Tetraacetyl dicyclopropyl hexaazaisowurtzitane, preparation method thereof and synthesis method of HNIW (hexaazaisowurtzitane)

Abstract

The invention discloses tetraacetyl dicyclopropyl hexaazaisowurtzitane, a preparation method thereof and a synthesis method of HNIW, and belongs to the technical field of chemical synthesis. The tetraacetyl dicyclopropyl hexaazaisowurtzitane disclosed by the invention is a novel hexaazaisowurtzitane derivative, and the preparation method of the tetraacetyl dicyclopropyl hexaazaisowurtzitane has the advantages of short reaction steps, simplicity in operation, easily available raw materials and industrial application potential. The tetraacetyl dicyclopropyl hexaazaisowurtzitane disclosed by the invention can be used for synthesizing hexanitrohexaazaisowurtzitane (HNIW) in one step through nitration, so that the synthesis process is simplified, and the production cost is reduced; the specific gravity of the leaving group cyclopropyl in the cyclopropylamine raw material is small, the atom economy is good, the utilization rate of the raw material is high, waste discharge is reduced, and the method conforms to the environmental protection concept of green economy.

Description

Technical Field

[0001] This invention relates to the field of chemical synthesis technology, specifically to tetraacetyldicyclopropylhexaazaisowurtzite and its preparation method, and the synthesis method of hexanitrohexaazaisowurtzite (HNIW). Background Technology

[0002] The structure of hexaazaisowulzane compounds was first reported in 1990 (Nielsen, A., et al., Polyaza polycyclics by condensation of aldehydes with amines. 2. Formation of 2, 4, 6, 8, 10, 12-hexabenzyl-2, 4, 6, 8, 10, 12-hexaazatetracyclo[5.5.0.0]). 5.9 .0 3.11 [dodecanes from glyoxal and benzylamines, Journal of Organic Chemistry, 1990. 55(5): 1459-1466], its unique three-dimensional cage-like skeleton structure and properties have always been favored by chemical researchers in various countries. Based on this structure, hexanitrohexaazaisowulzane, abbreviated as HNIW, belongs to the fourth generation of high-energy explosives. It is a new type of high-energy-density energetic material with good oxygen balance and enthalpy of formation. Moreover, its performance in terms of detonation velocity, detonation pressure, density and other properties is superior to that of traditional military main explosive octogen (HMX). It has shown good application performance in the field of solid propellants. Therefore, the synthesis of hexaazaisowulzane derivatives has always been a research hotspot. It has broad application prospects and research value in the field of materials. Currently, the industrial production routes for HNIW all use hexabenzylhexaazaisowrutzane (HBIW) as a precursor, mainly employing the TAIW process (Energetic Materials, 2009. 17(2):161-165.). This process consists of four steps: 1. Using benzylamine and glyoxal as raw materials, the precursor HBIW is prepared through a condensation reaction; 2. HBIW undergoes a first hydrogenolysis to remove benzyl and acetylation to obtain tetraacetyldibenzylhexaazaisowrutzane (TADB); 3. TADB undergoes a second hydrogenolysis to remove benzyl to obtain the nitration precursor tetraacetylhexaazaisowrutzane (TAIW); 4. TAIW is nitrated in a mixed acid system of fuming nitric acid and fuming sulfuric acid to obtain HNIW. After years of research by scholars from various countries, each step of this route has been fully optimized. Nevertheless, this process still suffers from problems such as cumbersome steps, complex processes, and high costs.

[0003] The main method for constructing the hexaazaisowrutzane skeleton is through the condensation reaction of primary amine compounds with glyoxal. Structural modification yields corresponding derivatives. Over the past few decades, several hexaazaisowrutzane derivatives have emerged, such as tetrapropionyldibenzylhexaazaisowrutzane, tetrapropionylhexaazaisowrutzane, hexapropionylhexaazaisowrutzane, tetrapropionyldiacetylhexaazaisowrutzane, tetrapropionyldicarboxylatedhexaazaisowrutzane, tetrabutyryldibenzylhexaazaisowrutzane, and tetrabutyryldicarboxylatedhexaazaisowrutzane, with the general formula WA. n B 6－n and WA n R 6－n (W is the parent compound of hexaazaisowrutzane; A is C1-C2) 10 Acyl group; B is benzyl group; R is C1-C1. 10 A series of hexaazaisowrutzane derivatives (WO9623792) containing alkyl or hydrogen groups (n being an integer from 1 to 6). However, the synthesis and development of these derivatives are usually based on the debenzylation of hexabenzylhexaazaisowrutzane, which limits the research and application of hexaazaisowrutzane derivatives. Summary of the Invention

[0004] One object of the present invention is to solve at least the above-mentioned problems and / or defects, and to provide at least the advantages described below.

[0005] Another objective of this invention is to provide tetraacetyldicyclopropylhexaazaisowurtzite, which is a novel hexaazaisowurtzite derivative and provides a reference for the synthetic research of hexaazaisowurtzite derivatives.

[0006] Another objective of this invention is to provide a method for preparing tetraacetyldicyclopropylhexaazaisowulzane, which has a short reaction step, simple operation, and readily available raw materials, and has potential for industrial application. The leaving group cyclopropyl accounts for a small proportion of the cyclopropylamine raw material, resulting in good atom economy, high raw material utilization, and reduced waste emissions, thus conforming to the environmental protection concept of green economy. Another objective of this invention is to provide a method for synthesizing hexanitrohexaazaisowrutzane (HNIW), which is synthesized in one step by nitration of tetraacetyldicyclopropylhexaazaisowrutzane, simplifying the synthesis process and reducing production costs.

[0007] To achieve these objectives and other advantages according to the present invention, tetraacetyldicyclopropylhexaazaisowulzane is provided, having the structure of the following formula (I): (I).

[0008] The objective of this invention can also be further achieved by a method for preparing tetraacetyldicyclopropylhexaazaisowrtzine, which includes the following steps: S1, cyclopropylamine and glyoxal were condensed in solvent one in the presence of an acid catalyst, followed by washing and vacuum drying to obtain hexacyclopropylhexaazaisowrutzane; S2. The hexacyclopropylhexaazaisowrutzane obtained in step S1 is subjected to hydrogenolysis and acylation in a hydrogen atmosphere in the presence of solvent II, acetic anhydride, a metal catalyst and a co-catalyst to obtain tetraacetyldicyclopropylhexaazaisowrutzane.

[0009] Preferably, in step S1, the molar ratio of glyoxal, cyclopropylamine and acid catalyst is 1:(2-5):(0.2-0.5).

[0010] Preferably, in step S1, the acid catalyst is one of acetic acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, hydrobromic acid, and trifluoroacetic acid; solvent one is a mixed solvent formed by deionized water and an organic solvent, wherein the organic solvent is one of methanol, ethanol, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and N,N-diethylformamide; and the volume ratio of deionized water to organic solvent one is 1:(10-15).

[0011] Preferably, step S1 specifically includes: placing a three-necked flask containing cyclopropylamine, deionized water, and an organic solvent in a magnetic stirrer and stirring at 900-1400 rpm, cooling the flask to below 10°C in an ice bath, adding an acid catalyst dropwise, stirring for 15 min, then adding 10-40 wt.% glyoxal aqueous solution dropwise, continuing stirring for 0.5-1 h after the addition is complete, and heating to 10-60°C after the appearance of a white solid, continuing the reaction for 15-20 h; after the reaction is complete, cooling the reaction solution to below 5°C in an ice bath, filtering it, washing the filter residue 3-5 times with ice-cold deionized water and ice-cold ethanol respectively, and drying the filter residue in a vacuum drying oven at 25-40°C for 10-16 hours to obtain hexacyclopropylhexaazaisowulzane.

[0012] Preferably, in step S2, the mass ratio of hexacyclopropylhexaazaisowulzane, acetic anhydride, the metal component in the metal catalyst, and the co-catalyst is 1:(1-2.5):(0.02-0.1):(0.1-1).

[0013] Preferably, in step S2, solvent two is one of methanol, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, and dichloromethane; the metal catalyst is one of Pd / C, Pd(OH)2 / C, Pd / Al2O3, Pd(OH)2 / Al2O3, Pt / C, Ru / C, and Rh / C; and the co-catalyst includes one of bromobenzene, p-bromotoluene, and 1,1,2-trichloroethane.

[0014] Preferably, step S2 specifically includes: placing the hexacyclopropylhexaazaisowrutzane obtained in S1 into a high-pressure reactor equipped with a stirring device, adding solvent 2, acetic anhydride, metal catalyst, and co-catalyst respectively, sealing the reactor and checking its airtightness, replacing the air in the reactor with hydrogen 3-5 times, then pressurizing the reactor with hydrogen to 0.4-6 MPa, heating the reactor and starting stirring at 1000-1200 rpm, reacting at 25-80℃ for 16-36 hours; after the reaction is completed, cooling the reaction solution to room temperature, filtering, extracting and collecting the organic phase, and purifying the organic phase by column chromatography to obtain tetraacetyldicyclopropylhexaazaisowrutzane.

[0015] The objective of this invention can also be further achieved by a method for synthesizing hexanitrohexaazaisowulzane, which includes the following steps: The nitrifying agent was placed in a three-necked flask and stirred at 900-1400 rpm. Tetraacetyldicyclopropylhexaazaisowrutzane was added in three portions at 10-30°C. The temperature was raised to 60-100°C and stirred continuously. The reaction was monitored by TLC. After the reaction was complete, the reaction solution was cooled to 10°C and slowly poured into ice water with stirring to dilute it. The solution was filtered, and the filter cake was washed with distilled water until neutral. It was then dried under vacuum at 50°C to obtain the final product, hexanitrohexaazaisowrutzane.

[0016] Preferably, the nitrating agent is HNO3, H2SO4 / HNO3, N2O4 / HNO3, N2O5 / HNO3, NH4NO3 / HNO3, or H3PW. 12 O 40 One of / HNO3, Ac2O / HNO3, KNO3 / H2SO4.

[0017] The present invention has at least the following beneficial effects: First, the tetraacetyldicyclopropylhexaazaisowurtzite of the present invention is a novel hexaazaisowurtzite derivative, which has not been reported in the literature and provides a reference for the synthesis research of hexaazaisowurtzite derivatives.

[0018] Secondly, the preparation method of tetraacetyldicyclopropylhexaazaisowoodsane of the present invention has a short reaction step, simple operation, readily available raw materials, a small proportion of the leaving group cyclopropyl in the cyclopropylamine raw material, good atom economy, high raw material utilization rate, reduced waste emissions, conforms to the environmental protection concept of green economy, and has potential for industrial application.

[0019] Third, the tetraacetyldicyclopropylhexaazaisowurtzite of the present invention can be synthesized into hexanitrohexaazaisowurtzite (HNIW) in one step by nitration, which simplifies the synthesis process and reduces production costs.

[0020] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Attached Figure Description

[0021] Figure 1 The mass spectrum of hexacyclopropylhexaazaisowrutzane prepared in Example 1 of this invention; Figure 2 This is a crystal structure diagram of the hexacyclopropylhexaazaisowrutzane prepared in Example 1 of the present invention; Figure 3 The mass spectrum of tetraacetyldicyclopropylhexaazaisowrutzane prepared in Example 1 of this invention; Figure 4 This is a crystal structure diagram of tetraacetyldicyclopropylhexaazaisowrutzane prepared in Example 1 of the present invention; Figure 5 The 1H NMR spectrum of tetraacetyldicyclopropylhexaazaisowulzane prepared in Example 1 of this invention. Detailed Implementation

[0022] The present invention will now be described in further detail with reference to the accompanying drawings, so that those skilled in the art can implement it based on the description.

[0023] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not imply the presence or addition of one or more other elements or combinations thereof.

[0024] It should be noted that, unless otherwise specified, the experimental methods described in the following implementation plan are all conventional methods, and the reagents and materials described are all commercially available unless otherwise specified.

[0025] Example 1 Tetraacetyldicyclopropylhexaazaisowrutzane (TADCPIW) has the structure of formula (I): (I).

[0026] The synthesis route is as follows: The specific synthesis steps are as follows: S1. A 500 mL three-necked flask containing 28.5 g cyclopropylamine, 25 mL deionized water, and 285 mL acetonitrile was placed in a magnetic stirrer and stirred at 1400 rpm. The mixture was cooled to below 10°C in an ice bath. 2.9 g perchloric acid (70 wt.%) was added dropwise to the mixed solvent through a constant-pressure dropping funnel at a flow rate of 5 mL / min. After stirring for 15 minutes, 14.5 g g glyoxal (40 wt.%) was added dropwise. Stirring continued for 1 hour after the addition was complete. When a white solid precipitated, the temperature was raised to 35°C, and the reaction was continued for 18 hours. After the reaction was complete, the reaction mixture was cooled to below 5°C in an ice bath and filtered. The residue was washed three times (15 mL each time) with ice-cold deionized water and ice-cold ethanol. The residue was then dried in a vacuum drying oven at 30°C for 14 hours to obtain 12.3 g hexacyclopropylhexaazaisowulzane (HCPIW), with a yield of 90.5%. 1 H NMR (400 MHz, CDCl3- d 1 )δ 4.14 (s, 4H), 3.99 (s, 2H), 2.63 – 2.58 (m, 2H), 2.44 – 2.39 (m, 4H), 0.45– 0.26 (m, 24H). S2. 5 g of hexacyclopropylhexaazaisowrtzine was placed in a 150 mL high-pressure reactor equipped with a stirrer. 80 mL of N,N-dimethylformamide, 7.5 g of acetic anhydride, 3 g of Pd / C (10%), and 2.5 g of p-bromotoluene were added. The reactor was sealed and its airtightness was checked. The air inside the reactor was rapidly replaced with hydrogen three times. Then, hydrogen was introduced into the reactor to pressurize it to 0.8 MPa. The reactor was heated and stirred at 1100 rpm for 18 hours at 60 °C. After the reaction was complete, the reaction mixture was cooled to room temperature, filtered, and extracted with dichloromethane. The resulting organic phase was purified by column chromatography (eluent: dichloromethane / methanol, v / v: 93:7) to obtain 0.73 g of tetraacetyldicyclopropylhexaazaisowrtzine (TADCPIW), with a yield of 14.3%.

[0027] Among them, the mass spectrometry of HCPIW is as follows: Figure 1 As shown, the crystal structure diagram of HCPIW is as follows. Figure 2 As shown; the mass spectrum of TADCPIW is as follows. Figure 3 As shown, the crystal structure diagram of TADCPIW is as follows. Figure 4 As shown, the 1H NMR spectrum of TADCPIW is as follows: Figure 5 As shown.

[0028] Example 2 The specific synthetic steps for tetraacetyldicyclopropylhexaazaisowrtzine (TADCPIW) are as follows: S1. A 500 mL three-necked flask containing 22.8 g cyclopropylamine, 16 mL deionized water, and 160 mL ethanol was placed in a magnetic stirrer and stirred at 1200 rpm. The mixture was cooled to below 10°C in an ice bath. 3.4 g trifluoroacetic acid was added dropwise to the mixed solvent through a constant-pressure dropping funnel at a flow rate of 5 mL / min. After stirring for 15 minutes, 14.5 g g glyoxal (40 wt.%) was added dropwise. After the addition was complete, stirring was continued for 1 hour. When a white solid precipitated, the temperature was raised to 40°C, and the reaction was continued for 18 hours. After the reaction was complete, the reaction mixture was cooled to below 5°C in an ice bath and filtered. The filter residue was washed five times (15 mL each time) with ice-cold deionized water and ice-cold ethanol. The filter residue was then dried in a vacuum drying oven at 40°C for 16 hours to obtain 12.1 g HCPIW, with a yield of 89%.

[0029] S2. Place 5 g of HCPIW in a 150 mL high-pressure reactor equipped with a stirrer. Add 80 mL of N,N-dimethylacetamide, 10 g of acetic anhydride, 5 g of Pd / Al2O3 (10%), and 1.5 g of bromobenzene. Seal the reactor and check its airtightness. Quickly replace the air in the reactor with hydrogen three times. Then, pressurize the reactor with hydrogen to 2.2 MPa, heat the reactor, and start stirring at 1100 rpm. React at 80 °C for 16 hours. After the reaction is complete, cool the reaction mixture to room temperature, filter, extract with dichloromethane, and purify the resulting organic phase by column chromatography (eluent: dichloromethane / methanol, volume ratio: 93:7) to obtain 0.86 g of TADCPIW, with a yield of 16.8%.

[0030] Example 3 The specific synthetic steps for tetraacetyldicyclopropylhexaazaisowrtzine (TADCPIW) are as follows: S1. A 250 mL three-necked flask containing 17 g cyclopropylamine, 8 mL deionized water, and 85 mL methanol was placed in a magnetic stirrer and stirred at 900 rpm. The mixture was cooled to below 10°C in an ice bath. 3.9 g hydrochloric acid (37 wt.%) was added dropwise to the mixed solvent through a constant-pressure dropping funnel at a flow rate of 5 mL / min. After stirring for 15 minutes, 14.5 g g glyoxal (40 wt.%) was added dropwise. After the addition was complete, stirring was continued for 0.6 hours. After a white solid precipitated, the temperature was raised to 25°C, and the reaction was continued for 20 hours. After the reaction was complete, the reaction mixture was cooled to below 5°C in an ice bath and then filtered. The filter residue was washed three times (15 mL each time) with ice-cold deionized water and ice-cold ethanol. The filter residue was then dried in a vacuum drying oven at 40°C for 12 hours to obtain 11.6 g HCPIW, with a yield of 85.3%.

[0031] S2. Place 5 g of HCPIW in a 50 mL high-pressure reactor equipped with a stirrer. Add 30 mL of tetrahydrofuran, 5 g of acetic anhydride, 2 g of Pt / C (10%), and 3.5 g of bromobenzene. Seal the reactor and check its airtightness. Quickly replace the air in the reactor with hydrogen five times. Then, pressurize the reactor with hydrogen to 1.5 MPa, heat the reactor, and start stirring at 1000 rpm. React at 40 °C for 24 hours. After the reaction is complete, cool the reaction mixture to room temperature, filter, extract with dichloromethane, and purify the resulting organic phase by column chromatography (eluent: dichloromethane / methanol, volume ratio: 93:7) to obtain 0.6 g of TADCPIW, with a yield of 11.7%.

[0032] Example 4 The specific synthetic steps for tetraacetyldicyclopropylhexaazaisowrtzine (TADCPIW) are as follows: S1. A 250 mL three-necked flask containing 11.5 g cyclopropylamine, 4 mL deionized water, and 60 mL N,N-dimethylformamide was placed in a magnetic stirrer and stirred at 900 rpm. The mixture was cooled to below 10°C in an ice bath. 3 g acetic acid was added dropwise to the mixed solvent through a constant-pressure dropping funnel at a flow rate of 5 mL / min. After stirring for 15 minutes, 14.5 g g glyoxal (40 wt.%) was added dropwise. After the addition was complete, stirring was continued for 0.8 hours. After a white solid precipitated, the temperature was raised to 50°C, and the reaction was continued for 16 hours. After the reaction was complete, the reaction mixture was cooled to below 5°C in an ice bath and then filtered. The filter residue was washed four times (15 mL each time) with ice-cold deionized water and ice-cold ethanol. The filter residue was then dried in a vacuum drying oven at 30°C for 14 hours to obtain 11.4 g HCPIW, with a yield of 83.9%.

[0033] S2. Place 5 g of HCPIW in a 100 mL high-pressure reactor equipped with a stirrer. Add 50 mL of ethanol, 10 g of acetic anhydride, 4 g of Rh / C (10%), and 0.5 g of 1,1,2-trichloroethane. Seal the reactor and check its airtightness. Quickly replace the air in the reactor with hydrogen four times. Then, pressurize the reactor with hydrogen to 6 MPa, heat the reactor, and start stirring at 1100 rpm. React at 60 °C for 20 hours. After the reaction is complete, cool the reaction mixture to room temperature, filter, and extract with dichloromethane. The resulting organic phase is purified by column chromatography (eluent: dichloromethane / methanol, volume ratio: 93:7) to obtain 0.93 g of TADCPIW, with a yield of 18.2%.

[0034] Example 5 The specific synthetic steps for tetraacetyldicyclopropylhexaazaisowrtzine (TADCPIW) are as follows: S1. A 250 mL three-necked flask containing 17.1 g cyclopropylamine, 10 mL deionized water, and 120 mL N-methylpyrrolidone was placed in a magnetic stirrer and stirred at 1000 rpm. The mixture was then cooled to below 10°C in an ice bath. 2.8 g concentrated nitric acid (68 wt.%) was added dropwise to the mixed solvent through a constant-pressure dropping funnel at a flow rate of 7 mL / min. After stirring for 15 minutes, 19.3 g g glyoxal (30 wt.%) was added dropwise. Stirring continued for 0.6 hours after the addition was complete. Once a white solid precipitated, the temperature was raised to 60°C, and the reaction was continued for 15 hours. After the reaction was complete, the reaction mixture was cooled to below 5°C in an ice bath and then filtered. The residue was washed five times (15 mL each time) with ice-cold deionized water and ice-cold ethanol, respectively. The residue was then dried in a vacuum drying oven at 25°C for 16 hours to obtain 10.6 g HCPIW, with a yield of 78.1%.

[0035] S2. Place 5 g of HCPIW in a 50 mL high-pressure reactor equipped with a stirrer. Add 25 mL of dichloromethane, 12.5 g of acetic anhydride, 2.5 g of Pd(OH)₂ / C (20%), and 5 g of 1,1,2-trichloroethane. Seal the reactor and check its airtightness. Quickly replace the air in the reactor with hydrogen three times. Then, pressurize the reactor to 5 MPa by introducing hydrogen gas. Heat the reactor and start stirring at 1000 rpm. React at 25°C for 36 hours. After the reaction is complete, cool the reaction mixture to room temperature, filter, and extract with dichloromethane. The resulting organic phase is purified by column chromatography (eluent: dichloromethane / methanol, volume ratio: 93:7) to obtain 0.82 g of TADCPIW, with a yield of 16.1%.

[0036] Example 6 The specific synthetic steps for tetraacetyldicyclopropylhexaazaisowrtzine (TADCPIW) are as follows: S1. A 500 mL three-necked flask containing 22.8 g cyclopropylamine, 12 mL deionized water, and 180 mL N,N-dimethylacetamide was placed in a magnetic stirrer and stirred at 1200 rpm. The mixture was cooled to below 10°C in an ice bath. 3.9 g concentrated sulfuric acid (98%) was added dropwise to the mixed solvent through a constant-pressure dropping funnel at a flow rate of 10 mL / min. After stirring for 15 minutes, 29 g g glyoxal (20 wt.%) was added dropwise. After the addition was complete, stirring was continued for 0.5 hours. When a white solid precipitated, the temperature was raised to 10°C, and the reaction was continued for 20 hours. After the reaction was complete, the reaction mixture was cooled to below 5°C in an ice bath and then filtered. The filter residue was washed five times (15 mL each time) with ice-cold deionized water and ice-cold ethanol. The filter residue was then dried in a vacuum drying oven at 40°C for 12 hours to obtain 11.1 g HCPIW, with a yield of 81.7%.

[0037] S2. Place 5 g of HCPIW in a 100 mL high-pressure reactor equipped with a stirrer. Add 50 mL of methanol, 7.5 g of acetic anhydride, 2 g of Pd(OH)2 / Al2O3 (5%), and 2.5 g of p-bromotoluene. Seal the reactor and check its airtightness. Quickly replace the air in the reactor with hydrogen five times. Then, pressurize the reactor with hydrogen to 4 MPa, heat the reactor, and start stirring at 1000 rpm. React at 40 °C for 24 hours. After the reaction is complete, cool the reaction mixture to room temperature, filter, extract with dichloromethane, and purify the resulting organic phase by column chromatography (eluent: dichloromethane / methanol, volume ratio: 93:7) to obtain 0.66 g of TADCPIW, with a yield of 12.9%.

[0038] Example 7 The specific synthetic steps for tetraacetyldicyclopropylhexaazaisowrtzine (TADCPIW) are as follows: S1. A 250 mL three-necked flask containing 8.6 g cyclopropylamine, 8 mL deionized water, and 80 mL N,N-diethylformamide was placed in a magnetic stirrer and stirred at 900 rpm. The mixture was cooled to below 10°C in an ice bath. 4.2 g hydrobromic acid (48 wt.%) was added dropwise to the mixed solvent through a constant-pressure dropping funnel at a flow rate of 10 mL / min. After stirring for 15 minutes, 29 g g glyoxal (10 wt.%) was added dropwise. After the addition was complete, stirring continued for 0.5 hours. Once a white solid precipitated, the temperature was raised to 30°C, and the reaction was continued for 18 hours. After the reaction was complete, the reaction mixture was cooled to below 5°C in an ice bath and then filtered. The residue was washed three times (15 mL each time) with ice-cold deionized water and ice-cold ethanol. The residue was then dried in a vacuum drying oven at 35°C for 10 hours to obtain 5.2 g HCPIW, with a yield of 76.5%.

[0039] S2. Place 5 g of HCPIW in a 150 mL high-pressure reactor equipped with a stirrer. Add 100 mL of N-methylpyrrolidone, 10 g of acetic anhydride, 2.5 g of Ru / C (10%), and 1.5 g of bromobenzene. Seal the reactor and check its airtightness. Quickly replace the air in the reactor with hydrogen five times. Then, pressurize the reactor with hydrogen to 0.4 MPa, heat the reactor, and start stirring at 1200 rpm. React at 80 °C for 32 hours. After the reaction is complete, cool the reaction mixture to room temperature, filter, extract with dichloromethane, and purify the resulting organic phase by column chromatography (eluent: dichloromethane / methanol, volume ratio: 93:7) to obtain 0.75 g of TADCPIW, with a yield of 14.7%.

[0040] Example 8 A one-step method for synthesizing hexanitrohexaazaisowurtzite (HNIW) from tetraacetyldicyclopropylhexaazaisowurtzite (TADCPIW) includes the following steps: 15 mL of fuming nitric acid was placed in a three-necked flask and stirred at 1200 rpm. 1 g of TADCPIW was added in portions at 15 °C, and the temperature was raised to 90 °C with continuous stirring. The reaction was monitored by TLC. After 9 h, the reaction was complete. The reaction solution was cooled to 10 °C and slowly poured into ice water with stirring to dilute. After filtration, the filter cake was washed with distilled water until neutral and then dried under vacuum at 50 °C to obtain 0.76 g of HNIW, with a yield of 72%. 1 H NMR (500 MHz, Acetone- d 6) δ 8.35 (s, 4H), 8.21 (s, 2H); 13 C NMR (201 MHz, Acetone- d6) δ 75.14, 72.19; IR (KBr): ν = 3034, 1604, 1565, 1323,1272, 990, 956, 942, 904, 880, 675 cm -1 HRMS (ESI) for C6H6N 12 O 12 (MH) ﹣ :calcd.437.0155, found 437.0159. Example 9 A one-step method for synthesizing hexanitrohexaazaisowurtzite (HNIW) from tetraacetyldicyclopropylhexaazaisowurtzite (TADCPIW) includes the following steps: 5 mL of fuming nitric acid and 10 mL of fuming sulfuric acid were placed in a three-necked flask and stirred at 1400 rpm. 1 g of TADCPIW was added in portions at 10 °C, and the temperature was raised to 60 °C with continuous stirring. The reaction was monitored by TLC. After 6 h, the reaction was complete. The reaction solution was cooled to 10 °C and slowly poured into ice water with stirring to dilute it. After filtration, the filter cake was washed with distilled water until neutral and then dried under vacuum at 50 °C to obtain 0.96 g of HNIW, with a yield of 91%.

[0041] Example 10 A one-step method for synthesizing hexanitrohexaazaisowurtzite (HNIW) from tetraacetyldicyclopropylhexaazaisowurtzite (TADCPIW) includes the following steps: 10 mL of 95% HNO3 and 0.5 g of N2O4 were placed in a three-necked flask and stirred at 1000 rpm. 1 g of TADCPIW was added in portions at 20 °C, and the temperature was raised to 80 °C with continuous stirring. The reaction was monitored by TLC. After 7 h, the reaction was complete. The reaction solution was cooled to 10 °C and slowly poured into ice water with stirring to dilute it. After filtration, the filter cake was washed with distilled water until neutral and then dried under vacuum at 50 °C to obtain 0.87 g of HNIW, with a yield of 83%.

[0042] Example 11 A one-step method for synthesizing hexanitrohexaazaisowurtzite (HNIW) from tetraacetyldicyclopropylhexaazaisowurtzite (TADCPIW) includes the following steps: 8 mL of 95% HNO3 and 0.5 g of N2O5 were placed in a three-necked flask and stirred at 1000 rpm. 1 g of TADCPIW was added in portions at 20 °C, and the temperature was raised to 80 °C with continuous stirring. The reaction was monitored by TLC. After 6 h, the reaction was complete. The reaction solution was cooled to 10 °C and slowly poured into ice water with stirring to dilute it. After filtration, the filter cake was washed with distilled water until neutral and then dried under vacuum at 50 °C to obtain 0.94 g of HNIW, with a yield of 89%.

[0043] Example 12 A one-step method for synthesizing hexanitrohexaazaisowurtzite (HNIW) from tetraacetyldicyclopropylhexaazaisowurtzite (TADCPIW) includes the following steps: 15 mL of 90% HNO3 and 0.6 g of NH4NO3 were placed in a three-necked flask and stirred at 1200 rpm. 1 g of TADCPIW was added in portions at 30 °C, and the temperature was raised to 100 °C with continuous stirring. The reaction was monitored by TLC. After 6 h, the reaction was complete. The reaction solution was cooled to 10 °C and slowly poured into ice water with stirring to dilute it. After filtration, the filter cake was washed with distilled water until neutral and then dried under vacuum at 50 °C to obtain 0.88 g of HNIW, with a yield of 84%.

[0044] Example 13 A one-step method for synthesizing hexanitrohexaazaisowurtzite (HNIW) from tetraacetyldicyclopropylhexaazaisowurtzite (TADCPIW) includes the following steps: Mix 5 mL of HNO3 (90%) with 0.15 g of H3PW 12 O 40 The mixture was placed in a three-necked flask and stirred at 900 rpm. 1 g of TADCPIW was added in portions at 25 °C, and the temperature was raised to 80 °C with continued stirring. The reaction was monitored by TLC. After 7 h, the reaction was complete. The reaction solution was cooled to 10 °C and slowly poured into ice water with stirring to dilute it. The mixture was filtered, and the filter cake was washed with distilled water until neutral. It was then dried under vacuum at 50 °C to obtain 0.91 g of HNIW, with a yield of 86%.

[0045] Example 14 A one-step method for synthesizing hexanitrohexaazaisowurtzite (HNIW) from tetraacetyldicyclopropylhexaazaisowurtzite (TADCPIW) includes the following steps: 10 mL of Ac₂O and 1.6 g of fuming nitric acid were placed in a three-necked flask and stirred at 1000 rpm. 1 g of TADCPIW was added in portions at 10 °C, and the temperature was raised to 70 °C with continuous stirring. The reaction was monitored by TLC. After 6 h, the reaction was complete. The reaction solution was cooled to 10 °C and slowly poured into ice water with stirring to dilute it. After filtration, the filter cake was washed with distilled water until neutral and then dried under vacuum at 50 °C to obtain 0.89 g of HNIW, with a yield of 85%.

[0046] Example 15 A one-step method for synthesizing hexanitrohexaazaisowurtzite (HNIW) from tetraacetyldicyclopropylhexaazaisowurtzite (TADCPIW) includes the following steps: 20 mL of fuming sulfuric acid and 1.5 g of KNO3 were placed in a three-necked flask and stirred at 1400 rpm. 1 g of TADCPIW was added in portions at 30 °C, and the temperature was raised to 60 °C with continuous stirring. The reaction was monitored by TLC. After 8 h, the reaction was complete. The reaction solution was cooled to 10 °C and slowly poured into ice water with stirring to dilute it. After filtration, the filter cake was washed with distilled water until neutral and then dried under vacuum at 50 °C to obtain 0.74 g of HNIW, with a yield of 70%.

[0047] Compared with the traditional route with its complex processes, the synthesis of HNIW in this invention simplifies the process from four steps to three steps, starting from the raw materials, thus reducing production costs. At the same time, the use of cyclopropylamine instead of benzylamine increases atom utilization, making it more environmentally friendly and possessing the potential for large-scale production and application prospects.

[0048] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. It can be applied to various fields suitable for the present invention. Other modifications can be readily made by those skilled in the art. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and examples shown and described herein.

Claims

1. Tetraacetyldicyclopropylhexaazaisowurtzitane, characterized in that It has the following formula (I) structure: （I）。 2. A process for the preparation of tetraacetyldicyclopropylhexaazaisowurtzitane according to claim 1, characterized in that It comprises the following steps: S1, the condensation reaction of cyclopropylamine and glyoxal in the presence of an acid catalyst in solvent one, washing, vacuum drying to obtain hexacyclopropylhexaazaisowurtzitane; S2, the hydrogenolysis and acylation reaction of hexacyclopropylhexaazaisowurtzitane obtained in step S1 in the presence of hydrogen, solvent two, acetic anhydride, metal catalyst and co-catalyst to obtain tetraacetyl dicyclopropylhexaazaisowurtzitane.

3. The process of claim 2 for the preparation of tetraacetyldicyclopropylhexaazaisowurtzitane, characterized in that, In step S1, the molar ratio of glyoxal, cyclopropylamine and acid catalyst is 1:(2-5):(0.2-0.5).

4. The process of claim 2 for the preparation of tetraacetyldicyclopropylhexaazaisowurtzitane, characterized in that, In step S1, the acid catalyst is one of acetic acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, hydrobromic acid and trifluoroacetic acid; the solvent one is a mixed solvent formed by deionized water and an organic solvent, and the organic solvent is one of methanol, ethanol, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl pyrrolidone and N,N-diethylformamide; in the solvent one, the volume ratio of deionized water to organic solvent is 1:(10-15).

5. The process of claim 4 for the preparation of tetraacetyldicyclopropylhexaazaisowurtzitane, characterized in that, Step S1 specifically includes: placing a three-necked flask containing cyclopropylamine, deionized water and an organic solvent in a magnetic stirrer to stir at a speed of 900-1400 rpm, and cooling to below 10°C in an ice bath, adding an acid catalyst dropwise, stirring for 15 min, then continuing to add 10-40wt.% glyoxal solution dropwise, continuing to stir for 0.5-1 h after the dropwise addition is completed, and then heating to 10-60°C after white solid precipitates, and continuing to react for 15-20 h; after the reaction is completed, the reaction liquid is cooled to below 5°C in an ice bath, and then filtered, washed with ice deionized water and ice ethanol for 3-5 times, and then dried in a vacuum drying oven at 25-40°C for 10-16 hours to obtain hexacyclopropylhexaazaisowurtzitane.

6. The process of claim 2 for the preparation of tetraacetyldicyclopropylhexaazaisowurtzitane, characterized in that, In step S2, the mass ratio of hexacyclopropylhexaazaisowurtzitane, acetic anhydride, metal component of metal catalyst and co-catalyst is 1:(1-2.5):(0.02-0.1):(0.1-1).

7. The process of claim 2 wherein the process is carried out in the presence of a solvent. In step S2, the solvent two is one of methanol, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl pyrrolidone, tetrahydrofuran and dichloromethane; the metal catalyst is one of Pd / C, Pd(OH)2 / C, Pd / Al2O3, Pd(OH)2 / Al2O3, Pt / C, Ru / C and Rh / C; the co-catalyst includes one of bromobenzene, p-bromotoluene and 1,1,2-trichloroethane.

8. The process of claim 2 for the preparation of tetraacetyldicyclopropylhexaazaisowurtzitane, characterized in that, The step S2 specifically comprises: placing the hexacyclopropyl hexaazaiswuzzan obtained in S1 into a high-pressure reaction kettle with a stirring device, adding solvent two, acetic anhydride, metal catalyst and co-catalyst respectively, sealing the reaction kettle and detecting the air tightness, replacing the air in the reaction kettle with hydrogen for 3-5 times, then pressurizing the kettle to 0.4-6 Mpa by hydrogen, heating the reaction kettle and starting stirring at 1000-1200 rpm, and reacting at 25-80℃ for 16-36 hours; after the reaction is completed, the reaction liquid is cooled to room temperature, filtered, extracted to collect the organic phase, and the organic phase is purified by column chromatography to obtain tetraacetyl dicyclopropyl hexaazaiswuzzan.

9. A method of synthesizing hexanitrohexaazaisowurtzitane, characterized in that, The method comprises the following steps: The nitration agent is placed in a three-necked flask and stirred at a speed of 900-1400 rpm, and tetraacetyl dicyclopropyl hexaazaiswuzzan is added in three portions at 10-30℃, and the temperature is raised to 60-100℃ for continuous stirring; the reaction is monitored by TLC, after the reaction is completed, the reaction liquid is reduced to 10℃, and is slowly poured into ice water for dilution under stirring, filtered, and the filter cake is washed with distilled water until neutral, and then dried at 50℃ under vacuum to obtain the final product hexanitro hexaazaiswuzzan.

10. The process for the synthesis of hexanitrohexaazaisowurtzitane according to claim 9, characterized in that, The nitrating agent is one of HNO3, H2SO4 / HNO3, N2O4 / HNO3, N2O5 / HNO3, NH4NO3 / HNO3, H3PW 12 O 40 / HNO3, Ac2O / HNO3, KNO3 / H2SO4.

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