CN105272929A - 5-nitryl-1,2,4-triazole-5-ketone compound of oxalyl dihydrazide - Google Patents

5-nitryl-1,2,4-triazole-5-ketone compound of oxalyl dihydrazide Download PDF

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Publication number
CN105272929A
CN105272929A CN201510731100.6A CN201510731100A CN105272929A CN 105272929 A CN105272929 A CN 105272929A CN 201510731100 A CN201510731100 A CN 201510731100A CN 105272929 A CN105272929 A CN 105272929A
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China
Prior art keywords
triazole
nitro
oxalyl
hydrazine
oxalyl hydrazine
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CN201510731100.6A
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贾思媛
王伯周
毕福强
霍欢
廉鹏
周诚
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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a 5-nitryl-1,2,4-triazole-5-ketone compound of oxalyl dihydrazide, wherein the structural formula of the compound is as follows: a figure (I). The 5-nitryl-1,2,4-triazole-5-ketone compound of the oxalyl dihydrazide is mainly applied to the technical field of explosives, propellants and fireworks.

Description

5-nitro-1,2, the 4-triazole-5-ketone salt compound of oxalyl hydrazine
Technical field
The present invention relates to a kind of 5-nitro-1,2,4-triazole-5-ketone salt compound of oxalyl hydrazine, belong to organic synthesis.
Background technology
The organic salt of oxalyl hydrazine, as a class height nitrogen heterocycles energetic materials, has high-energy, low signature, burning without residue, the advantage such as pollution-free, can be widely used in explosive, propelling agent and pyrotechnic field.In addition, because it has that nitrogen content is high, gas production rate is large and the advantage such as nontoxic, be expected to become the surrogate of sodiumazide and be used in air bag.Such as 2014, the people such as DennisFischer are at " Oxalylhydraziniumnitrateanddinitrate – efficiencymeetsperformance " Journalofenergeticmaterials, 14 (2), disclose the structure of dinitrate compound and the synthetic method of this compound of oxalyl hydrazine in 37-49 mono-literary composition, its structure is as shown in (II):
The density of this compound is 1.9g/cm 3, explosion velocity is 8594m/s, impact sensitivity 7J, friction sensitivity 200N, but this compound decomposition temperature and nitrogen content lower.
Summary of the invention
Technical problem to be solved by this invention is the deficiency and the defect that overcome background technology, provides a kind of decomposition temperature higher, 5-nitro-1,2, the 4-triazole-5-ketone salt compound of the oxalyl hydrazine that nitrogen content is higher.
5-nitro-1,2, the 4-triazole-5-ketone salt of oxalyl hydrazine of the present invention, its structural formula is as shown in (I):
The synthetic route of 5-nitro-1,2, the 4-triazole-5-ketone salt compound of oxalyl hydrazine of the present invention:
Be that raw material and hydrazine hydrate generation substitution reaction generate oxalyl hydrazine with oxalic acid diethyl ester, oxalyl hydrazine obtains 5-nitro-1,2, the 4-triazole-5-ketone salt compound of oxalyl hydrazine in ethanol with 5-nitro-1,2,4-triazole-5-ketone generation replacement(metathesis)reaction.
The synthetic method of 5-nitro-1,2, the 4-triazole-5-ketone salt of oxalyl hydrazine of the present invention, comprises the following steps:
(1) oxalyl hydrazine (ODH) synthesis
Under room temperature, by hydrazine hydrate join in acetonitrile, then drip diethyl oxalate, after dropwising, at room temperature reaction 4h, reacting liquid filtering, filter cake is through ethanol rinse, dry oxalyl hydrazine, and wherein the mol ratio of hydrazine hydrate and diethyl oxalate is 1:1
(2) 5-nitro-1,2, the 4-triazole-5-ketone salt synthesis of oxalyl hydrazine
Under room temperature, by 5-nitro-1,2,4-triazole-5-ketone is added to the water, and is warming up to 80 DEG C, adds oxalyl hydrazine in batches, after reinforced, at 80 DEG C of reaction 2h, cooling, reacting liquid filtering, filter cake is through water and ethanol rinse, dry solid oxalyl hydrazine 5-nitro-1,2,4-triazole-5-ketone salt, wherein the mol ratio of 5-nitro-1,2,4-triazole-5-ketone and oxalyl hydrazine is 1:1
Advantage of the present invention:
Its decomposition point of 5-nitro-1,2,4-triazole-5-ketone salt compound of oxalyl hydrazine of the present invention is 195.2 DEG C, and the decomposition point of the dinitrate of the oxalyl hydrazine of documents is 155 DEG C; The nitrogen content of 5-nitro-1,2, the 4-triazole-5-ketone salt of oxalyl hydrazine is 45%, and the nitrogen content of the dinitrate of the oxalyl hydrazine of documents is 34%.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Be below the embodiment that contriver provides, it should be noted that, these embodiments are preferably examples, are mainly used in understanding the present invention, but the invention is not restricted to these embodiments.
Embodiment 1
(1) oxalyl hydrazine (ODH) synthesis
Under room temperature, the hydrazine hydrate of 6mL80% (quality) is joined in 100mL acetonitrile, drip 7.31g (0.05mol) diethyl oxalate, after dropwising, at room temperature reaction 4h, reacting liquid filtering, filter cake is through ethanol rinse, dry oxalyl hydrazine 5.73g, yield 97%, purity 98%;
Infrared spectra: IR (KBr, cm -1), υ: 3284,3180,1646,1579,1531,1421,1319,1293,1255,1124,952,828,718;
Nuclear magnetic spectrum: 13cNMR (DMSO-d 6, ppm), δ: 158.4;
1HNMR(DMSO-d 6,ppm)δ:9.93(2H)，4.47(4H)
Ultimate analysis: molecular formula C 2h 6n 4o 2
Theoretical value (%): C20.34, N47.44, H5.12
Measured value (%): C20.15, N47.52, H4.78
The material that said structure appraising datum proved step obtains is ODH really
(2) 5-nitro-1,2, the 4-triazole-5-ketone salt synthesis of oxalyl hydrazine
Under room temperature, by 1.3g (10mmol) 5-nitro-1,2,4-triazole-5-ketone joins in 15mL water, is warming up to 80 DEG C, adds 1.18g (10mmol) oxalyl hydrazine in batches, after reinforced, at 80 DEG C of reaction 2h, cooling, reacting liquid filtering, filter cake is through water and ethanol rinse, dry faint yellow solid oxalyl hydrazine 5-nitro-1,2,4-triazole-5-ketone salt 2.1g, yield 88%.
Infrared spectra: IR (KBr, cm -1), υ: 3305,3210,3181,2964,2793,1682,1631,1510,1275,1100,1003,800; Nuclear magnetic spectrum: 13cNMR (DMSO-d 6, ppm), δ: 158.94,158.35,157.44;
1HNMR(DMSO-d 6,ppm)δ:9.89，4.70，3.28；
Ultimate analysis: molecular formula C 4h 8n 8o 5
Theoretical value (%): C19.35, N45.16, H3.23
Measured value (%): C19.51, N45.21, H3.13
The material that said structure appraising datum proved step obtains is 5-nitro-1,2, the 4-triazole-5-ketone salt of oxalyl hydrazine really
The performance of 5-nitro-1,2, the 4-triazole-5-ketone salt of oxalyl hydrazine
1, physical and chemical performance
Solubleness: easy molten dimethyl sulfoxide (DMSO), DMF; Be slightly soluble in ethanol, ethyl acetate, methylene dichloride, chloroform, ethylene dichloride, water etc.;
Density: 1.69g/cm 3gaussian09 program B3LYP method
2, fusing point decomposition point
Fusing point: 187.88 DEG C of DSC methods
Decomposition point: 195.52 DEG C of DSC methods
3, detonation property
Explosion velocity: density is 1.69g/cm 3, calculating explosion velocity is 7047.5m/sK-J equation
Detonation pressure: density is 1.69g/cm 3, calculating detonation pressure is 21.2GPaK-J equation
Quick-fried heat: density is 1.69g/cm 3, calculating quick-fried heat is 3342.7kJ/kgK-J equation
Enthalpies of Formation: density is 1.69g/cm 3, calculating Enthalpies of Formation is-335.36kJ/kgGaussian09 program B3LYP method
The purposes of 5-nitro-1,2, the 4-triazole-5-ketone salt of oxalyl hydrazine
5-nitro-1,2, the 4-triazole-5-ketone salt compound of oxalyl hydrazine of the present invention has that sensitivity is low, low signature, burning without residue, the advantage such as pollution-free, explosive, propelling agent and pyrotechnic field can be widely used in.In addition, because it has that nitrogen content is higher, gas production rate is large and the advantage such as nontoxic, be expected to become the surrogate of sodiumazide and be used in air bag.

Claims (1)

1. 5-nitro-1,2, the 4-triazole-5-ketone salt compound of an oxalyl hydrazine, its structural formula is as shown in (I):
CN201510731100.6A 2015-11-02 2015-11-02 5-nitryl-1,2,4-triazole-5-ketone compound of oxalyl dihydrazide Pending CN105272929A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105753798A (en) * 2016-03-24 2016-07-13 北京理工大学 Novel gas generation compounds
CN111807986A (en) * 2020-06-22 2020-10-23 江苏大学 Synthetic method of oxalyl hydrazine ligand and application of oxalyl hydrazine ligand in C-N bond coupling reaction
CN112125858A (en) * 2020-09-11 2020-12-25 南京理工大学 Gemini energetic ion compound and preparation method thereof

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US3960946A (en) * 1972-03-10 1976-06-01 Thiokol Corporation Process for the manufacture of oxalyl dihydrazide and the use of same as a coolant in gas generating compositions
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US3839105A (en) * 1972-03-10 1974-10-01 Thiokol Chemical Corp Oxalyl dihydrazide compositions and use as a coolant in gas generating process
US3960946A (en) * 1972-03-10 1976-06-01 Thiokol Corporation Process for the manufacture of oxalyl dihydrazide and the use of same as a coolant in gas generating compositions
WO1998004507A1 (en) * 1996-07-29 1998-02-05 Automotive Systems Laboratory, Inc. Thermally stable nonazide automotive airbag propellants
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CN103408454A (en) * 2013-08-16 2013-11-27 兰州大学 Preparation method of hydrazide compound
CN104458807A (en) * 2014-11-19 2015-03-25 西安近代化学研究所 Method for measuring nitration reaction heat effect in nitro energy compound preparation process
CN104447762A (en) * 2014-12-08 2015-03-25 北京理工大学 Energetic ionic salts of 7-nitryl-4-ketone-4,8-dihydro-[1,2,4] triazole [5,1-d] [1,2,3,5] tetrazine-2-oxide and preparation method of energetic ionic salt

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105753798A (en) * 2016-03-24 2016-07-13 北京理工大学 Novel gas generation compounds
CN111807986A (en) * 2020-06-22 2020-10-23 江苏大学 Synthetic method of oxalyl hydrazine ligand and application of oxalyl hydrazine ligand in C-N bond coupling reaction
CN112125858A (en) * 2020-09-11 2020-12-25 南京理工大学 Gemini energetic ion compound and preparation method thereof

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Application publication date: 20160127