3,4-b] pyridine -1- oxides.The theoretical calculation explosion velocity of the compound is only 7.51km/s, is unable to fully
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 pyrido furoxan energy-containing compound 4- amino -5- nitros-[1,2,5] Evil
Diazole [3,4-e] tetrazolium [1,5-a] pyridine -3- oxides and preparation method thereof.
In order to solve the above technical problems, one aspect of the present invention is：
A kind of pyrido furoxan energy-containing compound (is named as 4- amino -5- nitros-[1,2,5] oxadiazoles [3,4-e]
Tetrazolium [1,5-a] pyridine -3- oxides), structure is as follows：
The preparation method of above compound, includes the following steps：
Bis- chloro- 3,5- di nitryl pyridines of 4- amino -2,6- are dissolved in organic solvent by the first step, are added at room temperature folded
Sodium nitride is stirred to react 30min or more；
A small amount of concentrated hydrochloric acid is added into reaction mixture for second step, and temperature reaction for a period of time, waits after the completion of reacting, and mixes
It closes liquid and falls solvent through vacuum rotary steam, be dissolved in water, ethyl acetate extraction, organic phase is dry, vacuum distillation obtains target compound.
Wherein, in the first step, the molar ratio of bis- chloro- 3,5- di nitryl pyridines of 4- amino -2,6- and sodium azide is 1:2-
1:4。
In the first step, organic solvent includes acetonitrile, ethyl acetate, tetrahydrofuran, acetone, methanol, ethyl alcohol and its mixture,
It is preferred that any one in acetonitrile, tetrahydrofuran and acetone or combinations thereof.
In second step, the quality of concentrated hydrochloric acid is the 1/20~1/30 of bis- chloro- 3,5- di nitryl pyridines of 4- amino -2,6-, is mixed
The reaction temperature for closing liquid is 30-50 DEG C, reaction time 1-3h.
Compared with prior art, the present invention its remarkable advantage is：The present invention synthesizes the pyrido oxidation replaced entirely for the first time
Furazan energy-containing compound：[1,2,5] oxadiazoles [3,4-e] tetrazolium [1,5-a] pyridine -3- oxides, should for 4- amino -5- nitros -
The synthetic reaction step of energy-containing compound is simple, mild condition, does not need that special device, production safety be reliable, product postprocessing
Simply, small to environmental hazard, meet the basic demand of industry's enlarging production；Such compound has both tetrazolium, furoxan and ammonia
The structure of base nitropyridine, theoretical calculation explosion velocity reach 8754m/s, are possibly used for high-energy insensitive energetic material field.
Present invention is further described in detail below in conjunction with the accompanying drawings.
Description of the drawings
Fig. 1 pyrido furoxan energy-containing compounds of the present invention1H NMR spectras.
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.
4- amino -5- nitros-[point of 1,2,5] oxadiazoles [3,4-e] tetrazolium [1,5-a] pyridine -3- oxides of the present invention
Minor is C5H2N8O4, structural formula is：
4- amino -5- nitros-[the conjunction of 1,2,5] oxadiazoles [3,4-e] tetrazolium [1,5-a] pyridine -3- oxides of the present invention
It is at route：
4- amino -5- nitros-[the system of 1,2,5] oxadiazoles [3,4-e] tetrazolium [1,5-a] pyridine -3- oxides of the present invention
Preparation Method includes the following steps：
Bis- chloro- 3,5- di nitryl pyridines of 4- amino -2,6- are dissolved in suitable solvent, are added at room temperature by the first step
Sodium azide is stirred to react 1h；
A small amount of concentrated hydrochloric acid is added into reaction mixture for second step, and temperature reaction for a period of time, waits after the completion of reacting, and mixes
It closes liquid and falls solvent through vacuum rotary steam, be dissolved in water, ethyl acetate extraction, organic phase is dry, vacuum distillation obtains 4- amino -5- nitre
Base-[1,2,5] oxadiazoles [3,4-e] tetrazolium [1,5-a] pyridine -3- oxides.
Wherein, the molar ratio of bis- chloro- 3,5- di nitryl pyridines of 4- amino -2,6- and sodium azide is 1 in the first step:2-1:
4, the solvent for dissolving bis- chloro- 3,5- di nitryl pyridines of 4- amino -2,6- includes acetonitrile, ethyl acetate, tetrahydrofuran, third
Ketone, methanol, ethyl alcohol and its mixture.Wherein, reaction dissolvent preferred ingredient is acetonitrile, tetrahydrofuran and acetone.
In second step, the quality of concentrated hydrochloric acid is the 1/20~1/30 of bis- chloro- 3,5- di nitryl pyridines of 4- amino -2,6-, is mixed
The reaction temperature for closing liquid is 30~50 DEG C, reaction time 1-3h.
Embodiment 1
Bis- chloro- 3,5- di nitryl pyridines of 1.26g (5mmol) 4- amino -2,6- are dissolved in 15mL acetonitriles, are stirred at room temperature
Under the conditions of be added 0.65g (10mmol) sodium azide, be stirred to react 30min.1 drop concentrated hydrochloric acid is added into reaction mixture, rises
Temperature to 30 DEG C reaction 3h.After reaction, it by mixed liquor vacuum rotary steam, is dissolved in water, ethyl acetate extraction, organic phase drying,
Filtering, filtrate decompression distill to obtain yellow solid 4- amino -5- nitros-[1,2,5] oxadiazoles [3,4-e] tetrazolium [1,5-a] pyrrole
Pyridine -3- oxide 0.89g, yield 75%.m.p.150-151℃(dec.)；1H NMR(DMSO-d6,400MHz):δ10.17(s,
1H),9.50(s,1H)；13C NMR(DMSO-d6,100MHz):δ148.96,144.27,141.87,111.17,105.06；MS
(ESI)m/z:239.0 (M+H), are shown in Fig. 1.
There is compound the structure of tetrazolium, furoxan and amino nitro nitropyridine, theoretical calculation explosion velocity to reach simultaneously
8754m/s has potential application in high-energy insensitive energetic material field.
Embodiment 2
Two chloro- 3,5- di nitryl pyridines of 1.26g (5mmol) 4- amino -2,6- are dissolved in 15mL ethyl acetate and acetone
In the mixed solvent is added 0.98g (15mmol) sodium azide, is stirred to react 30min under the conditions of being stirred at room temperature.To reaction mixture
It is middle that 1 drop concentrated hydrochloric acid is added, it is warming up to 35 DEG C of reaction 2.5h.After reaction, it by mixed liquor vacuum rotary steam, is dissolved in water, acetic acid
Ethyl ester extracts, and organic phase is dry, filters, and filtrate decompression distills to obtain yellow solid 4- amino -5- nitros-[1,2,5] oxadiazoles
[3,4-e] tetrazolium [1,5-a] pyridine -3- oxide 0.71g, yield 60%.
Embodiment 3
Bis- chloro- 3,5- di nitryl pyridines of 1.26g (5mmol) 4- amino -2,6- are dissolved in 15mL ethyl alcohol, are stirred at room temperature
Under the conditions of be added 0.98g (15mmol) sodium azide, be stirred to react 30min.1 drop concentrated hydrochloric acid is added into reaction mixture, rises
Temperature to 50 DEG C reaction 1.5h.After reaction, it by mixed liquor vacuum rotary steam, is dissolved in water, ethyl acetate extraction is organic relevant
Dry, filtering, filtrate decompression distill to obtain yellow solid 4- amino -5- nitros-[1,2,5] oxadiazoles [3,4-e] tetrazolium [1,5-a]
Pyridine -3- oxide 0.62g, yield 52%.
Embodiment 4
Bis- chloro- 3,5- di nitryl pyridines of 1.26g (5mmol) 4- amino -2,6- are dissolved in 15mL acetone, are stirred at room temperature
Under the conditions of be added 1.30g (20mmol) sodium azide, be stirred to react 30min.1 drop concentrated hydrochloric acid is added into reaction mixture, rises
Temperature to 30 DEG C reaction 2h.After reaction, it by mixed liquor vacuum rotary steam, is dissolved in water, ethyl acetate extraction, organic phase drying,
Filtering, filtrate decompression distill to obtain yellow solid 4- amino -5- nitros-[1,2,5] oxadiazoles [3,4-e] tetrazolium [1,5-a] pyrrole
Pyridine -3- oxide 0.80g, yield 67%.
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 (7)
1. a kind of pyrido furoxan energy-containing compound, which is characterized in that its structure is as follows：
2. the preparation method of compound as described in claim 1, which is characterized in that include the following steps：
Bis- chloro- 3,5- di nitryl pyridines of 4- amino -2,6- are dissolved in organic solvent, Azide are added at room temperature by the first step
Sodium is stirred to react 30min or more；
Second step, a small amount of concentrated hydrochloric acid is added into reaction mixture, and temperature reaction for a period of time, waits after the completion of reacting, mixed liquor
Fall solvent through vacuum rotary steam, be dissolved in water, ethyl acetate extraction, organic phase is dry, vacuum distillation obtains target compound.
3. method as claimed in claim 2, which is characterized in that in the first step, bis- chloro- 3,5- dinitro pyridines of 4- amino -2,6-
The molar ratio of pyridine and sodium azide is 1:2~1:4.
4. method as claimed in claim 2, which is characterized in that in the first step, organic solvent includes acetonitrile, ethyl acetate, four
Hydrogen furans, acetone, methanol, ethyl alcohol and its mixture.
5. method as claimed in claim 2, which is characterized in that in the first step, organic solvent includes acetonitrile, tetrahydrofuran and third
Any one in ketone or combinations thereof.
6. method as claimed in claim 2, which is characterized in that in second step, the quality of concentrated hydrochloric acid is 4- amino -2,6- bis-
The 1/20~1/30 of chloro- 3,5- di nitryl pyridines quality.
7. method as claimed in claim 2, which is characterized in that in second step, the reaction temperature of mixed liquor is 30~50 DEG C, instead
It is 1~3h between seasonable.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112521402A (en) * | 2020-12-15 | 2021-03-19 | 北京理工大学 | 1,2, 4-oxadiazole [5,5] bicyclic fused ring compound and preparation method thereof |
| CN113321666A (en) * | 2020-02-28 | 2021-08-31 | 南京理工大学 | Energy-containing compound based on ring-merging framework and synthetic method thereof |
| CN115746021A (en) * | 2022-11-23 | 2023-03-07 | 中国工程物理研究院化工材料研究所 | Synthesis method of 7-amino-6-nitrobenzyl dioxidofurazan and isomer thereof |
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| CN103450108A (en) * | 2012-06-04 | 2013-12-18 | 南京理工大学 | Polyaminopolynitrobenzofuroxan metal complex and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113321666A (en) * | 2020-02-28 | 2021-08-31 | 南京理工大学 | Energy-containing compound based on ring-merging framework and synthetic method thereof |
| CN112521402A (en) * | 2020-12-15 | 2021-03-19 | 北京理工大学 | 1,2, 4-oxadiazole [5,5] bicyclic fused ring compound and preparation method thereof |
| CN115746021A (en) * | 2022-11-23 | 2023-03-07 | 中国工程物理研究院化工材料研究所 | Synthesis method of 7-amino-6-nitrobenzyl dioxidofurazan and isomer thereof |
| CN115746021B (en) * | 2022-11-23 | 2024-02-13 | 中国工程物理研究院化工材料研究所 | Synthesis method of 7-amino-6-nitrobenzofuroxan and isomer thereof |
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