Z-(4-amino-1, 2, 5 furazanyl)-5-nitrotetrazole-oxime compound, synthetic method and application

Abstract

The invention discloses a Z-(4-amino-1, 2, 5 furazanyl)-5-nitrotetrazole-oxime compound as well as a synthesis method and application thereof. The structural formula of the disclosed compound is shown as (I). The density and theoretical detonation velocity of the Z-(4-amino-1, 2, 5 furazanyl)-5-nitrotetrazole-oxime disclosed by the invention are remarkably improved compared with those of the existing substance, and the Z-(4-amino-1, 2, 5 furazanyl)-5-nitrotetrazole-oxime can be used as a novel energetic material. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the technical field of energetic materials, and specifically relates to a Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compound. Background Art

[0002] In the current literature reports, there is no high-energy structure of oxime-bridged tetrazole and furazan. Only VG Andrianov et al. have tried to use oxime to bridge isofurazan and imidazole ring. 3-(Imidazole-1-yl)-1,2,4-oxadiazole Z-oxime 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. Its structure is shown in (II):

[0003]

[0004] The density of this compound was calculated using Gaussian 09 program and was 1.672 g / cm 3 The detonation performance is calculated by EXPLO5, the theoretical detonation velocity is 6476m / s, and the theoretical detonation pressure is 15.0GPa. The density and energy level of this compound are low. Summary of the invention

[0005] In view of the shortcomings and defects of the prior art, the present invention provides a Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compound, the structural formula of the provided compound 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, which comprises: reacting 5-nitrotetrazole or a soluble salt of 5-nitrotetrazole with 4-chlorooxime-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 scheme, 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 dropwise an organic solvent solution of 4-chlorooxime-5-aminofurazan, and naturally heating the temperature to room temperature after the addition is completed to react and prepare Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compound.

[0010] Optionally, the reaction time is 2-4 hours. The organic solvent is selected from highly polar organic solvents such as acetone, acetonitrile, methanol, etc. After the reaction is completed, the product is recovered by removing the solvent, concentrating, recrystallizing and drying.

[0011] The density of the Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazolyl-oxime of the present invention is relatively high, with a density of 1.821 g / cm 3 , while the existing 3-(imidazole-1-yl)-l,2,4-oxadiazole Z-oxime has a density of 1.672 g / cm 3 The detonation performance of the Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazolyl-oxime of the present invention is significantly improved, with a theoretical detonation velocity of 8635 m / s and a theoretical detonation pressure of 31.17 GPa, while the theoretical detonation velocity of the existing 3-(imidazole-1-yl)-1,2,4-oxadiazole Z-oxime is 6476 m / s and the theoretical detonation pressure is 15.0 GPa. It can be used as an energetic material. DETAILED DESCRIPTION

[0012] Unless otherwise specified, the scientific and technical terms herein are understood according to the knowledge of ordinary technicians in the relevant field. It should also be understood that the temperatures and concentrations referred to herein are approximate values ​​and are used for illustrative purposes. Although methods and materials similar or equivalent to the methods and materials described herein can be used in the implementation of the present disclosure, some suitable methods and materials are described below.

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

[0014]

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

[0016] The present invention is further described in detail below in conjunction with the examples, but the scope of the present invention is not limited. The materials, methods, solution concentrations and embodiments described in the following examples are only exemplary and are not intended to be limiting. In the specific scheme, those skilled in the art can use conventional experimental means according to the disclosure of the present invention to optimize the values ​​of the operating parameters such as the material ratio, organic solvent type, concentration, temperature, reaction time, etc. 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 relevant commercially available products can be used.

[0018] Embodiment 1:

[0019] Under ice bath at 0°C, dissolve 5-nitrotetrazole sodium salt (0.3 g, 2.19 mmol) in 10 mL acetone, add dropwise 4-chlorooxime-5-aminofuroxan (0.4 g, 2.5 mmol) in 150 mL acetone solution, and after the addition is complete, warm to room temperature and react for 3 h;

[0020] After that, the acetone was removed by a rotary evaporator, and 30 mL of toluene solvent was added to the residue for multiple extractions. The system was then concentrated and recrystallized with 5 mL of a mixed solvent of ethyl acetate and ether; 0.35 g of the product Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime was obtained by filtration and drying, with a yield of 66.31% and a purity of 98.6% (HPLC).

[0021] Structure identification:

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

[0023] NMR spectrum: 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] Found values: C 19.73, H 1.51, N 51.86.

[0028] It is confirmed that the substance obtained by the above preparation method is Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazolyl-oxime. The properties of the obtained Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazolyl-oxime are further tested:

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

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

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

Claims

1. A Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazolyl-oxime compound, the structural formula of which is shown in formula (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 comprises: 5-nitrotetrazole or a soluble salt of 5-nitrotetrazole reacts with 4-chlorooxime-5-aminofurazan in an organic solvent at room temperature to prepare a Z-(4-amino-1,2,5-furazanyl)-5-nitrotetrazole-oxime compound.

3. The synthesis method according to claim 2, characterized in that The method comprises: dissolving 5-nitrotetrazole or a soluble salt of 5-nitrotetrazole in an organic solvent under the condition of -5 to 10°C, then dripping an organic solvent solution of 4-chlorooxime-5-aminofurazan, and naturally heating the temperature to room temperature after the dripping is completed to react and prepare a 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 2-4h.

5. The synthesis method according to claim 2, characterized in that The organic solvent is selected from highly polar organic solvents such as acetone, acetonitrile, methanol, etc.

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

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

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