Preparation method of 3-(4-nitrofurazan-3-oxymethyl)-3-azido methyl oxetane
By preparing 3-(4-nitrofura-3-oxymethyl)-3-azidomethyloxetane, the performance of oxetane energy-containing monomers due to their highly symmetrical structure is solved. Defects have achieved improvements in high energy, insensitivity, stability and mechanical properties.
Patent Information
- Application Number
- CN202311277669.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-09-28
- Publication Date
- 2025-02-18
- Estimated Expiration
- 2043-09-28
AI Technical Summary
Due to its highly symmetrical structure, the existing oxetane energy-containing monomers have an increase in the crystallization trend of monomers, which affects the polymerization process and cannot obtain polymers that meet the application standards.
By preparing 3-(4-nitrofuraz-3-oxymethyl)-3-azidomethyloxetane, 3-nitro-4-hydroxyfuraz and 3,3-dibromomethyl The base oxetane is the raw material, and the reaction is heated in an alkaline system, followed by azide reaction under an ice water bath to obtain the target product.
This method not only retains high-energy characteristics, but also overcomes sensitivity defects, improves oxygen equilibrium and thermal decomposition temperature, and significantly improves the mechanical properties of the polymer.
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Abstract
Description
Technical Field
[0001] The invention belongs to the field of insensitive energetic materials and relates to a method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane. Background Art
[0002] Since the 21st century, the effectiveness of high-precision ammunition in the war on terror has been obvious to all. Endless exploration to improve the effectiveness of single-shot ammunition and the pursuit of destroying key enemy targets with one round of ammunition at any cost has become a major trend in the field of energetic materials. However, practical cases have shown that in a real total war, even if all ammunition is fired, an astonishing amount of ammunition is required to completely destroy key targets, and these ammunition consumptions with increasingly fine division of labor are difficult to be replenished in a short period of time. To address this problem, modular energetic materials came into being.
[0003] Modular energetic materials are energetic materials that can be mass-produced and manufactured in series based on standardization. They can be combined with other units to form products through different forms of processing, so that they have certain relatively independent functions, and can be decomposed, combined, and interchangeable. They can be given a wide range of applications through reasonable structural design to meet the needs of different weapons and equipment, and can be mass-produced and scaled through standardized production. This is one of the main development directions in the field of energetic materials in the future. Research on the design, customization, and synthesis of modular energetic materials has recently received attention.
[0004] Oxetane, as a saturated four-membered cyclic ether monomer with dual active sites, can simultaneously carry two energetic groups to form a polymer skeleton. It is an important branch of energetic polymers and has broad application prospects. Furazan compounds are different from traditional energetic compounds. On the one hand, their molecular structures contain a large number of CN, C=N and N=N bonds, so they have very high formation enthalpy. In addition, the aromaticity of the furazan ring enhances the thermal stability of furazan derivatives, and the coplanarity of the furazan ring makes its density higher. On the other hand, due to the high electronegativity of nitrogen and oxygen atoms in furazan compounds, its nitrogen heteroaromatic ring system can form a large π bond of a benzene-like structure, which has the properties of insensitivity and thermal stability. Therefore, many of the furazan energetic derivatives have high energy density and high standard formation enthalpy (ΔH f ), high nitrogen content and excellent heat resistance. Oxyheterocyclobutane polymers with excellent mechanical properties and stable furazanyl energetic groups are very suitable for the application requirements of modular energetic materials. For example, "Furazanyl Ethers of Pentaerythritol Derivatives" Int Annu Conf ICT 28 th, 1997, 127: 176356. A preparation method of 3,3-bis(4-nitrofurazan-3-oxymethyl)oxetane is disclosed. The energetic monomer contains a furazan group and an oxetane base, has a high energy density, and has an application prospect as a multifunctional modular energetic material precursor. However, the oxetane ring carries two large side groups and is symmetrically distributed, which leads to a sudden increase in the crystallization trend of the monomer, and also seriously affects the subsequent polymerization process of the monomer, resulting in an inability to obtain a polymer that can meet the application standards, and is difficult to apply in practice. For this reason, it is necessary to design an energetic furazan-substituted oxetane compound that can retain the high-energy insensitivity characteristics of 3,3-bis(4-nitrofurazan-3-oxymethyl)oxetane while overcoming the performance defects caused by the highly symmetrical structure, which has considerable application prospects. Summary of the invention
[0005] In view of the deficiencies in the prior art, the object of the present invention is to provide a method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane. The novel multifunctional insensitive energetic material has good detonation performance and insensitivity characteristics, and at the same time, has the functions of a liquid phase carrier for melt-cast explosives, a monomer plasticizer, and a single explosive, and can also be polymerized and used as a structural energetic material or an energetic adhesive.
[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions to achieve the above problems:
[0007] The preparation method of 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane comprises the following steps:
[0008] Step 1, adding 3-nitro-4-hydroxyfurazan, 3,3-dibromomethyloxetane, a basic donor and a phase transfer catalyst to a polar aprotic solvent, stirring and reacting at 45 to 85° C. for 0.5 to 2 hours, then extracting, washing, drying, filtering, evaporating the solvent and recrystallizing to obtain an intermediate 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane;
[0009] Step 2: The intermediate 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane obtained in step 1 and an azidating agent are added to a polar aprotic solvent, and the mixture is stirred for reaction for 0.5 to 2 h in an ice-water bath, and then extracted, washed with water, dried, filtered, and the solvent is evaporated to obtain 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane.
[0010] The present invention also includes the following technical features:
[0011] Specifically, the alkaline donor is anhydrous potassium carbonate, cesium carbonate or ferric hydroxide.
[0012] Specifically, the phase transfer catalyst is tetrabutylammonium bromide, benzyltriethylammonium chloride, methyltrialkylammonium chloride or 18-crown ether-6.
[0013] Specifically, the molar ratio of the 3,3-dibromomethyloxetane, 3-nitro-4-hydroxyfurazan, alkaline donor, and phase transfer catalyst is 1:(0.67-1.25):(1.25-3):(0.013-0.04).
[0014] Specifically, the azidation reagent is sodium azide, trimethylsilyl azido, p-toluenesulfonyl azide, ethyl azidoacetate, tetrabutylammonium azide or tri-n-butyltin azide.
[0015] Specifically, the molar ratio of the intermediate 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane to the azidation reagent is 1:(0.8-1.5).
[0016] Specifically, the polar aprotic solvent is DMF, MeCN, Acetone or DMSO.
[0017] Compared with the prior art, the present invention has the following technical effects:
[0018] 1. The present invention uses easily available 3-nitro-4-hydroxyfurazan and commercially available 3,3-dibromomethyloxetane as raw materials, heats them in a solvent under a cheap and environmentally friendly alkaline system to obtain 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane, and then performs an azidation reaction in an ice-water bath to obtain 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane. The method has the advantages of easy availability of reaction raw materials, mild reaction conditions, safety and environmental protection, and simple reaction steps, which can be operated continuously and is convenient for industrial continuous production.
[0019] 2. The 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane obtained by the method of the present invention can not only retain the high-energy characteristics of 3,3-bis(azidomethyl)oxetane but also overcome the sensitivity defects caused by the introduction of energetic groups (friction sensitivity is increased from 4N to 200N, and impact sensitivity is increased from 0.49J to 40J, reaching the standard of insensitive energetic materials), and at the same time, its oxygen balance (from -123.8% to -81.25%) and thermal decomposition temperature (from 160°C to 252°C) are also significantly improved. The product exists in liquid state at room temperature, and subsequent polymerization tests show that its polymer has better mechanical properties.
[0020] 3. The 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane obtained by the method of the present invention introduces a variety of energetic groups into the same energetic monomer through molecular structure design, which can significantly improve the compatibility of the adhesive and make it more conducive to practical application. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] Figure 1 is the H NMR spectrum of 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane;
[0022] Figure 2 is the carbon NMR spectrum of 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane;
[0023] Figure 3 is the FTIR spectrum of 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane;
[0024] Figure 4 It is a high-resolution mass spectrum of 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane;
[0025] Figure 5 This is the DSC chart of 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane. DETAILED DESCRIPTION
[0026] The present invention provides a method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane, which uses 3-nitro-4-hydroxyfurazan and 3,3-dibromomethyloxetane as raw materials, heats them in a solvent under the action of an alkaline system and a phase transfer catalyst, and obtains 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane through a one-step reaction, and then reacts with an azidation reagent in an equal molar ratio at low temperature to obtain the target product 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane. The synthesis route is as follows:
[0027]
[0028] The following steps are involved:
[0029] Step 1, adding 3-nitro-4-hydroxyfurazan, 3,3-dibromomethyloxetane, a basic donor and a phase transfer catalyst to a polar aprotic solvent, stirring and reacting at 45 to 85° C. for 0.5 to 2 hours, then extracting, washing, drying, filtering, evaporating the solvent and recrystallizing to obtain an intermediate 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane;
[0030] Specifically, in step 1:
[0031] The alkaline donor is anhydrous potassium carbonate, cesium carbonate or ferric hydroxide.
[0032] The phase transfer catalyst is tetrabutylammonium bromide, benzyltriethylammonium chloride, methyltrialkylammonium chloride or 18-crown ether-6.
[0033] Preferably, the molar ratio of 3,3-dibromomethyloxetane, 3-nitro-4-hydroxyfuroxan, alkaline donor, and phase transfer catalyst is 1:(0.67-1.25):(1.25-3):(0.013-0.04).
[0034] Step 2: The intermediate 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane obtained in step 1 and an azidating agent are added to a polar aprotic solvent, and the mixture is stirred for reaction for 0.5 to 2 h in an ice-water bath, and then extracted, washed with water, dried, filtered, and the solvent is evaporated to obtain 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane.
[0035] Specifically, in step 2, the azidation reagent is sodium azide, trimethylsilyl azido, p-toluenesulfonyl azide, ethyl azidoacetate, tetrabutylammonium azide or tri-n-butyltin azide.
[0036] Preferably, the molar ratio of the intermediate 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane to the azidation reagent is 1:(0.8-1.5).
[0037] The polar aprotic solvent is DMF, MeCN, Acetone or DMSO.
[0038] Specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solution of this application fall within the protection scope of the present invention.
[0039] Embodiment 1:
[0040] This embodiment provides a method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane, comprising the following steps:
[0041] Step 1, 3-nitro-4-hydroxyfurazan (1.31 g, 0.01 mol), 3,3-dibromomethyloxetane (2.44 g, 0.01 mol), anhydrous potassium carbonate (2.82 g, 0.015 mol), phase transfer catalyst 18-crown ether-6 (0.05 g, 0.0002 mol), added dimethylformamide DMF (30 ml) at room temperature, stirred thoroughly, reacted at 65 ° C for 1.5 h, after the reaction was completed, water and dichloromethane were added for extraction, then washed with water, dried over anhydrous magnesium sulfate, filtered, evaporated the solvent, and recrystallized to finally obtain white crystals as an intermediate (2.3 g, yield 83.5%);
[0042] Step 2: Add the intermediate (1.39 g, 0.005 mol) obtained in step 1 and sodium azide (0.39 g, 0.006 mol) into 3 ml of DMF, stir and react for 2 h in an ice-water bath, then extract with ethyl acetate, wash with water, dry, filter and evaporate to obtain the target product as a yellow oil (1.22 g, yield 96%).
[0043] Structure identification:
[0044] (1) C NMR spectroscopy analysis
[0045] The obtained oily product was analyzed by carbon NMR spectroscopy. Figure 2 As shown, compared with the intermediate 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane, the characteristic peaks of 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane at 158.79ppm and 152.79ppm have not shifted, and the peak shape still maintains the high-low peak shape characteristic of nitrofurazan, indicating that the furazan nitro group still exists; the characteristic peaks of methyloxetane at 74.94ppm, 74.15ppm, and 43.37ppm have not changed much, shifting to 74.28ppm, 74.14ppm, and 42.76ppm respectively, indicating that the main body of methyloxetane has not changed. Correspondingly, the carbon spectrum peak of the bromomethyl group at 36.44ppm shifts to 52.65ppm downfield, indicating that the bromomethyl group is converted into the azidomethyl group with stronger electronegativity (weaker shielding effect). The hydrogen spectrum is as follows Figure 1 As shown, the area obtained by integrating the corresponding peaks is 1:2:1, which also confirms the successful synthesis of 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane.
[0046] (2) Infrared spectrum analysis
[0047] The obtained spectrum was compared with the intermediate 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane. Figure 3 As shown, it is located at 835cm -1The characteristic peak of 3,3-dibromomethyloxetane still exists, indicating that the oxetane structure still exists in the pure monomer; -1 The nitro infrared absorption peak at 2100cm -1 With 2150cm -1 The appearance of the characteristic absorption peak of the azido group indicates the successful synthesis of 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane.
[0048] (3) High-resolution mass spectrometry
[0049] The obtained light yellow liquid was subjected to high resolution mass spectrometry analysis. Figure 4 As shown, the highest peak in the obtained spectrum (257.06735) is completely consistent with the predicted molecular weight of the hydrogenated structure (257.0634), indicating the successful synthesis of 3,3-bis(4-nitrofurazan-3-oxymethyl)oxetane.
[0050] Embodiment 2:
[0051] This embodiment provides a method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane, comprising the following steps:
[0052] Step 1, 3-nitro-4-hydroxyfurazan (1.05 g, 0.008 mol), 3,3-dibromomethyloxetane (2.44 g, 0.01 mol), anhydrous cesium carbonate (9.78 g, 0.03 mol), phase transfer catalyst tetrabutylammonium bromide (0.13 g, 0.0004 mol), added to DMSO (30 ml) at room temperature, fully stirred, reacted at 65 ° C for 2 h, after the reaction, added water and dichloromethane for extraction, then washed with water, dried over anhydrous magnesium sulfate, filtered, evaporated the solvent, recrystallized, and finally obtained white crystals as an intermediate (2.0 g, yield 72.6%);
[0053] Step 2: Add the intermediate (2.0 g, 0.0068 mol) obtained in step 1 and sodium azide (0.65 g, 0.01 mol) into 3 ml of DMF, stir and react for 0.5 h in an ice-water bath, then extract with ethyl acetate, wash with water, dry, filter and evaporate to obtain the target product as a yellow oil (1.63 g, yield 94%).
[0054] Embodiment 3:
[0055] This embodiment provides a method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane, comprising the following steps:
[0056] Step 1, 3-nitro-4-hydroxyfurazan (1.31 g, 0.01 mol), 3,3-dibromomethyloxetane (3.66 g, 0.015 mol), ferric hydroxide (3.21 g, 0.03 mol), phase transfer catalyst benzyltriethylammonium chloride (0.046 g, 0.0002 mol), added to dimethylformamide DMF (30 ml) at room temperature, fully stirred, reacted at 65 ° C for 1.5 h, after the reaction, added water and dichloromethane for extraction, then washed with water, dried over anhydrous magnesium sulfate, filtered, evaporated the solvent, recrystallized, and finally obtained white crystals as an intermediate (1.78 g, yield 64.5%);
[0057] Step 2: Add the intermediate (1.78 g, 0.0064 mol) obtained in step 1 and sodium azide (0.78 g, 0.012 mol) to 3 ml of DMSO, stir and react for 2 h in an ice-water bath, then extract with ethyl acetate, wash with water, dry, filter and evaporate to obtain the target product as a yellow oil (1.39 g, yield 85%).
[0058] Embodiment 4:
[0059] This embodiment provides a method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane, comprising the following steps:
[0060] Step 1, 3-nitro-4-hydroxyfurazan (1.31 g, 0.01 mol), 3,3-dibromomethyloxetane (2.44 g, 0.01 mol), anhydrous potassium carbonate (2.82 g, 0.015 mol), and a phase transfer catalyst, methyltrialkylammonium chloride (0.08 g, 0.0002 mol), were added to Acetone (30 ml) at room temperature, stirred sufficiently, and reacted at 45° C. for 2 h. After the reaction was completed, water and dichloromethane were added for extraction, and then washed with water, dried over anhydrous magnesium sulfate, filtered, the solvent was evaporated, and recrystallized to finally obtain white crystals (1.14 g, yield 42.0%) as an intermediate;
[0061] Step 2: Add the intermediate obtained in step 1 (1.14 g, 0.0042 mol) and p-toluenesulfonyl azide (1.18 g, 0.006 mol) into 3 ml of DMF, stir and react for 0.5 h in an ice-water bath, then extract with ethyl acetate, wash with water, dry, filter and evaporate to obtain the target product as a yellow oil (1.00 g, yield 93%).
[0062] Embodiment 5:
[0063] This embodiment provides a method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane, comprising the following steps:
[0064] Step 1, 3-nitro-4-hydroxyfurazan (1.31 g, 0.01 mol), 3,3-dibromomethyloxetane (2.44 g, 0.01 mol), ferric hydroxide (1.60 g, 0.015 mol), phase transfer catalyst 18-crown ether-6 (0.05 g, 0.0002 mol), added to MeCN (30 ml) at room temperature, fully stirred, reacted at 65 ° C for 0.5 h, after the reaction, added water and dichloromethane for extraction, then washed with water, dried over anhydrous magnesium sulfate, filtered, evaporated the solvent, recrystallized, and finally obtained white crystals as an intermediate (1.8 g, yield 64.5%);
[0065] Step 2: Add the intermediate obtained in step 1 (1.8 g, 0.0065 mol) and trimethylsilyl azide (1.49 g, 0.013 mol) to 3 ml of DMF, stir and react for 2 h in an ice-water bath, then extract with ethyl acetate, wash with water, dry, filter and evaporate to obtain the target product as a yellow oil (1.60 g, yield 96%).
[0066] Embodiment 6:
[0067] This embodiment provides a method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane, comprising the following steps:
[0068] Step 1, 3-nitro-4-hydroxyfurazan (1.31 g, 0.01 mol), 3,3-dibromomethyloxetane (1.96 g, 0.008 mol), anhydrous potassium carbonate (2.82 g, 0.015 mol), phase transfer catalyst 18-crown ether-6 (0.05 g, 0.0002 mol), added to DMSO (30 ml) at room temperature, stirred thoroughly, reacted at 65 ° C for 1.5 h, after the reaction was completed, water and dichloromethane were added for extraction, then washed with water, dried over anhydrous magnesium sulfate, filtered, evaporated the solvent, and recrystallized to finally obtain white crystals as an intermediate (1.78 g, yield 64.6%);
[0069] Step 2: Add the intermediate (1.78 g, 0.0064 mol) obtained in step 1 and sodium azide (0.78 g, 0.012 mol) to 3 ml of DMF, stir and react for 2 h in an ice-water bath, then extract with ethyl acetate, wash with water, dry, filter and evaporate to obtain the target product as a yellow oil (1.20 g, yield 95%).
[0070] Embodiment 7:
[0071] This embodiment provides a method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane, comprising the following steps:
[0072] Step 1, 3-nitro-4-hydroxyfurazan (1.31 g, 0.01 mol), 3,3-dibromomethyloxetane (2.93 g, 0.012 mol), anhydrous potassium carbonate (2.82 g, 0.015 mol), phase transfer catalyst 18-crown ether-6 (0.13 g, 0.0005 mol), added dimethylformamide DMF (30 ml) at room temperature, stirred thoroughly, reacted at 85 ° C for 2 h, after the reaction was completed, water and dichloromethane were added for extraction, then washed with water, dried over anhydrous magnesium sulfate, filtered, evaporated the solvent, and recrystallized to finally obtain white crystals as an intermediate (2.0 g, yield 77.7%);
[0073] Step 2: Add the intermediate obtained in step 1 (2.0 g, 0.0077 mol) and tri-n-butyltin azide (4.0 g, 0.012 mol) to 3 ml of DMSO, stir and react for 2 h in an ice-water bath, then extract with ethyl acetate, wash with water, dry, filter and evaporate to obtain the target product as a yellow oil (1.46 g, yield 74%).
[0074] like Figure 5 As shown in Table 1, after the present invention introduces nitrofurazan into oxetane, the key parameters of energetic materials such as density, detonation performance, stability, and oxygen balance are significantly improved, while overcoming the performance defects caused by the highly symmetrical structure, and has considerable application prospects.
[0075] Table 1 Comparison of density, detonation velocity and sensitivity of 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane and BAMO
[0076]
Claims
1. A method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane, characterized in that: The following steps are involved: Step 1, adding 3-nitro-4-hydroxyfurazan, 3,3-dibromomethyloxetane, a basic donor and a phase transfer catalyst to a polar aprotic solvent, stirring and reacting at 45 to 85° C. for 0.5 to 2 hours, then extracting, washing, drying, filtering, evaporating the solvent and recrystallizing to obtain an intermediate 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane; Step 2: The intermediate 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane obtained in step 1 and an azidating agent are added to a polar aprotic solvent, and the mixture is stirred for reaction for 0.5 to 2 h in an ice-water bath, and then extracted, washed with water, dried, filtered, and the solvent is evaporated to obtain 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane.
2. The method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane according to claim 1, characterized in that: The alkaline donor is anhydrous potassium carbonate, cesium carbonate or ferric hydroxide.
3. The method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane according to claim 1, characterized in that: The phase transfer catalyst is tetrabutylammonium bromide, benzyltriethylammonium chloride, methyltrialkylammonium chloride or 18-crown ether-6.
4. The method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane according to claim 1, characterized in that: The molar ratio of the 3,3-dibromomethyloxetane, 3-nitro-4-hydroxyfuroxan, alkaline donor and phase transfer catalyst is 1:(0.67-1.25):(1.25-3):(0.013-0.04).
5. The method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane according to claim 1, characterized in that: The azidation reagent is sodium azide, trimethylsilyl azido, p-toluenesulfonyl azide, ethyl azidoacetate, tetrabutylammonium azide or tri-n-butyltin azide.
6. The method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane according to claim 1, characterized in that: The molar ratio of the intermediate 3-(4-nitrofurazan-3-oxymethyl)-3-bromomethyloxetane to the azidation reagent is 1:(0.8-1.5).
7. The method for preparing 3-(4-nitrofurazan-3-oxymethyl)-3-azidomethyloxetane according to claim 1, characterized in that: The polar aprotic solvent is DMF, MeCN, Acetone or DMSO.
Citation Information
Patent Citations
Propellant formulations based on dinitramide salts and energetic binders
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