CN106432113A - 1,1'-azo bis(5-chloro-3-nitro-1,2,4-triazole) compound - Google Patents

1,1'-azo bis(5-chloro-3-nitro-1,2,4-triazole) compound Download PDF

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Publication number
CN106432113A
CN106432113A CN201610807719.5A CN201610807719A CN106432113A CN 106432113 A CN106432113 A CN 106432113A CN 201610807719 A CN201610807719 A CN 201610807719A CN 106432113 A CN106432113 A CN 106432113A
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Prior art keywords
nitro
compound
chloro
azo
triazole
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CN106432113B (en
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李亚南
尉涛
舒远杰
毕福强
汪伟
王伯周
张生勇
翟连杰
霍欢
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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
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a 1,1'-azo bis(5-chloro-3-nitro-1,2,4-triazole) compound with a structural formula (I) shown in the specification. The 1,1'-azo bis(5-chloro-3-nitro-1,2,4-triazole) compound is mainly used for the field of explosives.

Description

Double (the 5- chloro- 3- nitro -1,2,4- triazole) compound of 1,1 '-azo
Technical field
The invention belongs to energetic material field is and in particular to a kind of 1,1 '-azo double (5- chloro- 3- nitro -1,2,4- tri- Azoles) compound.
Background technology
High Nitrogen Heterocyclic Energetic Compounds, because containing substantial amounts of N-N and N=N key in its molecule, can discharge a large amount of during decomposition Nitrogen, therefore the features such as there is high density, high positive generation heat and detonation product clean.In recent years, multiple nitro azoles contain energy Compound is synthesized in succession, such as：3,5- dinitro -1,2,4- triazole, 1- amino 3,5- dinitro -1,2,4- three Azoles, 4- amino -3, the nitro azole energy-containing compound that 5- binitropyrazole etc., wherein 1- amino replace, the introducing of amino is permissible Forming more intramoleculars and intermolecular hydrogen bonding, thus improving the heat stability of compound, reducing sensitivity；More due to defining N-N key, can increase compound generation heat.Simultaneously because the reactivity of amino is so as to can conduct on 1 N atom Containing derivative reaction intermediate further occurring, formed and contain N, N '-azo group, nitramino, trinitro- ethylamino etc. contain energy The high energy energetic material of group.In the design of new energetic material and building-up process, substantial amounts of experience and test result indicate that： The N-N containing in compound molecule be joined directly together number of nitrogen atoms more although successfully synthesizing more difficult, but obtain compound There is higher just generation heat, therefore there is excellent comprehensive detonation property.
Ping Yin et al. exists《N-Diazo-Bridged Nitroazoles:Catenated Nitrogen-Atom Chains Compatible with Nitro Functionalities》, Chem.Eur.J., 2014,20,6707-6712 mono- Disclosed herein 1, the structure of double (3- nitro -1,2, the 4- triazoles) compound of 1 '-azo and performance, its structure is as shown in (II)：
The density of this compound is 1.80g/cm3, calculate and generate hot 718.8kJ/mol, explosion velocity 8825m/s, detonation pressure 33.5GPa.But this compound density is less, it is less to generate heat, energy is relatively low.
Content of the invention
The technical problem to be solved is to overcome not enough present in background technology and defect, provides a kind of density Double (the 5- chloro- 3- nitro -1,2,4- triazole) compound of 1,1 ' larger, generation heat is larger, energy is higher-azo.
The synthetic route of the 1,1 ' of the present invention-azo double (5- chloro- 3- nitro -1,2,4- triazole) is as follows：
With 1- amino -3,5- dinitro -1,2,4- triazoles are raw material, with t-butyl hypochlorate, oxidative coupling, chloro occur Reaction generation 1,1 '-azo is double (5- chloro- 3- nitro -1,2,4- triazole).
The 1 of the present invention, double (5- chloro- 3- nitro -1,2, the 4- triazoles) compound of 1 '-azo, its structural formula is as shown in (I)：
The 1 of the present invention, the synthetic method of 1 '-azo double (5- chloro- 3- nitro -1,2,4- triazoles), comprise the following steps：Stir Mix down, 20 DEG C～25 DEG C, by 1- amino -3,5- dinitro -1,2,4- triazoles are added in anhydrous acetonitrile, 0 DEG C～5 DEG C additions time The chloric acid tert-butyl ester, is heated to 15 DEG C～45 DEG C reaction 15h～25h, adds ethyl acetate, cold water washs organic faciess, anhydrous Magnesium sulfate is dried, and removes organic solvent under reduced pressure and obtains 1, and 1 '-azo is double (5- chloro- 3- nitro -1,2,4- triazoles)；Wherein 1- amino- 3,5- dinitro -1,2,4- triazole is 1 with the mol ratio of t-butyl hypochlorate:1.5～2.5, the consumption of anhydrous acetonitrile is every gram 1- amino -3,5- dinitro -1,2,4- triazole 30.0～100.0mL.
Advantages of the present invention：
The 1 of the present invention, double (5- chloro- 3- nitro -1,2,4- triazoles) the compound density of 1 '-azo is larger, and its density is 1.922g/cm3, the 1 of documents, the density of 1 '-azo double (3- nitro -1,2,4- triazoles) is 1.80g/cm3；The present invention's 1,1 '-azo double (5- chloro- 3- nitro -1,2,4- triazoles) compound calculating generation heat is larger, and it generates heat for 774.8kJ/ Mol, the 1 of documents, the generation heat of 1 '-azo double (3- nitro -1,2,4- triazoles) is 718.8kJ/mol；The 1 of the present invention, Double (5- chloro- 3- nitro -1,2,4- triazoles) the compound energy of 1 '-azo is higher, and calculating its explosion velocity is 8827m/s, and detonation pressure is 35.8GPa, the 1 of documents, the calculating explosion velocity of 1 '-azo double (3- nitro -1,2,4- triazoles) is 8825m/s, and detonation pressure is 33.5GPa.
Specific embodiment
With reference to embodiment, the present invention is described in further details.
Embodiment 1
Under stirring, in 20 DEG C～25 DEG C of temperature, by 0.174g (1mmol) 1- amino -3,5- dinitro -1,2,4- triazoles add Enter in 7.0mL anhydrous acetonitrile, ice-water bath is cooled to 0 DEG C～5 DEG C, add 0.185g (1.7mmol) t-butyl hypochlorate, heating It is warming up to 25 DEG C～30 DEG C reaction 20h, add 30.0mL ethyl acetate, cold water (8.0mL × 5) washs organic faciess, anhydrous slufuric acid Magnesium is dried, and removes organic solvent under reduced pressure and obtains 1, double (5- chloro- 3- nitro -1,2, the 4- triazoles) 0.113g of 1 '-azo, and yield is 65.7%.
Structural Identification：
Infrared spectrum：IR(KBr,cm-1),υ：1650,1574,1507,1446,1388,1347,1303,1242,1218, 1097,1000,844,743,678,664,630,579
Nuclear magnetic spectrum：13CNMR(DMSO-d6,125MHz),δ：141.73,158.73
Elementary analysiss：Molecular formula C4N10O4Cl2
Theoretical value：C 14.87,N 43.36
Measured value：C 14.92,N 43.29
Mono-crystalline structures：This compound crystal is monoclinic system, and space group is P2 (1)/c, and crystallographic parameter is： α=90 °, β=105.495 (11) °, γ=90 °,Z= 4, μ=0.619mm-1, F (000)=640.
Said structure appraising datum confirms that obtaining material is strictly double (the 5- chloro- 3- nitro -1,2,4- three of 1,1 '-azo Azoles).
The performance of 1,1 '-azo double (5- chloro- 3- nitro -1,2,4- triazole)
(1) physical and chemical performance
Outward appearance：Yellowish-brown mealy crystal
Dissolubility：It is soluble in dimethyl sulfoxide, N,N-dimethylformamide, acetone, acetonitrile, methanol, ethanol, ethyl acetate Deng；
It is slightly soluble in water, ether, petroleum ether, hexamethylene etc.
Density：1.922g/cm3X- monocrystalline x ray diffractometer x
(2) detonation property
Explosion velocity：Density is 1.922g/cm3, calculating explosion velocity is 8827m/s K-J equation
Detonation pressure：Density is 1.922g/cm3, calculating detonation pressure is 35.8GPa K-J equation
Generate heat：Density is 1.922g/cm3, calculating and generating heat is 774.8kJ/mol K-J equation
Quick-fried heat：Density is 1.922g/cm3, calculating quick-fried heat is 6283.4kJ/kg K-J equation
The purposes of 1,1 '-azo double (5- chloro- 3- nitro -1,2,4- triazole)
Double (the 5- chloro- 3- nitro -1,2,4- triazole) compound of the 1,1 ' of the present invention-azo has that density is big, it is big to generate heat, The features such as energy is high, can apply to energetic material field.

Claims (1)

1. one kind 1, double (5- chloro- 3- nitro -1,2, the 4- triazoles) compound of 1 '-azo, its structural formula is as shown in (I)：
CN201610807719.5A 2016-09-07 2016-09-07 Bis- (the chloro- 3- nitros -1,2,4- triazoles of the 5-) compounds of 1,1 '-azos Active CN106432113B (en)

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Cited By (2)

* 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
CN114573518A (en) * 2022-03-14 2022-06-03 中国科学院上海有机化学研究所 4-cyano-5-nitro-1, 2, 3-triazole metal salt, and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5889161A (en) * 1998-05-13 1999-03-30 Sri International N,N'-azobis-nitroazoles and analogs thereof as igniter compounds for use in energetic compositions
CN104725328A (en) * 2015-03-20 2015-06-24 西安近代化学研究所 Synthesis method of 1,1'-azo-bis(3,5-dinitro-1,2,4-triazole)

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5889161A (en) * 1998-05-13 1999-03-30 Sri International N,N'-azobis-nitroazoles and analogs thereof as igniter compounds for use in energetic compositions
CN104725328A (en) * 2015-03-20 2015-06-24 西安近代化学研究所 Synthesis method of 1,1'-azo-bis(3,5-dinitro-1,2,4-triazole)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《J MOL MODEL》 *

Cited By (3)

* 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
CN114573518A (en) * 2022-03-14 2022-06-03 中国科学院上海有机化学研究所 4-cyano-5-nitro-1, 2, 3-triazole metal salt, and preparation method and application thereof
CN114573518B (en) * 2022-03-14 2024-02-06 中国科学院上海有机化学研究所 4-cyano-5-nitro-1, 2, 3-triazole metal salt, preparation method and application thereof

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