Tetrazole group-containing energetic compounds, methods for preparing the same, and applications thereof

Abstract

The application discloses an energetic compound containing a tetrazolyl group, which is a heterocyclic energetic compound with synergistic effect of C-N bond and C-C bond, and has high thermal stability and detonation performance. The application also discloses a method for preparing the energetic compound containing the tetrazolyl group, which introduces different heterocyclic rings by simultaneously performing energetic modification on the C position and the N position of 5-amino-3-cyano-1,2,4-triazole, and further modifies the energetic compound containing the tetrazolyl group with high thermal stability and detonation performance by using a nitro group. Meanwhile, the research blank in this aspect is filled.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of energetic materials, in particular to an energetic compound containing tetrazolyl and a preparation method thereof. BACKGROUND

[0002] Since the energetic materials were invented, the long-term development goal has been to obtain energetic materials with high detonation performance, high thermal stability and low sensitivity through the simplest synthetic route. For decades, through the unremitting efforts of energetic material scientists, many kinds of C-C bond connected or C-N bond connected binary system heterocyclic energetic compounds have been designed and synthesized. Since the formation enthalpy of C-N bond is higher than that of C-C bond, the binary system connected by C-N bond generally has higher energy. In general, they mostly have high formation enthalpy, high density, and exhibit excellent detonation performance and high thermal decomposition temperature. However, the research on the C-C bond and C-N bond connected ternary system heterocyclic energetic compounds obtained by simultaneously modifying the C site and N site has never been reported. SUMMARY

[0003] An object of the present application is to solve at least the above problems and / or defects, and to provide at least the advantages to be described later.

[0004] Another object of the present application is to provide an energetic compound containing tetrazolyl, which is a ternary system heterocyclic energetic compound with synergistic effect of C-N bond and C-C bond, and has high thermal stability and detonation performance.

[0005] Still another object of the present application is to provide a method for preparing an energetic compound containing tetrazolyl, which simultaneously modifies the C site and N site of 5-amino-3-cyano-1,2,4-triazole through two synthesis strategies, introduces different heterocycles, and further modifies with nitro group, to obtain several energetic compounds containing tetrazolyl which exhibit high thermal stability and detonation performance, and also fill the research gap in this aspect.

[0006] In order to achieve these objects and other advantages according to the present application, an energetic compound containing tetrazolyl is provided, which has the following formula (I):

[0007]

[0008] wherein X is a five-membered nitrogen heterocycle, Y is a substituted or unsubstituted five-membered nitrogen heterocycle, and R1 is a nitrogen-containing substituent.

[0009] Preferably, the energetic compound containing tetrazolyl has the following formula (II) or formula (III):

[0010]

[0011] Y1 is a substituted five-membered nitrogen heterocycle.

[0012] Preferably, Y1 is or

[0013] The object of the present application can also be further achieved by a method for preparing tetrazole group-containing energetic compounds, which uses 5-amino-3-cyano-1,2,4-triazole salt as raw material, modifies the N position and C position, and introduces different heterocycles to obtain tetrazole group-containing energetic compounds.

[0014] Preferably, the N position of the 5-amino-3-cyano-1,2,4-triazole salt is modified by N3CN, 1,3-dinitro-1,2,4-triazole or 1,3,4-trinitropyrazole.

[0015] Preferably, when the N position of the 5-amino-3-cyano-1,2,4-triazole salt is modified by N3CN, the molar ratio of the 5-amino-3-cyano-1,2,4-triazole salt to N3CN is 1:2.

[0016] Preferably, when the N position of the 5-amino-3-cyano-1,2,4-triazole salt is modified by 1,3-dinitro-1,2,4-triazole, the molar ratio of the 5-amino-3-cyano-1,2,4-triazole salt to 1,3-dinitro-1,2,4-triazole is 1:1.

[0017] Preferably, when the N position of the 5-amino-3-cyano-1,2,4-triazole salt is modified by 1,3,4-trinitropyrazole, the molar ratio of the 5-amino-3-cyano-1,2,4-triazole salt to 1,3,4-trinitropyrazole is 1:1.

[0018] Preferably, the C position in the 5-amino-3-cyano-1,2,4-triazole is modified by NaN3.

[0019] The object of the present application can also be further achieved by the use of the tetrazole group-containing energetic compounds in the preparation of energetic materials.

[0020] The present application at least includes the following beneficial effects:

[0021] 1. The tetrazole group-containing energetic compounds of the present application are ternary system heterocyclic energetic compounds with synergistic effect of C-N bond and C-C bond, have high thermal stability and detonation performance, fill the research gap in this aspect, and provide a new idea for the design and synthesis of energetic materials.

[0022] 2. The preparation method of the tetrazole group-containing energetic compound of the present application, by simultaneously performing energetic modification on C and N positions of 5-amino-3-cyano-1,2,4-triazole, introducing different heterocyclic rings, and further modifying with nitro group, the tetrazole group-containing energetic compound with high thermal stability and detonation performance is synthesized.

[0023] Other advantages, objects, and features of the present application will be understood by those skilled in the art from the following description, and will be further appreciated upon reading and comprehending the attached figures and claims. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 It is a single crystal structure diagram of compound 1 in the embodiment 1 of the present application;

[0025] Figure 2 It is a nuclear magnetic resonance hydrogen spectrum diagram of compound 1 in the embodiment 1 of the present application;

[0026] Figure 3 It is a nuclear magnetic resonance carbon spectrum diagram of compound 1 in the embodiment 1 of the present application;

[0027] Figure 4 It is a single crystal structure diagram of compound ATDT in the embodiment 1 of the present application;

[0028] Figure 5 It is a nuclear magnetic resonance hydrogen spectrum diagram of compound ATDT in the embodiment 1 of the present application;

[0029] Figure 6 It is a nuclear magnetic resonance carbon spectrum diagram of compound ATDT in the embodiment 1 of the present application;

[0030] Figure 7 It is a DSC diagram of compound ATDT in the embodiment 1 of the present application;

[0031] Figure 8 It is a nuclear magnetic resonance hydrogen spectrum diagram of compound 2 in the embodiment 2 of the present application;

[0032] Figure 9 It is a nuclear magnetic resonance carbon spectrum diagram of compound 2 in the embodiment 2 of the present application;

[0033] Figure 10 It is a single crystal structure diagram of compound ATNT in the embodiment 2 of the present application;

[0034] Figure 11 It is a nuclear magnetic resonance hydrogen spectrum diagram of compound ATNT in the embodiment 2 of the present application;

[0035] Figure 12 It is a nuclear magnetic resonance carbon spectrum diagram of compound ATNT in the embodiment 2 of the present application;

[0036] Figure 13DSC chart of compound ATNT in Example 2 of the present application;

[0037] Figure 14 single crystal structure chart of compound 3 in Example 3 of the present application;

[0038] Figure 15 nuclear magnetic resonance hydrogen spectrum chart of compound 3 in Example 3 of the present application;

[0039] Figure 16 nuclear magnetic resonance carbon spectrum chart of compound 3 in Example 3 of the present application;

[0040] Figure 17 single crystal structure chart of compound ATDNP in Example 3 of the present application;

[0041] Figure 18 nuclear magnetic resonance hydrogen spectrum chart of compound ATDNP in Example 3 of the present application;

[0042] Figure 19 nuclear magnetic resonance carbon spectrum chart of compound ATDNP in Example 3 of the present application;

[0043] Figure 20 DSC chart of compound ATDNP in Example 3 of the present application. DETAILED DESCRIPTION

[0044] The present application will be further described in detail by the following embodiments with reference to the accompanying drawings so as to be easily carried out by those skilled in the art according to the description.

[0045] It should be understood that the terms such as "have", "contain" and "include" used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0046] It should be noted that the experimental methods in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials can be obtained from commercial channels unless otherwise specified.

[0047] <Example 1>

[0048] The tetrazole-containing energetic compound ATDT has the following structural formula:

[0049]

[0050] The specific synthesis route is as follows:

[0051]

[0052] The specific synthesis steps are as follows:

[0053] (1) Synthesis of compound 1:

[0054] ACT-K (1.47 g, 10 mmol) was dissolved in 20 mL water, and a freshly prepared N3CN (20 mmol) acetonitrile solution (30 mL) was slowly added at 0 °C. After the addition was completed, the ice bath was removed, and the system was slowly returned to room temperature. The stirring was continued for 7 h. The solvent was blown off by air until solid was precipitated in the system. Filtration, washing with acetonitrile, and drying yielded compound 1 (1.21 g, 56%) as a light yellow solid.

[0055] The single crystal structure of compound 1 is shown in Figure 1 , the proton nuclear magnetic resonance spectrum is shown in Figure 2 , and the carbon nuclear magnetic resonance spectrum is shown in Figure 3 .

[0056] (2) Synthesis of compound ATDT

[0057] Compound 1 (215 mg, 1 mmol) was dissolved in 10 mL water, and NaN3 (71.5 mg, 1.1 eq) and ZnCl2 (163.6 mg, 1.2 eq) were sequentially added at room temperature. After the addition was completed, the system was refluxed for 2 h, cooled to room temperature, acidified with 20% HCl, and adjusted to pH 1-2. White solid was precipitated, and filtration, washing with water yielded ATDT (198 mg, 90%).

[0058] The single crystal structure of compound ATDT is shown in Figure 4 , the proton nuclear magnetic resonance spectrum is shown in Figure 5 , the carbon nuclear magnetic resonance spectrum is shown in Figure 6 , and the DSC graph is shown in Figure 7 .

[0059] <Example 2>

[0060] The energetic compound ATNT containing a tetrazole group has the following structural formula:

[0061]

[0062] The specific synthesis route is as follows:

[0063]

[0064] The specific synthesis steps are as follows:

[0065] (1) Synthesis of compound 2:

[0066] ACT-K (735 mg, 5 mmol) was dispersed in 10 mL methanol, and an equivalent amount of 1,3-dinitro-1,2,4-triazole in methanol and an equivalent amount of K2CO3 (690 mg, 5 mmol) were added. The stirring was continued at room temperature for 6 h. The solvent was removed by vacuum evaporation to obtain a residue, which was dissolved in a small amount of water, and the pH was adjusted to 6 with 10% HCl. Yellow solid was precipitated, and filtration, washing with water yielded compound 2 (442 mg, 2 mmol).

[0067] The nuclear magnetic resonance hydrogen spectrum of compound 2 is shown in Figure 8 , and the nuclear magnetic resonance carbon spectrum is shown in Figure 9 .

[0068] (2) Synthesis of compound ATNT:

[0069] Compound 2 (221 mg, 1 mmol) was dissolved in 10 mL of water, and NaN3(71.5 mg, 1.1 eq) and ZnCl2(163.6 mg, 1.2 eq) were added in turn at room temperature. After addition, it was refluxed for 4 h, cooled to room temperature, acidified with 20% HCl, and adjusted to pH 1-2. White solid was precipitated, filtered, and washed with water to obtain ATNT (243 mg, 92%).

[0070] The single crystal structure of compound ATNT is shown in Figure 10 , the nuclear magnetic resonance hydrogen spectrum is shown in Figure 11 , and the nuclear magnetic resonance carbon spectrum is shown in Figure 12 , and the DSC graph is shown in Figure 13 .

[0071] <Example 3>

[0072] The energetic compound ATDNP containing a tetrazole group has the following structural formula:

[0073]

[0074] The specific synthesis route is as follows:

[0075]

[0076] The specific synthesis steps are as follows:

[0077] (1) Synthesis of compound 3:

[0078] ACT-K (735 mg, 5 mmol) was dispersed in 10 mL of methanol, and an equivalent amount of 1,3,4-trinitropyrazole in methanol and an equivalent amount of K2CO3(690 mg, 5 mmol) were added. It was stirred at room temperature for 6 h, and the solvent was removed by vacuum rotary evaporation to obtain a residue. The residue was dissolved in a small amount of water, adjusted to pH 6 with 10% HCl, extracted with ethyl acetate, washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate, column chromatographed (PE:EA = 1:2), and the organic phase was combined and vacuum rotary evaporated to obtain compound 3 (463 mg, 35%).

[0079] The single crystal structure of compound 3 is shown in Figure 14 , the nuclear magnetic resonance hydrogen spectrum (CD3CN) is shown in Figure 15 , and the nuclear magnetic resonance carbon spectrum (DMSO) is shown in Figure 16 .

[0080] (2) Synthesis of compound ATDNP:

[0081] Compound 3 (265 mg, 1 mmol) was dissolved in 10 mL of water, and NaN3 (71.5 mg, 1.1 eq) and ZnCl2 (163.6 mg, 1.2 eq) were added sequentially at room temperature. After addition, the mixture was refluxed for 2 h, cooled to room temperature, acidified with 20% HCl, and the pH was adjusted to 1-2. A white solid precipitated, which was filtered and washed with water to obtain ATDNP (278 mg, 90%).

[0082] The single crystal structure of compound 3 is shown in Figure 17 , H NMR spectrum is shown in Figure 18 , the C NMR spectrum is shown in Figure 19 , DSC diagram see Figure 20 .

[0083] <Example 4>

[0084] The performance comparison of the tetrazolyl-containing energetic compounds ATDT, ATNT, ATDNP synthesized in the present invention and the existing energetic compounds RDX, 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) and hexanitrostilbene (HNS) is shown in Table 1 below.

[0085] Table 1 Test and calculated properties of compound 1 with TNT and TATB

[0086]

[0087] a Melting temperature, b Decomposition temperature (heating rate is 5℃min -1 ), c Density measured by gas pycnometer method (25℃), d Calculate the enthalpy of formation - Gauss 09 (revised E.01), e The detonation velocity calculated by EXPLO5 V6.02, f Detonation pressure and g impact sensitivity calculated by EXPLO5 V6.02, h Friction sensitivity.

[0088] As shown in the table above, the thermal decomposition temperature of the tetrazolyl-containing energetic compound ATNT reaches 361°C, exceeding that of conventional heat-resistant explosives HNS and TATB. All three novel tetrazolyl-containing energetic compounds exhibit excellent detonation performance (D: 8375-8502 m s⁻¹, P: 26.2-29.3 GPa). More notably, they possess ultra-low mechanical sensitivity (IS > 60 J, FS > 360 N), providing strong support for the storage and transportation of the compounds. These three compounds achieve a good balance between energy and safety. Therefore, the tetrazolyl-containing energetic compounds ATDT, ATNT, and ATDNP of the present invention have great application prospects in the field of energetic materials.

[0089] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and exemplary embodiments. They can be applied to a variety of fields suitable for the present invention. Further modifications will be readily apparent to those skilled in the art. Therefore, the present invention is not limited to the specific details and illustrations shown and described herein without departing from the general concept defined by the claims and their equivalents.

Claims

1. An energetic compound containing a tetrazolyl group having the following structure: , ,or .

2. Use of the tetrazolyl-containing energetic compound according to claim 1 in the preparation of energetic materials.

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