CN104725328A - Synthesis method of 1,1'-azo-bis(3,5-dinitro-1,2,4-triazole) - Google Patents

Synthesis method of 1,1'-azo-bis(3,5-dinitro-1,2,4-triazole) Download PDF

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Publication number
CN104725328A
CN104725328A CN201510125465.4A CN201510125465A CN104725328A CN 104725328 A CN104725328 A CN 104725328A CN 201510125465 A CN201510125465 A CN 201510125465A CN 104725328 A CN104725328 A CN 104725328A
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triazole
dinitrobenzene
azo
amino
virahol
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李亚南
王伯周
舒远杰
汪营磊
刘宁
李祥志
李辉
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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention discloses a synthesis method of a 1,1'-azo-bis(3,5-dinitro-1,2,4-triazole) compound, which comprises the following steps: while stirring, adding 1-amino-3,5-dinitro-1,2,4-triazole into anhydrous acetonitrile at 20-25 DEG C, keeping introducing nitrogen in the reaction bulb, adding butyl hypochlorate at 0-5 DEG C, heating to 15-45 DEG C, reacting for 10-30 hours, adding isopropanol, stirring, filtering, eluting the filter cake with isopropanol, washing with cold water, and drying to obtain the 1,1'-azo-bis(3,5-dinitro-1,2,4-triazole). The method is mainly used for synthesizing the 1,1'-azo-bis(3,5-dinitro-1,2,4-triazole).

Description

1, the synthetic method of 1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole)
Technical field
The invention belongs to energetic material field, be specifically related to a kind of 1, the synthetic method of 1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole).
Background technology
Triazole species energy-containing compound, because containing a large amount of C-N, N-N, C=N and N=N keys in molecule, discharges a large amount of nitrogen, has the features such as high compactness, high Enthalpies of Formation and environmental friendliness, and become explosive area research focus during decomposition.In recent years, multiple nitro azole energy-containing compound is synthesized out in succession, such as: 3,5-binitropyrazole, 3,5-dinitrobenzene-1,2,4-triazole, 4-amino-3,5-binitropyrazole etc., but also fewer about nitro-triazole nitrogen amic research report, H atom is relatively more active on 1 N of nitro-triazole compounds, introduces amino and can be formed in molecule and intermolecular hydrogen bonding, thus improve the thermostability of compound, reduce sensitivity; Simultaneously due to the existence of N-N key, Heat of Formation can be increased.Nitro-triazole nitrogen amide is all right as containing energy intermediate, and amino can form nitramino, trinitro-ethylamino, azo-group etc. further containing energy group.Such as T.M. deng amino-3,5-dinitrobenzene-1,2, the 4-triazole compounds (ADNT) of 1-disclosed in people, theoretical density is 1.88g/cm 3, explosion velocity is 8981m/s as calculated, and detonation pressure is 38.2GPa, Enthalpies of Formation 258.3kJ/mol.
U.S. Bottaro, J.C.; Schmitt, R.J.; Penwell, P.E. " N, N'-azobis-nitroazoles and analogs thereofasigniter compounds for use in energetic compositions ", 1999, US 5889161 discloses 1,1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole) structure, have no relevant performance data report, this compound structure is as follows:
Calculate through contriver, 1, (BDNTA) is a kind of energy to 1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole), density is better than ADNT containing N 6many nitros azole energy-containing compound of structure, its density is 1.92g/cm 3, explosion velocity is 9411.9m/s, and detonation pressure is 38.7GPa, Enthalpies of Formation 471.1kJ/mol, is a kind of energetic material of high comprehensive performance.Therefore, synthesizing this compound has its realistic meaning, but this United States Patent (USP) does not disclose the synthetic technological condition of BDNTA, yield and structural characterization data.
" Amination of energetic anions:high-performing energetic materials ", DaltonTransactions, 2012,41, a kind of 2 are disclosed in 9451-9459 literary composition, the synthetic method of 2 '-azo two (5-nitro tetrazolium), the method is under ice-water bath cooling conditions, with 2-amino-5-nitro tetrazolium for raw material, dichloroisocyanuric acid sodium (NaDCl) is oxidative coupling reagent, by oxidative coupling reaction synthesis 2,2 '-azo two (5-nitro tetrazolium), but do not disclose the synthesis yield of this compound.Its synthetic route is as follows:
The method needs to prepare oxidative coupling reagent in advance, needs omnidistance cold condition in experiment reaction process, and whole preparation manipulation process need passes through neutralization, filters, concentrates, repeatedly washs operation stepss such as (deacidifying, except alkali).And the density of this compound is less, explosion velocity is lower.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiency and defect that exist in background technology, provide that a kind of reaction conditions is gentle, operating process is easy 1, and the synthetic method of 1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole).
Of the present invention 1, the synthetic route of 1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole) is as follows:
In order to solve the problems of the technologies described above, of the present invention 1, the synthetic method of 1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole), 1, the structural formula of 1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole) is as shown in (I):
With 1-amino-3,5-dinitrobenzene-1,2,4-triazole compounds is raw material, its structural formula is as shown in (II), comprise the following steps: under stirring, 20 DEG C ~ 25 DEG C, by 1-amino-3,5-dinitrobenzene-1,2,4-triazole joins in anhydrous acetonitrile, keeps logical nitrogen in reaction flask, 0 DEG C ~ 5 DEG C add t-butyl hypochlorate, be heated to 15 DEG C ~ 45 DEG C reaction 10h ~ 30h, add Virahol and stir, filter, filter cake is through Virahol drip washing, cold wash, dry 1,1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole); Wherein 1-amino-3, the mol ratio of 5-dinitrobenzene-1,2,4-triazole and t-butyl hypochlorate is 1:1 ~ 3, the consumption of anhydrous acetonitrile is every gram of 1-amino-3,5-dinitrobenzene-1,2,4-triazole 50.0 ~ 200.0mL, the consumption of Virahol is every gram of 1-amino-3,5-dinitrobenzene-1,2,4-triazole 5.0 ~ 40.0mL.
The present invention preferred 1,1 '-azo two (3,5-binitropyrazole) synthetic method, comprise the following steps: under stirring, temperature 20 DEG C ~ 25 DEG C, by 1-amino-3,5-dinitrobenzene-1,2,4-triazole joins in anhydrous acetonitrile, keeps logical nitrogen in reaction flask, 0 DEG C ~ 5 DEG C add t-butyl hypochlorate, be heated to 20 DEG C ~ 25 DEG C reaction 20h, add Virahol and stir, filter, filter cake is through Virahol drip washing, cold wash, dry 1,1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole); Wherein the mol ratio of amino-3,5-dinitrobenzene-1,2, the 4-triazoles of 1-and t-butyl hypochlorate is 1:1.3, the consumption of anhydrous acetonitrile is every gram of 1-amino-3,5-dinitrobenzene-1,2,4-triazole 100.0mL, the consumption of Virahol is every gram of 1-amino-3,5-dinitrobenzene-1,2,4-triazole 20.0mL.
Advantage of the present invention:
Of the present invention 1, 1 '-azo two (3, 5-dinitrobenzene-1, 2, 4-triazole) synthesising method reacting condition gentle, operating process is easy, the method is reacted at ambient temperature, after filtration, washing operation prepares 1, 1 '-azo two (3, 5-dinitrobenzene-1, 2, 4-triazole), yield is 41.5%, purity is 98.3%, and in documents 2, the synthetic method of 2 '-azo two (5-nitro tetrazolium), need to react under ice-water bath condition, through neutralization, filter, concentrated, repeatedly wash (deacidification, except alkali) etc. operation preparation 2, 2'-azo two (5-nitro tetrazolium).
Embodiment
Below in conjunction with embodiment, the present invention is described in further details.
Embodiment 1
Under stirring, temperature 20 DEG C ~ 25 DEG C, by 0.10g (0.58mmol) 1-amino-3,5-dinitrobenzene-1,2,4-triazole joins in 10.0mL anhydrous acetonitrile, and in reaction flask, keep logical nitrogen, 0 DEG C ~ 5 DEG C add 0.082g (0.75mmol) t-butyl hypochlorate, be heated to 20 DEG C ~ 25 DEG C reaction 20h, add 1.0mL Virahol to stir, filter, filter cake through Virahol drip washing, cold wash, dry 1,1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole) 0.041g, yield is 41.5%.
Structural Identification:
Infrared spectra: IR (KBr, cm -1), υ: 1661,1657 (C=N), 1570,1371,1329 (-NO 2), 1397,1250,1122,1012 (triazole ring)
Nuclear magnetic spectrum: 13cNMR (DMSO-d 6, 125MHz), δ: 133.45,141.66
Ultimate analysis: molecular formula C 4n 12o 8
Theoretical value: C 13.96, N 48.84
Measured value: C 13.92, N 48.87
Mass spectrum: (EI) m/z:344 [M +].
Said structure appraising datum confirms that obtaining material is 1 really, 1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole).
Embodiment 2
Under stirring, temperature 20 DEG C ~ 25 DEG C, by 0.10g (0.58mmol) 1-amino-3,5-dinitrobenzene-1,2,4-triazole joins in 5.0mL anhydrous acetonitrile, and in reaction flask, keep logical nitrogen, 0 DEG C ~ 5 DEG C add 0.062g (0.58mmol) t-butyl hypochlorate, be heated to 20 DEG C ~ 25 DEG C reaction 20h, add 0.5mL Virahol to stir, filter, filter cake through Virahol drip washing, cold wash, dry 1,1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole) 0.030g, yield is 30.3%.
Embodiment 3
Under stirring, temperature 20 DEG C ~ 25 DEG C, by 0.10g (0.58mmol) 1-amino-3,5-dinitrobenzene-1,2,4-triazole joins in 15.0mL anhydrous acetonitrile, and in reaction flask, keep logical nitrogen, 0 DEG C ~ 5 DEG C add 0.19g (1.74mmol) t-butyl hypochlorate, be heated to 20 DEG C ~ 25 DEG C reaction 20h, add 3.0mL Virahol to stir, filter, filter cake through Virahol drip washing, cold wash, dry 1,1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole) 0.039g, yield is 39.4%.
Embodiment 4
Under stirring, temperature 20 DEG C ~ 25 DEG C, by 0.10g (0.58mmol) 1-amino-3,5-dinitrobenzene-1,2,4-triazole joins in 20.0mL anhydrous acetonitrile, and in reaction flask, keep logical nitrogen, 0 DEG C ~ 5 DEG C add 0.062g (0.58mmol) t-butyl hypochlorate, be heated to 10 DEG C ~ 15 DEG C reaction 10h, add 4.0mL Virahol to stir, filter, filter cake through Virahol drip washing, cold wash, dry 1,1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole) 0.025g, yield is 25.3%.
Embodiment 5
Under stirring, temperature 20 DEG C ~ 25 DEG C, by 0.10g (0.58mmol) 1-amino-3,5-dinitrobenzene-1,2,4-triazole joins in 15.0mL anhydrous acetonitrile, and in reaction flask, keep logical nitrogen, 0 DEG C ~ 5 DEG C add 0.19g (1.74mmol) t-butyl hypochlorate, be heated to 40 DEG C ~ 45 DEG C reaction 30h, add 1.0mL Virahol to stir, filter, filter cake through Virahol drip washing, cold wash, dry 1,1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole) 0.031g, yield is 31.3%.
Embodiment 6
Under stirring, temperature 20 DEG C ~ 25 DEG C, by 0.10g (0.58mmol) 1-amino-3,5-dinitrobenzene-1,2,4-triazole joins in 10.0mL anhydrous acetonitrile, and in reaction flask, keep logical nitrogen, 0 DEG C ~ 5 DEG C add 0.10g (0.92mmol) t-butyl hypochlorate, be heated to 30 DEG C ~ 35 DEG C reaction 25h, add 1.5mL Virahol to stir, filter, filter cake through Virahol drip washing, cold wash, dry 1,1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole) 0.041g, yield is 41.5%.
Embodiment 7
Under stirring, temperature 20 DEG C ~ 25 DEG C, by 0.10g (0.58mmol) 1-amino-3,5-dinitrobenzene-1,2,4-triazole joins in 10.0mL anhydrous acetonitrile, and in reaction flask, keep logical nitrogen, 0 DEG C ~ 5 DEG C add 0.19g (1.74mmol) t-butyl hypochlorate, be heated to 25 DEG C ~ 30 DEG C reaction 15h, add 2.5mL Virahol to stir, filter, filter cake through Virahol drip washing, cold wash, dry 1,1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole) 0.038g, yield is 38.4%.
Embodiment 8
Under stirring, temperature 20 DEG C ~ 25 DEG C, by 0.10g (0.58mmol) 1-amino-3,5-dinitrobenzene-1,2,4-triazole joins in 10.0mL anhydrous acetonitrile, and in reaction flask, keep logical nitrogen, 0 DEG C ~ 5 DEG C add 0.082g (0.75mmol) t-butyl hypochlorate, be heated to 20 DEG C ~ 25 DEG C reaction 24h, add 2.0mL Virahol to stir, filter, filter cake through Virahol drip washing, cold wash, dry 1,1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole) 0.041g, yield is 41.5%.

Claims (2)

1. one kind 1, the synthetic method of 1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole), 1, two (3,5-dinitrobenzene-1,2, the 4-triazole) structural formula of 1 '-azo is as shown in (I):
With 1-amino-3,5-dinitrobenzene-1,2,4-triazole is raw material, its structural formula is as shown in (II), comprise the following steps: under stirring, 20 DEG C ~ 25 DEG C, by 1-amino-3,5-dinitrobenzene-1,2,4-triazole joins in anhydrous acetonitrile, keeps logical nitrogen in reaction flask, 0 DEG C ~ 5 DEG C add t-butyl hypochlorate, be heated to 15 DEG C ~ 45 DEG C reaction 10h ~ 30h, add Virahol and stir, filter, filter cake is through Virahol drip washing, cold wash, dry 1,1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole); Wherein 1-amino-3, the mol ratio of 5-dinitrobenzene-1,2,4-triazole and t-butyl hypochlorate is 1:1 ~ 3, the consumption of anhydrous acetonitrile is every gram of 1-amino-3,5-dinitrobenzene-1,2,4-triazole 50.0 ~ 200.0mL, the consumption of Virahol is every gram of 1-amino-3,5-dinitrobenzene-1,2,4-triazole 5.0 ~ 40.0mL.
2. according to claim 11, two (3, the 5-dinitrobenzene-1,2 of 1 '-azo, 4-triazole) synthetic method, comprise the following steps: under stirring, temperature 20 DEG C ~ 25 DEG C, by 1-amino-3,5-dinitrobenzene-1,2,4-triazole joins in anhydrous acetonitrile, keeps logical nitrogen in reaction flask, 0 DEG C ~ 5 DEG C add t-butyl hypochlorate, be heated to 20 DEG C ~ 25 DEG C reaction 20h, add Virahol and stir, filter, filter cake is through Virahol drip washing, cold wash, dry 1,1 '-azo two (3,5-dinitrobenzene-1,2,4-triazole); Wherein the mol ratio of amino-3,5-dinitrobenzene-1,2, the 4-triazoles of 1-and t-butyl hypochlorate is 1:1.3, the consumption of anhydrous acetonitrile is every gram of 1-amino-3,5-dinitrobenzene-1,2,4-triazole 100.0mL, the consumption of Virahol is every gram of 1-amino-3,5-dinitrobenzene-1,2,4-triazole 20.0mL.
CN201510125465.4A 2015-03-20 2015-03-20 Synthesis method of 1,1'-azo-bis(3,5-dinitro-1,2,4-triazole) Pending CN104725328A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106432113A (en) * 2016-09-07 2017-02-22 西安近代化学研究所 1,1'-azo bis(5-chloro-3-nitro-1,2,4-triazole) compound
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 (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999058506A1 (en) * 1998-05-13 1999-11-18 Sri International N,n'-azobis-nitroazoles and analogs thereof as igniter compounds for use in energetic compositions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999058506A1 (en) * 1998-05-13 1999-11-18 Sri International N,n'-azobis-nitroazoles and analogs thereof as igniter compounds for use in energetic compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
THOMAS M. KLAPöTKE，ET AL.: "Amination of energetic anions: high-performing energetic materials", 《DALTON TRANSACTIONS》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106432113A (en) * 2016-09-07 2017-02-22 西安近代化学研究所 1,1'-azo bis(5-chloro-3-nitro-1,2,4-triazole) compound
CN106432113B (en) * 2016-09-07 2018-10-12 西安近代化学研究所 Bis- (the chloro- 3- nitros -1,2,4- triazoles of the 5-) compounds of 1,1 '-azos
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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