Synthetic 1, 5-diazabicyclo [3.1. 0] hexane compound as well as preparation method and application thereof

Abstract

The invention provides a synthesized 1, 5-diazabicyclo [3.1. 0] hexane compound as well as a preparation method and application thereof, and belongs to the technical field of organic synthesis and liquid propellants. The preparation method comprises the following steps: dispersing 1, 3-propane diamine in a proper amount of a chlorinated hydrocarbon solvent, sequentially adding corresponding aldehyde or ketone, a proper amount of trifluoromethane sulfonate and diisopropylethylamine, after half an hour, slowly adding N-chlorosuccinimide, continuously reacting for 6-48 hours, adding a proper amount of water for quenching reaction, extracting by using dichloromethane, concentrating filtrate, and performing column chromatography to obtain the corresponding 1, 3-propane diamine. The invention relates to a 1, 5-diazabicyclo [3.1. 0] hexane compound. Tests prove that the 1, 5-diazabicyclo [3.1. 0] hexane compound can be rapidly and spontaneously ignited with fuming nitric acid and dinitrogen tetroxide, and can be used as a green fuel for replacing methylhydrazine to show a good application prospect in the field of two-component liquid propellants.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis and liquid propellant, and in particular relates to a synthetic 1,5-diazabicyclo[3.1.0]hexane compound, a preparation method and an application thereof. Background Art

[0002] Hypergolic liquid propellants achieve spontaneous ignition through direct contact between fuel and oxidizer. They do not require external auxiliary facilities such as ignition devices and catalysts, thereby greatly reducing the weight and volume of the power system. They have the advantages of high specific impulse, long life, multiple starts, and precise and adjustable thrust. They are widely used in the main power and attitude and orbit control systems of launch vehicles, satellites, spacecraft and equipment. The fuels used in traditional hypergolic liquid propellants are mainly hydrazine compounds such as methylhydrazine and unsymmetrical dimethylhydrazine, which are extremely toxic and carcinogenic, flammable and explosive, and increase the safety risks and use costs of fuel storage and refueling. Therefore, the development of green hypergolic fuels has become a hot topic in the field of advanced aerospace power research.

[0003] The Scheneider team at the U.S. Air Force Laboratory reported for the first time that dicyandiamide ionic liquids can undergo a self-ignition reaction with fuming nitric acid, opening up the research precedent for ionic liquids as self-igniting propellants and green fuels (Energy & Fuels, 2008, 22, 2871-2872). Subsequently, more than ten units or teams quickly followed up, including Professor Shreeve, senior advisor to the US Department of Defense (Chemical Reviews, 2014, 114, 10527-10574; Journal of Materials Chemistry, 2012, 22, 11022-11024), Professor Rogers, winner of the US Green Chemistry Presidential Challenge Award (Inorganic Chemistry, 2014, 53, 4770-4776), Professor Zhang Yanqiang of the Institute of Process Engineering of the Chinese Academy of Sciences (Angewandte Chemie International Edition, 2011, 50, 9554-9562), China Academy of Engineering Physics, Beijing Institute of Technology, etc., designed and synthesized a large number of self-igniting ionic liquid fuels, and carried out physical and chemical characterization and combustion performance research. Patent CN201811608166.6 reports a self-igniting N-alkyltriazole dicyanoborane complex and its preparation method: first, 1,2,4-triazole and a halogenated hydrocarbon compound are reacted through N-alkylation, and then coordinated with sodium cyanoborohydride through N-boration to form a target product; it has a short ignition delay time with fuming nitric acid. Patent CN202210035348.9 relates to a method for preparing a self-igniting ionic liquid containing bis(1,2,3-triazole) borohydride anion, using 1,2,3-triazole as a raw material, reacting with borohydride metal salt to prepare bis(1,2,3-triazole) borohydride metal salt, and then exchanging with the ionic liquid to obtain the target product, and its ignition delay time with fuming nitric acid is 25-130ms. Patent CN201811608166.6 involves a multi-substituted azine compound or rocket kerosene added with such a compound, which can form spontaneous combustion when in contact with oxidants such as nitrogen tetroxide and nitric acid, and can be used as a green self-igniting fuel for bicomponent liquid propellants. These fuels are mainly boron-containing and azole-containing ionic liquids, and very few molecular fuels are involved.

[0004] 1,5-diazabicyclo[3.1.0]hexane molecules have a highly strained ring structure and have received extensive attention in the research of energetic materials and high-energy fuels; however, publicly reported synthesis methods are extremely limited. Punniyamurthy, Guha, Trushkov et al. reported a method for synthesizing 1,5-diazabicyclo[3.1.0]hexane compounds using tert-butyl hypochlorite as a chlorinating agent (Chemical Communications 2024, 60, 3441-3444; Journal of Organic Chemistry 2023, 88, 9447-9458; European Journal of Organic Chemistry 2019, 5475-5485). Tert-butyl hypochlorite is a strong oxidant that is easily decomposed and exploded and is difficult to transport (stored at -20°C); whether it is for laboratory research or as an industrial raw material, most of them are self-produced. These factors greatly limit the synthesis and application of 1,5-diazabicyclo[3.1.0]hexane compounds. The Beijing Aerospace Experimental Technology Research Institute uses a saturated sodium hypochlorite solution method to prepare 1,5-diazabicyclo[3.1.0]hexane compounds, which is accompanied by the production of a large amount of sodium chloride inorganic salt byproducts, and the post-processing is cumbersome and complicated, and the overall yield is not high, which does not conform to the concept of green chemistry (Industrial & Engineering Chemistry Research, 2017, 56, 2883-2888; Propellants, Explosives, Pyrotechnics, 2017, 42, 477-483). Therefore, it is of great significance to develop a new method for the efficient synthesis of 1,5-diazabicyclo[3.1.0]hexane compounds and its application. Summary of the invention

[0005] The present invention aims to provide a method for synthesizing 1,5-diazabicyclo[3.1.0]hexane compounds and application thereof. The method is simple and practical to operate, the raw materials are readily available, the yield is high, and the use of explosive dangerous goods such as tert-butyl hypochlorite and sodium hypochlorite can be avoided. The method is safe and reliable, and the reaction is environmentally friendly.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows.

[0007] A method for synthesizing 1,5-diazabicyclo[3.1.0]hexane compounds comprises the following steps:

[0008] In the first step, 1,3-propylenediamine is dispersed in an appropriate amount of chlorinated hydrocarbon solvent, and the corresponding aldehyde or ketone, an appropriate amount of trifluoromethanesulfonate and diisopropylethylamine are added in sequence at a temperature of -20-50°C. After stirring for half an hour, a mixed solution is obtained.

[0009] In the second step, N-chlorosuccinimide is slowly added to the mixed solution obtained in the first step, and the reaction is continued for 6-48 hours, followed by post-treatment to obtain the product.

[0010] Furthermore, the post-treatment process of the second step is: adding an appropriate amount of water to quench the reaction after the reaction, extracting with dichloromethane, concentrating the filtrate, and performing column chromatography to obtain the corresponding 1,5-diazabicyclo[3.1.0]hexane compounds;

[0011] Furthermore, the molar ratio of the 1,3-propylenediamine, aldehyde or ketone, diisopropylethylamine and N-chlorosuccinimide is 1:1-3:1-2.5:1-3; the molar ratio of the trifluoromethanesulfonate to 1,3-propylenediamine is 1:20-1:200.

[0012] Furthermore, the trifluoromethanesulfonate is one of copper (II) trifluoromethanesulfonate, cuprous (I) trifluoromethanesulfonate, zinc trifluoromethanesulfonate, silver trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, scandium trifluoromethanesulfonate, lithium trifluoromethanesulfonate, and iron (III) trifluoromethanesulfonate, preferably silver trifluoromethanesulfonate.

[0013] Furthermore, the chlorinated hydrocarbon solvent is dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, preferably dichloromethane.

[0014] Furthermore, in the first step, the molar concentration of 1,3-propylenediamine in the chlorinated hydrocarbon solvent is 0.2-0.4 mol / L.

[0015] Furthermore, in the second step, the reaction temperature is preferably 0°C; and the reaction time is preferably 24h.

[0016] A synthetic 1,5-diazabicyclo[3.1.0]hexane compound is prepared by the above method. The structural formula of the 1,5-diazabicyclo[3.1.0]hexane compound is as follows: Among them, R 1 is hydrogen, alkyl, cyclopropyl, allyl or phenyl containing 1 to 4 carbon atoms; R 2 It is hydrogen, alkyl, cyclopropyl, allyl or phenyl containing 1 to 4 carbon atoms.

[0017] An application of synthesizing 1,5-diazabicyclo[3.1.0]hexane compounds, and an application of 1,5-diazabicyclo[3.1.0]hexane compounds in bicomponent liquid propellants. Specifically: 1,5-diazabicyclo[3.1.0]hexane compounds can be used as a green and non-toxic fuel to replace the currently used toxic methylhydrazine and unsymmetrical dimethylhydrazine fuels, and are applied to bicomponent liquid propellants. They can be quickly and spontaneously ignited when in contact with fuming nitric acid and nitrogen tetroxide, and the ignition delay time is between 8-95ms, which meets the design requirements of rocket engines and has good application prospects.

[0018] The beneficial effects of the present invention are:

[0019] (1) The present invention is the first to introduce N-chlorosuccinimide as a chlorinating agent into the synthesis of 1,5-diazabicyclo[3.1.0]hexane compounds, thereby avoiding the use of explosive dangerous goods such as tert-butyl hypochlorite and sodium hypochlorite. The entire process is safe and reliable, and the operation is simple and practical.

[0020] (2) The present invention provides a new method for synthesizing 1,5-diazabicyclo[3.1.0]hexane compounds using silver trifluoromethanesulfonate as catalyst, which provides ideas and guidance for the design and synthesis of new nitrogen-containing strained ring substances. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Liquid H NMR spectrum of the synthesized 1,5-diazabicyclo[3.1.0]hexane;

[0022] Figure 2 Liquid NMR carbon spectrum of the synthesized 1,5-diazabicyclo[3.1.0]hexane;

[0023] Figure 3 High-speed photography photos of the spontaneous combustion of synthesized 6-cyclopropyl-1,5-diazabicyclo[3.1.0]hexane and dinitrogen tetroxide; among them, (a) is the free dripping process of 6-cyclopropyl-1,5-diazabicyclo[3.1.0]hexane; (b) is the first contact between 6-cyclopropyl-1,5-diazabicyclo[3.1.0]hexane droplets and dinitrogen tetroxide; (c) is the first spontaneous ignition of 6-cyclopropyl-1,5-diazabicyclo[3.1.0]hexane and dinitrogen tetroxide; (d) is the stable combustion of 6-cyclopropyl-1,5-diazabicyclo[3.1.0]hexane and dinitrogen tetroxide. DETAILED DESCRIPTION

[0024] The present invention is further described in detail below with reference to the accompanying drawings and embodiments.

[0025] Example 1: Optimization of reaction conditions for the synthesis of 6-phenyl-1,5-diazabicyclo[3.1.0]hexane

[0026]

[0027] Table 1 Optimization of reaction conditions a

[0028] Serial number catalyst Solvents Temperature(℃) Time (h) <![CDATA[Yield (%) b > 1 <![CDATA[Cu(OTf)2]]> Dichloromethane 0 8 48 2 Cu(OTf) Dichloromethane 0 8 15 3 <![CDATA[Zn(OTf)2]]> Dichloromethane 0 8 25 4 oeLh Dichloromethane 0 8 72 5 <![CDATA[Mg(OTf)2]]> Dichloromethane 0 8 26 6 <![CDATA[Sc(OTf)3]]> Dichloromethane 0 6 0 7 <![CDATA[Fe(OTf)3]]> Dichloromethane 0 6 0 8 AaC Dichloromethane 0 8 35 9 AgCl Dichloromethane 0 6 0 10 oeLh Methanol 0 8 55 11 oeLh Ethylene dichloride 0 8 71 12 oeLh Chloroform 0 8 66 13 oeLh Toluene 0 8 12 14 oeLh Dichloromethane 50 8 50 15 oeLh Dichloromethane -20 8 12 16 oeLh Dichloromethane 0 24 92 <![CDATA[17 c ]]> oeLh Dichloromethane 0 48 92 18 none Dichloromethane 0 8 6

[0029] a Reaction conditions: benzaldehyde A1 (1 mmol), 1,3-propylenediamine (1.1 mmol), solvent 5 mL, catalyst amount (1 mol%), N-chlorosuccinimide (1.1 mmol). b Isolated yield. c 0.5mol%AgOTf

[0030] In order to achieve efficient preparation of 1,5-diazabicyclo[3.1.0]hexane compounds, benzaldehyde A1 and 1,3-propylenediamine were selected as model substrates to optimize the synthetic reaction conditions. The results of metal salt screening showed that silver trifluoromethanesulfonate had the best reaction activity, with a yield of 72% (Table 1, No. 4). The activities of metal salts such as copper, zinc, magnesium, scandium, and iron were all low (Table 1, No. 1-7). The results of silver salt counterion screening showed that silver chloride had no catalytic activity and the yield of silver acetate was only 35% (Table 1, No. 8-9). Polar solvents are beneficial to the reaction, and non-polar solvents such as toluene greatly reduce the yield (Table 1, No. 10-13). Reaction temperature studies have shown that temperatures above or below 0°C will result in reduced yields (Table 1, No. 14-15). Extending the reaction time to 24 hours can increase the yield to 92% (Table 1, No. 16); reducing the amount of catalyst to 0.5 mol%, the reaction yield is not affected (Table 1, No. 17). Without the addition of a catalyst, the reaction almost does not occur (Table 1, No. 18), which may be because the activity of N-chlorosuccinimide as a chlorinating agent is significantly lower than that of tert-butyl hypochlorite and sodium hypochlorite. Therefore, the optimal reaction conditions for synthesizing 1,5-diazabicyclo[3.1.0]hexane compounds from aldehyde or ketone compounds through chlorination / condensation / cyclization reactions are: aldehyde or ketone (1 mmol), 1,3-propylenediamine (1.1 mmol), dichloromethane 5 mL, silver trifluoromethanesulfonate (0.5 mol%), N-chlorosuccinimide (1.1 mmol), diisopropylethylamine (1.1 mmol), reaction temperature of 0°C, and reaction time of 24 h.

[0031] Example 2: Synthesis of 1,5-diazabicyclo[3.1.0]hexane derivatives catalyzed by silver trifluoromethanesulfonate

[0032] The specific steps are as follows: add 1,3-propylenediamine and dichloromethane to the reaction bottle, add the corresponding aldehyde or ketone, 0.5mol% AgOTf and diisopropylethylamine in turn at 0°C, slowly add N-chlorosuccinimide after half an hour, continue the reaction for 24 hours, add an appropriate amount of water to quench the reaction, extract with dichloromethane, concentrate the filtrate, and obtain the corresponding 1,5-diazabicyclo[3.1.0]hexane compounds by column chromatography. The experimental results show that under standard reaction conditions, most aldehyde substrates (alkyl, cyclopropyl or phenyl substituted) can obtain high yields (80-92%) (Table 2, serial numbers 1-7). The yield of ketone substrates (alkyl, cyclopropyl or phenyl substituted) was reduced to a certain extent, mainly due to their large steric hindrance, especially dicyclopropyl ketone. After 48 hours of reaction, the product 6,6-dicyclopropyl-1,5-diazabicyclo[3.1.0]hexane B14 only obtained a 50% yield (Table 2, sequence number 14).

[0033] Table 2 Synthesized 1,5-diazabicyclo[3.1.0]hexane compounds

[0034]

[0035]

[0036]

[0037] The liquid NMR spectroscopy characterization data of some products are shown below.

[0038] 6-phenyl-1,5-diazabicyclo[3.1.0]hexane B1, liquid NMR spectrum characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ7.31-7.21(m,5H), 3.52-3.46(m,2H), 3.11-3.07(m,3H), 1.90-1.78(m,2H).

[0039] 1,5-diazabicyclo[3.1.0]hexane B2, liquid NMR spectrum characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ3.35 (dd, J=12.0, 8.0Hz, 2H), 2.99 (td, J=12.0, 8.0Hz, 2H), 2 .57(d,J=4.0Hz,1H),2.22(d,J=4.0Hz,1H),1.87–1.77(m,1H),1.77-1.64(m,1H). 13 C NMR (101MHz, CDCl3) δ51.17, 46.74, 20.18.

[0040] 6-Methyl-1,5-diazabicyclo[3.1.0]hexane B3, liquid NMR spectrum characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ3.27-3.32(dt,2H),2.85-2.93(dt,2H),2.26-2.30(q,1H),1.58-1.77(m,2H),1.12-1.13(d,3H); 13 C NMR (101MHz, CDCl3) δ52.4, 51.0, 22.0, 17.7.

[0041] 6-ethyl-1,5-diazabicyclo[3.1.0]hexane B4, liquid NMR spectrum characterization data are as follows: 1 HNMR (400MHz, CDCl3) δ3.30-3.20(m,2H),2.92-2.87(m,2H),2.15(t,1H),1.78-1.61(m,2H),1.42-1.36(m,2H),0.89(t,3H).

[0042] 6,6-Dimethyl-1,5-diazabicyclo[3.1.0]hexane B9, liquid NMR spectrum characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ3.20-3.24(dt,2H),2.80-2.91(dt,2H),2.22-2.25(q,1H),1.51-1.67(m,2H),1.02-1.08(d,3H); 13 C NMR (101MHz, CDCl3) δ52.4, 51.0, 22.0, 17.7, 17.2.

[0043] 6-Methyl-6-ethyl-1,5-diazabicyclo[3.1.0]hexane B10, liquid NMR spectrum characterization data are as follows: 1 H NMR (400MHz, CDCl3) δ3.22-3.12(m,2H),2.80-2.71(m,2H),2.25-2.11(m,1H),1.94-1.81(m,1H),1.34(q,2H),1.02(s,3H),0.84(t,3H).

[0044] 6,6-Diethyl-1,5-diazabicyclo[3.1.0]hexane B16, liquid NMR spectrum characterization data are as follows: 1H NMR (400MHz, CDCl3) δ3.28-3.10(m,2H),2.84-2.70(m,2H),2.46-2.28(m,1 H),2.18-2.00(m,1H),1.44(q,2H),1.38(q,2H),1.04(t,3H),0.85(t,3H).

[0045] Table 3 Toxicity of synthesized 1,5-diazabicyclo[3.1.0]hexane compounds and their spontaneous combustion properties with oxidants

[0046]

[0047] The present invention uses the TEST (Toxicity Estimation Software Tool) toxicity calculation software developed by the United States Environmental Protection Agency (USEPA) to analyze the LD of the 1,5-diazabicyclo[3.1.0]hexane compounds prepared in Example 2. 50 Toxicity (median lethal dose in mice) (Table 3). 50 The smaller the value, the more toxic the compound. The calculation results show that the LD50 of 1,5-diazabicyclo[3.1.0]hexane is 50 Between 738.2-5719.2mg / kg (methylhydrazine LD 50 The toxicity of methylhydrazine is 1 / 23 to 1 / 176, and they are all low-toxic compounds that can be used as green and non-toxic fuels for bicomponent liquid propellants.

[0048] Example 3: Spontaneous combustion test of 1,5-diazabicyclo[3.1.0]hexane compounds and oxidants

[0049] The ignition delay time of the fuel and the oxidant is one of the key indicators for the application of the two-component liquid propellant. A long ignition delay time may cause the accumulation of propellant in the engine at startup, resulting in a pressure spike or even an explosion. Therefore, the ignition delay time of the fuel and the oxidant should be as short as possible. The specific implementation steps of the spontaneous combustion test are: use a syringe to drop about 50uL of the 1,5-diazabicyclo[3.1.0]hexane compound synthesized in Example 2 into a flask containing 10mL of fuming nitric acid or nitrogen tetroxide, and use a high-speed camera to record the time interval from the beginning of contact with fuming nitric acid or nitrogen tetroxide to the appearance of an obvious flame at a shooting speed of 1000 frames per second. Repeat three times and take the average value; the results of the spontaneous combustion test are listed in Table 3.

[0050] From the results analysis in Table 3, it can be seen that the prepared 1,5-diazabicyclo[3.1.0]hexane compounds can spontaneously ignite when in contact with fuming nitric acid and nitrogen tetroxide. The spontaneous ignition delay time with the oxidant fuming nitric acid is between 8-42ms, among which the ignition delay time of 6-cyclopropyl-1,5-diazabicyclo[3.1.0]hexane reaches 8ms, which is equivalent to methylhydrazine (Table 3, No. 7), showing good application prospects. The ignition delay time with the oxidant nitrogen tetroxide is slightly longer than that of nitric acid, but still less than 100ms, among which the ignition delay time of 6-cyclopropyl-1,5-diazabicyclo[3.1.0]hexane is the shortest, reaching 13ms (Table 3, No. 7). The ignition delay time of the 16 1,5-diazabicyclo[3.1.0]hexane compounds prepared by the present invention, fuming nitric acid and dinitrogen tetroxide is between 8 and 95 ms, which preliminarily meets the design requirements of bipropellant rocket engines and shows their application prospects as green and non-toxic fuels for bipropellant liquid propellants.

[0051] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. All modifications, equivalent substitutions, improvements, etc. made within the design concept of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for synthesizing 1,5-diazabicyclo[3.1.0]hexane compounds, characterized in that: The following steps are involved: The first step is to disperse 1,3-propylenediamine in a chlorinated hydrocarbon solvent, wherein the molar concentration of 1,3-propylenediamine in the chlorinated hydrocarbon solvent is 0.2-0.4 mol / L, and then add aldehyde or ketone, an appropriate amount of trifluoromethanesulfonate and diisopropylethylamine in sequence at a temperature of -20-50°C, and stir to react for half an hour to obtain a mixed solution; In the second step, N-chlorosuccinimide is slowly added to the mixed solution obtained in the first step, and the reaction is continued for 6-48 hours, followed by post-treatment to obtain the product.

2. A method for synthesizing 1,5-diazabicyclo[3.1.0]hexane compounds according to claim 1, characterized in that: The molar ratio of the 1,3-propylenediamine, aldehyde or ketone, diisopropylethylamine and N-chlorosuccinimide is 1:1-3:1-2.5:1-3; the molar ratio of the trifluoromethanesulfonate and 1,3-propylenediamine is 1:20-1:

200.

3. A method for synthesizing 1,5-diazabicyclo[3.1.0]hexane compounds according to claim 1, characterized in that: The trifluoromethanesulfonate is one of copper (II) trifluoromethanesulfonate, cuprous (I) trifluoromethanesulfonate, zinc trifluoromethanesulfonate, silver trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, scandium trifluoromethanesulfonate, lithium trifluoromethanesulfonate, and iron (III) trifluoromethanesulfonate; the chlorinated hydrocarbon solvent is dichloromethane, chloroform, 1,2-dichloroethane, and carbon tetrachloride.

4. A method for synthesizing 1,5-diazabicyclo[3.1.0]hexane compounds according to claim 3, characterized in that: The trifluoromethanesulfonate is preferably silver trifluoromethanesulfonate; and the chlorinated hydrocarbon solvent is preferably dichloromethane.

5. A method for synthesizing 1,5-diazabicyclo[3.1.0]hexane compounds according to claim 1, characterized in that: In the second step, the reaction temperature is preferably 0°C, and the reaction time is preferably 24h.

6. A method for synthesizing 1,5-diazabicyclo[3.1.0]hexane compounds according to claim 1, characterized in that: The post-treatment process of the second step is: adding water to quench the reaction after the reaction, extracting with dichloromethane, concentrating the filtrate, and performing column chromatography to obtain the corresponding 1,5-diazabicyclo[3.1.0]hexane compounds.

7. A method for synthesizing 1,5-diazabicyclo[3.1.0]hexane compounds, characterized in that: The 1,5-diazabicyclo[3.1.0]hexane compound is obtained by the preparation method according to any one of claims 1 to 6, and the structural formula of the compound is as follows: Among them, R 1 is hydrogen, alkyl, cyclopropyl, allyl or phenyl containing 1 to 4 carbon atoms; R 2 It is hydrogen, alkyl, cyclopropyl, allyl or phenyl containing 1 to 4 carbon atoms.

8. An application of the synthesis of 1,5-diazabicyclo[3.1.0]hexane compounds according to claim 7, characterized in that: The 1,5-diazabicyclo[3.1.0]hexane compounds are used in two-component liquid propellants.

9. The use of the synthetic 1,5-diazabicyclo[3.1.0]hexane compound according to claim 8, characterized in that: The 1,5-diazabicyclo[3.1.0]hexane compound is used as a green and non-toxic fuel in a two-component liquid propellant. When it comes into contact with fuming nitric acid and nitrogen tetroxide, it can spontaneously ignite rapidly, and the ignition delay time is between 8 and 95 ms.

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