CN105111156A - 2-amino-5, 5'-dinitro-3, 3'-bis (1, 2, 4-triazole) compound - Google Patents

2-amino-5, 5'-dinitro-3, 3'-bis (1, 2, 4-triazole) compound Download PDF

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Publication number
CN105111156A
CN105111156A CN201510603835.0A CN201510603835A CN105111156A CN 105111156 A CN105111156 A CN 105111156A CN 201510603835 A CN201510603835 A CN 201510603835A CN 105111156 A CN105111156 A CN 105111156A
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Prior art keywords
triazole
bis
amino
compound
dinitrobenzene
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CN201510603835.0A
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CN105111156B (en
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李亚南
罗义芬
王伯周
舒远杰
毕福强
张生勇
李祥志
翟连杰
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Xian Modern Chemistry Research Institute
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Xian Modern Chemistry Research Institute
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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
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/14—Nitrogen atoms

Abstract

The invention discloses a 2-amino-5, 5'-dinitro-3, 3'-bis (1, 2, 4-triazole) compound. The structural formula is described as (I) referring to the description. The 2-amino-5, 5'-dinitro-3, 3'-bis (1, 2, 4-triazole) compound is mainly applied to the field of energetic materials.

Description

Amino-5,5 '-dinitrobenzene-3,3 '-bis-(1,2, the 4-triazole) compound of 2-
Technical field
The present invention relates to a kind of energetic material, be specifically related to amino-5,5 '-dinitrobenzene-3,3 '-bis-(1,2, the 4-triazole) compound of a kind of 2-.
Background technology
In recent years, rich nitrogen energy-containing compound, as the energetic material of a class unique properties, because of end product mainly friendly, the free of contamination nitrogen of build environment of its burning or blast, and is usually applied to the research field such as explosive, propelling agent.Containing a large amount of N-N and N=N keys in this type of molecular structure of compounds, during decomposition, a large amount of nitrogen can be discharged, produce higher-energy; Stimulate insensitive to heat, friction, electrical spark etc., and have the features such as higher density, just Heat of Formation are large, better heat stability, therefore, countries in the world energetic material investigator creates larger concern to this compounds.Filter out part energy-containing compound simultaneously and carry out the research of its explorative research in fields such as the low sense explosive of high energy, gas-evolution agents.The people such as such as AlexanderA.Dippold are at " InsensitiveNitrogen-RichEnergeticCompoundsBasedonthe5,5 '-Dinitro-3,3 '-bi-1,2,4-triazol-2-ideAnion ", Eur.J.Inorg.Chem.2012,3474-3484 mono-discloses 5,5 '-dinitrobenzene-3 in literary composition, 3 '-bis-(1,2,4-triazole) structure of compound and the calculated performance of this compound, its structure is as shown in (II):
The calculated performance of this compound: nitrogen content is 49.6%, explosion velocity is 8413m/s, and detonation pressure is 32.0GPa, and Heat of Formation is 285.0kJ/mol.But this compound Heat of Formation is less, energy is lower.
Summary of the invention
Technical problem to be solved by this invention is the deficiency and the defect that overcome background technology, provides amino-5,5 '-dinitrobenzene-3,3 '-bis-(1,2, the 4-triazole) compound of the 2-that a kind of Heat of Formation is higher, energy is larger.
The synthetic route of amino-5,5 '-dinitrobenzene-3,3 '-bis-(1,2, the 4-triazole) compound of 2-of the present invention is as follows:
With the single sodium salt of 5,5 '-dinitrobenzene-3,3 '-bis-(1,2,4-triazole) for raw material, generate amino-5,5 '-dinitrobenzene-3,3 '-bis-(1,2, the 4-triazole) of 2-with hydroxylamine acid generation amination reaction.
Amino-5,5 '-dinitrobenzene-3,3 '-bis-(1,2, the 4-triazole) compound of 2-of the present invention, its structural formula is as shown in (I):
The synthetic method of amino-5,5 '-dinitrobenzene-3,3 '-bis-(1,2, the 4-triazole) of 2-of the present invention, comprises the following steps:
Under stirring at 20 ~ 25 DEG C, successively by 0.5g (2.02mmol) 5, 5 '-dinitrobenzene-3, 3 '-bis-(1, 2, 4-triazole) single sodium salt, 0.4g (3.77mol) sodium carbonate joins in 10.0mL water, be heated to 70 DEG C, drip the hydroxylamine acid aqueous solution of 2.0mL containing 0.46g (4.03mmol) hydroxylamine acid, after dropwising, add 0.7g (8.33mol) sodium bicarbonate in batches, at temperature 70 ~ 75 DEG C reaction 2.5h, reaction solution is cooled to 20 ~ 25 DEG C, with 36% ~ 38% (quality) concentrated hydrochloric acid adjust ph to 4 ~ 5, reacting liquid filtering, filter cake is through washing, dry 2-amino-5, 5 '-dinitrobenzene-3, 3 '-bis-(1, 2, 4-triazole).
Advantage of the present invention
Amino-5, the 5 '-dinitrobenzene-3,3 '-bis-(1,2 of 2-of the present invention, 4-triazole) compound Heat of Formation is higher, and its Heat of Formation is 490.7kJ/mol, 5 of documents, 5 '-dinitrobenzene-3, the Heat of Formation of 3 '-bis-(1,2,4-triazole) is 285.0kJ/mol; Amino-5, the 5 '-dinitrobenzene-3,3 '-bis-(1 of 2-of the present invention, 2,4-triazole) compound energy is higher, and calculating its explosion velocity is 8900.4m/s, detonation pressure is 35.9GPa, and quick-fried heat is 5666.9kJ/kg, 5 of documents, 5 '-dinitrobenzene-3, the calculating explosion velocity of 3 '-bis-(1,2,4-triazole) is 8413.0m/s, detonation pressure is 32.0GPa, and quick-fried heat is 4888.0kJ/kg.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The synthesis of amino-5,5 '-dinitrobenzene-3,3 '-bis-(1,2, the 4-triazole) of 2-
Under stirring at 20 ~ 25 DEG C, successively by 0.5g (2.02mmol) 5, 5 '-dinitrobenzene-3, 3 '-bis-(1, 2, 4-triazole) single sodium salt, 0.4g (3.77mol) sodium carbonate joins in 10.0mL water, be heated to 70 DEG C, drip the hydroxylamine acid aqueous solution of 2.0mL containing 0.46g (4.03mmol) hydroxylamine acid, after dropwising, add 0.7g (8.33mol) sodium bicarbonate in batches, at temperature 70 ~ 75 DEG C reaction 2.5h, reaction solution is cooled to 20 ~ 25 DEG C, with 36% ~ 38% (quality) concentrated hydrochloric acid adjust ph to 4 ~ 5, reacting liquid filtering, filter cake is through washing, dry 2-amino-5, 5 '-dinitrobenzene-3, 3 '-bis-(1, 2, 4-triazole) 0.146g, yield is 30.1%.
Structural Identification:
Infrared spectra: IR (KBr, cm -1), υ: 3567 (-NH), 3446,3384 (-NH 2), 1553,1529,1388,1312 (-NO 2), 1647,1042,839 (triazole ring)
Nuclear magnetic spectrum: 1hNMR (DMSO-d 6, 500MHz), δ: 3.393 (s, 1H, NH), 7.926 (s, 2H, NH 2); 13cNMR (DMSO-d 6, 125MHz), δ: 144.15,151.76,157.74,166.21
Ultimate analysis: molecular formula C 4h 3n 9o 4
Theoretical value: C19.92, H1.25, N52.28
Measured value: C19.87, H1.29, N52.32
Mass spectrum: (APCI) m/z:240 [M-H] -.
Said structure appraising datum confirms that obtaining material is amino-5,5 '-dinitrobenzene-3,3 '-bis-(1,2, the 4-triazole) of 2-really.
The performance of amino-5,5 '-dinitrobenzene-3,3 '-bis-(1,2, the 4-triazole) of 2-
(1) physical and chemical performance
Outward appearance: pale pink solid
Solubleness: be soluble in DMF, acetone, acetonitrile, methyl alcohol, ethanol etc.; Be slightly soluble in methylene dichloride, ether, sherwood oil, hexanaphthene etc.
Density: 1.88g/cm 3gaussian09 program B3LYP method nitrogen content: 52.3%
(2) detonation property
The purposes of amino-5,5 '-dinitrobenzene-3,3 '-bis-(1,2, the 4-triazole) of 2-
Amino-5,5 '-dinitrobenzene-3,3 '-bis-(1,2, the 4-triazole) compound of 2-of the present invention has that nitrogen content is high, Heat of Formation large, energy high, can be applied to energetic material field as high energy material component.

Claims (1)

1. 2-amino-5,5 '-dinitrobenzene-3,3 '-bis-(1,2,4-triazole) compound, its structural formula is as shown in (I):
CN201510603835.0A 2015-09-21 2015-09-21 2 amino, 5,5 ' dinitro, 3,3 ' double (1,2,4 triazole) compounds Active CN105111156B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109020906A (en) * 2018-06-14 2018-12-18 西南科技大学 A kind of energy-containing compound and its synthetic method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ALEXANDER A.DIPPOLD，ET AL.: "Insensitive Nitrogen-Rich Energetic Compounds Based on the 5,5’-Dinitro-3,3’-bi-1,2,4-triazol-2-ide Anion", 《EUR.J.INORG.CHEM.》 *
LULU HUANG，ET AL.: "APPLICATIONS OF ENERGETIC MATERIALS BY A THEORETICAL METHOD(DISCOVER ENERGETIC MATERIALS BY A THEORETICAL METHOD)", 《INTERNATIONAL JOURNAL OF ENERGETIC MATERIALS AND CHEMICAL PROPULSION》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109020906A (en) * 2018-06-14 2018-12-18 西南科技大学 A kind of energy-containing compound and its synthetic method and application

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