Hexaazaisowurtzitane derivatives, processes for their preparation, and processes for the synthesis of hniw

Abstract

The application discloses a hexaazaisowurtzitane derivative and a preparation method and a synthesis method of HNIW, and belongs to the technical field of chemical synthesis.The preparation method of the hexaazaisowurtzitane derivative has the advantages of short reaction steps, simple operation, easily available raw materials and industrial application potential.The hexaazaisowurtzitane derivative can be used to synthesize hexanitrohexaazaisowurtzitane (HNIW) through nitration, so that the synthesis process is simplified and the production cost is reduced; the leaving group cyclopropyl accounts for a small proportion of 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 field of chemical synthesis, in particular to hexaazaisowurtzitane derivatives and a preparation method thereof, and a synthesis method of hexanitrohexaazaisowurtzitane (HNIW). BACKGROUND

[0002] Hexanitrohexaazaisowurtzitane, also known as HNIW, is a new type of high-energy density energetic material, which has a unique three-dimensional cage skeleton structure. It was first reported by Dr. Nielsen from the United States 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). Due to the good oxygen balance and enthalpy of formation of HNIW, as well as the excellent performance in detonation velocity, detonation pressure, density and other properties, it has a wide range of applications in weapon warheads and solid propellants, and its comprehensive performance is better than that of traditional military main explosive octogen (HMX).

[0003] Currently, the industrial production route of HNIW is to use hexabenzylhexaazaisowurtzitane (HBIW) as the precursor, and the main process route is TAIW method (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, TADB is obtained by once hydrogenolysis and acetylation of HBIW; 3, TADB is obtained by twice hydrogenolysis and debenzylization of TADB; 4, HNIW is obtained by nitration of TAIW in a nitro-sulfur mixed acid system. After years of research by scholars in various countries, the process of each step has been fully optimized. However, the process route still has some problems, for example: 1, the process is complex, the production cycle is long, and the nitration precursor is single; 2, the condensation reaction for preparing HBIW has low yield and purity; 3, the atom economy is poor, and only the amino group of benzylamine is an effective group, and the benzyl group accounts for a large proportion of benzylamine; 4, the benzyl group is difficult to be directly nitrated into nitro group, which causes the by-products of incomplete debenzylization in the hydrogenolysis process to seriously affect the yield and purity of HNIW; 5, both hydrogenolysis processes are gas-liquid-solid three-phase reactions and need to use noble metal palladium as catalyst, and the process operation is complex and the cost is high. Therefore, it is of great significance to develop a new method for preparing HNIW by using a new type of hexaazaisowurtzitane derivative as a nitration precursor. SUMMARY

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

[0005] Another object of the present application is to provide a variety of hexaazaisowurtzitane derivatives, which provide a reference for the synthesis research of hexaazaisowurtzitane derivatives.

[0006] Still another object of the present application is to provide a method for preparing hexaazaisowurtzitane derivatives, which has short reaction steps, simple operation, easily available raw materials, small proportion of cyclopropyl as a leaving group in cyclopropylamine raw material, good 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.

[0007] Still another object of the present application is to provide a synthesis method of hexanitrohexaazaisowurtzitane (HNIW), which is synthesized by nitration of hexaazaisowurtzitane derivative in one step, simplifies the synthesis process, reduces the production cost, and provides a research basis and reference value for the process route development of HNIW.

[0008] In order to achieve these objects and other advantages according to the present application, a hexaazaisowurtzitane derivative is provided, which has the following structure:

[0009] , or .

[0010] The object of the present application can be further achieved by a method for preparing hexaazaisowurtzitane derivatives, 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 hexaazaisowurtzitane derivatives.

[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 to 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 warming to 10-60℃, 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, and the filter residue is washed with ice deionized water and ice ethanol for 3-5 times, respectively, and then 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:(0.3-2):(0.01-0.08):(0.1-0.8).

[0017] Preferably, in step S2, the solvent II is one of methanol, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, dichloromethane and cyclohexane; 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 comprises: 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, rapidly replacing the air in the reaction kettle with hydrogen for 3-5 times, then pressurizing the kettle with hydrogen to 0.2-4 Mpa, heating the reaction kettle and starting stirring at 1000-1200 rpm, and reacting at 25-60℃ for 4-15 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 the hexaazaisowurtzitane derivative.

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

[0020] At 0-25℃, the hexaazaisowurtzitane derivative and the nitrating agent are placed in a three-necked flask, the temperature is raised to 35-90℃ and stirring is performed at a speed of 900-1400 rpm; 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, the filter cake is washed to neutral with distilled water, and then vacuum dried at 50℃ to obtain the final product hexanitrohexaazaisowurtzitane.

[0021] Preferably, the nitrating 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 hexaazaisowurtzitane derivative of the present application has not been reported in the literature, which provides a reference for the synthesis research of hexaazaisowurtzitane derivatives, and can be applied to various nitration systems and can be flexibly used to meet different production needs.

[0024] Second, the preparation method of the hexaazaisowurtzitane derivative of the application has short reaction steps, simple operation, and easily available raw materials, and has industrial application potential.

[0025] Third, the hexaazaisowurtzitane derivative of the application can be used to synthesize hexanitrohexaazaisowurtzitane (HNIW) through nitration, which simplifies the synthesis process and reduces the production cost. The cyclopropyl group is easy to be nitrated, and the by-product that is not completely reacted in the hydrogenation process has little effect on the yield and purity of HNIW. The proportion of the leaving group cyclopropyl in the cyclopropylamine raw material is small, the atomic economy is good, the raw material utilization rate is high, the waste discharge is reduced, and the green environmental protection concept of green economy is met.

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

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

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

[0029] Figure 3 Mass spectrum of monoacetyl pentacyclopropylhexaazaisowurtzitane (MAPCPIW) prepared in Example 1 of the application;

[0030] Figure 4 Crystal structure diagram of monoacetyl pentacyclopropylhexaazaisowurtzitane (MAPCPIW) prepared in Example 1 of the application;

[0031] Figure 5 Nuclear magnetic hydrogen spectrum of monoacetyl pentacyclopropylhexaazaisowurtzitane (MAPCPIW) prepared in Example 1 of the application;

[0032] Figure 6 Mass spectrum of diacetyl tetacyclopropylhexaazaisowurtzitane (DAQCPIW) prepared in Example 7 of the application;

[0033] Figure 7 Crystal structure diagram of diacetyl tetacyclopropylhexaazaisowurtzitane (DAQCPIW) prepared in Example 7 of the application;

[0034] Figure 8 Nuclear magnetic hydrogen spectrum of diacetyl tetacyclopropylhexaazaisowurtzitane (DAQCPIW) prepared in Example 7 of the application;

[0035] Figure 9The mass spectra of triacetyltricyclopropylhexaazaisowrutzane (TATCPIW) prepared in Example 10 of this invention;

[0036] Figure 10 This is a crystal structure diagram of triacetyltricyclopropylhexaazaisowrutzane (TATCPIW) prepared in Example 10 of the present invention;

[0037] Figure 11 The 1H NMR spectrum of triacetyltricyclopropylhexaazaisowrutzane (TATCPIW) prepared in Example 10 of this invention. Detailed Implementation

[0038] 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.

[0039] 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.

[0040] 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.

[0041] Example 1

[0042] Acetylpentacyclopropylhexaazaisowrtzine (MAPCPIW) has the following structure:

[0043] .

[0044] The synthesis route is as follows:

[0045]

[0046] The specific synthesis steps are as follows:

[0047] 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 min, 14.5 g of glyoxal (40 wt.%) was added dropwise, after the dropwise addition was completed, the stirring was continued for 1 h, after the white solid was precipitated, the temperature was raised to 35°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 was filtered under suction, and 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 h to obtain 12.3 g of hexacyclopropylhexaazaisowurtzitane (HCPIW), yield: 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).

[0048] S2, 5 g of HCPIW was mixed with 2.5 g of acetic anhydride, 1 g of Pd(OH)2 / Al2O3 (5%), 1 g of bromobenzene and 25 mL of dichloromethane in a 50 mL high-pressure reaction kettle, the reaction kettle was sealed and the air tightness was detected, after the air in the reaction kettle was replaced with hydrogen gas for 3 times, the pressure was increased to 0.2 Mpa, and the stirring was continued at 25°C at a speed of 1000 rpm. The reaction was monitored by TLC, and after 5 h, the reaction was stopped, the reaction mixture was filtered, extracted with dichloromethane, and then the organic phase was subjected to column chromatography (eluent: dichloromethane / methanol, volume ratio: 98:2) to obtain 3.19 g of MAPCPIW, yield: 63.5%.

[0049] The mass spectrum of HCPIW is shown in Figure 1 , the crystal structure diagram of HCPIW is shown in Figure 2 , the mass spectrum of MAPCPIW is shown in Figure 3 , the crystal structure diagram of MAPCPIW is shown in Figure 4 , and the nuclear magnetic hydrogen spectrum of MAPCPIW is shown in Figure 5 .

[0050] Example 2

[0051] Monoacetyl pentacyclopropyl hexaazaisowurtzitane (MAPCPIW) is different from Example 1 in that the specific synthesis steps are as follows:

[0052] S1, a 500 mL three-necked flask containing 22.8 g of cyclopropylamine, 16 mL of deionized water and 160 mL of acetonitrile was placed in a magnetic stirrer and stirred at a speed of 1200 rpm, and cooled to below 10°C in an ice bath, 3.4 g of trifluoroacetic acid 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 added dropwise, after the dropwise addition was completed, the stirring was continued for 1 hour, after the white solid was precipitated, the temperature was raised to 40°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 then filtered under suction, 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 16 hours to obtain 12.1 g of HCPIW, yield: 89%.

[0053] Example 3

[0054] Monoacetyl pentacyclopropyl hexaazaiswuidane (MAPCPIW), the difference between the specific synthesis steps and Example 1 is that:

[0055] 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 dropwise, after the dropwise addition was completed, the stirring was continued for 0.6 hours, after the white solid was precipitated, the temperature was raised 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 filtered under suction, 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 hexacyclopropyl hexaazaiswuidane, yield: 85.3%.

[0056] Example 4

[0057] Monoacetyl pentacyclopropyl hexaazaiswuidane (MAPCPIW), the difference between the specific synthesis steps and Example 1 is that:

[0058] S1, a 250 mL three-necked flask containing 11.5 g of cyclopropylamine, 4 mL of deionized water and 60 mL of DMF 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 g of acetic acid was added 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 added dropwise, and after the addition was completed, the stirring was continued for 0.8 hours, and after the white solid was precipitated, the temperature was raised to 50°C, and the reaction was continued for 16 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 4 times (15 mL / time). Then the filter residue was dried in a vacuum drying oven at 30°C for 14 hours to obtain 11.4 g of hexacyclopropylhexaazaisowurtzitane, yield: 83.9%.

[0059] Example 5

[0060] Monoacetyl pentacyclopropylhexaazaisowurtzitane (MAPCPIW), the difference between the specific synthesis steps and Example 1 is that:

[0061] S2, 5 g of HCPIW was mixed with 4 g of acetic anhydride, 1.5 g of Pd / C (10%), 0.5 g of 1,1,2-trichloroethane and 80 mL of N,N-dimethylformamide in a 150 mL high-pressure reaction kettle, the reaction kettle was sealed and the air tightness was detected, after 4 times of rapid replacement of air in the reaction kettle with hydrogen, the pressure was increased to 0.6 Mpa, and the stirring was continued at 40°C at a speed of 1200 rpm. TLC monitoring of the reaction, after 6 h, the reaction was stopped, the reaction mixture was filtered, extracted with dichloromethane, and the obtained organic phase was subjected to column chromatography (eluent: dichloromethane / methanol, volume ratio: 98:2) to obtain 3.08 g of MAPCPIW, yield: 61.3%.

[0062] Example 6

[0063] Monoacetyl pentacyclopropylhexaazaisowurtzitane (MAPCPIW), the difference between the specific synthesis steps and Example 1 is that:

[0064] S2, 5 g HCPIW was mixed with 1.5 g acetic anhydride, 1 g Pt / C (10%), 1.5 g p- bromotoluene and 100 mL methanol in a 150 mL high-pressure reactor, the reactor was sealed and the air tightness was detected, the reactor was pressurized to 0.8 Mpa after 4 times of rapid replacement of air in the reactor with hydrogen, and the stirring was continued at 1100 rpm and 35℃. TLC monitoring of the reaction, the reaction was stopped after 4 h, the reaction mixture was filtered, extracted with dichloromethane, and the obtained organic phase was column chromatographed (eluent: dichloromethane / methanol, volume ratio: 98:2) to obtain 2.89 g MAPCPIW, yield: 57.5%.

[0065] Example 7

[0066] Diacyl-tetracyclopropylhexaazaisowurtzitane (DAQCPIW) has the structure as shown in the following formula:

[0067] .

[0068] The synthesis route is as follows:

[0069]

[0070] The specific synthesis steps are as follows:

[0071] S1, the same as step S1 in Example 1. S2, 5 g HCPIW was mixed with 5 g acetic anhydride, 1.2 g Pd(OH)2 / C (20%), 2 g 1,1,2-trichloroethane and 80 mL N,N-dimethylacetamide in a 150 mL high-pressure reactor, the reactor was sealed and the air tightness was detected, the reactor was pressurized to 1.5 Mpa after 5 times of rapid replacement of air in the reactor with hydrogen, and the stirring was continued at 1100 rpm and 45℃. TLC monitoring of the reaction, the reaction was stopped after 8 h, the reaction mixture was filtered, extracted with dichloromethane, and the obtained organic phase was column chromatographed (eluent: dichloromethane / methanol, volume ratio: 96:4) to obtain 2.66 g DAQCPIW, yield: 52.7%.

[0072] The mass spectrum of DAQCPIW is shown in Figure 6 , the crystal structure diagram of DAQCPIW is shown in Figure 7 , and the nuclear magnetic hydrogen spectrum of DAQCPIW is shown in Figure 8 .

[0073] Example 8

[0074] Diacyl-tetracyclopropylhexaazaisowurtzitane (DAQCPIW) has the structure as shown in the following formula:

[0075] S2, 5 g HCPIW was mixed with 7 g acetic anhydride, 2 g Rh / C (10%), 2.5 g p- bromotoluene and 50 mL cyclohexane in a 100 mL high-pressure reactor, the reactor was sealed and tested for air tightness, and the air in the reactor was replaced with hydrogen gas for 3 times, then pressurized to 2.5 Mpa, and stirred at 1000 rpm at 50°C. TLC monitoring of the reaction, after 10 h the reaction was stopped, the reaction mixture was filtered, extracted with dichloromethane, and the organic phase obtained was column chromatographed (eluent: dichloromethane / methanol, volume ratio: 96:4) to obtain 2.28 g DAQCPIW, yield: 45.2%.

[0076] Example 9

[0077] Diacyl tetra-cyclopropyl hexa-aza isowurtzitane (DAQCPIW), the specific synthesis steps are different from those of Example 7:

[0078] S2, 5 g HCPIW was mixed with 7 g acetic anhydride, 2 g Rh / C (10%), 2.5 g p- bromotoluene and 50 mL cyclohexane in a 100 mL high-pressure reactor, the reactor was sealed and tested for air tightness, and the air in the reactor was replaced with hydrogen gas for 3 times, then pressurized to 2.5 Mpa, and stirred at 1000 rpm at 50°C. TLC monitoring of the reaction, after 10 h the reaction was stopped, the reaction mixture was filtered, extracted with dichloromethane, and the organic phase obtained was column chromatographed (eluent: dichloromethane / methanol, volume ratio: 96:4) to obtain 2.28 g DAQCPIW, yield: 45.2%.

[0079] Example 10

[0080] Triacetyl tri-cyclopropyl hexa-aza isowurtzitane (TATCPIW) has the following structure:

[0081] .

[0082] The synthesis route is as follows:

[0083]

[0084] The specific synthesis steps are as follows:

[0085] S1, same as step S1 in example 1. S2, 5 g HCPIW was mixed with 10 g acetic anhydride, 3 g Ru / C (10%), 4 g p-bromotoluene and 80 mL N-methylpyrrolidone in a 150 mL high-pressure reactor, the reactor was sealed and tested for air tightness, and then pressurized to 4 MPa after the air in the reactor was replaced with hydrogen gas for 5 times. The reaction was carried out at 60°C with continuous stirring at 1200 rpm. TLC was used to monitor the reaction, and the reaction was stopped after 15 h. The reaction mixture was filtered and extracted with dichloromethane, and then the organic phase obtained was subjected to column chromatography (eluent: dichloromethane / methanol, volume ratio: 94:6) to obtain 1.67 g TATCPIW, yield: 32.9%.

[0086] The mass spectrum of TATCPIW is shown in Figure 9 The crystal structure of TATCPIW is shown in Figure 10 The nuclear magnetic hydrogen spectrum of TATCPIW is shown in Figure 11 .

[0087] Example 11

[0088] Triacetyltricyclopropylhexaazaisowurtzitane (TATCPIW) has the following specific synthesis steps, which are different from those of example 10:

[0089] S2, 5 g HCPIW was mixed with 8 g acetic anhydride, 2 g Pd(OH)2 / C (20%), 3 g 1,1,2-trichloroethane and 50 mL tetrahydrofuran in a 100 mL high-pressure reactor, the reactor was sealed and tested for air tightness, and then pressurized to 3 MPa after the air in the reactor was replaced with hydrogen gas for 3 times. The reaction was carried out at 55°C with continuous stirring at 1000 rpm. TLC was used to monitor the reaction, and the reaction was stopped after 12 h. The reaction mixture was filtered and extracted with dichloromethane, and then the organic phase obtained was subjected to column chromatography (eluent: dichloromethane / methanol, volume ratio: 94:6) to obtain 1.88 g TATCPIW, yield: 37.1%.

[0090] Example 12

[0091] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) has the following synthesis route:

[0092]

[0093] The specific synthesis steps are as follows:

[0094] To a three-necked flask, 5 mL fuming nitric acid and 5 mL fuming sulfuric acid were stirred at 1000 rpm, 1 g MAPCPIW was added portionwise at 0 °C, and the temperature was raised to 35 °C while stirring. The reaction was monitored by TLC, and after 3 h the reaction was complete. The reaction was cooled to 10 °C, and slowly poured into ice water with stirring. The solid was filtered, washed with distilled water until neutral, and dried at 50 °C under vacuum to give 0.51 g HNIW, yield: 47.7%. 1 H NMR (500 MHz, Acetone- d 6) delta 8.35 (s, 4H), 8.21 (s,2H); 13 C 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.

[0095] Example 13

[0096] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) differs from that of Example 12 in the specific synthesis steps:

[0097] To a three-necked flask, 5 mL fuming nitric acid and 5 mL fuming sulfuric acid were stirred at 1000 rpm, 1 g MAPCPIW was added portionwise at 0 °C, and the temperature was raised to 35 °C while stirring. The reaction was monitored by TLC, and after 3 h the reaction was complete. The reaction was cooled to 10 °C, and slowly poured into ice water with stirring. The solid was filtered, washed with distilled water until neutral, and dried at 50 °C under vacuum to give 0.51 g HNIW, yield: 47.7%.

[0098] Example 14

[0099] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) differs from that of Example 12 in the specific synthesis steps:

[0100] Put 15 mL Ac2O and 2.5 g fuming nitric acid in a three-necked flask, stirring at 1400 rpm, add 1 g MAPCPIW in batches at 10°C, and continue stirring while warming to 55°C. Monitor the reaction by TLC, and after 3 h the reaction is complete. Cool the reaction liquid to 10°C, slowly pour into ice water under stirring, dilute, filter, wash the filter cake with distilled water until neutral, and dry at 50°C under vacuum to obtain 0.48 g HNIW, yield: 44.9%.

[0101] Example 15

[0102] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) has the following synthetic route:

[0103]

[0104] The specific synthesis steps are as follows:

[0105] Put 5 mL HNO3 (90%) and 0.2 g H3PW 12 O 40 in a three-necked flask, stirring at 900 rpm, add 1 g DAQCPIW in batches at 15°C, and continue stirring while warming to 70°C. Monitor the reaction by TLC, and after 5 h the reaction is complete. Cool the reaction liquid to 10°C, slowly pour into ice water under stirring, dilute, filter, wash the filter cake with distilled water until neutral, and dry at 50°C under vacuum to obtain 0.68 g HNIW, yield: 63.9%.

[0106] Example 16

[0107] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) has the following synthetic route:

[0108] Put 15 mL HNO3 (95%) and 1 g N2O4 in a three-necked flask, stirring at 1100 rpm, add 1 g DAQCPIW in batches at 20°C, and continue stirring while warming to 65°C. Monitor the reaction by TLC, and after 5 h the reaction is complete. Cool the reaction liquid to 10°C, slowly pour into ice water under stirring, dilute, filter, wash the filter cake with distilled water until neutral, and dry at 50°C under vacuum to obtain 0.66 g HNIW, yield: 62.1%.

[0109] Example 17

[0110] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW) has the following synthetic route:

[0111] Put 10 mL HNO3 (95%) and 0.5 g N2O5 in a three-necked flask, stirring at 1000 rpm, add 1 g DAQCPIW in batches at 15℃, and continue stirring at 65℃. Monitor the reaction by TLC, and after 4 h, the reaction is complete. Cool the reaction liquid to 10℃, slowly pour into ice water under stirring, dilute, filter, wash the filter cake with distilled water until neutral, and dry at 50℃ under vacuum to obtain 0.71 g HNIW, yield: 66.8%.

[0112] Example 18

[0113] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW), the synthesis route of which is as follows:

[0114]

[0115] The specific synthesis steps are as follows:

[0116] Put 15 mL fuming nitric acid in a three-necked flask, stirring at 1200 rpm, add 1 g TATCPIW in batches at 25℃, and continue stirring at 80℃. Monitor the reaction by TLC, and after 6 h, the reaction is complete. Cool the reaction liquid to 10℃, slowly pour into ice water under stirring, dilute, filter, wash the filter cake with distilled water until neutral, and dry at 50℃ under vacuum to obtain 0.74 g HNIW, yield: 69.9%.

[0117] Example 19

[0118] A method for synthesizing hexanitrohexaazaisowurtzitane (HNIW), the specific synthesis steps of which are different from those of Example 18.

[0119] Put 10 mL HNO3 (90%) and 0.5 g NH4NO3 in a three-necked flask, stirring at 1000 rpm, add 1 g TATCPIW in batches at 25℃, and continue stirring at 90℃. Monitor the reaction by TLC, and after 6 h, the reaction is complete. Cool the reaction liquid to 10℃, slowly pour into ice water under stirring, dilute, filter, wash the filter cake with distilled water until neutral, and dry at 50℃ under vacuum to obtain 0.83 g HNIW, yield: 78.5%.

[0120] Compared with the traditional route with complex processes, the synthesis of hexanitrohexaazaisowurtzitane (HNIW) in the present application is simplified from four-step process to three-step process from the starting material, which reduces the production cost, and uses cyclopropylamine instead of benzylamine, increases the atomic utilization rate, is more green and environmentally friendly, and has large-scale production potential and application prospect.

[0121] While embodiments of the application have been disclosed in connection with the above specification, it will be apparent to those skilled in the art that numerous modifications can be made thereto without departing from the scope of the application as set forth in the claims and equivalents thereof. Accordingly, it is intended that all such modifications come within the scope of the claims and equivalents thereof.

Claims

1. A hexaazaisowrtzane derivative, characterized in that, It has the following structure: , or .

2. A method for preparing the hexaazaisowrtzane derivative as described in claim 1, characterized in that, 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 acetylation in a hydrogen atmosphere in the presence of solvent II, acetic anhydride, metal catalyst and co-catalyst to obtain hexaazaisowrutzane derivatives. The acid catalyst is one of acetic acid, hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, hydrobromic acid, and trifluoroacetic acid. Solvent 1 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; in Solvent 1, the volume ratio of deionized water to organic solvent is 1:(10-15). Solvent 2 is one of methanol, ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, dichloromethane, and cyclohexane; 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 method for preparing hexaazaisowrtzane derivatives as described in claim 2, 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 method for preparing hexaazaisowrtzane derivatives as described in claim 2, characterized in that, Step S1 specifically includes: placing a three-necked flask containing cyclopropylamine, deionized water, and 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 white solid precipitates out, 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.

5. The method for preparing hexaazaisowrtzane derivatives as described in claim 2, characterized in that, In step S2, the mass ratio of hexacyclopropylhexaazaisowulzane, acetic anhydride, the metal component in the metal catalyst, and the co-catalyst is 1:(0.3-2):(0.01-0.08):(0.1-0.8).

6. The method for preparing hexaazaisowrtzane derivatives as described in claim 2, characterized in that, Step S2 specifically includes: placing the hexacyclopropylhexaazaisowrtzane obtained in S1 into a high-pressure reactor equipped with a stirrer, adding solvent 2, acetic anhydride, metal catalyst, and co-catalyst respectively, sealing the reactor and checking its airtightness, rapidly replacing the air in the reactor with hydrogen 3-5 times, then pressurizing the reactor with hydrogen to 0.2-4 MPa, heating the reactor and starting stirring at 1000-1200 rpm, reacting at 25-60℃ for 4-15 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 the hexaazaisowrtzane derivative.

7. A method for synthesizing hexanitrohexaazaisowulzane, characterized in that, Includes the following steps: At 0-25°C, the hexaazaisowrtzane derivative of claim 1 and the nitrating agent are placed in a three-necked flask, heated to 35-90°C and stirred at 900-1400 rpm; the reaction is monitored by TLC. After the reaction is complete, the reaction solution is cooled to 10°C, slowly poured into ice water for dilution while stirring, filtered, and the filter cake is washed with distilled water until neutral, and then dried under vacuum at 50°C to obtain the final product hexanitrohexaazaisowrtzane; wherein the nitrating agent is HNO3, H2SO4 / HNO3, N2O4 / HNO3, N2O5 / HNO3, NH4NO3 / HNO3, or H3PW. 12 O 40 One of / HNO3, AC2O / HNO3, and KNO3 / H2SO4.

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