CN105017261B - 1,4-diazidomethyl-3,6-dinitropyrazolo[4,3-c] pyrazole compound - Google Patents
1,4-diazidomethyl-3,6-dinitropyrazolo[4,3-c] pyrazole compound Download PDFInfo
- Publication number
- CN105017261B CN105017261B CN201510500439.5A CN201510500439A CN105017261B CN 105017261 B CN105017261 B CN 105017261B CN 201510500439 A CN201510500439 A CN 201510500439A CN 105017261 B CN105017261 B CN 105017261B
- Authority
- CN
- China
- Prior art keywords
- binitropyrazoles
- pyrazoles
- pyrazole compound
- azido
- nitrae
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 *c1n[n](*)c2c1[n](*)nc2N*O Chemical compound *c1n[n](*)c2c1[n](*)nc2N*O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Plural Heterocyclic Compounds (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a 1,4-diazidomethyl-3,6-dinitropyrazolo[4,3-c] pyrazole compound. The structural formula of the 1,4-diazidomethyl-3,6-dinitropyrazolo[4,3-c] pyrazole compound is shown as (I) (please see the specification for the (I)). The 1,4-diazidomethyl-3,6-dinitropyrazolo[4,3-c] pyrazole compound is mainly used for the field of energetic materials.
Description
Technical field
The present invention relates to a kind of energetic material, and in particular to a kind of-two azido-methyl -3 of Isosorbide-5-Nitrae, 6- binitropyrazoles [4,3-
C] and pyrazole compound.
Background technology
Many nitrogen energy-containing compounds are the energetic materials of a class unique properties, are shown in fields such as explosive, propellants good
Good application prospect.The many nitrogen energy-containing compounds of pyrazolo pyrazoleses because of its compact structure, with density it is high, just generating it is hot it is big,
The features such as heat stability is good, becomes one of widely studied field of current energetic material.Contain in such molecular structure of compounds
Substantial amounts of C-N, C=N, N-N and N=N key, discharges a large amount of nitrogen during decomposition, produce higher-energy, and friction, electric spark etc. are pierced
Swash insensitive, therefore can be used for the low sense explosive of high energy, gas-forming agent, burning ratemodifier, low characteristic signal propellant etc., become
The research direction of countries in the world energetic material researcher common concern.For example Jiaheng Zhang et al. exist《Thermally
Stable3,6-Dinitropyrazolo[4,3-c]pyrazole-based Energetic Materials》,
Chemistry-An Asian Journal, 2014,9,2953-2960 mono- are disclosed herein 3,6- binitropyrazoles [4,3-c]
And the calculating performance of the structure and the compound of pyrazole compound, its structure is as shown in (II):
The calculating performance of the compound:Nitrogen content is 42.42%, and explosion velocity is 8250m/s, and detonation pressure is 27.4GPa, generates heat
For 322.6kJ/mol.But the compound nitrogen content is relatively low, energy is less.
The content of the invention
The technical problem to be solved is to overcome the shortcomings of background technology and defect, there is provided a kind of nitrogen content compared with
Larger bis- azido-methyls -3,6- binitropyrazoles [4,3-c] of 1,4- of high, energy pyrazole compound.
The synthetic route of bis- azido-methyls -3,6- binitropyrazoles [4,3-c] of 1,4- pyrazole compound of the present invention is such as
Under:
With 3,6- binitropyrazoles [4,3-c] and pyrazoles be raw material, first with formaldehyde occur condensation reaction generate Isosorbide-5-Nitrae-two
Methylol -3,6- binitropyrazoles [4,3-c] pyrazoles, then generate Isosorbide-5-Nitrae-dichloromethyl -3,6- bis- with thionyl chloride reaction
Nitropyrazole [4,3-c] pyrazoles, finally with-two azido-methyl -3 of reaction of sodium azide generation Isosorbide-5-Nitrae, 6- binitropyrazoles [4,
3-c] and pyrazoles.
- two azido-methyl -3 of Isosorbide-5-Nitrae of the present invention, 6- binitropyrazoles [4,3-c] pyrazole compound, its structural formula is such as
(I) shown in:
The synthetic method of-two azido-methyl -3 of Isosorbide-5-Nitrae of the present invention, 6- binitropyrazoles [4,3-c] pyrazoles, including it is following
Step:
(1) synthesis of 1,4- dihydroxymethyls -3,6- binitropyrazoles [4,3-c] pyrazoles
Under stirring, successively by 3,6- binitropyrazoles [4,3-c] and pyrazoles, ethyl acetate are added to the sulfur of 10% (quality)
In aqueous acid, control temperature is less than 5 DEG C, and the formalin of Deca 37%~40% (quality), after completion of dropping, is warming up to
20 DEG C of reaction 20h, reactant liquor is extracted with ethyl acetate, and anhydrous magnesium sulfate is dried extract, removes ethyl acetate under reduced pressure, dry
1,4- dihydroxymethyls -3,6- binitropyrazoles [4,3-c] pyrazoles;Wherein 3,6- binitropyrazoles [4,3-c] pyrazoles and first
The mol ratio of aldehyde is 1:2~14.
(2) synthesis of 1,4- dichloromethyls -3,6- binitropyrazoles [4,3-c] pyrazoles
Under stirring, successively by thionyl chloride, Isosorbide-5-Nitrae-dihydroxymethyl -3,6- binitropyrazoles [4,3-c] pyrazoles is added to
In flask, after adding, be warming up to 95 DEG C of reaction 5h, reaction terminates rear vacuum rotary steam and removes remaining thionyl chloride, gained solid in
It is dried with potassium hydroxide under vacuum, with water recrystallization, dry Isosorbide-5-Nitrae-dichloromethyl -3,6- binitropyrazoles [4,3-c] pyrrole
Azoles;The consumption of wherein thionyl chloride be every gram of 1,4- dihydroxymethyls -3,6- binitropyrazoles [4,3-c] pyrazoles 2.0~
10.0mL。
(3) synthesis of bis- azido-methyls -3,6- binitropyrazoles [4,3-c] of 1,4- pyrazoles
Under stirring, successively by acetone, Isosorbide-5-Nitrae-dichloromethyl -3,6- binitropyrazoles [4,3-c] pyrazoles, Hydrazoic acid,sodium salt add
Enter in flask, after adding, be warming up to 45 DEG C of reaction 48h, reaction after terminating is poured reactant liquor in frozen water into, filtration, filter cake Jing water
Wash, dry bis- azido-methyls -3,6- binitropyrazoles [4,3-c] of 1,4- pyrazoles;Wherein 1,4- dichloromethyls -3,6- dinitros
Base pyrazoles [4,3-c] pyrazoles and the mol ratio of Hydrazoic acid,sodium salt are 1:2~8.
Advantages of the present invention
- two azido-methyl -3 of Isosorbide-5-Nitrae of the present invention, 6- binitropyrazoles [4,3-c] pyrazole compound nitrogen content is higher, its
Nitrogen content is 54.54%, and the nitrogen content of 3, the 6- binitropyrazoles [4,3-c] pyrazoles of documents is 42.42%;The present invention
- two azido-methyl -3 of Isosorbide-5-Nitrae, 6- binitropyrazoles [4,3-c] pyrazole compound energy is higher, calculating its explosion velocity is
8422.8m/s, detonation pressure is 29.5GPa, and the enthalpy of formation is 751.9kJ/mol, 3, the 6- binitropyrazoles [4,3-c] of documents and
The calculating explosion velocity of pyrazoles is 8250m/s, and detonation pressure is 27.4GPa, and it is 322.6kJ/mol to generate heat.
Specific embodiment
With reference to embodiments the present invention is described in further detail.
Embodiment 1
(1) synthesis of 1,4- dihydroxymethyls -3,6- binitropyrazoles [4,3-c] pyrazoles
Under stirring, successively by 0.5g (2.53mmol) 3,6- binitropyrazoles [4,3-c] and pyrazoles, 20.0mL ethyl acetate
It is added in the aqueous sulfuric acid of 15.0mL 10% (quality), control temperature is less than 5 DEG C, Deca 1.64g37%~40% (matter
Amount) formalin, after completion of dropping, be warming up to 20 DEG C of reaction 20h, reactant liquor is extracted with ethyl acetate (25.0mL × 3),
Anhydrous magnesium sulfate is dried extract, removes ethyl acetate under reduced pressure, dry Isosorbide-5-Nitrae-dihydroxymethyl -3,6- binitropyrazoles [4,3-
C] and pyrazoles 0.394g, yield is 60.4%.
Structural Identification:
Infrared spectrum:IR(KBr,cm-1),υ:3537(-OH),2991,2925(-CH2),1532,1393,1365(-
NO2), 1298,1181,1081 (pyrazolo pyrazoles ring skeletons)
Nuclear magnetic spectrum:1HNMR(DMSO-d6,500MHz),δ:5.832~5.845 (d, 4H, 2CH2), 7.387~7.417
(t,2H,2OH);13CNMR(DMSO-d6,125MHz),δ:75.88,130.94,137.50
Elementary analysiss:Molecular formula C6H6N6O6
Theoretical value:C 27.92,H 2.34,N 32.55
Measured value:C 27.87,H 2.37,N 32.60
Mass spectrum:(ESI)m/z:281[M+Na]+。
Said structure appraising datum confirms that it is strictly 1,4- dihydroxymethyls -3,6- binitropyrazoles [4,3-c] to obtain material
And pyrazoles.
(2) synthesis of 1,4- dichloromethyls -3,6- binitropyrazoles [4,3-c] pyrazoles
Under stirring, successively by 11.0mL thionyl chlorides, 1.5g (5.81mmol) Isosorbide-5-Nitrae-dihydroxymethyl -3,6- binitropyrazoles
[4,3-c] pyrazoles are added in flask, and 95 DEG C of reaction 5h are warming up to after adding, and it is remaining that reaction terminates rear vacuum rotary steam removing
Thionyl chloride, gained solid are dried with potassium hydroxide under vacuum, with water recrystallization, dry Isosorbide-5-Nitrae-dichloromethyl -3,6- bis-
Nitropyrazole [4,3-c] pyrazoles 1.58g, yield is 92.1%.
Structural Identification:
Infrared spectrum:IR(KBr,cm-1),υ:3066,3002,2924(-CH2),1547,1400(-NO2),1286,
1132,1053 (pyrazolo pyrazoles ring skeletons)
Nuclear magnetic spectrum:1HNMR(DMSO-d6,500MHz),δ:5.893(s,4H,2CH2);13CNMR(DMSO-d6,
125MHz),δ:75.89,130.96,137.51
Elementary analysiss:Molecular formula C6H4N6O4Cl2
Theoretical value:C 24.43,H 1.37,N 28.48
Measured value:C 24.53,H 1.31,N 28.39
Mass spectrum:(ESI)m/z:295[M]+。
Said structure appraising datum confirms that it is strictly 1,4- dichloromethyls -3,6- binitropyrazoles [4,3-c] to obtain material
And pyrazoles.
(3) synthesis of bis- azido-methyls -3,6- binitropyrazoles [4,3-c] of 1,4- pyrazoles
Under stirring, successively by 1.6g (5.42mmol) Isosorbide-5-Nitrae-dichloromethyl -3,6- binitropyrazoles [4,3-c] pyrazoles,
20.0mL acetone, 1.05g (16.15mmol) Hydrazoic acid,sodium salt are added in flask, and 45 DEG C of reaction 48h, reaction are warming up to after adding
Reactant liquor is poured in frozen water after end, filter, filter cake Jing washings, dry-two azido-methyl -3 of Isosorbide-5-Nitrae, 6- binitropyrazoles
[4,3-c] pyrazoles 1.06g, yield is 63.5%.
Structural Identification:
Infrared spectrum:IR(KBr,cm-1),υ:3056(-CH2),2115(-N3),1547,1400(-NO2),1303,1223,
1054 (pyrazolo pyrazoles ring skeletons)
Nuclear magnetic spectrum:1HNMR(DMSO-d6,500MHz),δ:6.030(s,4H,2CH2);13CNMR(DMSO-d6,
125MHz),δ:66.52,131.61,138.14
Elementary analysiss:Molecular formula C6H4N12O4
Theoretical value:C 23.38,H 1.31,N 54.54
Measured value:C 23.46,H 1.26,N 54.57
Mass spectrum:(ESI)m/z:308[M]+。
Said structure appraising datum confirms that it is strictly bis- azido-methyl -3,6- binitropyrazole [4,3- of 1,4- to obtain material
C] and pyrazoles.
The performance of bis- azido-methyls -3,6- binitropyrazoles [4,3-c] of 1,4- pyrazoles
(1) physical and chemical performance
Outward appearance:Orange powder shape solid
Dissolubility:It is soluble in dimethyl sulfoxide, N,N-dimethylformamide, acetone, acetonitrile etc.;Be slightly soluble in dichloromethane,
Water, ether, petroleum ether, ethyl acetate etc.
Density:1.81g/cm309 program B3LYP methods of Gaussian
(2) detonation property
The purposes of bis- azido-methyls -3,6- binitropyrazoles [4,3-c] of 1,4- pyrazoles
Bis- azido-methyls -3,6- binitropyrazoles [4,3-c] of 1,4- pyrazole compound of the present invention have nitrogen content it is high,
The features such as heat is big, energy is high is generated, energetic material field can be applied to as high energy material component.
Claims (1)
1. a kind of-two azido-methyl -3 of Isosorbide-5-Nitrae, 6- binitropyrazoles [4,3-c] pyrazole compound, its structural formula is as shown in (I):
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510500439.5A CN105017261B (en) | 2015-08-14 | 2015-08-14 | 1,4-diazidomethyl-3,6-dinitropyrazolo[4,3-c] pyrazole compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510500439.5A CN105017261B (en) | 2015-08-14 | 2015-08-14 | 1,4-diazidomethyl-3,6-dinitropyrazolo[4,3-c] pyrazole compound |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105017261A CN105017261A (en) | 2015-11-04 |
CN105017261B true CN105017261B (en) | 2017-04-12 |
Family
ID=54407608
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510500439.5A Expired - Fee Related CN105017261B (en) | 2015-08-14 | 2015-08-14 | 1,4-diazidomethyl-3,6-dinitropyrazolo[4,3-c] pyrazole compound |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105017261B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115260101B (en) * | 2022-08-18 | 2023-12-19 | 北京理工大学 | 1- (diazidomethyl) -3, 4-binitro-1H-pyrazol-5-amine and synthetic method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102336711A (en) * | 2011-07-25 | 2012-02-01 | 西安近代化学研究所 | 4-amino-3,5-dinitropyrazole lead salt as well as preparation method and application thereof |
US8957208B1 (en) * | 2014-01-15 | 2015-02-17 | National Tsing Hua University | Heteroleptic iridium complex bearing diazolate chelate |
CN104693206A (en) * | 2015-01-30 | 2015-06-10 | 西安近代化学研究所 | 1, 4-dinitro oxymethyl-3, 6-dinitro parazole [4, 3-c] pyrazole compound |
-
2015
- 2015-08-14 CN CN201510500439.5A patent/CN105017261B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102336711A (en) * | 2011-07-25 | 2012-02-01 | 西安近代化学研究所 | 4-amino-3,5-dinitropyrazole lead salt as well as preparation method and application thereof |
US8957208B1 (en) * | 2014-01-15 | 2015-02-17 | National Tsing Hua University | Heteroleptic iridium complex bearing diazolate chelate |
CN104693206A (en) * | 2015-01-30 | 2015-06-10 | 西安近代化学研究所 | 1, 4-dinitro oxymethyl-3, 6-dinitro parazole [4, 3-c] pyrazole compound |
Non-Patent Citations (3)
Title |
---|
1,4-二氨基-3,6-二硝基吡唑[4,3-c]并吡唑的合成、热性能及量子化学研究;李亚南,等;《有机化学》;20121231;第32卷;第580-588页 * |
二硝基吡唑并吡唑(DNPP)合成工艺研究;罗义芬,等;《含能材料》;20070630;第15卷(第3期);第205-208页 * |
氮杂芳香类高能化合物的密度泛函理论研究;李玉芳;《南京理工大学硕士学位论文》;20100115;第18-27页 * |
Also Published As
Publication number | Publication date |
---|---|
CN105017261A (en) | 2015-11-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105669582A (en) | 5,5'-azodi(1-nitriminotetrazolate)bi-potassium compound | |
CN105669574B (en) | 3 fluorine are together with the triazole compounds of dinitro methyl 1,2,4 | |
Yongjin et al. | High energy density material (HEDM)‐Progress in research azine energetic compounds | |
CN105017261B (en) | 1,4-diazidomethyl-3,6-dinitropyrazolo[4,3-c] pyrazole compound | |
CN104693206B (en) | 1,4-dinitro oxygen methyl-3,6-binitropyrazole [4,3-c] pyrazole compound | |
CN108689959B (en) | Compounds and energetic ionic salts thereof | |
CN107698532A (en) | The diazanyl tetrazine salt compound of 1,5 dinitro aminotetrazole two | |
CN107488181A (en) | The binitropyrazole of 1,4 dinitro amido 3,6 [4,3 c] and the diazanyl tetrazine salt compound of pyrazoles two | |
CN105111213B (en) | 1,4-dyhydroxy-3,6-dinitropyrazole[4,3-c]benzothiazolyl compound | |
Yin et al. | Nitrogen-rich salts of 1-aminotetrazol-5-one: oxygen-containing insensitive energetic materials with high thermal stability | |
CN105294580A (en) | Compound 3,5-diamino-2,6-dinitropyrazine-1-oxide and preparation method thereof | |
CN108424398B (en) | 1,5- dinitro aminotetrazole 4- amino -1,2,4- triazole salt compound | |
CN106432113B (en) | Bis- (the chloro- 3- nitros -1,2,4- triazoles of the 5-) compounds of 1,1 '-azos | |
CN105646390B (en) | 3,4 pairs of (dinitro ylmethyl) furoxan dihydrazinites | |
CN105111156B (en) | 2 amino, 5,5 ' dinitro, 3,3 ' double (1,2,4 triazole) compounds | |
CN105949219B (en) | The oxide of the triazole of 4 amino 1,2,3 [4,5 e] furazano [3,4 b] pyrazine 6 | |
CN105153053B (en) | A kind of 3 together with 1,2,4 triazole of dinitro methyl synthetic method | |
CN105111157A (en) | 2, 2'-diamino-5, 5'-dinitro-3, 3'-bis (1, 2, 4-triazole) compound | |
CN102863595B (en) | Fullerene itaconic acid metal salt derivative as well as preparation method and application thereof | |
CN108299326B (en) | 1,5- dinitro aminotetrazole -3,4- diamino furazan salt compound | |
CN105198823B (en) | 4,6 dinitro benzos connect the oxide dicyandiamidines salt compound of triazole 1 | |
CN105820131A (en) | Di(3-nitro-1,2,4-triazole-5-yl)methylene glycol compound | |
CN108424399B (en) | 1,5- dinitro aminotetrazole -1- hydroxyl -5- Aminotetrazole salt compound | |
CN108285435B (en) | 1,5- dinitro aminotetrazole dicyandiamidines salt compound | |
Gao et al. | Hypergolic ionic liquid fuels and oxidizers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170412 Termination date: 20200814 |