Tetraacetyldicyclopropylhexaazaisowurtzitane, a process for its preparation, a process for the synthesis of hniw

Abstract

The application discloses tetraacetyldicyclopropylhexaazaisowurtzitane and a preparation method thereof, and a synthesis method of HNIW, and belongs to the technical field of chemical synthesis. The tetraacetyldicyclopropylhexaazaisowurtzitane is a new hexaazaisowurtzitane derivative, the preparation method has short reaction steps, simple operation, and raw materials are easy to obtain, and has industrial application potential. The tetraacetyldicyclopropylhexaazaisowurtzitane can be used for synthesizing hexanitrohexaazaisowurtzitane (HNIW) through nitration, the synthesis process is simplified, and the production cost is reduced; the leaving group cyclopropyl has a small proportion in the cyclopropylamine raw material, has good atom economy, has high raw material utilization, reduces waste emission, and meets the environmental protection concept of green economy.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical synthesis, and particularly relates to tetraacetyldicyclopropylhexaazaisowurtzitane and a preparation method thereof, and a synthesis method of hexanitrohexaazaisowurtzitane (HNIW). BACKGROUND

[0002] Hexaazaisowurtzitane compounds were first reported in 1990 (Nielsen, A., et al., Polyazapolycyclics 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), and the unique three-dimensional cage skeleton structure and properties have been favored by chemical researchers all over the world. Hexanitrohexaazaisowurtzitane, abbreviated as HNIW, is a new type of high-energy density energetic material, which belongs to the fourth generation of high-energy explosives, has good oxygen balance and enthalpy of formation, and has better performance than traditional military main explosive octogen (HMX) in terms of detonation velocity, detonation pressure, density and other performances, and shows good application performance in the field of solid propellants. Therefore, the synthesis of hexaazaisowurtzitane derivatives has been a research hotspot, and it has wide application prospect and research value in the field of materials. At present, the industrial production route of HNIW is mainly based on hexabenzylhexaazaisowurtzitane (abbreviated as HBIW) as a precursor, and the TAIW process route is mainly adopted (Energetic Materials, 2009. 17(2): 161-165.). The process route includes four steps: 1. The precursor HBIW is prepared by condensation reaction with benzylamine and glyoxal as raw materials; 2. HBIW is acetylated after one-step hydrogenolysis to obtain tetraacetyldibenzylhexaazaisowurtzitane (abbreviated as TADB); 3. TADB is obtained by two-step hydrogenolysis to obtain the nitration precursor tetraacetyldicyclopropylhexaazaisowurtzitane (abbreviated as 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 all over the world, the process of each step has been fully optimized. However, this process route still has problems such as complicated steps, complex process and high cost.

[0003] The main way to construct the hexaazaisowurtzitane skeleton structure is to synthesize it by condensation reaction of primary amine compound and glyoxal, and the corresponding derivatives can be obtained by structural modification. In the past few decades, some hexaazaisowurtzitane derivatives have gradually emerged, such as tetrapropionyl dibenzyl hexaazaisowurtzitane, tetrapropionyl hexaazaisowurtzitane, hexapropionyl hexaazaisowurtzitane, tetrapropionyl diacetyl hexaazaisowurtzitane, tetrapropionyl diformyl hexaazaisowurtzitane, tetrabutyryl dibenzyl hexaazaisowurtzitane, tetrabutyryl hexaazaisowurtzitane, tetrabutyryl diformyl hexaazaisowurtzitane, and a series of hexaazaisowurtzitane derivatives with the general formula of WA n B 6－n and WA n R 6－n (W is a hexaazaisowurtzitane parent; A is C1-C 10 acyl; B is benzyl; R is C1-C 10 alkyl or hydrogen; n is an integer of 1-6) (WO9623792). However, the synthesis and development of these derivatives are usually based on the debenzoylation of hexabenzyl hexaazaisowurtzitane, which has certain limitations for the research and application of hexaazaisowurtzitane derivatives. SUMMARY

[0004] An object of the present application is to solve at least the above problems and / or defects, and to provide at least the advantages to be described later.

[0005] Another object of the present application is to provide tetraacetyldicyclopropyl hexaazaisowurtzitane, which is a new hexaazaisowurtzitane derivative, and provides a reference for the synthesis research of hexaazaisowurtzitane derivatives.

[0006] Another object of the present application is to provide a method for preparing tetraacetyldicyclopropyl hexaazaisowurtzitane, which has short reaction steps, simple operation, easy-to-obtain raw materials, and potential for industrial application; the leaving group cyclopropyl accounts for a small proportion of the cyclopropylamine raw material, has good atom economy, high utilization rate of raw materials, reduces waste emissions, and meets the environmental protection concept of green economy

[0007] Still another object of the present application is to provide a synthesis method of hexanitrohexaazaisowurtzitane (HNIW), which is synthesized by nitration of tetraacetyldicyclopropyl hexaazaisowurtzitane in one step, simplifying the synthesis process and reducing production cost.

[0008] In order to achieve these objects and other advantages according to the present application, there is provided tetraacetyldicyclopropyl hexaazaisowurtzitane, which has the following formula (I):

[0009] (I).

[0010] The object of the present application can be further achieved by a method for preparing tetraacetyldicyclopropylhexaazaisowurtzitane, comprising the following steps:

[0011] S1, condensation reaction of cyclopropylamine and glyoxal in the presence of an acid catalyst in a solvent one, washing, vacuum drying to obtain hexacyclopropylhexaazaisowurtzitane;

[0012] S2, hydrogenolysis and acylation reaction of hexacyclopropylhexaazaisowurtzitane obtained in step S1 in the presence of hydrogen atmosphere, a solvent two, acetic anhydride, a metal catalyst and a co-catalyst to obtain tetraacetyldicyclopropylhexaazaisowurtzitane.

[0013] Preferably, in step S1, the molar ratio of glyoxal, cyclopropylamine and acid catalyst is 1: (2-5): (0.2-0.5).

[0014] 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; 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-methylpyrrolidone and N, N-diethylformamide; in the solvent one, the volume ratio of deionized water and organic solvent is 1: (10-15).

[0015] Preferably, in step S1, it specifically comprises: 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℃ under ice bath, adding the acid catalyst dropwise, stirring for 15 min, then continuously adding 10-40wt.% glyoxal aqueous solution dropwise, continuing to stir for 0.5-1 h after the dropwise addition is completed, and then heating to 10-60℃ 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℃ under ice bath, and then filtered, washed with ice deionized water and ice ethanol for 3-5 times, and dried in a vacuum drying oven at 25-40℃ for 10-16 hours to obtain hexacyclopropylhexaazaisowurtzitane.

[0016] Preferably, 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).

[0017] Preferably, in step S2, the solvent II 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.

[0018] Preferably, step S2 specifically includes: placing the hexacyclopropylhexaazaisowurtzitane obtained in S1 into a high-pressure reaction kettle with a stirring device, respectively adding the solvent II, acetic anhydride, the metal catalyst and the co-catalyst, 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 with hydrogen to 0.4-6 MPa, 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, the organic phase is collected by filtration and extraction, and the organic phase is purified by column chromatography to obtain tetraacetyldicyclopropylhexaazaisowurtzitane.

[0019] The object of the present application can also be further achieved by a method for synthesizing hexanitrohexaazaisowurtzitane, comprising the following steps:

[0020] The nitration agent is placed in a three-necked flask and stirred at a speed of 900-1400 rpm, and tetraacetyldicyclopropylhexaazaisowurtzitane 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, and the filter cake is washed to neutral with distilled water, and then dried at 50℃ under vacuum to obtain the final product hexanitrohexaazaisowurtzitane.

[0021] Preferably, the nitration agent is one of HNO3, H2SO4 / HNO3, N2O4 / HNO3, N2O5 / HNO3, NH4NO3 / HNO3, H3PW 12 O 40 / HNO3, Ac2O / HNO3, KNO3 / H2SO4.

[0022] The present application at least includes the following beneficial effects:

[0023] Firstly, the tetraacetyldicyclopropylhexaazaisowurtzitane of the present application is a new hexaazaisowurtzitane derivative, which has not been reported in the literature, and provides a reference for the synthesis of hexaazaisowurtzitane derivatives.

[0024] Secondly, the preparation method of the tetraacetyldicyclopropylhexaazaisowurtzitane has short reaction steps, simple operation, easily available raw materials, small proportion of the leaving group cyclopropyl in the cyclopropylamine raw material, high atom economy, high utilization rate of raw materials, reduced waste emissions, conforms to the environmental protection concept of green economy, and has industrial application potential.

[0025] Thirdly, the tetraacetyldicyclopropylhexaazaisowurtzitane can be used to synthesize hexanitrohexaazaisowurtzitane (HNIW) through nitration, which simplifies the synthesis process and reduces the production cost.

[0026] Other advantages, objects and features of the present application will be apparent from the following description, and will be understood by those skilled in the art. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 Mass spectrum of the hexacyclopropylhexaazaisowurtzitane prepared in Example 1 of the present application;

[0028] Figure 2 Crystal structure diagram of the hexacyclopropylhexaazaisowurtzitane prepared in Example 1 of the present application;

[0029] Figure 3 Mass spectrum of the tetraacetyldicyclopropylhexaazaisowurtzitane prepared in Example 1 of the present application;

[0030] Figure 4 Crystal structure diagram of the tetraacetyldicyclopropylhexaazaisowurtzitane prepared in Example 1 of the present application;

[0031] Figure 5 Nuclear magnetic hydrogen spectrum of the tetraacetyldicyclopropylhexaazaisowurtzitane prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0032] The present application will be further described in detail below with reference to the accompanying drawings, so that those skilled in the art can implement the present application according to the description.

[0033] It should be understood that the terms such as "have", "contain" and "include" used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0034] It should be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials can be obtained from commercial channels unless otherwise specified.

[0035] Example 1

[0036] The tetraacetyldicyclopropylhexaazaisowurtzitane (TADCPIW) has the following formula (I):

[0037] (I).

[0038] The synthetic route is as follows:

[0039]

[0040] The specific synthesis steps are as follows:

[0041] S1, a 500 mL three-necked flask containing 28.5 g of cyclopropylamine, 25 mL of deionized water and 285 mL of acetonitrile was placed in a magnetic stirrer for stirring at a speed of 1400 rpm, and was cooled to below 10°C in an ice bath. 2.9 g of perchloric acid (70 wt.%) was added dropwise to the above-mentioned mixed solvent at a flow rate of 5 mL / min through a constant pressure dropping funnel. After stirring for 15 minutes, 14.5 g of glyoxal (40 wt.%) was added dropwise. After the dropwise addition was completed, stirring was continued for 1 hour. After white solid precipitated, the temperature was raised to 35°C, and the reaction was continued for 18 hours. After the reaction was completed, the reaction mixture was cooled to below 5°C in an ice bath, and was subjected to suction filtration. The filter residue was washed with ice deionized water and ice ethanol for 3 times (15 mL / time). Subsequently, the filter residue was dried in a vacuum drying oven at 30°C for 14 hours to obtain 12.3 g of hexacyclopropylhexaazaisowurtzitane (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).

[0042] S2, 5 g of hexacyclopropylhexaazaisowurtzitane was placed in a 150 mL high-pressure reaction kettle with a stirring device. 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 respectively. The reaction kettle was sealed and the air tightness was detected. The air in the reaction kettle was replaced with hydrogen gas for 3 times, and then the hydrogen gas was pressurized to 0.8 Mpa. The reaction kettle was heated and stirred at 1100 rpm at 60°C for 18 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered, and extracted with dichloromethane. The obtained organic phase was purified by column chromatography (eluent: dichloromethane / methanol, volume ratio: 93:7) to obtain 0.73 g of tetraacetyldicyclopropylhexaazaisowurtzitane (TADCPIW) with a yield of 14.3%.

[0043] The mass spectrum of HCPIW is as follows: Figure 1The crystal structure of HCPIW is shown in Figure 1. Figure 2 The mass spectrum of TADCPIW is shown in Figure 2. Figure 3 The crystal structure of TADCPIW is shown in Figure 3. Figure 4 The nuclear magnetic hydrogen spectrum of TADCPIW is shown in Figure 4. Figure 5

[0044] Example 2

[0045] The specific synthesis steps of tetraacetyldicyclopropylhexaazaisowurtzitane (TADCPIW) are as follows:

[0046] S1, place a 500 mL three-necked flask containing 22.8 g of cyclopropylamine, 16 mL of deionized water and 160 mL of ethanol in a magnetic stirrer and stir at a speed of 1200 rpm, and cool to below 10°C in an ice bath, add 3.4 g of trifluoroacetic acid to the above mixture at a flow rate of 5 mL / min through a constant pressure dropping funnel, stir for 15 minutes, then add 14.5 g of glyoxal (40 wt.%), continue to stir for 1 hour after the dropwise addition is completed, and then warm to 40°C, continue to react for 18 hours. After the reaction is completed, cool the reaction mixture to below 5°C in an ice bath, and filter it, and wash the filter residue with ice deionized water and ice ethanol for 5 times (15 mL / time). Then dry the filter residue in a vacuum drying oven at 40°C for 16 hours to obtain 12.1 g of HCPIW with a yield of 89%.

[0047] S2, take 5 g of HCPIW and place it in a 150 mL high-pressure reaction kettle with a stirring device, add 80 mL of N,N-dimethylacetamide, 10 g of acetic anhydride, 5 g of Pd / Al2O3 (10%), and 1.5 g of bromobenzene, respectively, seal the reaction kettle and check the airtightness, replace the air in the reaction kettle with hydrogen gas 3 times, then pressurize the kettle to 2.2 Mpa with hydrogen gas, heat the reaction kettle and start stirring at 1100 rpm, and react at 80°C for 16 hours. After the reaction is completed, cool the reaction mixture to room temperature, filter, extract with dichloromethane, and then purify the obtained 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%.

[0048] Example 3

[0049] The specific synthesis steps of tetraacetyldicyclopropylhexaazaisowurtzitane (TADCPIW) are as follows:

[0050] ​S1, a 250 mL three-necked flask containing 17 g of cyclopropylamine, 8 mL of deionized water and 85 mL of methanol was placed in a magnetic stirrer and stirred at a speed of 900 rpm, and cooled to below 10°C in an ice bath, 3.9 g of hydrochloric acid (37 wt.%) was added dropwise to the above mixed solvent at a flow rate of 5 mL / min through a constant pressure dropping funnel, after stirring for 15 minutes, 14.5 g of glyoxal (40 wt.%) was continuously added, after the addition was completed, it was continuously stirred for 0.6 hours, after the white solid was precipitated, it was warmed to 25°C, and the reaction was continued for 20 hours. After the reaction was completed, the reaction mixture was cooled to below 5°C in an ice bath, and then it was suction filtered, and the filter residue was washed with ice deionized water and ice ethanol for 3 times (15 mL / time). Then the filter residue was dried in a vacuum drying oven at 40°C for 12 hours to obtain 11.6 g of HCPIW with a yield of 85.3%.

[0051] S2, 5 g of HCPIW was placed in a 50 mL high-pressure reaction kettle with stirring device, 30 mL of tetrahydrofuran, 5 g of acetic anhydride, 2 g of Pt / C (10%), and 3.5 g of bromobenzene were added respectively, the reaction kettle was sealed and the air tightness was detected, the air in the reaction kettle was replaced with hydrogen for 5 times, then the hydrogen pressure in the kettle was increased to 1.5 Mpa, the reaction kettle was heated and stirred at 1000 rpm, and the reaction was carried out at 40°C for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered, and the organic phase obtained after dichloromethane extraction was purified by column chromatography (eluent: dichloromethane / methanol, volume ratio: 93:7) to obtain 0.6 g of TADCPIW with a yield of 11.7%.

[0052] Example 4

[0053] Tetraacetyldicyclopropylhexaazaisowurtzitane (TADCPIW) was synthesized as follows:

[0054] S1, a 250 mL three-necked flask containing 17 g of cyclopropylamine, 8 mL of deionized water and 85 mL of methanol was placed in a magnetic stirrer and stirred at a speed of 900 rpm, and cooled to below 10°C in an ice bath, 3.9 g of hydrochloric acid (37 wt.%) was added dropwise to the above mixed solvent at a flow rate of 5 mL / min through a constant pressure dropping funnel, after stirring for 15 minutes, 14.5 g of glyoxal (40 wt.%) was continuously added, after the addition was completed, it was continuously stirred for 0.6 hours, after the white solid was precipitated, it was warmed to 25°C, and the reaction was continued for 20 hours. After the reaction was completed, the reaction mixture was cooled to below 5°C in an ice bath, and then it was suction filtered, and the filter residue was washed with ice deionized water and ice ethanol for 3 times (15 mL / time). Then the filter residue was dried in a vacuum drying oven at 40°C for 12 hours to obtain 11.6 g of HCPIW with a yield of 85.3%.

[0055] S2, take 5 g HCPIW into a 100 mL autoclave with stirring device, add 50 mL ethanol, 10 g acetic anhydride, 4 g Rh / C (10%), 0.5 g 1,1,2-trichloroethane respectively, seal the autoclave and check the airtightness, replace the air in the autoclave with hydrogen gas rapidly for 4 times, then pressurize the autoclave to 6 Mpa with hydrogen gas, heat the autoclave and start stirring at 1100 rpm, react at 60°C for 20 hours. After the reaction is completed, cool the reaction mixture to room temperature, filter, extract with dichloromethane, and then purify the organic phase obtained after extraction with dichloromethane by column chromatography (eluent: dichloromethane / methanol, volume ratio: 93:7) to obtain 0.93 g TADCPIW, with a yield of 18.2%.

[0056] Example 5

[0057] Tetraacetyldicyclopropylhexaazaisowurtzitane (TADCPIW) is specifically synthesized as follows:

[0058] S1, place a 250 mL three-necked flask containing 17.1 g of cyclopropylamine, 10 mL of deionized water and 120 mL of N-methylpyrrolidone in a magnetic stirrer and stir at a speed of 1000 rpm, and cool to below 10°C in an ice bath, add 2.8 g of concentrated nitric acid (68 wt.%) to the above mixed solvent at a flow rate of 7 mL / min through a constant pressure dropping funnel, stir for 15 minutes, then continue to add 19.3 g of glyoxal (30 wt.%), continue to stir for 0.6 hours after the addition is completed, and then warm up to 60°C, continue to react for 15 hours. After the reaction is completed, cool the reaction mixture to below 5°C in an ice bath, then filter it, and wash the filter residue with ice deionized water and ice ethanol for 5 times (15 mL / time). Then dry the filter residue in a vacuum drying oven at 25°C for 16 hours to obtain 10.6 g of HCPIW, with a yield of 78.1%.

[0059] S2, take 5 g HCPIW into a 50 mL autoclave with stirring device, add 25 mL dichloromethane, 12.5 g acetic anhydride, 2.5 g Pd(OH)2 / C (20%), 5 g 1,1,2-trichloroethane respectively, seal the autoclave and check the airtightness, replace the air in the autoclave with hydrogen gas rapidly for 3 times, then pressurize the autoclave to 5 Mpa with hydrogen gas, heat the autoclave and start stirring at 1000 rpm, react at 25°C for 36 hours. After the reaction is completed, cool the reaction mixture to room temperature, filter, extract with dichloromethane, and then purify the organic phase obtained after extraction with dichloromethane by column chromatography (eluent: dichloromethane / methanol, volume ratio: 93:7) to obtain 0.82 g TADCPIW, with a yield of 16.1%.

[0060] Example 6

[0061] Tetraacetyldicyclopropylhexaazaisowurtzitane (TADCPIW) was synthesized as follows:

[0062] S1, A 500 mL three-necked flask containing 22.8 g of cyclopropylamine, 12 mL of deionized water and 180 mL of N,N-dimethylacetamide was placed in a magnetic stirrer and stirred at a speed of 1200 rpm, and cooled to below 10°C in an ice bath. 3.9 g of concentrated sulfuric acid (98%) was added dropwise to the above mixture at a flow rate of 10 mL / min through a constant pressure dropping funnel. After stirring for 15 minutes, 29 g of glyoxal (20 wt.%) was added dropwise, and after the addition was completed, stirring was continued for 0.5 hours. After the appearance of white solid, the temperature was raised to 10°C, and the reaction was continued for 20 hours. After the reaction was completed, the reaction mixture was cooled to below 5°C in an ice bath, and then subjected to suction filtration. The filter residue was washed with ice deionized water and ice ethanol for 5 times (15 mL / time). Then the filter residue was dried in a vacuum drying oven at 40°C for 12 hours to obtain 11.1 g of HCPIW with a yield of 81.7%.

[0063] S2, 5 g of HCPIW was placed in a 100 mL high-pressure reaction kettle with stirring device, 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 were added respectively. The reaction kettle was sealed and the air tightness was detected. The air in the reaction kettle was replaced with hydrogen gas for 5 times, and then the hydrogen gas was pressurized to 4 Mpa. The reaction kettle was heated and stirred at 1000 rpm at 40°C for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered, and the organic phase obtained after dichloromethane extraction was purified by column chromatography (eluent: dichloromethane / methanol, volume ratio: 93:7) to obtain 0.66 g of TADCPIW with a yield of 12.9%.

[0064] Example 7

[0065] Tetraacetyldicyclopropylhexaazaisowurtzitane (TADCPIW) was synthesized as follows:

[0066] S1, A 250 mL three-necked flask containing 8.6 g of cyclopropylamine, 8 mL of deionized water and 80 mL of N,N-dimethylformamide was placed in a magnetic stirrer and stirred at a speed of 900 rpm, and cooled to below 10°C in an ice bath, 4.2 g of hydrobromic acid (48 wt.%) was added dropwise to the above mixed solvent at a flow rate of 10 mL / min through a constant pressure dropping funnel, after stirring for 15 min, 29 g of glyoxal (10 wt.%) was continuously added dropwise, after the dropwise addition was completed, the stirring was continued for 0.5 h, and after the white solid was precipitated, the temperature was raised to 30°C, and the reaction was continued for 18 h. After the reaction was completed, the reaction mixture was cooled to below 5°C in an ice bath, and then it was subjected to suction filtration, and the filter cake was washed with ice deionized water and ice ethanol for 3 times (15 mL / time). Then the filter cake was dried in a vacuum drying oven at 35°C for 10 h to obtain 5.2 g of HCPIW with a yield of 76.5%.

[0067] S2, 5 g of HCPIW was placed in a 150 mL high-pressure reaction kettle with a stirring device, 100 mL of N-methylpyrrolidone, 10 g of acetic anhydride, 2.5 g of Ru / C (10%), and 1.5 g of bromobenzene were added respectively, the reaction kettle was sealed and the air tightness was detected, the air in the reaction kettle was replaced with hydrogen for 5 times, then the hydrogen pressure in the kettle was increased to 0.4 Mpa, the reaction kettle was heated and stirred at 1200 rpm, and the reaction was carried out at 80°C for 32 h. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered, and the organic phase obtained after dichloromethane extraction was purified by column chromatography (eluent: dichloromethane / methanol, volume ratio: 93:7) to obtain 0.75 g of TADCPIW with a yield of 14.7%.

[0068] Example 8

[0069] A one-step method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) from tetraacetyldicyclopentylhexaazaisowurtzitane (TADCPIW) includes the following steps:

[0070] 15 mL of fuming nitric acid was placed in a three-necked flask and stirred at a speed of 1200 rpm, 1 g of TADCPIW was added in batches at 15°C, and the temperature was raised to 90°C while stirring. TLC was used to monitor the reaction, and the reaction was complete after 9 h. The reaction liquid was cooled to 10°C, and then it was slowly poured into ice water for dilution under stirring. The filter cake was washed with distilled water until it was neutral, and then it was dried at 50°C under vacuum to obtain 0.76 g of HNIW with a yield of 72%. 1 H NMR (500 MHz, Acetone- d 6) delta 8.35 (s, 4H), 8.21 (s, 2H); 13C NMR (201 MHz, Acetone- d 6) δ 75.14, 72.19; IR (KBr): nu = 3034, 1604, 1565, 1323,1272, 990, 956, 942, 904, 880, 675 cm -1 ; HRMS (ESI) for C6H6N 12 O 12 (M-H) ﹣ :calcd.437.0155, found 437.0159.

[0071] Example 9

[0072] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) from tetraacetyldicyclopentylhexaazaisowurtzitane (TADCPIW) in one step, comprising the following steps:

[0073] Put 5 mL fuming nitric acid and 10 mL fuming sulfuric acid in a three-necked flask, stirring at 1400 rpm, add 1 g TADCPIW in batches at 10 °C, and continue stirring at 60 °C. Monitor the reaction by TLC, and after 6 h the reaction is complete. Cool the reaction liquid to 10 °C, slowly pour into ice water under stirring for dilution, filter, wash the filter cake with distilled water until neutral, and dry at 50 °C under vacuum to obtain 0.96 g HNIW, with a yield of 91%.

[0074] Example 10

[0075] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) from tetraacetyldicyclopentylhexaazaisowurtzitane (TADCPIW) in one step, comprising the following steps:

[0076] Put 10 mL HNO3 (95%) and 0.5 g N2O4 in a three-necked flask, stirring at 1000 rpm, add 1 g TADCPIW in batches at 20 °C, and continue stirring at 80 °C. Monitor the reaction by TLC, and after 7 h the reaction is complete. Cool the reaction liquid to 10 °C, slowly pour into ice water under stirring for dilution, filter, wash the filter cake with distilled water until neutral, and dry at 50 °C under vacuum to obtain 0.87 g HNIW, with a yield of 83%.

[0077] Example 11

[0078] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) from tetraacetyldicyclopentylhexaazaisowurtzitane (TADCPIW) in one step, comprising the following steps:

[0079] In a three-necked flask, 8 mL of HNO3(95%) and 0.5 g of N2O5 were stirred at 1000 rpm, 1 g of TADCPIW was added in batches at 20°C, and the stirring was continued at 80°C. The reaction was monitored by TLC, and after 6 h, the reaction was complete. The reaction solution was cooled to 10°C, and slowly poured into ice water under stirring for dilution. Filtration was performed, and the filter cake was washed with distilled water until neutral. After drying at 50°C under vacuum, 0.94 g of HNIW was obtained with a yield of 89%.

[0080] Example 12

[0081] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) from tetraacetyldicyclopentadienehexaazaisowurtzitane (TADCPIW) in one step, comprising the following steps:

[0082] In a three-necked flask, 15 mL of HNO3(90%) and 0.6 g of NH4NO3 were stirred at 1200 rpm, 1 g of TADCPIW was added in batches at 30°C, and the stirring was continued at 100°C. The reaction was monitored by TLC, and after 6 h, the reaction was complete. The reaction solution was cooled to 10°C, and slowly poured into ice water under stirring for dilution. Filtration was performed, and the filter cake was washed with distilled water until neutral. After drying at 50°C under vacuum, 0.88 g of HNIW was obtained with a yield of 84%.

[0083] Example 13

[0084] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) from tetraacetyldicyclopentadienehexaazaisowurtzitane (TADCPIW) in one step, comprising the following steps:

[0085] In a three-necked flask, 5 mL of HNO3(90%) and 0.15 g of H3PW 12 O 40 were stirred at 900 rpm, 1 g of TADCPIW was added in batches at 25°C, and the stirring was continued at 80°C. The reaction was monitored by TLC, and after 7 h, the reaction was complete. The reaction solution was cooled to 10°C, and slowly poured into ice water under stirring for dilution. Filtration was performed, and the filter cake was washed with distilled water until neutral. After drying at 50°C under vacuum, 0.91 g of HNIW was obtained with a yield of 86%.

[0086] Example 14

[0087] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) from tetraacetyldicyclopentadienehexaazaisowurtzitane (TADCPIW) in one step, comprising the following steps:

[0088] In a three-necked flask, 10 mL of Ac2O and 1.6 g of fuming nitric acid were stirred at a speed of 1000 rpm, 1 g of TADCPIW was added in batches at 10°C, and the stirring was continued at 70°C. The reaction was monitored by TLC, and after 6 h, the reaction was complete. The reaction solution was cooled to 10°C, and slowly poured into ice water under stirring for dilution. The filter cake was washed with distilled water until neutral, and dried at 50°C under vacuum to obtain 0.89 g of HNIW, with a yield of 85%.

[0089] Example 15

[0090] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) from tetraacetyldicyclopentylhexaazaisowurtzitane (TADCPIW) by one-step method, comprising the following steps:

[0091] In a three-necked flask, 20 mL of fuming sulfuric acid and 1.5 g of KNO3 were stirred at a speed of 1400 rpm, 1 g of TADCPIW was added in batches at 30°C, and the stirring was continued at 60°C. The reaction was monitored by TLC, and after 8 h, the reaction was complete. The reaction solution was cooled to 10°C, and slowly poured into ice water under stirring for dilution. The filter cake was washed with distilled water until neutral, and dried at 50°C under vacuum to obtain 0.74 g of HNIW, with a yield of 70%.

[0092] Compared with the traditional route with complex process, the synthesis of HNIW in the present application simplifies the synthesis route from four steps to three steps from the starting material, reduces the production cost, replaces benzylamine with cyclopropylamine, increases the atomic utilization rate, is more green and environmentally friendly, and has large-scale production potential and application prospect.

[0093] Although the embodiments of the present application have been disclosed as above, they are not limited to the applications listed in the specification and embodiments. They can be fully applied to various fields suitable for the present application. Additional modifications can be easily made by those skilled in the art. Therefore, the present application is not limited to specific details and examples shown and described herein without departing from the general concept defined by the claims and their equivalent scope.

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 ring propylamine and glyoxal are condensed in the solvent one in the presence of the acid catalyst, washed, vacuum dried to obtain the hexacyclopropyl hexaazaisowurtzitane; S2, the hexacyclopropyl hexaazaisowurtzitane obtained in step S1 is subjected to hydrogenolysis and acylation reaction in the presence of hydrogen atmosphere, solvent two, acetic anhydride, metal catalyst and co-catalyst to obtain tetraacetyl dicyclopropyl hexaazaisowurtzitane; 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 and organic solvent is 1: (10-15); 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 is one of bromobenzene, p-bromotoluene and 1, 1, 2-trichloroethane.

3. The process of claim 2 for the preparation of tetraacetyldicyclopropylhexaazaisowurtzitane, characterized in that, In step S1, the molar ratio of glyoxal, ring propylamine 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 three-necked flask containing ring propylamine, deionized water and organic solvent is placed in the magnetic stirrer to stir at a speed of 900-1400 rpm, and the temperature is lowered to below 10 DEG C in ice bath, and the acid catalyst is added dropwise, and after stirring for 15 min, 10-40wt.% glyoxal aqueous solution is continuously added dropwise, and after the addition is completed, the stirring is continued for 0.5-1 h, and after the white solid is precipitated, the temperature is raised to 10-60 DEG C, and the reaction is continued for 15-20 h; After the reaction is completed, the reaction liquid is cooled to below 5 DEG C in ice bath, and is subjected to suction filtration, and the filter residue is washed with ice deionized water and ice ethanol for 3-5 times, and the filter residue is dried in a vacuum drying oven at 25-40 DEG C for 10-16 hours to obtain hexacyclopropyl hexaazaisowurtzitane.

5. The process of claim 2, wherein the process is carried out at a temperature of about 0 °C to about 10 °C. In step S2, the mass ratio of hexacyclopropyl hexaazaisowurtzitane, acetic anhydride, metal component of metal catalyst and co-catalyst is 1: (1-2.5) : (0.02-0.1) : (0.1-1).

6. The process of claim 2 for the preparation of tetraacetyldicyclopropylhexaazaisowurtzitane, characterized in that, The step S2 specifically comprises: placing the hexacyclopropyl hexaazaisowurtzitane obtained in S1 into a high-pressure reaction kettle with a stirring device, adding solvent two, acetic anhydride, a metal catalyst and a cocatalyst 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 with hydrogen, heating the reaction kettle and starting the 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, the organic phase is collected by filtration and extraction, and the organic phase is purified by column chromatography to obtain tetraacetyl dicyclopropyl hexaazaisowurtzitane.

7. A method of synthesizing hexanitrohexaazaisowurtzitane, characterized in that, comprises the following steps: The nitration agent is placed in a three-necked flask and stirred at a speed of 900-1400 rpm, and the tetraacetyldicyclopropylhexaazaisowurtzitane of claim 1 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 solution is reduced to 10℃, and 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 hexanitrohexaazaisowurtzitane; wherein the nitration 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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