CN114634462B - Furazan-containing cyclonitrate simulated energetic compound or usable salt thereof and preparation method thereof - Google Patents
Furazan-containing cyclonitrate simulated energetic compound or usable salt thereof and preparation method thereof Download PDFInfo
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- CN114634462B CN114634462B CN202210401201.7A CN202210401201A CN114634462B CN 114634462 B CN114634462 B CN 114634462B CN 202210401201 A CN202210401201 A CN 202210401201A CN 114634462 B CN114634462 B CN 114634462B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/08—1,2,5-Oxadiazoles; Hydrogenated 1,2,5-oxadiazoles
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/36—Compositions containing a nitrated organic compound the compound being a nitroparaffin
- C06B25/40—Compositions containing a nitrated organic compound the compound being a nitroparaffin with two or more nitroparaffins present
Abstract
The invention discloses an energy-containing compound or a usable salt thereof, which is prepared by introducing oxadiazole ring and azo group into furazan-linked ring, wherein the coordinated oxygen on the furazan ring can effectively improve the density, and the azo group can effectively improve the nitrogen content and the formation enthalpy, so that the energy-containing compound is more advantageous in the application of energy-containing materials. The invention synthesizes the neutral nitrate imitation compound containing the furazan ring and the energetic salt containing the furazan ring by multi-step reaction starting from the known available raw materials, the detonation performance of the synthesized nitrate imitation compound has obvious advantages in the currently known neutral nitrate imitation compound, and the compound has great potential for being used as a propellant oxidant.
Description
Technical Field
The invention relates to the technical field of energetic materials, in particular to a furazan-containing cyclonitrate imitation energetic compound or a usable salt thereof and a preparation method thereof.
Background
With the continuous expansion of the types of energetic materials and the continuous improvement of the requirements of weaponry on the performance of the energetic materials, the high-energy density material has the characteristics of high energy, high density, high thermal stability, insensitivity to external stimuli and the like, so that the high-energy and low-sensitivity energetic compounds become hot explosive materials, and the core of the high-energy and low-sensitivity energetic compounds as the high-energy density materials becomes a hot spot for the research of the energetic materials in recent years.
In the research of high-energy energetic materials, energetic compounds with high detonation performance as propellant oxidants are also the direction of efforts of researchers.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
It is still another object of the present invention to provide an furazan ring nitrate containing energy-containing compound or a useful salt thereof that effectively increases the density of the energy-containing compound by introducing oxadiazole rings of different structures into the furazan bridge ring, making it more advantageous in energetic material applications.
Still another object of the present invention is to provide a process for preparing furoxan-containing cyclic haloforms of energetic compounds or useful salts thereof which, starting from known available raw materials, synthesizes neutral haloforms of the compounds and furoxan-containing cyclic energetic salts by a multi-step reaction work, the synthesized haloforms having the highest detonation properties among the neutral haloforms currently known, with great potential for use as propellant oxidants.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided an furazan-containing cyclic nitrate imitation energetic compound or a usable salt thereof, wherein the energetic salt has the structure of the following formula (I):
wherein R is 1 Is a nitrogen-containing linear group; r is R 2 Containing oxadiazole ring groups, R 3 Is an oxadiazole ring-containing group.
Preferably, wherein, when R 2 And R is R 3 Is thatThe energetic compound is in an salified structure.
Preferably, wherein R 1 is-NH-NH-or-N=N-.
Preferably, wherein, when R2 and R 3 Is thatThe energetic compound has a salified structure, and the salified compound is ammonium salt, hydroxylamine salt or hydrazine salt.
The object of the invention can be further achieved by a process for the preparation of furoxan-containing cyclic nitroisokinetic energetic compounds or their useful salts, comprising the steps of:
step one, synthesis of intermediate Compounds of formula (III)
Using the available compound of the formula (II) as a raw material, and obtaining a compound of the formula (III) through multi-step reaction;
step two, synthesis of Compounds of formula (I)
Reacting the compound of formula (III) obtained in the step one with a basic compound or further reacting the product obtained after the reaction with the basic compound to obtain a compound of formula (I);
preferably, wherein, in the compound of formula (III), R 4 Is-n=n-.
Preferably, in the second step, the alkaline compound is ammonia water or hydrazine hydrate.
Preferably, in the second step, the molar ratio of the compound of formula (III) to the basic compound is 1:10.
The invention at least comprises the following beneficial effects:
1. according to the invention, the oxadiazole ring with different structures is introduced into the furazan bridge ring, and the coordinated oxygen on the furazan ring can effectively improve the density of the energetic compound, so that the furazan bridge ring has more advantages in the application of energetic materials.
2. According to the preparation method of the furoxan-containing cyclonitrate-imitated energetic compound or the usable salt thereof, the furoxan-containing compound and the furoxan-containing cyclonitrate-imitated energetic compound are synthesized through multiple steps of reaction work from known available raw materials, the detonation performance of the synthesized neutral furoxan-containing compound has obvious advantages in the currently known neutral furoxan-containing compound, and the compound has great potential for being used as a propellant oxidant.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a single crystal structure diagram of Compound 3 in example 1 of the present invention;
FIG. 2 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 3 in example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance carbon spectrum of compound 3 in example 1 of the present invention;
FIG. 4 is a single crystal structure diagram of Compound 5 in example 1 of the present invention;
FIG. 5 is a DSC of Compound 5 of example 1 of the present invention;
FIG. 6 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 5 in example 1 of the present invention;
FIG. 7 is a nuclear magnetic resonance carbon spectrum of compound 5 in example 1 of the present invention;
FIG. 8 is a single crystal structure of Compound 6 in example 1 of the present invention;
FIG. 9 is a DSC of Compound 6 of example 1 of the present invention;
FIG. 10 is a nuclear magnetic resonance hydrogen spectrum of compound 6 in example 1 of the present invention;
FIG. 11 is a nuclear magnetic resonance carbon spectrum of compound 6 in example 1 of the present invention;
FIG. 12 is a DSC of Compound 7 of example 2 of the present invention;
FIG. 13 is a nuclear magnetic resonance hydrogen spectrum of compound 7 in example 2 of the present invention
FIG. 14 is a nuclear magnetic resonance carbon spectrum of compound 7 in example 2 of the present invention;
FIG. 15 is a DSC of compound 8 of example 3 of the present invention;
FIG. 16 is a chart showing the hydrogen nuclear magnetic resonance spectrum of Compound 8 in example 3 of the present invention;
FIG. 17 is a nuclear magnetic resonance spectrum of compound 8 in example 3 of the present invention;
FIG. 18 is a single crystal structure of Compound 9 in example 4 of the present invention;
FIG. 19 is a DSC of Compound 9 of example 4 of the present invention;
FIG. 20 is a nuclear magnetic resonance spectrum of compound 9 in example 4 of the present invention;
FIG. 21 is a nuclear magnetic resonance spectrum of compound 9 in example 4 of the present invention.
Detailed Description
The present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
The experimental methods described in the following embodiments are conventional methods unless otherwise indicated, and the reagents and materials are commercially available.
Example 1 >
The furazan ring-containing energetic salt 6 has the following structural formula:
the specific synthetic route is as follows:
the specific synthesis steps are as follows:
step one, synthesis of Compound 3
Compound 1 (1 g,6.3 mmol) was dissolved in 20mL acetonitrile and methyl malonate acyl chloride (0.86 g,6.4 mmol) was added in one portion, the solution became clear, and after 2min, again became cloudy, the precipitate was filtered off after 3h, the solvent was removed by rotary evaporation, washed with water and dried under vacuum at 70℃to give white compound 2 (1.47 g, 90.24%). Compound 2 (1 g,3.86 mmol) was dissolved in 15mL of acetonitrile at ambient temperature and Cs was added 2 CO 3 (1.26 g,3.86 mmol) and stirring for 1h, the solution gradually forms a yellow precipitate, the solvent is removed by rotary evaporation of the suspension after the reaction, washing with water and vacuum drying to give a pale solutionYellow compound 3 (0.48 g, 51.6%). The monocrystal structure of the compound 3 is shown in figure 1, the nuclear magnetic resonance hydrogen spectrogram is shown in figure 2, and the nuclear magnetic resonance carbon spectrogram is shown in figure 3.
Step two, synthesis of Compound 5
In a three-necked flask, compound 3 (1 g,4.15 mmol) and CHCl were charged 3 (10 mL) adding concentrated HCl (10 mL) to the system, dissolving Compound 3 in concentrated hydrochloric acid, and then adding KMnO dropwise to the system 4 (0.76 g,4.8 mmol) 15mL aqueous solution, controlling the temperature not higher than 30 ℃, reacting at normal temperature for 5h, then the reaction system turns red, and adding 5%H dropwise 2 O 2 Removal of excess KMnO 4 The solvent was removed by rotary evaporation after separation to give compound 4 (0.9 g, 90.75%) as a viscous red solid. Ice bath at-5℃to compound 10 (0.9 g,1.88 mmol) was added dropwise concentrated H 2 SO 4 (5 mL) was dissolved thoroughly, and 2.5mL of fuming nitric acid was added using a dropping funnel; reaction at-5 ℃ for 30min followed by slow warming overnight, yellow precipitate appeared in the system, filtration and washing with 3x10mL trifluoroacetic acid gave yellow compound 5 (0.76 g, 61.34%) after drying.
The single crystal structure diagram of the compound 5 is shown in fig. 4, the DSC diagram of the compound 5 is shown in fig. 5, the nuclear magnetic resonance hydrogen spectrum diagram is shown in fig. 6, and the nuclear magnetic resonance carbon spectrum diagram is shown in fig. 7.
Step three, synthesis of Compound 6
Compound 5 (0.66 g,1 mmol) was added to 8mL of water to form a suspension, 0.68g (10 mmol) of ammonia was added dropwise under stirring at normal temperature, the reaction was continued at normal temperature for 6 hours, the yellow precipitate in the reaction system gradually became a dark brown precipitate, the brown precipitate was collected by filtration and dried under vacuum at 50℃to give orange compound 6 (0.46 g) in 79.5% yield.
The single crystal structure diagram of the compound 6 is shown in fig. 8, the DSC diagram is shown in fig. 9, the nuclear magnetic resonance hydrogen spectrum is shown in fig. 10, and the nuclear magnetic resonance carbon spectrum is shown in fig. 11.
Example 2 >
The furazan ring-containing energetic salt 7 has the following structural formula:
the specific synthetic route is as follows:
the specific synthesis steps are as follows:
compound 6 (0.58 g,1 mmol) was suspended in 15mL of water at 0deg.C, and 50% H was added dropwise 2 SO 4 (3 mL), extracted with 3X10mL diethyl ether after 10min, the organic phases combined and dried over anhydrous sodium sulfate, and 50% aqueous hydroxylamine solution (0.15 g,2.2 mmol) was added dropwise to the reaction solution after filtration, and the precipitate was collected by filtration after 20min and dried under vacuum to give orange compound 7 (0.46 g, 75.4%).
The DSC diagram of the compound 7 is shown in fig. 12, the nuclear magnetic resonance hydrogen spectrum is shown in fig. 13, and the nuclear magnetic resonance carbon spectrum is shown in fig. 14.
Example 3 >
The furazan ring-containing energetic salt 8 has the following structural formula:
the specific synthetic route is as follows:
the specific synthesis steps are as follows:
compound 5 (0.66 g,1 mmol) was added portionwise to 8mL of acetonitrile at ambient temperature to give a dark red solution, 0.5g (10 mmol) of hydrazine hydrate in acetonitrile (5 mL) was added dropwise to the reaction solution, the reaction solution was stirred overnight, the precipitate was collected by filtration and dried under vacuum to give an orange solid, i.e. hydrazine salt 8 (0.42 g, 68.8%).
The DSC diagram of the compound 8 is shown in fig. 15, the nuclear magnetic resonance hydrogen spectrum is shown in fig. 16, and the nuclear magnetic resonance carbon spectrum is shown in fig. 17.
Example 4 >
A nitroimitation compound 9 having the structural formula:
the specific synthetic route is as follows:
the specific synthesis steps are as follows:
compound 6 (576 mg,1 mmol) was dissolved in concentrated H 2 SO 4 (3.0 mL) and cooled to-5 ℃. To the fuming HN0 within 30 minutes 3 (1.5 mL) was added dropwise. During this addition, the temperature of the reaction was kept below 0 ℃. After that, the reaction mixture was stirred at ice temperature for 1 hour and at room temperature for 5 hours. A yellow precipitate formed and the reaction mixture was poured into cold water. The precipitate was collected by filtration, washed with cold water (2.0 mL) and dried at room temperature to give compound 9 (231 mg, 36.5% yield) as a pure yellow solid.
The single crystal structure diagram of the compound 9 is shown in fig. 18, the DSC diagram is shown in fig. 19, the nuclear magnetic resonance hydrogen spectrum is shown in fig. 20, and the nuclear magnetic resonance carbon spectrum is shown in fig. 21.
Example 5 >
Performance comparison of energetic compounds 6-9 synthesized in the examples of the present invention with the existing explosives black soljin (RDX) and HMX:
the performance of compounds 6-9 and RDX, HMX are compared to Table 1 below.
Table 1: test and calculation performance of Compounds 6-9, RDX and HMX
The properties of the 4 furazan ring-containing energetic compounds are compared with those of the existing high-performance energetic materials. From the comparison of detonation velocity D and detonation pressure P, the properties of the 4 furoxan-containing ring energetic compounds can be known: energetic compounds 6, 7, 9 are all superior to RDX,6 approaching HMX; and 7 and 9 are also superior to HMX and are good explosives. 8 is close to RDX and the energetic salts 6, 7, 8 are far more sensitive than RDX and HMX. The neutral nitro-imitation compound 9 has very high detonation performance, and from the aspect of the performance, the neutral nitro-imitation compound has the highest detonation performance among the currently known neutral nitro-imitation compounds, and has great potential for being used as a propellant oxidant.
The formation enthalpy and the density jointly determine detonation velocity and detonation pressure, and the detonation velocity and the detonation pressure are key to the performance of the energetic material, and are higher and better; impact sensitivity and friction sensitivity are key to the use, and the higher the insensitive, the more insensitive the insensitive energy-containing material has good stability and safer use and storage.
According to the invention, a series of energetic salts containing the furazan ring are obtained by introducing the binitro and the furazan ring into an oxadiazole ring energetic framework, and then the neutral nitrate imitation compound is obtained by nitrifying ammonium salts. The structure is confirmed by nuclear magnetism, mass spectrum and monocrystal, so that the nitrogen and oxygen content of the compound is improved, and the density, oxygen balance and detonation performance of the energetic molecule are improved. The invention also discloses a method for preparing the furoxan-containing cyclonitrate imitation energetic compound or the usable salt thereof, which starts from the known available raw materials, realizes the synthesis of the novel furoxan-containing cyclonitrate imitation energetic compound or the usable salt thereof through multi-step reaction, and provides a novel thought for synthesizing the novel high-energy-density energetic compound in the energetic material.
The furazan ring has higher oxygen balance, and the introduction of coordinated oxygen can effectively improve the density, so that the furazan ring is more advantageous in the application of energetic materials.
Although embodiments of the invention have been disclosed above, they are not limited to the use listed in the specification and embodiments. It can be applied to various fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art. Therefore, the invention is not to be limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (3)
1. A furazan-containing cyclic nitrate simulated energetic compound or a useful salt thereof having the structure:
2. a process for preparing the furazan-containing cyclic nitrate simulated energetic compound or a usable salt thereof according to claim 1, comprising the steps of:
step one, synthesis of intermediate Compounds of formula (III)
Using the available compound of the formula (II) as a raw material, and obtaining a compound of the formula (III) through multi-step reaction;
step two, synthesis of furazan-containing cyclonitrate simulated energetic compound or usable salt thereof
Reacting the compound shown in the formula (III) obtained in the step I with an alkaline compound, or further reacting the product obtained after the reaction of the alkaline compound to obtain an furazan-containing cyclonitrate simulated energetic compound or a usable salt thereof;
wherein, in the compound of formula (III), R 4 And (2) N=N-, wherein the alkaline compound is ammonia water or hydrazine hydrate.
3. The process according to claim 2, wherein in step two, the molar ratio of the compound of formula (III) to the basic compound is 1:10.
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| CN115368314A (en) * | 2022-08-22 | 2022-11-22 | 北京理工大学 | Nitro-imitation energetic compound containing oxadiazole ring and preparation method thereof |
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