A novel fluoroges-dinitrofuran-type energetic compound, its preparation method and application

Abstract

This invention discloses a novel fluoro-dinitrofuranzan-type energetic compound, its preparation method, and its applications. The preparation method of the novel fluoro-dinitrofuranzan-type energetic compound provided by this invention includes the following steps: First, the dipotassium salt of 4-gamma-dinitro-3-nitraminofuran from methylene chelate is fluorinated and then hydrolyzed with an alkaline solution to obtain the potassium salt of 4-fluoro-dinitro-3-nitraminofuran. This potassium salt is then acidified to obtain 4-fluoro-dinitro-3-nitraminofuran, which is then reacted with ammonia and hydroxylamine, respectively, to obtain its corresponding ammonium and hydroxylamine salts. The novel fluoro-dinitrofuranzan-type energetic compound provided by this invention has the advantages of high oxygen content, high theoretical energy, and good thermal stability, and can be used as a high-energy oxidant in the field of propellants.

Description

Technical Field

[0001] This invention relates to the field of energetic materials synthesis technology, and more specifically, to a novel fluoro-dinitrofuran-type energetic compound, its preparation method, and its application. Background Technology

[0002] Energetic materials, including explosives, propellants, and pyrotechnics, are widely used in weaponry and aerospace. They store and release energy through bonding and bond breaking, with energy levels depending on crystal density, standard enthalpy of formation, and oxygen balance. Optimizing the molecular structure of energetic compounds and designing and synthesizing new ones can comprehensively improve their physicochemical properties. The synthesis and application of novel energetic compounds can continuously drive the upgrading of weaponry.

[0003] The development of energetic compounds has mainly progressed through the following stages: 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitro-1,3,5-azacyclohexane (RDX), 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX), and hexanitrohexaazaisowulzane (CL-20). While the energy levels of energetic compounds are increasing, their safety performance is gradually declining due to the increasing introduction of explosive groups such as nitro groups. The goal of synthesizing novel energetic compounds is to obtain new materials with higher energy performance, better safety, and better environmental compatibility. To reconcile the contradiction between the energy level and sensitivity of energetic compounds, polynitro-rich nitrogen-containing heterocyclic high-energy compounds are designed and synthesized. Utilizing the conjugated skeleton constructed from azaaromatic rings reduces the degree of molecular charge separation caused by explosive groups, thus ensuring safety while improving the overall energy level of the compound.

[0004] Therefore, this invention is proposed. Summary of the Invention

[0005] The purpose of this invention is to overcome the defects of the prior art and provide a novel fluoro-dinitrofuran-type energetic compound, its preparation method, and its application.

[0006] The technical problem solved by this invention is achieved by the following technical solution.

[0007] This invention provides a novel fluorogestanilide dinitrofuranzan energetic compound, comprising 4-fluorogestanilide dinitro-3-nitraminofuranzan and its salts, the structural formula of which is shown below:

[0008]

[0009] This invention also provides a method for preparing the above-mentioned novel fluoro-dinitrofuran-type energetic compounds, comprising the following steps:

[0010] S1. Using the 4-gamma-dinitro-3-nitraminofurazan dipotassium salt 2 of methylene syn., the 4-gamma-dinitro-3-nitraminofurazan dipotassium salt of methylene syn. was fluorinated to obtain 4-fluorogamma-dinitro-3-nitraminofurazan 3 of methylene syn. After alkaline hydrolysis of compound 3, the potassium salt 4 of 4-fluorogamma-dinitro-3-nitraminofurazan was obtained.

[0011] S2 and compound 4, after acidification, yield 4-fluorogesyldinitro-3-nitraminofuran 5;

[0012] S3 and compound 5 react with an ammonia reagent to give ammonium salt 6 of 4-fluoroges-dinitro-3-nitraminofuran;

[0013] S4 and compound 5 react with 50% hydroxylamine solution to give hydroxylamine salt 7 of 4-fluoroges-dinitro-3-nitramine-furazan.

[0014] The present invention also provides a novel fluoro-dinitrofuran-type energetic compound as an oxidant for the preparation of solid propellants.

[0015] The present invention has the following beneficial effects:

[0016] This invention provides a novel fluoroglycinyl dinitrofuranzan energetic compound, its preparation method, and its applications. The novel fluoroglycinyl dinitrofuranzan energetic compound provided by this invention includes 4-fluoroglycinyl dinitro-3-nitroaminofuranzan and its salts. The potassium and ammonium salts of the above-mentioned novel fluoroglycinyl dinitrofuranzan energetic compounds provided by this invention, as determined by DSC, have thermal decomposition temperatures above 170℃, which is higher than most previously reported fluoroglycinyl dinitrogenous energetic compounds, demonstrating that the target compounds provided by this invention have better thermal stability. Furthermore, the novel fluoroglycinyl dinitrofuranzan energetic compounds provided by this invention have the advantages of positive oxygen balance, high energy density, and good thermal stability, which is of great significance for improving the energy level of solid propellants. Attached Figure Description

[0017] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 The synthetic route for raw material 2;

[0019] Figure 2 This is a synthetic route diagram of 4-fluoroges-dinitro-3-nitroaminofuran and its salts in the embodiments of the present invention;

[0020] Figure 3 The novel energetic compound 4-fluorogesyldinitro-3-nitraminofurazan potassium salt (4) provided in Example 1 of this invention 13 C NMR spectrum;

[0021] Figure 4 The novel energetic compound 4-fluorogesyldinitro-3-nitraminofurazan potassium salt (4) provided in Example 1 of this invention 1 F NMR spectrum;

[0022] Figure 5 TG-DSC thermal analysis curve of the novel energetic compound 4-fluorogesyldinitro-3-nitraminofurazan potassium salt (4) provided in Example 1 of this invention;

[0023] Figure 6 The novel energetic compound 4-fluorogesyldinitro-3-nitraminofurazanammonium salt (6) provided in Example 1 of this invention 13 C NMR spectrum;

[0024] Figure 7 TG-DSC thermal analysis curve of the novel energetic compound 4-fluoroges-dinitro-3-nitraminofurazanium salt (6) provided in Example 1 of this invention;

[0025] Figure 8 The infrared spectrum of the novel energetic compound 4-fluoroges-dinitro-3-nitraminofurazanium salt (6) provided in Example 1 of this invention;

[0026] Figure 9 The novel energetic compound 4-fluorogesyldinitro-3-nitraminofurazanolamine salt (7) provided in Example 1 of this invention 13 C NMR spectrum;

[0027] Figure 10 The infrared spectrum of the novel energetic compound 4-fluoroges-dinitro-3-nitraminofurazanolamine salt (7) provided in Example 1 of this invention;

[0028] Figure 11 The TG-DSC thermal analysis curve of the novel energetic compound 4-fluoroges-dinitro-3-nitroaminofuran hydroxylamine salt (7) provided in Example 1 of this invention. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0030] This invention provides a novel fluoro-dinitrofuranzan-type energetic compound, its preparation method, and its applications. The energetic compound and its salt provided by this invention have high oxygen content, high energy density, and good thermal stability, and can be used as high-energy oxidants in fields such as solid propellants. This invention successfully prepared the target compound and its nitrogen-rich salt. The synthetic route adopts room temperature nitration, with mild reaction conditions, and has potential for industrial application.

[0031] The following is a detailed description of a novel fluoro-dinitrofuran-type energetic compound, its preparation method, and its application, provided by embodiments of the present invention.

[0032] In a first aspect, embodiments of the present invention provide a novel fluorogamma-dinitrofuran energetic compound, which includes 4-fluorogamma-dinitro-3-nitraminofuran and its salts, and its structural formula is shown below:

[0033] The above-mentioned 4-fluoroges-dinitro-3-nitroaminofuran and its salts, The decomposition temperature is 188.6℃. The decomposition temperature is 173.4℃. The thermal decomposition temperature is 124℃, and all of the above compounds are positive oxygen equilibrium compounds, making them good energetic oxidizing agents.

[0034] Secondly, embodiments of the present invention also provide a method for preparing the above-mentioned novel fluoro-dinitrofuran-type energetic compounds, comprising the following steps:

[0035] S1. Using the bispotassium salt (2) of 4-gamma-dinitro-3-nitraminofurazan of methylene syn as raw material, compound 2 is fluorinated to obtain 4-fluorogamma-dinitro-3-nitraminofurazan of methylene syn. After alkaline hydrolysis, compound (3) is given as potassium salt (4) of 4-fluorogamma-dinitro-3-nitraminofurazan.

[0036] S2 and compound (4) were acidified to obtain 4-fluoro-dinitro-3-nitraminofurazan (5);

[0037] S3, compound (5) reacts with ammonia reagent to give ammonium salt (6) of 4-fluoroges-dinitro-3-nitraminofuran;

[0038] S4, compound (5) reacts with hydroxylamine solution to give hydroxylamine salt (7) of 4-fluoroges-dinitro-3-nitramine-furazan.

[0039] Specifically, the synthetic route for the dipotassium salt (2) of 4-genomicdinitro-3-nitroaminofuran from the methylene group can be found in [link to relevant documentation]. Figure 1 :

[0040]

[0041] Using the dipotassium salt (2) of 4-genomicdinitro-3-nitroaminofurozan from the methylene group as a raw material, it was energetically derivatized. By introducing fluorine atoms and nitrogen-rich ion salts, energetic ionic salts of fluoro-genomicdinitrofurozan were synthesized to improve their energy and thermal stability. The synthetic route is described in [reference needed]. Figure 2 :

[0042]

[0043] The above raw material (2) was fluorinated to obtain 4-fluoro-dinitro-3-nitramine-furazan (3) with a methylene chain. Compound (3) was cleaved under alkaline conditions to obtain the potassium salt (4) of 4-fluoro-dinitro-3-nitramine-furazan. Compound (4) was acidified to obtain 4-fluoro-dinitro-3-nitramine-furazan (5). Compound (5) was reacted with ammonia reagent and hydroxylamine aqueous solution to prepare the corresponding ammonium salt (6) and hydroxylamine salt (7). The above preparation method has mild nitration conditions, moderate yield and low cost. The series of target molecules designed and synthesized have high oxygen balance, high energy density and good thermal stability, and have good application prospects as oxidants in the field of solid propellants.

[0044] The following is a detailed description of the preparation method of the novel fluoroges(2-)-dinitrofuranzan-type energetic compounds provided in the embodiments of the present invention:

[0045] First, 3-amino-4-aminooximefurazan was synthesized in a one-pot process using commercially available malononitrile and hydroxylamine hydrochloride. Then, 3-amino-4-chlorooximefurazan was obtained via a substitution reaction, followed by a condensation reaction with formaldehyde to yield methylene-based 3-amino-4-chlorooximefurazan (1). After nitration of compound (1) using a fuming nitric acid / trifluoroacetic anhydride nitration system at 5-30°C, it was reacted with potassium iodide to prepare the dipotassium salt (2) of methylene-based 3-gesidonitro-3-nitraminofurazan. The synthetic route is as follows: Figure 1 As shown. The potassium salt (2) obtained above reacts with a fluorinating reagent to obtain 4-fluoroglycine-3-nitraminofurazan (3). Compound (3) is treated with potassium hydroxide to break the methylene group, resulting in the potassium salt (4) of 4-fluoroglycine-3-nitraminofurazan. Compound (4) is acidified to obtain the corresponding organic compound 4-fluoroglycine-3-nitraminofurazan (5). Compound (5) reacts with ammonia reagent and hydroxylamine aqueous solution to prepare the corresponding ammonium salt (6) and hydroxylamine salt (7).

[0046] The specific steps are as follows:

[0047] Preparation of S0, the dipotassium salt of 4-ges-dinitro-3-nitraminofurozan (2): 3-amino-4-aminooximefurozan was synthesized by a one-pot reaction of malononitrile and hydroxylamine hydrochloride. Then, a diazotization substitution reaction was performed under the action of hydrochloric acid and sodium nitrite to obtain 3-amino-4-chlorooximefurozan. This was then condensed with formaldehyde in 1M hydrochloric acid to obtain 3-amino-4-chlorooximefurozan (1). Compound (1) was nitrated using dichloromethane as an inert solvent and a fuming nitric acid / trifluoroacetic anhydride nitration system at 5-30℃. The reaction solution was poured into an ice-water mixture, and the product was extracted with dichloromethane and concentrated by rotary evaporation to obtain a yellow oily liquid. The oily liquid was further treated with a methanol solution of KI, stirred at 5-30℃ for 15-17 h, and filtered to obtain a yellow solid, yielding compound (2).

[0048] S1. Preparation of target compound (4): The potassium salt of 4-gemethylene dinitro-3-nitraminofurozan (2) was suspended in anhydrous acetonitrile. Selectfluor (1-chloromethyl-4-fluoro-1,4-diazobicyclo[2.2.2]octane bis(tetrafluoroborate)) was added. The reaction temperature was 5-30℃ and the reaction time was 3h. After the reaction was completed, the solvent was removed by rotary evaporation. Anhydrous diethyl ether was added and stirred for 30min. The mixture was filtered, and the filtrate was removed by rotary evaporation to obtain a yellow oily liquid, which was compound (3). A methanol solution of KOH was added to the yellow oily liquid (3), and the mixture was stirred at 5-30℃ for 10-24h. After filtration, washing with methanol, and air drying, the potassium salt of 4-fluorogemethylene dinitro-3-nitraminofurozan (4) was obtained.

[0049] S2. Preparation of target compound (5): Compound (4) was acidified with hydrochloric acid or 20% dilute sulfuric acid, stirred at 5-30℃ for 10-20 min, extracted with ethyl acetate, the product was dissolved in the ethyl acetate phase, the ethyl acetate was removed, and a pale yellow solid 4-fluoroges-dinitro-3-nitroaminofuran (5) was obtained.

[0050] S3. Preparation of target compound (6): Dissolve compound (5) in the reaction solvent, introduce ammonia or add ammonium bicarbonate into it, stir at 5-30℃ for 5-18h, remove the reaction solvent and water by vacuum distillation, and obtain the ammonium salt (6) of 4-fluoroges-dinitro-3-nitroaminofuran, which is a pale yellow solid.

[0051] S4. Preparation of target compound (7): Dissolve compound (5) in the reaction solvent, add 50wt% hydroxylamine solution to it, stir at 5-30℃ for 10-15h, remove the reaction solvent and water by vacuum distillation, and obtain the white solid hydroxylamine salt of 4-fluoroges-dinitro-3-nitroaminofuran (7).

[0052] Furthermore, in step S1, when adding KOH to a methanol solution to perform alkaline hydrolysis on 4-fluorogesyldinitro-3-nitroaminofuran (3) of the methylene group, the reaction time should be controlled to be 10-24 h. If the reaction time is too long during alkaline hydrolysis, the product may decompose or other byproducts may be generated. The byproducts are unstable and will undergo rapid oxidative decomposition upon contact with air, making it impossible to further prepare 4-fluorogesyldinitro-3-nitroaminofuran salt. Therefore, alkaline hydrolysis is the key step of the reaction, and it has been observed that the alkaline hydrolysis time should preferably not exceed 24 h.

[0053] Further, in step S1, the molar ratio of the 4-genomicdinitro-3-nitroaminofuran dipotassium salt (2) of methylene chelate to Selectfluor is (1:2) to (1:6).

[0054] Further, in step S1, the molar ratio of 4-fluoro-dinitro-3-nitroaminofuran (3) of methylene chelate to KOH is (1:5) to (1:12).

[0055] Furthermore, in step S2, the acid used for acidification is hydrochloric acid or 20% dilute sulfuric acid.

[0056] Further, in step S3, the molar ratio of 4-fluoro-dinitro-3-nitroaminofuran (5) to the ammonia reagent is (1:1) to (1:5).

[0057] Further, in step S4, the molar ratio of 4-fluoro-dinitro-3-nitramino-furazan (5) to hydroxylamine is (1:1) to (1:8).

[0058] Furthermore, in steps S3 and S4, the reaction solvent includes one of methanol, ethanol, acetonitrile, acetone, tetrahydrofuran, or ethyl acetate.

[0059] The features and performance of the present invention will be further described in detail below with reference to embodiments.

[0060] Example 1

[0061] Step S0: See Figure 1 Using commercially available malononitrile as a raw material, 3-amino-4-aminooximefurazan was synthesized in a one-pot reaction with hydroxylamine hydrochloride. Then, 3-amino-4-chlorooximefurazan was obtained through a substitution reaction, and then condensed with formaldehyde to obtain methylene-linked 3-amino-4-chlorooximefurazan (1). After nitrification of compound 1 with fuming nitric acid / trifluoroacetic anhydride at 5-30℃, it was reacted with potassium iodide to prepare the dipotassium salt of methylene-linked 3-gesidonitro-3-nitraminofurazan (2).

[0062] Step S1: See Figure 2Add 2 g (3.6 mmol) of the dipotassium salt of 3-methyl-2-dinitro-3-nitroaminofuran (2) to a 250 mL round-bottom flask, add 90 mL of anhydrous acetonitrile, stir at 25 °C for 30 min to partially dissolve, and add 4.25 g (12 mmol) of Selectfluor in portions to the mixture. Stir at 25 °C for 3 h. After the reaction is complete, remove the solvent by vacuum distillation to obtain a yellow oily liquid. Add anhydrous diethyl ether (150 mL) and stir for 30 min. Filter to remove the residue, and remove the solvent by vacuum distillation of the filtrate to obtain a pale yellow oily liquid, which is 4-fluoro-2-dinitro-3-nitroaminofuran (3). A methanol solution of KOH was prepared (2.0 g KOH dissolved in 20 mL anhydrous methanol), added to the above oily liquid (3), stirred for 16 h, filtered and dried to obtain 0.52 g of pale yellow solid, which is the potassium salt of 4-fluoroges-dinitro-3-nitroaminofuran (4), with a total yield of 25%.

[0063] Characterization of the potassium salt of 4-fluorogesyldinitro-3-nitroaminofuran (4) is described in [reference needed]. Figure 3-5 :

[0064] Depend on Figure 3 visible: 13 CNMR (125MHz, D2O, 25°C): δ=167.12, 158.77, 151.85ppm.

[0065] Depend on Figure 4 visible: 1 FNMR (500MHz, D2O, 25°C): δ=148.26ppm.

[0066] Depend on Figure 5 It can be seen that the thermal decomposition temperature of the potassium salt of 4-fluoroges-dinitro-3-nitroaminofuran (4) is 188.6℃;

[0067] Step S2: Dissolve 0.26 g (0.9 mmol) of the potassium salt of 4-fluoroges(dinitro-3-nitraminofurozan) (4) in 20 mL of 20% dilute sulfuric acid at 25 °C, and extract with 30 mL of ethyl acetate in two portions. The product dissolves in the ethyl acetate phase. Remove the ethyl acetate and remove water with anhydrous magnesium sulfate to obtain a pale yellow clear liquid. Remove the solvent by vacuum distillation to obtain 0.195 g of pale yellow solid 4-fluoroges(dinitro-3-nitraminofurozan) (5), with a yield of 86%.

[0068] Step S3: Dissolve 0.252 g (1 mmol) of 4-fluoro-dinitro-3-nitraminofurozan (5) in ethyl acetate, add 0.08 g (1 mmol) of NH4HCO3, stir at 25 °C for 15 h, and a pale yellow product precipitates in ethyl acetate. After filtration, washing with ethyl acetate and drying, 0.124 g of the ammonium salt of 4-fluoro-dinitro-3-nitraminofurozan (6) is obtained, with a yield of 46%.

[0069] Characterization of the ammonium salt of 4-fluoroges-dinitro-3-nitraminofuran (6) is described in [reference needed]. Figure 6-8 :

[0070] Depend on Figure 6 visible: 13 CNMR (125MHz, D2O, 25℃): δ=167.20, 158.83, 151.91ppm;

[0071] Depend on Figure 7 visible: I R(KBr,ν / cm -1 ): 3174, 1616, 1460, 1408, 1339cm -1 .

[0072] Depend on Figure 8 It can be seen that the thermal decomposition temperature of the ammonium salt of 4-fluoroges-dinitro-3-nitroaminofuran (6) is 173.4℃;

[0073] Step S4: Dissolve 0.252 g (1 mmol) of 4-fluoro-dinitro-3-nitraminofurozan (5) in ethyl acetate, add excess 0.48 mL (8 mmol) of 50% wt hydroxylamine aqueous solution, stir at 25 °C for 3 h to obtain a pale yellow aqueous solution, blow off the water, wash with anhydrous ethanol, filter and dry to obtain 0.068 g of white solid, which is the hydroxylamine salt of 4-fluoro-dinitro-3-nitraminofurozan (7), with a yield of 24%.

[0074] Characterization of the hydroxylamine salt of 4-fluoroges-dinitro-3-nitroaminofuran (7) is described in [reference needed]. Figure 9-11 :

[0075] Depend on Figure 9 visible: 13 CNMR (125MHz, D3O, 25℃): δ=167.2086, 158.8256, 151.9149;

[0076] Depend on Figure 10 visible: I R(KBr,ν / cm -1 ): 3436, 3173, 1654, 1507, 1400, 1325cm -1 .

[0077] Depend on Figure 11 It can be seen that the thermal decomposition temperature of the hydroxylamine salt (7) of 4-fluoro-dinitro-3-nitroaminofuran is 154.8℃.

[0078] As can be seen, in Example 1 of this invention, a novel energetic compound, 4-fluoro-dinitro-3-nitraminofurazan, and its salt were prepared by studying the 4-fluoro-dinitro-3-nitraminofurazan of methylene chelate. This method is simple to synthesize, has mild reaction conditions, and moderate yield, which is beneficial for practical engineering applications.

[0079] Example 2

[0080] Step S1: See Figure 2 1.12 g (2 mmol) of the dipotassium salt of 3-methyl-2-dinitro-3-nitroaminofuran (2) was added to a 250 mL round-bottom flask, followed by 60 mL of anhydrous acetonitrile. The mixture was stirred at 25 °C for 30 min to partially dissolve the solid. 2.84 g (8 mmol) of Selectfluor was added in portions to the mixture. The mixture was stirred at 5 °C for 3 h. After the reaction was complete, the solvent was removed by vacuum distillation to obtain a pale yellow solid. Anhydrous diethyl ether (100 mL) was added and stirred for 30 min. The white residue was removed by filtration, and the solvent was removed by vacuum distillation of the filtrate to obtain a pale yellow oily liquid, which was 4-fluoro-2-dinitro-3-nitroaminofuran (3). A methanol solution of KOH was prepared (1.8 g KOH dissolved in 18 mL of anhydrous methanol), added to the above oily liquid (3), stirred for 16 h, filtered and dried to obtain 0.12 g of pale yellow solid, which is the potassium salt of 4-fluoroges-dinitro-3-nitroaminofuran (4), with a total yield of 10%.

[0081] Step S2: Dissolve 0.24 g (0.83 mmol) of the potassium salt of 4-fluoroges(dinitro-3-nitraminofurozan) (4) in 20 mL of 20% dilute hydrochloric acid, and extract with 30 mL of ethyl acetate in two portions. The product dissolves in the ethyl acetate phase. Remove the ethyl acetate and remove water with anhydrous sodium sulfate to obtain a pale yellow clear liquid. Remove the solvent by vacuum distillation to obtain 0.18 g of pale yellow solid 4-fluoroges(dinitro-3-nitraminofurozan) (5), with a yield of 86%.

[0082] Step S3: Dissolve 0.19 g (0.75 mmol) of 4-fluoro-dinitro-3-nitroaminofurozan (5) in ethyl acetate, add 0.06 g (0.75 mmol) of NH4HCO3, stir at 5 °C for 15 h, and a pale yellow product precipitates in ethyl acetate. After filtration, washing with ethyl acetate and drying, 0.091 g of ammonium salt of product 4-fluoro-dinitro-3-nitroaminofurozan (6) is obtained, with a yield of 45%.

[0083] Step S4: Dissolve 0.19 g (0.75 mmol) of 4-fluoro-dinitro-3-nitraminofuroxanzane in ethyl acetate, add excess 0.48 mL (8 mmol) of 50 wt% hydroxylamine aqueous solution, stir at 5 °C for 3 h to obtain a pale yellow aqueous solution, blow off the water, wash with anhydrous ethanol, filter and dry to obtain 0.046 g of white solid, which is the hydroxylamine salt of 4-fluoro-dinitro-3-nitraminofuroxanzane (7), with a yield of 22%.

[0084] Example 3

[0085] Step S1: See Figure 2 1.12 g (2 mmol) of the dipotassium salt of 3-methyl-2-dinitro-3-nitraminofuran (2) was added to a 250 mL round-bottom flask, followed by 60 mL of anhydrous acetonitrile. The mixture was stirred at 5 °C for 30 min to partially dissolve the solid. 4.26 g (12 mmol) of Selectfluor was added in portions to the mixture. The mixture was stirred at 5 °C for 3 h. After the reaction was complete, the solvent was removed by vacuum distillation to obtain a pale yellow solid. 100 mL of anhydrous diethyl ether was added and stirred for 30 min. The white residue was removed by filtration, and the solvent was removed by vacuum distillation of the filtrate to obtain a pale yellow oily liquid, which was 4-fluoro-2-dinitro-3-nitraminofuran (3). A methanol solution of KOH was prepared (1.8 g KOH dissolved in 18 mL of anhydrous methanol), added to the above oily liquid (3), stirred for 16 h, filtered and dried to obtain 0.14 g of pale yellow solid, which is the potassium salt of 4-fluoroges-dinitro-3-nitroaminofuran (4), with a total yield of 12%.

[0086] Step S2: Dissolve 0.20 g (0.69 mmol) of the potassium salt of 4-fluoroges(dinitro-3-nitraminofurozan) (4) in 20 mL of 20% dilute sulfuric acid, and extract with 30 mL of ethyl acetate in two portions. The product dissolves in the ethyl acetate phase. Remove the ethyl acetate and remove the water with anhydrous sodium sulfate to obtain a pale yellow clear liquid. Remove the solvent by vacuum distillation to obtain 0.15 g of pale yellow solid 4-fluoroges(dinitro-3-nitraminofurozan) (5), with a yield of 86%.

[0087] Step S3: Dissolve 0.19 g (0.75 mmol) of 4-fluoro-dinitro-3-nitroaminofurozan (5) in ethyl acetate, stir at 5 °C, and purge with ammonia for 30 min. The solution becomes turbid and a pale yellow product precipitates in ethyl acetate. After filtration, washing with ethyl acetate and drying, 0.086 g of ammonium salt of 4-fluoro-dinitro-3-nitroaminofurozan (6) is obtained, with a yield of 43%.

[0088] Step S4: Dissolve 0.20 g (0.79 mmol) of 4-fluoro-dinitro-3-nitraminofurozan in ethyl acetate, add excess 0.48 mL (8 mmol) of 50 wt% hydroxylamine aqueous solution, stir at 5 °C for 3 h to obtain a pale yellow aqueous solution, blow off the water, wash with anhydrous ethanol, filter and dry to obtain 0.045 g of white solid, which is the hydroxylamine salt of 4-fluoro-dinitro-3-nitraminofurozan (7), with a yield of 20%.

[0089] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A novel fluoro-dinitrofuranzan-type energetic compound, characterized in that, The novel fluorogestanilofurazan-type energetic compounds include 4-fluorogestanilo-3-nitroaminofurazan and its salts, with the following structural formulas: 、 、 、 。 2. The novel fluoroglycine-dinitrofuranzan-type energetic compound according to claim 1, characterized in that, The decomposition temperature is 188.6℃. The decomposition temperature is 173.4℃. The thermal decomposition temperature is 154.8℃.

3. The novel fluoroglycine-dinitrofuranzan-type energetic compound according to claim 1, characterized in that, The 4-fluorogestigma-3-nitraminofuran and its salts are all positive oxygen equilibrium compounds.

4. A method for preparing a novel fluoroglycine dinitrofuran-type energetic compound according to any one of claims 1-3, characterized in that, The synthetic route for the novel fluoro-dinitrofuranzan-type energetic compounds is as follows: Includes the following steps: S1. Using the bispotassium salt 2 of 4-methyl-2-dinitro-3-nitraminofurazan from methylene syn as raw material, compound 2 is fluorinated to obtain 4-fluoro-2-dinitro-3-nitraminofurazan from methylene syn. After alkaline hydrolysis, compound 3 is given as the potassium salt 4 of 4-fluoro-2-dinitro-3-nitraminofurazan. S2 and compound 4, after acidification, yield 4-fluorogesyldinitro-3-nitraminofuran 5; S3 and compound 5 react with an ammonia reagent to give ammonium salt 6 of 4-fluoroges-dinitro-3-nitraminofuran; S4 and compound 5 react with hydroxylamine solution to give hydroxylamine salt 7 of 4-fluorogesyldinitro-3-nitramino-furazan.

5. The method for preparing the novel fluoroges(2-)-dinitrofuranzan-type energetic compound according to claim 4, characterized in that, In step S1, the fluorinating agent is Selectfluor, and the reaction solvent is anhydrous acetonitrile.

6. The method for preparing the novel fluoroges(2-)-dinitrofuranzan-type energetic compound according to claim 5, characterized in that, The molar ratio of the 4-genomicdinitro-3-nitroaminofuran dipotassium salt 2 of methylene chelate to Selectfluor is (1:4) to (1:6).

7. The method for preparing the novel fluoroges(2-)-dinitrofuranzan energetic compound according to claim 5, characterized in that, The reaction temperature is 5-30℃, and the reaction time is 2-6h.

8. The method for preparing the novel fluoroges(2-)-dinitrofuranzan-type energetic compound according to claim 5, characterized in that, After the reaction was completed, the reaction solvent was removed by rotary evaporation. Anhydrous diethyl ether was added and stirred for 30 min. The mixture was then filtered, and the filtrate was removed by rotary evaporation to obtain a yellow oily liquid, 4-fluoroges-dinitro-3-nitraminofuran 3.

9. The method for preparing the novel fluoroges(2-)-dinitrofuranzan-type energetic compound according to claim 4, characterized in that, In step S1, the base used in the alkaline hydrolysis reaction is KOH, and the reaction solvent is methanol.

10. The method for preparing the novel fluoroges(2-)-dinitrofuranzan-type energetic compound according to claim 9, characterized in that, The molar ratio of 4-fluoro-dinitro-3-nitroaminofuran 3 to KOH is (1:5) to (1:12).

11. The method for preparing the novel fluoroges(2-)-dinitrofuranzan-type energetic compound according to claim 9, characterized in that, The alkaline hydrolysis reaction temperature is 5-30℃, and the reaction time is 10-24h.

12. The method for preparing the novel fluoroges(2-)-dinitrofuranzan-type energetic compound according to claim 9, characterized in that, After the alkaline hydrolysis reaction was completed, the potassium salt of 4-fluorogesyldinitro-3-nitroaminofuran was obtained by filtration, washing with methanol and air drying.

13. The method for preparing the novel fluoroges(2-)-dinitrofurans(2-)-energetic compounds according to claim 4, characterized in that, In step S2, the acid used for acidification is hydrochloric acid or 20% dilute sulfuric acid.

14. The method for preparing the novel fluoroges(2-)-dinitrofuranzan-type energetic compound according to claim 13, characterized in that, The acidification temperature is 5-30℃ and the acidification time is 30min.

15. The method for preparing the novel fluoroges(2-)-dinitrofuran-type energetic compound according to claim 13, characterized in that, After acidification, the product was extracted with ethyl acetate and dissolved in the ethyl acetate phase. The ethyl acetate was removed to obtain a pale yellow solid, 4-fluoro-dinitro-3-nitroaminofuran 5.

16. The method for preparing the novel fluoroges(2-)-dinitrofurans(2-)-energetic compounds according to claim 4, characterized in that, In step S3, the ammonia reagent includes one or more of ammonia gas or ammonium bicarbonate.

17. The method for preparing the novel fluoroges(2-)-dinitrofuranzan-type energetic compound according to claim 16, characterized in that, The molar ratio of 4-fluoro-dinitro-3-nitroaminofuran 5 to ammonia reagent is (1:1) to (1:5).

18. The method for preparing the novel fluoroges(2-)-dinitrofuranzan energetic compound according to claim 16, characterized in that, The reaction solvent includes one or more of methanol, ethanol, acetonitrile, acetone, tetrahydrofuran, and ethyl acetate.

19. The method for preparing the novel fluoroges(2-)-dinitrofurans(2-)-energetic compounds according to claim 16, characterized in that, The reaction temperature is 5-30℃, and the reaction time is 5-18h.

20. The method for preparing the novel fluoroges(2-)-dinitrofuranzan-type energetic compound according to claim 16, characterized in that, After the reaction was completed, the reaction solvent and water were removed by vacuum distillation to obtain the pale yellow solid ammonium salt 6 of 4-fluorogesyldinitro-3-nitroaminofuran.

21. The method for preparing the novel fluoroges(2-)-dinitrofuranzan-type energetic compounds according to claim 4, characterized in that, In step S4, the concentration of the hydroxylamine solution is 50 wt%.

22. The method for preparing the novel fluoro-dinitrofuran-type energetic compound according to claim 21, characterized in that, The molar ratio of 4-fluoro-dinitro-3-nitramino-furazan 5 to hydroxylamine is (1:1) to (1:10).

23. The method for preparing the novel fluoroges(21)-type energetic compound, characterized in that, The reaction solvent includes one of methanol, ethanol, acetonitrile, acetone, tetrahydrofuran, and ethyl acetate.

24. The method for preparing the novel fluoro-dinitrofuran-type energetic compound according to claim 21, characterized in that, The reaction temperature is 5-30℃, and the reaction time is 10-15h.

25. The method for preparing the novel fluoroges(21)-type energetic compound according to claim 21, characterized in that, After the reaction was complete, the reaction solvent and water were removed by vacuum distillation to obtain the white solid hydroxylamine salt 7 of 4-fluoroges-dinitro-3-nitroaminofuran.

26. The novel fluoroglycine dinitrofuran energetic compound according to any one of claims 1-3 or the novel fluoroglycine dinitrofuran energetic compound prepared by the preparation method according to any one of claims 4-25 is used as an oxidant in the preparation of solid propellants.

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