Hexaazaisowurtzitane derivative, preparation method thereof and synthesis method of HNIW (hexaazaisowurtzitane)
By combining the condensation reaction of cyclopropylamine with glyoxal and hydrogenolysis acylation with a one-step nitration method, the problems of complex and high cost in HNIW synthesis have been solved, achieving efficient and environmentally friendly HNIW production.
Patent Information
- Application Number
- CN202511822787.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-05
- Publication Date
- 2026-01-02
- Estimated Expiration
- 2045-12-05
AI Technical Summary
Existing HNIW synthesis processes are complex, have long production cycles, low yields and purity, poor atom economy, and high costs, and the byproducts have a significant impact during hydrogenolysis.
The hexanitrohexaazaisowulzane was prepared by condensation reaction of cyclopropylamine and glyoxal, followed by hydrogenolysis and acylation in a hydrogen atmosphere, and finally nitration. This process simplifies the steps and reduces the cost.
It simplifies the synthesis process, improves raw material utilization, reduces waste emissions, lowers production costs, and increases the yield and purity of HNIW, which aligns with the concept of a green economy.
Smart Images
Figure CN121248615A_ABST
Abstract
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] 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 materials, 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: , or .
[0009] The object of the present application can be further achieved by a method for preparing hexaazaisowurtzitane derivatives, comprising the following steps: S1, condensation reaction of cyclopropylamine and glyoxal in the presence of an acid catalyst in a solvent 1, washing, vacuum drying to obtain hexacyclopropylhexaazaisowurtzitane; S2, hydrogenolysis and acylation reaction of hexacyclopropylhexaazaisowurtzitane obtained in step S1 in the presence of hydrogen atmosphere, a solvent 2, acetic anhydride, a metal catalyst and a co-catalyst to obtain hexaazaisowurtzitane derivatives.
[0010] Preferably, in step S1, the molar ratio of glyoxal, cyclopropylamine and acid catalyst is 1:(2-5):(0.2-0.5).
[0011] 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 1 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 1, the volume ratio of deionized water to organic solvent is 1:(10-15).
[0012] Preferably, in step S1, the method 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, and then dried in a vacuum drying oven at 25-40℃ for 10-16 hours to obtain hexacyclopropylhexaazaisowurtzitane.
[0013] Preferably, in step S2, the mass ratio of hexacyclopropylhexaazaisowurtzitane, acetic anhydride, metal component of the metal catalyst and co-catalyst is 1:(0.3-2):(0.01-0.08):(0.1-0.8).
[0014] 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.
[0015] 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, 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.
[0016] The purpose of the present application can be further achieved by a method for synthesizing hexanitrohexaazaisowurtzitane, which comprises the following steps: 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, filtration is performed, the filter cake is washed with distilled water until neutral, and vacuum drying is performed at 50℃ to obtain the final product hexanitrohexaazaisowurtzitane.
[0017] 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.
[0018] The present application at least includes the following beneficial effects: 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.
[0019] Secondly, the preparation method of the hexaazaisowurtzitane derivative of the present application has short reaction steps, simple operation and easily available raw materials, and has potential for industrial application.
[0020] Thirdly, the hexaazaisowurtzitane derivative of the present 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, the by-product which 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 environmental protection concept of green economy is met.
[0021] Other advantages, objects, and features of the present application will be apparent from the following description, and will be understood by persons skilled in the art. BRIEF DESCRIPTION OF DRAWINGS
[0022] Figure 1 Mass spectrum of hexacyclopropylhexaazaisowurtzitane prepared in Example 1 of the present application; Figure 2 Crystal structure diagram of hexacyclopropylhexaazaisowurtzitane prepared in Example 1 of the present application; Figure 3 Mass spectrum of monoacetylpentacyclopropylhexaazaisowurtzitane (MAPCPIW) prepared in Example 1 of the present application; Figure 4 Crystal structure diagram of monoacetylpentacyclopropylhexaazaisowurtzitane (MAPCPIW) prepared in Example 1 of the present application; Figure 5 Nuclear magnetic hydrogen spectrum of monoacetylpentacyclopropylhexaazaisowurtzitane (MAPCPIW) prepared in Example 1 of the present application; Figure 6 Mass spectrum of diacetyltetracyclopropylhexaazaisowurtzitane (DAQCPIW) prepared in Example 7 of the present application; Figure 7 Crystal structure diagram of diacetyltetracyclopropylhexaazaisowurtzitane (DAQCPIW) prepared in Example 7 of the present application; Figure 8 Nuclear magnetic hydrogen spectrum of diacetyltetracyclopropylhexaazaisowurtzitane (DAQCPIW) prepared in Example 7 of the present application; Figure 9 Mass spectrum of triacetyltetracyclopropylhexaazaisowurtzitane (TATCPIW) prepared in Example 10 of the present application; Figure 10 Crystal structure diagram of triacetyltetracyclopropylhexaazaisowurtzitane (TATCPIW) prepared in Example 10 of the present application; Figure 11 Nuclear magnetic hydrogen spectrum of triacetyltetracyclopropylhexaazaisowurtzitane (TATCPIW) prepared in Example 10 of the present application. Detailed Implementation
[0023] 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.
[0024] 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.
[0025] 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.
[0026] Example 1 Acetylpentacyclopropylhexaazaisowrtzine (MAPCPIW) has the following structure: .
[0027] 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. After the addition was complete, stirring was continued for 1 hour. After 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 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 30°C for 14 hours to obtain 12.3 g hexacyclopropylhexaazaisowrtzane (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). S2. 5 g HCPIW was mixed with 2.5 g acetic anhydride, 1 g Pd(OH)2 / Al2O3 (5%), 1 g bromobenzene, and 25 mL dichloromethane in a 50 mL high-pressure reactor. The reactor was sealed and its airtightness was checked. Hydrogen was introduced to rapidly replace the air in the reactor three times, and the pressure was increased to 0.2 MPa. The reactor was stirred continuously at 1000 rpm at 25 °C. The reaction was monitored by TLC. After 5 h, the reaction was stopped. The reaction mixture was filtered, extracted with dichloromethane, and the resulting organic phase was subjected to column chromatography (eluent: dichloromethane / methanol, volume ratio: 98:2) to obtain 3.19 g MAPCPIW, yield: 63.5%.
[0028] 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 spectra of MAPCPIW are as follows. Figure 3 As shown, the crystal structure diagram of MAPCPIW is as follows. Figure 4 As shown, the 1H NMR spectrum of MAPCPIW is as follows: Figure 5 As shown.
[0029] Example 2 The specific synthesis steps of monoacetylpentacyclopropylhexaazaisowrutzane (MAPCPIW) differ from those in Example 1 in that: S1. A 500 mL three-necked flask containing 22.8 g cyclopropylamine, 16 mL deionized water, and 160 mL acetonitrile 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 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 16 hours to obtain 12.1 g HCPIW, yield: 89%.
[0030] Example 3 The specific synthesis steps of monoacetylpentacyclopropylhexaazaisowrutzane (MAPCPIW) differ from those in Example 1 in that: 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 hexacyclopropylhexaazaisowrtzane, yield: 85.3%.
[0031] Example 4 The specific synthesis steps of monoacetylpentacyclopropylhexaazaisowrutzane (MAPCPIW) differ from those in Example 1 in that: S1. A 250 mL three-necked flask containing 11.5 g cyclopropylamine, 4 mL deionized water, and 60 mL DMF 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 residue was washed four 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 11.4 g hexacyclopropylhexaazaisowulzane, yield: 83.9%.
[0032] Example 5 The specific synthesis steps of monoacetylpentacyclopropylhexaazaisowrutzane (MAPCPIW) differ from those in Example 1 in that: S2. 5 g HCPIW was mixed with 4 g acetic anhydride, 1.5 g Pd / C (10%), 0.5 g 1,1,2-trichloroethane, and 80 mL N,N-dimethylformamide in a 150 mL high-pressure reactor. The reactor was sealed and its airtightness was checked. Hydrogen was introduced to rapidly replace the air in the reactor four times, and the pressure was increased to 0.6 MPa. The reactor was stirred continuously at 1200 rpm at 40 °C. The reaction was monitored by TLC. After 6 h, the reaction was stopped. The reaction mixture was filtered, extracted with dichloromethane, and the resulting organic phase was subjected to column chromatography (eluent: dichloromethane / methanol, volume ratio: 98:2) to obtain 3.08 g MAPCPIW, yield: 61.3%.
[0033] Example 6 The specific synthesis steps of monoacetylpentacyclopropylhexaazaisowrutzane (MAPCPIW) differ from those in Example 1 in that: S2. Mix 5 g HCPIW 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. Seal the reactor and check its airtightness. Purge the air in the reactor with hydrogen gas four times, then pressurize to 0.8 MPa and stir continuously at 1100 rpm at 35 °C. Monitor the reaction by TLC. Stop the reaction after 4 h. Filter the reaction mixture, extract with dichloromethane, and then perform column chromatography (eluent: dichloromethane / methanol, volume ratio: 98:2) to obtain 2.89 g MAPCPIW, yield: 57.5%.
[0034] Example 7 Diacetyltetracyclopropylhexaazaisowrutzane (DAQCPIW) has the following structure: .
[0035] The synthesis route is as follows: The specific synthesis steps are as follows: S1. Same as step S1 in Example 1. S2. Take 5 g HCPIW, 5 g acetic anhydride, 1.2 g Pd(OH)2 / C (20%), 2 g 1,1,2-trichloroethane, and 80 mL N,N-dimethylacetamide, and mix them in a 150 mL high-pressure reactor. Seal the reactor and check its airtightness. Purge the air in the reactor with hydrogen five times to rapidly replace it, then pressurize to 1.5 MPa. Stir continuously at 1100 rpm at 45°C. Monitor the reaction by TLC. Stop the reaction after 8 h. Filter the reaction mixture, extract with dichloromethane, and then perform column chromatography (eluent: dichloromethane / methanol, volume ratio: 96:4) to obtain 2.66 g DAQCPIW, yield: 52.7%.
[0036] Among them, the mass spectrometry of DAQCPIW is as follows: Figure 6 As shown, the crystal structure diagram of DAQCPIW is as follows. Figure 7 As shown, the 1H NMR spectrum of DAQCPIW is as follows: Figure 8 As shown.
[0037] Example 8 The specific synthesis steps of diacetyltetracyclopropylhexaazaisowrtzine (DAQCPIW) differ from those in Example 7 in that: 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 its airtightness was checked. Hydrogen was introduced to rapidly replace the air in the reactor three times, and the pressure was increased to 2.5 MPa. The mixture was stirred continuously at 1000 rpm at 50 °C. The reaction was monitored by TLC. After 10 h, the reaction was stopped. The reaction mixture was filtered, extracted with dichloromethane, and the resulting organic phase was subjected to column chromatography (eluent: dichloromethane / methanol, volume ratio: 96:4) to obtain 2.28 g DAQCPIW, yield: 45.2%.
[0038] Example 9 The specific synthesis steps of diacetyltetracyclopropylhexaazaisowrtzine (DAQCPIW) differ from those in Example 7 in that: S2. 5 g HCPIW was mixed with 6 g acetic anhydride, 2 g Pd / Al2O3 (10%), 2 g bromobenzene, and 90 mL ethanol in a 150 mL high-pressure reactor. The reactor was sealed and its airtightness was checked. Hydrogen was introduced to rapidly replace the air in the reactor four times, and the pressure was increased to 2 MPa. The reactor was stirred continuously at 1200 rpm at 45 °C. The reaction was monitored by TLC. After 10 h, the reaction was stopped. The reaction mixture was filtered, extracted with dichloromethane, and the resulting organic phase was subjected to column chromatography (eluent: dichloromethane / methanol, volume ratio: 96:4) to obtain 2.41 g DAQCPIW, yield: 47.7%.
[0039] Example 10 Triacetyltricyclopropylhexaazaisowrtzine (TATCPIW) has the following structure: .
[0040] The synthesis route is as follows: The specific synthesis steps are as follows: S1. Same as step S1 in Example 1. S2. Mix 5 g HCPIW 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. Seal the reactor and check its airtightness. Purge the air in the reactor with hydrogen five times to rapidly replace it, then pressurize to 4 MPa. Stir continuously at 1200 rpm at 60°C. Monitor the reaction by TLC. Stop the reaction after 15 h. Filter the reaction mixture, extract with dichloromethane, and then perform column chromatography (eluent: dichloromethane / methanol, volume ratio: 94:6) to obtain 1.67 g TATCPIW, yield: 32.9%.
[0041] Among them, the mass spectrometry of TATCPIW is as follows: Figure 9 As shown, the crystal structure diagram of TATCPIW is as follows. Figure 10 As shown, the 1H NMR spectrum of TATCPIW is as follows: Figure 11 As shown.
[0042] Example 11 The specific synthesis steps of triacetyltricyclopropylhexaazaisowrutzane (TATCPIW) differ from those in Example 10 in that: 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 its airtightness was checked. Hydrogen was introduced to rapidly replace the air in the reactor three times, and the pressure was increased to 3 MPa. The reactor was stirred continuously at 1000 rpm at 55 °C. The reaction was monitored by TLC. After 12 h, the reaction was stopped. The reaction mixture was filtered, extracted with dichloromethane, and the resulting organic phase was subjected to column chromatography (eluent: dichloromethane / methanol, volume ratio: 94:6) to give 1.88 g TATCPIW, yield: 37.1%.
[0043] Example 12 A method for synthesizing hexanitrohexaazaisowrtzane (HNIW) is described below: The specific synthesis steps are as follows: 5 mL of fuming nitric acid and 5 mL of fuming sulfuric acid were placed in a three-necked flask and stirred at 1000 rpm. 1 g of MAPCPIW was added in portions at 0 °C, and the temperature was raised to 35 °C with continuous stirring. The reaction was monitored by TLC. After 3 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 0.51 g of 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 (MH) ﹣ :calcd. 437.0155, found 437.0159. Example 13 A method for synthesizing hexanitrohexaazaisowrtzane (HNIW) differs from that in Example 12 in the following specific synthetic steps: 15 mL of fuming sulfuric acid and 1 g of KNO3 were placed in a three-necked flask and stirred at 1200 rpm. 1 g of MAPCPIW was added in portions at 10 °C, and the temperature was raised to 45 °C with continuous stirring. The reaction was monitored by TLC. After 4 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 0.42 g of HNIW, yield: 39.3%.
[0044] Example 14 A method for synthesizing hexanitrohexaazaisowrtzane (HNIW) differs from that in Example 12 in the following specific synthetic steps: 15 mL of Ac₂O and 2.5 g of fuming nitric acid were placed in a three-necked flask and stirred at 1400 rpm. 1 g of MAPCPIW was added in portions at 10 °C, and the temperature was raised to 55 °C with continuous stirring. The reaction was monitored by TLC. After 3 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 0.48 g of HNIW, yield: 44.9%.
[0045] Example 15 A method for synthesizing hexanitrohexaazaisowrtzane (HNIW) is described below: The specific synthesis steps are as follows: Mix 5 mL of HNO3 (90%) with 0.2 g of H3PW 12 O 40 The mixture was placed in a three-necked flask and stirred at 900 rpm. 1 g of DAQCPIW was added in portions at 15°C, and the temperature was raised to 70°C with continued stirring. The reaction was monitored by TLC. After 5 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 0.68 g of HNIW, yield: 63.9%.
[0046] Example 16 A method for synthesizing hexanitrohexaazaisowrutzane (HNIW) differs from that in Example 15 in the following specific synthetic steps: 15 mL of 95% HNO3 and 1 g of N2O4 were placed in a three-necked flask and stirred at 1100 rpm. 1 g of DAQCPIW was added in portions at 20 °C, and the temperature was raised to 65 °C with continuous stirring. The reaction was monitored by TLC. After 5 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 0.66 g of HNIW, yield: 62.1%.
[0047] Example 17 A method for synthesizing hexanitrohexaazaisowrutzane (HNIW) differs from that in Example 15 in the following specific synthetic steps: 10 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 DAQCPIW was added in portions at 15°C, and the temperature was raised to 65°C with continuous stirring. The reaction was monitored by TLC. After 4 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 0.71 g of HNIW, yield: 66.8%.
[0048] Example 18 A method for synthesizing hexanitrohexaazaisowrtzane (HNIW) is described below: The specific synthesis steps are as follows: 15 mL of fuming nitric acid was placed in a three-necked flask and stirred at 1200 rpm. 1 g of TATCPIW was added in portions at 25 °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 0.74 g of HNIW, yield: 69.9%.
[0049] Example 19 A method for synthesizing hexanitrohexaazaisowrutzane (HNIW) differs from that in Example 18 in the following specific synthetic steps: 10 mL of 90% HNO3 and 0.5 g of NH4NO3 were placed in a three-necked flask and stirred at 1000 rpm. 1 g of TATCPIW was added in portions at 25°C, and the temperature was raised to 90°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 0.83 g of HNIW, yield: 78.5%.
[0050] Compared with the traditional route with complex processes, the synthesis of hexanitrohexaazaisowrutzane (HNIW) in this invention simplifies the process from four steps to three steps, 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.
[0051] 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. 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 hexacyclopropylhexaazaisowrtzane obtained in step S1 is subjected to hydrogenolysis and acetylation reactions in a hydrogen atmosphere in the presence of solvent II, acetic anhydride, a metal catalyst and a co-catalyst to obtain the hexaazaisowrtzane derivative.
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, 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, and the organic solvent is one of methanol, ethanol, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and N,N-diethylformamide; in solvent one, the volume ratio of deionized water to organic solvent is 1:(10-15).
5. The method for preparing hexaazaisowrtzane derivatives as described in claim 4, 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.
6. 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).
7. The method for preparing hexaazaisowrtzane derivatives as described in claim 2, characterized in that, In step S2, solvent two 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.
8. 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.
9. A method for synthesizing hexanitrohexaazaisowulzane, characterized in that, Includes the following steps: At 0-25°C, the hexaazaisowrtzane derivative and nitrating agent were placed in a three-necked flask, heated to 35-90°C and stirred at 900-1400 rpm; 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 for dilution while stirring. The solution was filtered, and the filter cake was washed with distilled water until neutral and then dried under vacuum at 50°C to obtain the final product hexanitrohexaazaisowrtzane.
10. The method for synthesizing hexanitrohexaazaisowulzane as described in claim 9, characterized in that, The nitrating agents are HNO3, H2SO4 / HNO3, N2O4 / HNO3, N2O5 / HNO3, NH4NO3 / HNO3, and H3PW. 12 O 40 One of / HNO3, AC2O / HNO3, KNO3 / H2SO4.
Citation Information
Patent Citations
Method for synthesis of hexanitrohexaazaisowurtsitane
IN202311030463A
Catalitic synthesis of caged polynitramine compounds
US8017768B1