6,10,10-trinitro-2-oxa-6-azadamantane-4,8,9-triol trinitrate and a process for its preparation

Abstract

This invention discloses a method for preparing 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate, belonging to the field of organic synthesis technology. Using 1,3,5,7-cyclooctatetraene as a starting material, the method involves oxidative cyclization, ammonolytic cyclization, Boc protection and silane ether protection, secondary alcohol oxidation, deBoc acetylation, oximeization, geminitrohydration, and nitration to finally synthesize 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate. The synthesis method is simple, and the final product exhibits stable properties. This invention addresses the lack of research on "azaadamantanes" (alkanes with nitrogen and oxygen heteroatoms synergistically introduced onto the same adamantane skeleton) and the general lack of substituents available for in-depth functionalization in existing adamantane skeleton construction methods. Furthermore, it introduces six explosive groups into the synthesized skeleton, resulting in a product with high density and excellent detonation performance.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate and its preparation method. Background Technology

[0002] Adamantanes, as a class of typical cage-like compounds with high symmetry and a rigid framework, contain multiple bridgehead and bridge-site carbon atoms that can be used for functionalization modification, providing a good structural basis for constructing multi-substituted energetic derivatives. By replacing some carbon atoms in the adamantane framework with heteroatoms such as nitrogen and oxygen, not only can the oxygen balance of the molecule be improved, but the molecular packing ability of adamantane-like energetic derivatives can also be enhanced, thereby increasing their crystal density and improving detonation performance to a certain extent, thus expanding the performance boundaries of this class of energetic compounds.

[0003] Azaadamantanes are a representative class of organic cage-like compounds, whose structural units are widely found in various natural products, drug molecules, and organic catalyst systems, and have shown important application value in fields such as biomedicine, luminescent materials, and energetic materials. Numerous reports have been published in recent years on the synthesis of the azaadamantane skeleton and its energetic derivatives, the most representative of which is the synthesis of 2,9,9,10,10-pentanitro-2-azaadamantane-4,6,8-triol trinitrate reported by Zhou Qi et al. in 2025. Zhou Q, Li H, Zhu L, et al. Construction of an all- bridge carbon-oxidized 2-azaadamantane skeleton and synthesis of two energetic derivatives[J]. Org Lett, 2025, 27(13): 3164-3169. It successfully introduced eight explosive groups into the azaadamantane skeleton, exhibiting excellent performance.

[0004] Oxadamantanes are a representative class of cage-like organic compounds, whose structural units have been reported in various natural products and drug molecules. In the field of energetic materials research, introducing oxygen atoms into the cage-like framework is considered an effective structural control method. This strategy not only helps improve the oxygen balance of energetic compounds but may also positively influence their crystal density, thermal stability, and detonation performance. The most representative example is 9,10-bis(nitroxymethyl)-9,10-diiodo-2,4,6,8-tetraoxadamantane, published by Li Bing et al. in 2025. Li B, Cai R, Yu M, et al. Synthesis of a 2,4,6,8-tetraoxaadamantane-based 3D energetic biocidal agent via stepwise cyclization strategy[J]. Org Lett, 2025, 27(22): 5589-5594. Its crystal density is as high as 2.532 g·cm³. -3 The calculated detonation velocity is 5486 m·s. -1 The explosion pressure is 18.51 GPa, and the thermal decomposition temperature is 181 ℃.

[0005] Currently, significant progress has been made in constructing adamantane skeletons with single-type heteroatoms (aza- or oxa-) and synthesizing their energetic derivatives. However, research on "aza-oxa-adamantane" systems, which synergistically introduce both nitrogen and oxygen heteroatoms onto the same skeleton, is extremely limited. The few existing reports of adamantane skeletons generally lack substituents suitable for in-depth functionalization, making it difficult to derive high-value energetic compounds. Synthetic methods in this area have not yet been systematically developed. Therefore, how to efficiently construct adamantane skeletons with multiple substituents and high symmetry remains a crucial scientific problem that urgently needs to be solved in this field. Summary of the Invention

[0006] 1. Purpose of the invention To address the problems of existing oxadamantane skeletons lacking multiple substituents, making it difficult to derive high-value energetic compounds, and the limited energetic performance of single heteroatom adamantanes, the present invention aims to provide a 6,10,10-trinitro-2-oxa-6-azadamantane-4,8,9-triol trinitrate and its preparation method.

[0007] 2. Technical Solution To achieve the objective of this invention, the technical solution adopted by this invention is as follows: This invention provides 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate, with the following structural formula: .

[0008] The present invention also provides a method for preparing 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate, comprising the following steps: S1: 3,8,11-trioxane [4.4.1.0] was prepared by oxidative cyclization of 1,3,5,7-cyclooctatetraene with peroxyacetone. 2,4 .0 7,9 Undecane-5,10-diol; S2: 3,8,11-trioxane [4.4.1.0] 2,4 .0 7,9 Undecane-5,10-diol undergoes a cyclization reaction with saturated ammonia solution, and the crude product is then directly reacted with triethylamine and ditert-butyl dicarbonate to prepare 6-tert-butoxycarbonyl-2-oxa-6-azaadamantane-4,8,9,10-tetraol. S3: Dissolve 6-tert-butoxycarbonyl-2-oxa-6-azaadamantane-4,8,9,10-tetraol in a solvent, add imidazole first after an ice bath reaction, and then add tert-butyldimethylchlorosilane to prepare 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-ol; S4: 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-ol was dissolved in a solvent, and after an ice bath, Dys-Martin oxidant was added to prepare 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one; S5: 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one was added to a mixture of dichloromethane and trifluoroacetic acid and reacted. After evaporation to dryness, N,N-diisopropylethylamine, 4-dimethylaminopyridine and acetic anhydride were added sequentially to prepare 6-acetyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one. S6: 6-Acetyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one was reacted with sodium acetate and hydroxylamine hydrochloride, and then the crude product was reacted with dinitrogen pentoxide to prepare 6-acetyl-10,10-dinitro-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane; S7: 6,10,10-tinitro-2-oxa-6-adamantane was prepared by sequentially subjecting 6-acetyl-10,10-dinitro-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-adamantane to siloxy nitration and N-acetyl nitration in a mixed acid system of fuming nitric acid and fuming sulfuric acid, to trinitrate of 6,10,10-trinitro-2-oxa-6-adamantane-4,8,9-triol.

[0009] Furthermore, in step S1 above, peroxyacetone is generated by the reaction of potassium persulfate and acetone.

[0010] Furthermore, the oxidation cyclization reaction temperature in step S1 above is 50-60 ℃.

[0011] Furthermore, in step S2 above, the saturated ammonia solution is a methanol solution saturated with ammonia.

[0012] Furthermore, in step S2 above, the cyclization reaction temperature is 110-140℃; the cyclization reaction time is 24-48 h, 3,8,11-trioxane [4.4.1.0] 2,4 .0 7,9 The molar ratio of undecane-5,10-diol to ammonia is 1:(40-50).

[0013] Further, the solvent in step S3 above is N,N-dimethylformamide, the molar ratio of 6-tert-butoxycarbonyl-2-oxa-6-azaadamantane-4,8,9,10-tetraol to imidazole is 1:(4-4.5), and the molar ratio of 6-tert-butoxycarbonyl-2-oxa-6-azaadamantane-4,8,9,10-tetraol to tert-butyldimethylchlorosilane is 1:(3-3.4).

[0014] Further, in step S4 above, the solvent is dichloromethane, and the molar ratio of 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-ol to the Dys-Martin oxidant is 1:(3-4).

[0015] Furthermore, in step S5 above, the molar ratio of 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one to trifluoroacetic acid is 1:(40-50).

[0016] Further, in step S5 above, the molar ratio of 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one to N,N-diisopropylethylamine is 1:(3-6), and the molar ratio of 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one to acetic anhydride is 1:(20-30).

[0017] Furthermore, in step S6 above, the molar ratio of 6-acetyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one to dinitrogen pentoxide is 1:(6-10).

[0018] Furthermore, in step S7 above, the volume ratio of fuming sulfuric acid to fuming nitric acid is 1:(1.5-2.5). This invention uses 1,3,5,7-cyclooctatetraene as a raw material and, through key steps such as oxidative cyclization, ammonolytic cyclization, protection / deprotection, oximeization, gemnitration, and nitration, introduces six explosive groups to synthesize the target compound 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate, which belongs to the cage-like energetic compound category.

[0019] 3. Beneficial effects Compared with the prior art, the advantages of this invention are as follows: (1) The present invention rapidly and efficiently constructs a multi-substituted 2-oxa-6-azaadadamane skeleton, making up for the scarcity of methods for constructing multi-substituted azaadadamane skeletons.

[0020] (2) The present invention provides a 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate, which synergistically introduces nitrogen atom, oxygen atom and nitroxy group, improves the oxygen balance of the energetic compound, gives it higher density and energy, has superior detonation performance, and can be used to prepare high-performance explosives.

[0021] (3) The present invention provides a method for preparing 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate, which is simple to operate, has a high yield, and produces good product performance. Attached Figure Description

[0022] Figure 1 It is 3,8,11-trioxane [4.4.1.0] 2,4 .0 7,9 Undecane-5,10-diol 1 H NMR spectrum.

[0023] Figure 2 It is 3,8,11-trioxane [4.4.1.0] 2,4 .0 7,9 Undecane-5,10-diol 13 C10 NMR spectrum.

[0024] Figure 3 It is 6-tert-butoxycarbonyl-2-oxa-6-azaadamantane-4,8,9,10-tetraol 1 H NMR spectrum.

[0025] Figure 4 It is 6-tert-butoxycarbonyl-2-oxa-6-azaadamantane-4,8,9,10-tetraol 13 C10 NMR spectrum.

[0026] Figure 5 It is 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-ol 1 H NMR spectrum.

[0027] Figure 6 It is 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-ol 13 C10 NMR spectrum.

[0028] Figure 7 It is 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one 1 H NMR spectrum.

[0029] Figure 8 It is 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one 13 C10 NMR spectrum.

[0030] Figure 9 It is 6-acetyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one 1 H NMR spectrum.

[0031] Figure 10 It is 6-acetyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one 13 C10 NMR spectrum.

[0032] Figure 11 It is 6-acetyl-10,10-dinitro-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane. 1 H NMR spectrum.

[0033] Figure 12 It is 6-acetyl-10,10-dinitro-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane. 13 C10 NMR spectrum.

[0034] Figure 13 It is 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate. 1 H NMR spectrum.

[0035] Figure 14 It is 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate. 13 C10 NMR spectrum.

[0036] Figure 15 This is the FT-IR spectrum of 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate.

[0037] Figure 16 This is the TG-DSC spectrum of 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate.

[0038] Figure 17 This is the single-crystal X-ray diffraction pattern of 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate. Detailed Implementation

[0039] The present invention will be further described below with reference to specific embodiments.

[0040] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the term “and / or” as used herein includes any and all combinations of one or more of the associated listed items.

[0041] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0042] As used herein, the term “about” is used to provide for the flexibility and imprecision associated with a given term, measure, or value. Those skilled in the art can readily determine the degree of flexibility for a particular variable.

[0043] As used herein, the term “at least one of…” is intended to be synonymous with “one or more of…”. For example, “at least one of A, B, and C” explicitly includes only A, only B, only C, and combinations thereof.

[0044] Concentration, amount, and other numerical data may be presented in range format herein. It should be understood that such range format is used solely for convenience and brevity and should be flexibly interpreted to include not only the values ​​explicitly stated as the limits of the range, but also all individual values ​​or subranges encompassed within the range, as if each value and subrange were explicitly stated. For example, a range of values ​​from about 1 to about 4.5 should be interpreted to include not only the explicitly stated limits of 1 to 4.5, but also individual numbers (such as 2, 3, 4) and subranges (such as 1 to 3, 2 to 4, etc.). The same principle applies to ranges that describe only a single value, such as "less than about 4.5," which should be interpreted to include all the values ​​and ranges described above. Furthermore, this interpretation should apply regardless of the breadth of the range or characteristic described.

[0045] Example 1 This embodiment provides a method for synthesizing 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate.

[0046] The overall synthesis route is shown below: .

[0047] S1: 3,8,11-trioxane [4.4.1.0] 2,4 .0 7,9 Preparation of undecane-5,10-diol ; Add 50 mL of deionized water and NaHCO3 (16.8 g, 88 mmol) to a 250 mL flask, stir until the solid dissolves, and cool in an ice bath for 15 min. Then add ethyl acetate (50 mL) and acetone (26 mL) to the 250 mL flask, followed by the addition of compound 1,3,5,7-cyclooctatetraene (1 mL, 0.925 g, 8.8 mmol). Stir for 5 min until the system stabilizes, then slowly add a saturated solution (50 mL, one drop every 5 seconds) of potassium persulfate (27.3 g, 88 mmol) using a constant pressure dropping funnel. After the addition is complete, stir in an ice bath for 10 min. Move the flask to room temperature and, once the temperature stabilizes, heat at 60 °C for 24 hours. After 24 hours, heating was stopped and the mixture was allowed to cool down before being placed in an ice bath. Acetone (26 mL) was added to the system, and potassium persulfate (27.3 g, 88 mmol) was added in batches (one addition every 15 min, for a total of four additions). After the addition was completed, the mixture was moved to room temperature and allowed to stand for 10 min before being transferred to a metal bath and heated to 60 °C to continue the reaction for 24 hours.

[0048] Undissolved solids were removed by filtration. The mixture was treated with a 10% sodium thiosulfate aqueous solution until the aqueous phase did not change color on starch-KI test paper. The mixture was extracted 20 times with ethyl acetate. The organic phases were combined and dried over anhydrous sodium sulfate. The mixture was then evaporated in a water bath at 40°C until the solvent was evaporated to dryness. The mixture was then subjected to silica gel column chromatography, eluted with petroleum ether:ethyl acetate (V:V = 1.5:1), to give 0.76 g of white solid, with a yield of 46%.

[0049] Spectral information: 1 H NMR (500 MHz, Acetone-d6) δ 4.09 (dd, J = 32.8, 6.7 Hz, 4H), 3.49 (d, J = 4.0 Hz, 2H), 3.27 (d, J = 2.9 Hz, 2H) ppm. 13 C NMR (126 MHz, Acetone-d6) δ 206.51, 67.04, 64.49, 55.51, 48.84, 30.30, 30.15, 29.99, 29.84, 29.68, 29.53, 29.38 ppm. IR (thin film, v cm) -1): 3495, 3440, 2957, 2880, 1695, 1432, 1399, 1349, 1278, 1218, 1128, 1075, 1031, 1004, 927, 850, 795, 734, 699, 664, 598. The product is 3,8,11-trioxane [4.4.1.0] 2,4 .0 7,9 Undecane-5,10-diol.

[0050] Preparation of S2: 6-tert-butoxycarbonyl-2-oxa-6-azaadamantane-4,8,9,10-tetraol ; Pre-dry the glassware required for the experiment. Compound 3,8,11-trioxane [4.4.1.0] 2,4 .0 7,9 Undecane-5,10-diol was pre-dried using a diaphragm pump, and then the compound 3,8,11-trioxane [4.4.1.0] was weighed. 2,4 .0 7,9 Undecane-5,10-diol (0.38 g, 2 mmol) was added to a 60 mL pressure-resistant tube, along with 2 mL of anhydrous methanol. The tube was sealed in a sealed bag and frozen at -20 °C for 15 min. A suitable amount of freshly prepared ammonia-saturated methanol solution was added (prepared by purging ammonia into an anhydrous methanol solution for one hour under ice bath conditions, then adding 16 mL to the pressure-resistant tube). The system was sealed and slowly brought to room temperature, then heated to 120 °C and maintained at this temperature for 36 hours. After the reaction was complete, the solution was transferred to a round-bottom flask and rotary evaporated in a water bath at 40 °C until the solvent was evaporated to dryness, yielding a dark brown foamy solid. The solid was not separated. 20 mL of anhydrous methanol, triethylamine (2.8 mL, 2.02 g, 10 eq), and di-tert-butyl dicarbonate (1.85 mL, 1.75 g, 4 eq) were added to the crude product, and the mixture was refluxed overnight under nitrogen protection.

[0051] After the reaction was complete, the solvent was evaporated in a water bath at 48°C until it was completely evaporated. The mixture was then subjected to silica gel column chromatography, eluted with petroleum ether:ethyl acetate (V:V = 1:4), to give 0.55 g of a white solid compound, with a yield of 90%.

[0052] Spectral information: 1H NMR (500 MHz, Methanol-d4) δ 4.35 (dd, J = 4.9, 2.5 Hz, 1H), 4.31 (dd, J = 4.9, 2.5 Hz, 1H), 4.23 (s, 1H), 4.20 (s, 1H), 4.13 (t, J = 4.3 Hz,2H), 3.70 (d, J = 5.3 Hz, 2H), 1.43 (s, 9H) ppm. 13 C NMR (126 MHz, Methanol-d4) δ 156.90, 80.54, 73.93, 73.78, 64.54, 64.32, 63.45, 63.22, 55.44, 54.02, 27.77. IR (thin film, v cm) -1 ): 3366, 2927, 1417, 1361, 1249, 1160, 1064, 1028,971, 935, 899, 836, 734. The product is 6-tert-butoxycarbonyl-2-oxa-6-azaadamantane-4,8,9,10-tetraol.

[0053] Preparation of S3: 6-tert-Butoxycarbonyl-4,8,9-tris(tert-Butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-ol ; Before use, the glassware required for the experiment must be pre-dried (strictly dehydrated). Weigh 0.55 g (1.8 mmol) of compound 6-tert-butoxycarbonyl-2-oxa-6-azaadamantane-4,8,9,10-tetraol into a 100 mL single-necked flask. After drying the flask under vacuum at 50 °C in a water bath, add 20 mL of N,N-dimethylformamide and place it in an ice-water bath. After the system temperature stabilizes, add imidazole (0.55 g, 4.5 eq) to the system. React in an ice bath for 15 min, then add tert-butyldimethylchlorosilane (0.92 g, 3.4 eq) and react in an ice bath for 10 min. Then move the flask to room temperature and react at room temperature for 12 hours.

[0054] After the reaction was completed, the entire system was directly evaporated under vacuum at 60°C in a water bath until the solvent was evaporated to dryness. Silica gel column chromatography was performed, eluting with petroleum ether:ethyl acetate (V:V = 20:1), and the solution was evaporated to dryness to give 0.71 g of a white solid compound, with a yield of 51%.

[0055] Spectral information: 1H NMR (500 MHz, Chloroform-d) δ 4.37 (dd, J = 5.0, 2.5 Hz, 1H), 4.20 (d, J = 4.9 Hz, 2H), 4.08 (d, J = 4.8 Hz, 1H), 3.64 (d, J = 4.8 Hz, 2H), 3.53(d, J = 4.6 Hz, 2H), 1.38 (s, 9H), 0.83 (d, J = 1.8 Hz, 27H), 0.00 (s, 12H). 13 C NMR (126 MHz, Chloroform-d) δ 156.26, 80.37, 77.41, 77.16, 76.90,74.18, 73.72, 73.35, 73.13, 66.01, 65.92, 65.84, 65.67, 65.09, 65.02, 64.25,64.00, 55.87, 55.45, 54.09, 53.74, 28.57, 28.50, 26.04, 25.97, 25.92, 25.86,25.82, 25.80, 18.30, -4.62. IR (thin film, v cm) -1 ): 3456, 2931, 2893, 2859, 1700, 1678, 1469, 1416, 1370, 1293, 1252, 1173, 1093, 995, 949, 918, 836, 716, 713, 672. The product is 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-ol.

[0056] Preparation of S4: 6-tert-Butoxycarbonyl-4,8,9-tris(tert-Butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one ; The glassware required for the experiment was dried in advance. 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-ol (0.71 g, 1.098 mmol) was weighed into a 100 mL round-bottom flask, and 20 mL of anhydrous dichloromethane (DCM) was added. After nitrogen protection, the mixture was stirred in an ice bath for 10 min. After the system cooled and stabilized, 1.4 g (3 eq) of Desmond oxidant was weighed and added to the system. After 10 min in an ice bath, the mixture was moved to room temperature and reacted for 48 hours.

[0057] After the reaction was completed, the solvent was evaporated in a water bath at 40°C until it was completely evaporated. The mixture was then subjected to silica gel column chromatography and eluted with petroleum ether:ethyl acetate (V:V = 25:1) to give 0.64 g of a transparent, viscous oily substance (solid-like substance), with a yield of 90%.

[0058] Spectral information: 1 H NMR (500 MHz, Chloroform-d) δ 5.88 – 5.81 (m, 1H), 5.71 (d, J =10.3 Hz, 1H), 4.65 (d, J = 4.1 Hz, 1H), 4.42 (d, J = 5.4 Hz, 1H), 4.23 (s,1H), 3.67 (d, J = 5.3 Hz, 1H), 1.43 (s, 3H), 0.89 (s, 27H), 0.09 (s, 18H). 13 C NMR (126 MHz, Chloroform-d) δ 200.26, 199.42, 155.65, 153.55,153.51, 91.48, 91.05, 81.06, 80.22, 74.30, 73.86, 72.64, 71.73, 69.52, 69.32,64.27, 63.72, 61.38, 59.60, 55.04, 53.55, 28.23, 25.63, 25.59, 18.15, 17.91,17.83, -4.81, -4.97, -5.01, -5.07, -5.11. IR (thin film, v cm) -1 ): 2962, 2930, 2857, 1731, 1702, 1471, 1390, 1362, 1254, 1164, 1098, 1062, 1026, 995, 936, 897, 839, 781, 735. The product is 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one.

[0059] Preparation of S5: 6-Acetyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one ; The instrument was pre-dried before the experiment. Compound 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one (0.64 g, 0.99 mmol) was weighed into a 100 mL round-bottom flask, and 10 mL of anhydrous dichloromethane was added. Trifluoroacetic acid (10 mL) was added to a constant-pressure dropping funnel. The entire system was protected with nitrogen and placed in an ice bath for 15 min. After the system stabilized, the constant-pressure dropping funnel was opened and trifluoroacetic acid was slowly added dropwise (one drop per second). After the addition was completed, the reaction was continued in an ice bath for 10 min, and then moved to room temperature. The reaction was carried out at room temperature for 2 hours.

[0060] After the reaction was complete, the solvent was evaporated in a water bath at 45°C until it was completely evaporated. The residual trifluoroacetic acid in the system was removed by azeotropic reaction of anhydrous dichloromethane and cyclohexane. 15 mL of anhydrous dichloromethane was added, and N,N-diisopropylethylamine (0.52 mL, 0.38 g, 3 eq) was slowly added dropwise using a syringe under an ice-water bath. After the addition was completed, the mixture was moved to room temperature and reacted for 4 hours. Then, 4-dimethylaminopyridine (DMAP, 0.012 g, 0.1 eq) and acetic anhydride (0.93 mL, 1.01 g, 10 eq) were added, and the mixture was reacted overnight at room temperature.

[0061] After the reaction was completed, the solvent was evaporated in a water bath at 55°C using a vacuum pump until it was completely evaporated. Rapid silica gel column chromatography was then performed (to reduce the possibility of intermediate product deterioration). The product was eluted with petroleum ether:ethyl acetate (V:V = 10:1) to give 0.42 g of a transparent, oily, viscous solid, with a yield of 64%.

[0062] Spectral information: 1 H NMR (500 MHz, Chloroform-d) δ 4.66 (t, J = 2.3 Hz, 1H), 4.61 –4.58 (m, 1H), 4.00 (s, 1H), 3.92 (d, J = 8.7 Hz, 2H), 3.85 – 3.82 (m, 2H),2.10 (d, J = 2.2 Hz, 3H), 0.89 (d, J = 4.0 Hz, 27H), 0.12 (s, 18H). 13C NMR (126 MHz, Chloroform-d) δ 204.77, 199.42, 169.48, 169.44,94.61, 90.89, 82.03, 80.47, 75.88, 74.50, 74.27, 72.19, 71.10, 69.50, 67.36,66.78, 65.15, 59.19, 57.99, 55.81, 28.93, 25.23, 22.52, 21.97, 18.10, -4.78. IR (thin film, v cm) -1 ): 2960, 2931, 2856, 1734, 1692, 1470, 1415, 1361,1252, 1162, 1096, 1063, 1027, 996, 935, 898, 839, 781, 734. The product is 6-acetyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one.

[0063] Preparation of S6: 6-Acetyl-10,10-dinitro-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-adamantane ; The instruments used in the experiment were pre-dried. Compound 6-acetyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one (0.42 g, 0.63 mmol) was weighed into a 100 mL round-bottom flask, 20 mL of anhydrous acetonitrile was added, and anhydrous sodium sulfate (4 g) was used to remove water. Anhydrous sodium acetate (0.42 g, 8 eq) was added and the mixture was stirred for 5 min. Hydroxylamine hydrochloride (0.27 g, 6 eq) was weighed and added to the system. The reaction was carried out overnight under nitrogen protection.

[0064] After filtering to remove solids, the mixture was evaporated to dryness in a water bath at 48°C and transferred to a three-necked flask. 15 mL of anhydrous dichloromethane, 4 g of anhydrous sodium sulfate, and 0.38 g (10 eq) of urea were added. The mixture was heated to reflux at 50°C under nitrogen protection until the temperature of the system stabilized. Freshly prepared dinitrogen pentoxide (0.96 g, 14 eq) was weighed and dissolved in a constant-pressure dropping funnel using DCM. The DCM solution of dinitrogen pentoxide was slowly added to the system. The system quickly turned dark green, and the color gradually deepened and then faded as dinitrogen pentoxide was added. After the addition was complete, the green color of the system disappeared. The reaction was maintained at 50°C for 1.5 hours. After the reaction was completed, the mixture was cooled to room temperature and quenched with ice-cold saturated sodium bicarbonate solution. The organic phases were extracted separately with ethyl acetate and dichloromethane and then combined. The mixture was dehydrated with anhydrous sodium sulfate and evaporated in a water bath at 40°C until the solvent was evaporated to dryness. The mixture was then subjected to silica gel column chromatography and eluted with petroleum ether:ethyl acetate (V:V = 15:1) to give 0.11 g of a yellow, oily, viscous solid, with a yield of 28%.

[0065] Spectral information: 1 H NMR (500 MHz, Chloroform-d) δ 6.09 (s, 1H), 5.14 (s, 1H), 4.87 (d,J = 6.2 Hz, 2H), 4.77 (s, 1H), 4.51 (s, 1H), 3.57 (d,J = 4.9 Hz, 1H), 2.11(s, 3H), 0.90 – 0.83 (m, 27H), 0.09 (s, 18H). 13 C NMR (126 MHz, Chloroform-d) δ 169.57, 130.91, 128.84, 109.18,108.95, 74.18, 74.07, 74.01, 70.59, 70.41, 67.77, 67.08, 65.89, 65.56, 64.73,64.10, 63.30, 56.61, 55.37, 50.07, 49.72, 31.59, 30.58, 29.70, 25.70, 25.58,25.56, 25.52, 25.49, 22.65, 22.47, 21.76, 21.15, 19.19, 18.00, 17.96, 17.86, 17.78, 14.12, 13.73, -5.16. IR (thin film, v cm)-1 ): 2961, 2932, 2857, 1704, 1556, 1528, 1364, 1472,1418, 1251, 1163, 1102, 1065, 1029, 996, 936, 899, 840, 782, 735. The product is 6-acetyl-10,10-dinitro-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane.

[0066] Preparation of S7: 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate ; The compound 6-acetyl-10,10-dinitro-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane (0.11 g, 0.17 mmol) was transferred to a 50 mL round-bottom flask, dried under vacuum in a water bath at 50 °C, and then placed in an ice bath. In a separate 25 mL round-bottom flask, 4 mL of fuming nitric acid (98%, analytical grade) was added under ice bath conditions. The mixture was stirred at low temperature for 15 min under ice bath conditions. Then, 2 mL of fuming sulfuric acid (20%, analytical grade) was slowly added dropwise. After the addition was complete, stirring was continued for 15 min to prepare a nitrate-sulfuric acid mixture. This mixture was then poured into 6-acetyl-10,10-dinitro-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane and reacted under ice bath conditions. After 10 min, the ice bath was removed, and the mixture was slowly raised to room temperature. Then, it was placed in an oil bath and heated to 70 °C for 6 hours. After the reaction was completed, the mixture was quenched with ice water, and a white solid turbidity appeared. The solvent was removed by filtration, and the white solid was subjected to column chromatography, eluted with petroleum ether:ethyl acetate (V:V = 15:1). The solid was then rotary evaporated in a water bath at 45 °C to give 0.015 g of a pale yellow solid, with a yield of 20%.

[0067] Spectral information: 1 H NMR (500 MHz, Chloroform-d) δ 6.80 (s, 1H), 5.71 (d, J = 4.9 Hz, 1H), 5.57 (d, J = 3.1 Hz, 1H), 5.53 (s, 1H), 5.34 (d, J = 4.1 Hz, 1H), 5.19(d, J = 5.0 Hz, 1H), 4.54 (d, J = 5.2 Hz, 1H). 13C NMR (126 MHz, Chloroform-d) δ 106.65, 71.70, 71.32, 69.58, 67.24,66.28, 51.93, 50.30. IR (thin film, v cm) -1 ): 3022, 2924, 2853, 1665, 1592, 1464, 1273, 1115, 1050, 954, 907, 811, 736, 659, 588, 522, 474. The product is 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate.

[0068] The structure was optimized using the DFT-B3LYP method and a 6-311++G* array. The detonation properties of the compound were calculated using the Gaussian 09 (A.02) program, and the heat of formation was estimated using the semi-empirical MO-PM3 method. The calculated detonation velocity and detonation pressure were corrected using the EXPLO 5 (version 6.05.04) program based on density, formula, and heat of formation. Theoretically, the density of the compound was calculated to be 1.89 g·cm³. -3 The detonation velocity is 8758 m / s. -1 The burst pressure was 35.242 GPa. The calculated density and the measured single-crystal density were 1.886 g·cm³. -3 The error is extremely small, and the calculation results are reliable.

[0069] The thermal stability of this compound was studied using thermogravimetric analysis (TG) and differential scanning calorimetry (DSC), and its characterization spectra are shown below. Figure 16 As shown. By Figure 16 As shown, no obvious melting point peak was observed, but there was a significant exothermic peak at 185℃, indicating vigorous exothermic reaction at 185℃. These results indicate that 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate has good thermal stability.

Claims

1,6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate, characterized in that, The structural formula is shown below: 。 2. A method for preparing 6,10,10-trinitro-2-oxa-6-azaadamantane-4,8,9-triol trinitrate, characterized in that, Includes the following steps: S1: 3,8,11-trioxane [4.4.1.0] was prepared by oxidative cyclization of 1,3,5,7-cyclooctatetraene with peroxyacetone. 2,4 .0 7,9 Undecane-5,10-diol; S2: 3,8,11-trioxane [4.4.1.0] 2,4 .0 7,9 Undecane-5,10-diol undergoes a cyclization reaction with saturated ammonia solution, and the crude product is then directly reacted with triethylamine and ditert-butyl dicarbonate to prepare 6-tert-butoxycarbonyl-2-oxa-6-azaadamantane-4,8,9,10-tetraol. S3: Dissolve 6-tert-butoxycarbonyl-2-oxa-6-azaadamantane-4,8,9,10-tetraol in a solvent, add imidazole first after an ice bath reaction, and then add tert-butyldimethylchlorosilane to prepare 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-ol; S4: 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-ol was dissolved in a solvent, and after an ice bath, Dys-Martin oxidant was added to prepare 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one; S5: 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one was added to a mixture of dichloromethane and trifluoroacetic acid and reacted. After evaporation to dryness, N,N-diisopropylethylamine, 4-dimethylaminopyridine and acetic anhydride were added sequentially to prepare 6-acetyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one. S6: 6-Acetyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one was reacted with sodium acetate and hydroxylamine hydrochloride, and then the crude product was reacted with dinitrogen pentoxide to prepare 6-acetyl-10,10-dinitro-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane; S7: 6,10,10-tinitro-2-oxa-6-adamantane was prepared by sequentially subjecting 6-acetyl-10,10-dinitro-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-adamantane to siloxy nitration and N-acetyl nitration in a mixed acid system of fuming nitric acid and fuming sulfuric acid, to trinitrate of 6,10,10-trinitro-2-oxa-6-adamantane-4,8,9-triol.

3. The preparation method according to claim 2, characterized in that, The oxidative cyclization reaction temperature in step S1 is 50-60 °C.

4. The preparation method according to claim 2, characterized in that, The cyclization reaction temperature in step S2 is 110-140℃; the cyclization reaction time is 24-48 h, 3,8,11-trioxane [4.4.1.0] 2,4 .0 7,9 The molar ratio of undecane-5,10-diol to ammonia is 1:(40-50).

5. The preparation method according to claim 2, characterized in that, The solvent mentioned in step S3 is N,N-dimethylformamide, the molar ratio of 6-tert-butoxycarbonyl-2-oxa-6-azaadamantane-4,8,9,10-tetraol to imidazole is 1:(4-4.5), and the molar ratio of 6-tert-butoxycarbonyl-2-oxa-6-azaadamantane-4,8,9,10-tetraol to tert-butyldimethylchlorosilane is 1:(3-3.4).

6. The preparation method according to claim 2, characterized in that, The solvent in step S4 is dichloromethane, and the molar ratio of 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-ol to the Dys-Martin oxidant is 1:(3-4).

7. The preparation method according to claim 2, characterized in that, The molar ratio of 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one to trifluoroacetic acid in step S5 is 1:(40-50).

8. The preparation method according to claim 2 or 7, characterized in that, In step S5, the molar ratio of 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one to N,N-diisopropylethylamine is 1:(3-6), and the molar ratio of 6-tert-butoxycarbonyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one to acetic anhydride is 1:(20-30).

9. The preparation method according to claim 2, characterized in that, In step S6, the molar ratio of 6-acetyl-4,8,9-tris(tert-butyldimethylsiloxy)-2-oxa-6-azaadamantane-10-one to dinitrogen pentoxide is 1:(6-10).

10. The preparation method according to claim 2, characterized in that, The volume ratio of fuming sulfuric acid to fuming nitric acid in step S7 is 1:(1.5-2.5).

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