A z-(4-amino-1,2,5 furazanyl)-5-nitrotetrazole-oxime compound, synthesis method and application

Abstract

The application discloses a Z-(4-amino-1,2,5 furazanyl)-5-nitrotetrazole-oxime compound, a synthesis method and application. The structural formula of the disclosed compound is shown as (I). The density and the theoretical detonation velocity of the Z-(4-amino-1,2,5 furazanyl)-5-nitrotetrazole-oxime of the application are significantly improved compared with existing substances, and the Z-(4-amino-1,2,5 furazanyl)-5-nitrotetrazole-oxime can be used as a new energetic material.

Description

Technical Field

[0001] This invention belongs to the field of energetic materials technology, specifically relating to a Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compound. Background Technology

[0002] Currently, no high-energy structures of oxime-bridged tetrazolium and furazolidone have been reported in the literature. Only VG Andrianov et al. have attempted to use oxime groups to bridge isofuranozone and imidazole rings. The structure of 3-(imidazol-1-yl)-1,2,4-oxadiazole oxime is reported in the literature Rearrangements of 1-oxa-2-azoles. 7. Synthesis and heterocyclization of 3-acyl-1,2,4-oxadiazoleoxime. Chemistry of Heterocyclic Compounds, 27.8 (1991): 901-902. is shown in (II).

[0003]

[0004] The density of this compound, calculated using the Gaussian 09 program, is 1.672 g / cm³. 3 The detonation performance was calculated using EXPLO5, with a theoretical detonation velocity of 6476 m / s and a theoretical detonation pressure of 15.0 GPa. This compound has relatively low density and energy levels. Summary of the Invention

[0005] To address the shortcomings and defects of existing technologies, this invention provides a Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compound, the structural formula of which is shown in formula (I):

[0006]

[0007]

[0008] The present invention also provides a method for synthesizing the above-mentioned Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compound, the method comprising: reacting 5-nitrotetrazole or a soluble salt of 5-nitrotetrazole with 4-geselooxime-5-aminofurazan in an organic solvent at room temperature to prepare the Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compound.

[0009] In a further embodiment, the preparation method includes: dissolving 5-nitrotetrazole or a soluble salt of 5-nitrotetrazole in an organic solvent at -5 to 10°C, then adding an organic solvent solution of 4-geschlorooxime-5-aminofurazan dropwise, and after the addition is complete, naturally heating to room temperature to prepare Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compound.

[0010] Optionally, the reaction time is 2-4 hours. The organic solvent used is a highly polar organic solvent such as acetone, acetonitrile, or methanol. After the reaction, the product is recovered by solvent removal, concentration, recrystallization, and drying.

[0011] The Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime of this invention has a high density of 1.821 g / cm³. 3 The existing density of 3-(imidazol-1-yl)-1,2,4-oxadiazole Z-oxime is 1.672 g / cm³. 3 The Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime of this invention exhibits significantly improved detonation performance, with a theoretical detonation velocity of 8635 m / s and a theoretical detonation pressure of 31.17 GPa, while the existing 3-(imidazol-1-yl)-1,2,4-oxadiazole Z-oxime has a theoretical detonation velocity of 6476 m / s and a theoretical detonation pressure of 15.0 GPa. It can be used as an energetic material. Detailed Implementation

[0012] Unless otherwise specified, the scientific and technical terms used herein are for the understanding of one of ordinary skill in the art. It should also be understood that temperatures and concentrations used herein are approximate values ​​for illustrative purposes. While similar or equivalent methods and materials may be used in the implementation of this disclosure, some suitable methods and materials are described below.

[0013] The synthetic route for the compound Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime of this invention is as follows:

[0014]

[0015] Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime was prepared by reacting 5-nitrotetrazole or its soluble salt with 4-ges-chlorooxime-5-aminofurazan as starting material in an organic solvent.

[0016] The present invention will be further described in detail below with reference to embodiments, but this does not limit the scope of the invention. The materials, methods, solution concentrations, and embodiments described in the following embodiments are merely exemplary and are not intended to be limiting. In specific solutions, those skilled in the art can use conventional experimental methods based on the disclosure of the present invention to optimize the values ​​of operating parameters such as the ratio of substances, type of organic solvent, concentration, temperature, and reaction time involved in the method to achieve the purpose of the present invention.

[0017] The raw materials used in the following examples are all known compounds and can be commercially available products.

[0018] Example 1:

[0019] At 0°C in an ice bath, 0.3 g of sodium 5-nitrotetrazole (2.19 mmol) was dissolved in 10 mL of acetone, and 150 mL of acetone solution of 4-geschlorooxime-5-aminofuran (0.4 g, 2.5 mmol) was added dropwise. After the addition was complete, the mixture was allowed to rise to room temperature and reacted for 3 h.

[0020] Acetone was then removed by rotary evaporation, and the residue was extracted multiple times with 30 mL of toluene solvent. The system was then concentrated and recrystallized with 5 mL of a mixture of ethyl acetate and diethyl ether. After filtration and drying, 0.35 g of product Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime was obtained, with a yield of 66.31% and a purity of 98.6% (HPLC).

[0021] Structural assessment:

[0022] Infrared spectrum: IR(KBr), v(cm) -1 ): 3458,2864,1628,1533,1388,1313,1043,1011,946,867,738;

[0023] Nuclear magnetic resonance spectroscopy: 1 HNMR(DMSO-d6,500MHz), δ:14.60(1H,s,OH),6.52(2H,s,NH2);

[0024] 13 C NMR (DMSO-d6, 125MHz), δ: 131.82, 140.01, 155.08, 166.50ppm.;

[0025] Elemental analysis: Molecular formula: C4H3N9O4

[0026] Theoretical values: C 19.92, H 1.25, N 52.28;

[0027] Measured values: C 19.73, H 1.51, N 51.86.

[0028] The substance obtained by the above preparation method was confirmed to be Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime. Further testing was conducted on the properties of the obtained Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime.

[0029] (1) The density calculated using Gaussian 09 program is 1.82 g / cm³. 3 .

[0030] (2) Detonation performance: The detonation velocity was calculated to be 8635.8 m / s, the detonation pressure was 31.2 GPa, and the detonation heat was -5230 kJ / kg using EXPLO5 6.04 software; the enthalpy of formation was calculated to be 539.82 kJ / mol using the Gaussian 09 program B3LYP / 6-31G** method.

[0031] Based on the above performance test results, it can be seen that the compound of the present invention has high sealing and energy levels, and can be widely used as an energetic material in the fields of explosives, propellants and pyrotechnics.

Claims

1. A Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compound, the structural formula of which is shown in Formula (I): （I）。 2. The method for synthesizing the Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compound according to claim 1, characterized in that, The method includes reacting 5-nitrotetrazole or a soluble salt of 5-nitrotetrazole with 4-geschlorooxime-5-aminofurazan in an organic solvent at room temperature to prepare Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compounds.

3. The synthesis method according to claim 2, characterized in that, The method includes: dissolving 5-nitrotetrazole or a soluble salt of 5-nitrotetrazole in an organic solvent at -5 to 10°C, then adding an organic solvent solution of 4-ges-chlorooxime-5-aminofurazan dropwise, and then allowing the temperature to rise naturally to room temperature to prepare the Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compound.

4. The synthesis method according to claim 2, characterized in that, The reaction time is 2-4 hours.

5. The synthesis method according to claim 2, characterized in that, The organic solvent is selected from acetone, acetonitrile, or methanol.

6. The synthesis method according to claim 2, characterized in that, After the reaction is completed, the product is recovered by solvent removal, concentration, recrystallization and drying.

7. The application of the Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compound of claim 1 as an energetic material.

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