Light-driven preparation method of dibenzo-1, 3a, 4, 6a-tetraaza-pentalene compound

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to a light-driven preparation method of a dibenzo-1, 3a, 4, 6a-tetraaza-pentalene compound. The preparation method comprises the following steps: dissolving an ortho-ortho'diazido azobenzene compound in an organic solvent to obtain an ortho-ortho 'diazido azobenzene compound solution; visible light is adopted to irradiate the ortho-ortho 'diazido azobenzene compound solution for a reaction, the dibenzo-1, 3a, 4, 6a-tetraazapentalene compound is obtained, the wavelength of the visible light is 300-400 nm, the reaction temperature is 15-40 DEG C, and the reaction time is 15-60 min. The preparation method provided by the invention has the characteristics of mild conditions, high yield, environmental friendliness and safety in operation, overcomes the defects of the traditional thermal synthesis process, can realize industrial large-scale production, and has remarkable economic value.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis technology, specifically relating to a light-driven preparation method for dibenzo-1,3a,4,6a-tetraazapentaene compounds. Background Technology

[0002] Currently, heat-resistant explosives, characterized by their excellent thermal stability, are crucial for applications in both military and civilian sectors that require reliability under extreme conditions. This includes military applications such as flexible linear shaped charges (FLSCs) and sheet explosives, as well as civilian applications such as oil well perforation operations. A representative example is tetranitrodibenzo-1,3a,4,6a-tetraazapentaene (TACOT), which possesses an extremely high decomposition temperature. However, the synthesis of such advanced energetic compounds often depends on the availability of their key heterocyclic precursors.

[0003] For example, dibenzo-1,3a,4,6a-tetraazapentaene (DBTP) is a key intermediate in the synthesis of materials such as the heat-resistant explosive TACOT. Since its initial report, the synthesis of DBTP has relied on the thermal denitrification reaction of o-o-diazidoazobenzene (DAZB), requiring prolonged heating at approximately 170°C in expensive high-boiling solvents such as decahydronaphthalene. This energy-intensive process not only raises safety concerns but also limits scalability and functional group tolerance, making it difficult to meet the requirements for green, safe, and sustainable synthesis. Summary of the Invention

[0004] The purpose of this invention is to provide a light-driven preparation method for dibenzo-1,3a,4,6a-tetraazapentaene compounds. The preparation method provided by this invention has the characteristics of mild conditions, high yield, environmental friendliness, and safe operation. It overcomes the defects of traditional thermal synthesis processes, can be industrialized and scaled up, and has significant economic value.

[0005] To achieve the above objectives, the present invention provides the following technical solution: This invention provides a method for preparing dibenzo-1,3a,4,6a-tetraazapentaene compounds, comprising the following steps: Dissolving o-o-'-diazidoazobenzene compounds in an organic solvent yields an o-o-'-diazidoazobenzene compound solution; The solution of the ortho- ortho-diazidoazobenzene compound was irradiated with visible light to produce the dibenzo-1,3a,4,6a-tetraazapentaene compound. The wavelength of the visible light was 300-400 nm, the reaction temperature was 15-40°C, and the reaction time was 15-60 min. The structural formulas of the ortho-ortho-diazidoazobenzene compounds and the dibenzo-1,3a,4,6a-tetraazapentaene compounds are shown in Formula 1 and Formula 2: Formula 1 Formula 2; In Formulas 1 and 2: R is selected from one or more of H, C1-10 alkyl, halogen and C1-10 alkoxy, and the number of R is 1 to 4.

[0006] Preferably, the dibenzo-1,3a,4,6a-tetraazapentaene compound is selected from any one of the following structures: , , , , .

[0007] Preferably, the organic solvent includes methanol, ethanol, or an aprotic organic solvent.

[0008] Preferably, the aprotic organic solvent includes acetonitrile and / or halogenated hydrocarbon solvents; the halogenated hydrocarbon solvents include dichloromethane and / or trichloromethane.

[0009] Preferably, the molar concentration of the o-o-diazidoazobenzene compound in the o-o-diazidoazobenzene compound solution is 0.0001~0.02 mol / L.

[0010] Preferably, the wavelength of the visible light is 340 nm.

[0011] Preferably, the visible light irradiation power is 5~20 W.

[0012] Preferably, the visible light irradiation power is 10 W.

[0013] Preferably, the reaction temperature is 20~30℃.

[0014] Preferably, the reaction time is 20-40 min; the reaction is carried out in an inert gas atmosphere or air, the inert gas including nitrogen and / or rare gases.

[0015] This invention provides a method for preparing dibenzo-1,3a,4,6a-tetraazapentaene compounds, comprising the following steps: dissolving an o-o-diazidoazobenzene compound in an organic solvent to obtain an o-o-diazidoazobenzene compound solution; irradiating the o-o-diazidoazobenzene compound solution with visible light to induce a reaction, thereby obtaining the dibenzo-1,3a,4,6a-tetraazapentaene compounds, wherein the wavelength of the visible light is 300-400 nm, the reaction temperature is 15-40°C, and the reaction time is 15-60 min; the structural formulas of the o-o-diazidoazobenzene compound and the dibenzo-1,3a,4,6a-tetraazapentaene compounds are shown in Formula 1 and Formula 2; in Formula 1 and Formula 2: R is selected from one or more of H, C1-10 alkyl, halogen, and C1-10 alkoxy, and the number of R is 1-4. This invention successfully synthesized a structurally complex nitrogen-rich compound (i.e., dibenzo-1,3a,4,6a-tetraazapentaene) under visible light irradiation using o-o-diazidoazobenzene compounds (compounds with the structure shown in Formula 1, including DAZB) as reaction substrates. Compared with the traditional polyazidopentabenzene thermal synthesis route (which requires high temperature (170°C) and high-boiling solvents), the preparation method provided by this invention has milder reaction conditions, significantly shorter reaction time, and the yield of the target product, dibenzo-1,3a,4,6a-tetraazapentaene compounds (including DBTP), exceeds 70%. The preparation method provided by this invention significantly improves the energy efficiency, operational safety, and cost-effectiveness of the DBTP synthesis process, and is of great significance for the green preparation of DBTP.

[0016] In summary, this invention establishes an efficient and controllable photochemical synthesis route for dibenzo-1,3a,4,6a-tetraazapentaene compounds (including DBTP), a key precursor of the heat-resistant explosive TACOT. This invention provides a green synthesis strategy characterized by significant energy, time, and cost savings while offering a yield of up to 73.4%. Attached Figure Description

[0017] Figure 1 Thermochemical and photochemical synthesis routes for DBTP; Figure 2 The 1H NMR spectrum of the target product DBTP in this embodiment of the invention; Figure 3 The image shows the carbon NMR spectrum of the target product DBTP in this embodiment of the invention. Detailed Implementation

[0018] This invention provides a method for preparing dibenzo-1,3a,4,6a-tetraazapentaene compounds, comprising the following steps: Dissolving o-o-'-diazidoazobenzene compounds in an organic solvent yields an o-o-'-diazidoazobenzene compound solution; The solution of the ortho- ortho-diazidoazobenzene compound was irradiated with visible light to produce the dibenzo-1,3a,4,6a-tetraazapentaene compound. The wavelength of the visible light was 300-400 nm, the reaction temperature was 15-40°C, and the reaction time was 15-60 min. The structural formulas of the ortho-ortho-diazidoazobenzene compounds and the dibenzo-1,3a,4,6a-tetraazapentaene compounds are shown in Formula 1 and Formula 2: Formula 1 Formula 2; In Formulas 1 and 2: R is selected from one or more of H, C1-10 alkyl, halogen and C1-10 alkoxy, and the number of R is 1 to 4.

[0019] In this invention, unless otherwise specified, all raw materials / components used in the preparation are commercially available products well known to those skilled in the art.

[0020] In this invention, in Formulas 1 and 2: R is preferably selected from one or more of H, C1-5 alkyl, halogen, and C1-5 alkoxy. The halogen is preferably selected from one or more of Cl, Br, and I. The number of R can be 1, 2, 3, or 4.

[0021] In the embodiments of the present invention, in Formula 1: R can specifically be H, methyl, Cl or methoxy; the number of R can specifically be 1 or 2.

[0022] In this invention, the ortho-ortho-diazidoazobenzene compounds are preferably selected from any of the following structures: , , , , .

[0023] In this invention, the dibenzo-1,3a,4,6a-tetraazapentaene compound is preferably selected from any of the following structures: , , , , .

[0024] This invention involves dissolving o-o-'-diazidoazobenzene compounds in an organic solvent to obtain an o-o-'-diazidoazobenzene compound solution.

[0025] In this invention, the ortho- ortho-diazidoazobenzene compounds can be prepared using methods well known to those skilled in the art, for example, by referring to "Aromatic Azapentalenes. I. Dibenzo-1,3a,4,6a-tetraazapentalene and Dibenzo-1,3a,6,6a-tetraazapentalene. New Heteroaromatic Systems." (Carboni, RA; Kauer, JC; Castle, JE; Simmons, EJ Am. Chem. Soc. 1967, 89, 2618–2625. https: / / doi.org / 10.1021 / ja00987a020.).

[0026] In this invention, when R is H, the o-o-o'-diazidoazobenzene compound is specifically o-o-o'-diazidoazobenzene. In a specific embodiment of this invention, the preparation method of o-o-o'-diazidoazobenzene may include the following steps: dissolving 1,2-diaminobenzene (1.08 g, 10 mmol) in ethyl acetate (17.62 g, 200 mmol), then adding lead dioxide (7.18 g, 30 mmol) to the solution, and heating to 70°C for 3 hours. After the reaction is complete, cooling to 35-40°C, adding 3.3 g of activated carbon to the reaction system, and stirring for 30 minutes. The mixture is then filtered, the filter cake is washed with a large amount of ethyl acetate, and the filtrate is collected. Finally, sulfuric acid (1.96 g, 20 mmol) is slowly added dropwise to the filtrate. After the addition is complete, the filter cake is collected by filtration and dried to obtain the sulfate of 4,4'-diaminoazobenzene (DAAB·H2SO4). o-,o-'-diazidoazobenzene (DAZB) was prepared according to the literature method: DAAB·H₂SO₄ (0.93 g, 3 mmol) was dissolved in a mixture of sulfuric acid (2.94 g, 30 mmol) and water (10.8 mL) under ice-water bath conditions. Sodium nitrite solution (0.621 g, 9 mmol, 0.5 mL water) was added to this mixture, and the mixture was stirred vigorously for 1 hour. Then, sodium azide solution (0.59 g, 9 mmol, 0.5 mL water) was added, and stirring continued for 2 hours. Finally, the filter cake was collected by filtration, washed with a small amount of ethanol, and dried to obtain a brownish-yellow powder, which is o-,o-'-diazidoazobenzene.

[0027] In this invention, when R is a substituent other than H, the preparation method of o-o-'-diazidoazobenzene compounds is basically the same as the preparation method of o-o-'-diazidoazobenzene described above, except that the above-mentioned raw material 1,2-diaminobenzene is replaced with R-substituted 1,2-diaminobenzene, and the preparation is carried out according to the above preparation method.

[0028] In this invention, the organic solvent preferably includes methanol, ethanol, or an aprotic organic solvent. The aprotic organic solvent preferably includes acetonitrile (MeCN) and / or halogenated hydrocarbon solvents. The halogenated hydrocarbon solvent preferably includes dichloromethane (DCM) and / or trichloromethane (TCM). In embodiments of this invention, the aprotic organic solvent can be DCM or MeCN.

[0029] In this invention, the molar concentration of the o-o-diazidoazobenzene compound in the o-o-diazidoazobenzene compound solution is preferably 0.0001~0.02 mol / L, more preferably 0.0005~0.015 mol / L, and even more preferably 0.001~0.013 mol / L. In the examples, it can be 0.0018 mol / L, 0.0054 mol / L, 0.0072 mol / L, or 0.0108 mol / L.

[0030] After obtaining the o-o-o'-diazidoazobenzene compound solution, the present invention uses visible light to irradiate the o-o-o'-diazidoazobenzene compound solution to react and obtain the dibenzo-1,3a,4,6a-tetraazapentaene compound. The wavelength of the visible light is 300~400 nm, the reaction temperature is 15~40℃, and the reaction time is 15~60 min.

[0031] In this invention, the reaction is preferably carried out in a photochemical reactor. The reaction is preferably carried out in an inert gas atmosphere or in air. The inert gas preferably includes nitrogen and / or rare gases. In embodiments of the invention, the reaction can be carried out in flowing inert gas or air.

[0032] In this invention, the wavelength of visible light is preferably 340 nm. The irradiation power of the visible light is preferably 5~20 W, and in the embodiments it can be 5 W, 10 W, 15 W or 20 W.

[0033] In this invention, the reaction temperature is preferably 20-30°C, and in the embodiments it can be 25°C. The reaction time is preferably 20-40 min, and most preferably 30 min.

[0034] In this invention, thin-layer chromatography (TLC) is used to detect the extent of the reaction. After the reaction is completed, a reaction solution is obtained. Preferably, the reaction is post-processed to obtain the dibenzo-1,3a,4,6a-tetraazapentaene compound. The post-processing preferably includes sequential vacuum concentration and column chromatography separation. The eluent used for column chromatography separation preferably includes petroleum ether and ethyl acetate, and the volume ratio of petroleum ether to ethyl acetate is preferably 20-25:1.

[0035] The dibenzo-1,3a,4,6a-tetraazapentaene compounds obtained in this invention are white solid products, and their structures are identified using nuclear magnetic resonance spectroscopy (NMR).

[0036] In summary, this invention provides a photochemical synthesis route for the preparation of dibenzo-1,3a,4,6a-tetraazapentaene compounds. The preparation method provided by this invention successfully reduces the reaction temperature from 170°C in traditional processes to room temperature, shortens the reaction time from several hours to approximately 30 minutes, and uses low-cost, environmentally friendly solvents. This method has significant advantages such as simple process, mild conditions, high yield, good safety, and environmental friendliness, providing a practical and feasible method for the green, efficient, and large-scale preparation of dibenzo-1,3a,4,6a-tetraazapentaene compounds, and has broad application prospects in functional materials, energetic materials, and other fields.

[0037] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0038] Example 1 o-o-o'-diazisazobenzene (DAZB) was dissolved in dichloromethane at room temperature (25°C) to prepare a 0.0072 M solution. The solution was placed in a photochemical reactor and irradiated with an LED light source of 10 W at a center wavelength of 340 nm for 30 min under continuous purging of inert gas (nitrogen) or air. After the reaction, the product was concentrated under reduced pressure and separated by column chromatography (eluting solvents were petroleum ether and ethyl acetate, with a volume ratio of 20:1) to obtain a white solid product. Nuclear magnetic resonance (NMR) spectroscopy identified it as the target compound DBTP, with a yield of 73.4% and a purity >98%. Figure 2 The 1H NMR spectrum of the target product DBTP in Example 1 of this invention; Figure 3 The carbon NMR spectrum of the target product DBTP in Example 1 of this invention: DBTP: IR (KBr, cm -1): 3063, 2924, 2122, 1069, 1484, 1435, 1382, 1329,1255, 1155, 1104, 935, 810, 749, 730, 629, cm -1 . 1 H NMR (400 MHz, DMSO- d 6 ) δ:8.267 (d, J = 8.4 Hz, 2H), 7.975 (d, J = 8.8 Hz, 2H), 7.697-7.656 (m, 2H), 7.475-7.436 (m, 2H). 13 C NMR (100 MHz, DMSO- d 6 ) δ: 145.85, 128.08, 121.97, 117.28,116.61, 111.92. HRMS (ESI - ) ( m / z calcd for C 12 H7N4207.0676, found 209.08276. Example 2 o-o-o'-diazisazobenzene (DAZB) was dissolved in dichloromethane at room temperature (25°C) to prepare a 0.0054 M solution. The solution was placed in a photochemical reactor and irradiated with an LED light source of 10 W at a center wavelength of 340 nm for 30 min under continuous purging of inert gas (nitrogen) or air. After the reaction, the product was concentrated under reduced pressure and separated by column chromatography (eluting solvents were petroleum ether and ethyl acetate, with a volume ratio of 20:1) to obtain a white solid product. Nuclear magnetic resonance (NMR) spectroscopy identified it as the target compound DBTP, with a yield of 70.5%.

[0039] Example 3 o-o-o'-diazisazobenzene (DAZB) was dissolved in dichloromethane at room temperature (25°C) to prepare a 0.0108 M solution. The solution was placed in a photochemical reactor and irradiated with an LED light source of 10 W at a center wavelength of 340 nm for 30 min under continuous purging of inert gas (nitrogen) or air. After the reaction, the solution was concentrated under reduced pressure and separated by column chromatography (eluting solvents were petroleum ether and ethyl acetate, with a volume ratio of 20:1) to obtain a white solid product. Nuclear magnetic resonance (NMR) spectroscopy identified the product as the target compound DBTP, with a yield of 68.4%.

[0040] Example 4 At room temperature (25°C), o-o-o'-diazisazobenzene (DAZB) was dissolved in acetone to prepare a 0.0018 M solution. The solution was placed in a photochemical reactor and irradiated with an LED light source of 10 W at a center wavelength of 340 nm for 30 min under continuous purging of inert gas (nitrogen) or air. After the reaction, the product was concentrated under reduced pressure and separated by column chromatography (eluting solvents were petroleum ether and ethyl acetate, with a volume ratio of 20:1) to obtain a white solid product. Nuclear magnetic resonance (NMR) spectroscopy identified it as the target compound DBTP, with a yield of 58.2%.

[0041] Example 5 At room temperature (25°C), o-o-o'-diazisazobenzene (DAZB) was dissolved in acetone to prepare a 0.0018 M solution. The solution was placed in a photochemical reactor and irradiated with an LED light source of 10 W at a center wavelength of 340 nm for 50 min under continuous purging of inert gas (nitrogen) or air. After the reaction, the product was concentrated under reduced pressure and separated by column chromatography (eluting solvents were petroleum ether and ethyl acetate, with a volume ratio of 20:1) to obtain a white solid product. Nuclear magnetic resonance (NMR) spectroscopy identified it as the target compound DBTP, with a yield of 50%.

[0042] Example 6: Compared with Example 1, methanol was used as the reaction solvent. o-o-o'-diazisazobenzene (DAZB) was dissolved in methanol at room temperature (25°C) to prepare a 0.0072 M solution. The solution was placed in a photochemical reactor and irradiated with an LED light source of 10 W at a center wavelength of 340 nm for 30 min under continuous purging of inert gas (nitrogen) or air. After the reaction, the product was concentrated under reduced pressure and separated by column chromatography (eluting solvents were petroleum ether and ethyl acetate, with a volume ratio of 20:1) to obtain a white solid product. Nuclear magnetic resonance (NMR) spectroscopy identified it as the target compound DBTP, with a yield of 44%.

[0043] Example 7: Compared with Example 1, ethanol was used as the reaction solvent. At room temperature (25°C), o-o-o'-diazisazobenzene (DAZB) was dissolved in ethanol to prepare a 0.0072 M solution. The solution was placed in a photochemical reactor and irradiated with an LED light source of 10 W at a center wavelength of 340 nm for 30 min under continuous purging of inert gas (nitrogen) or air. After the reaction, the product was concentrated under reduced pressure and separated by column chromatography (eluting solvents were petroleum ether and ethyl acetate, with a volume ratio of 20:1) to obtain a white solid product. Nuclear magnetic resonance (NMR) spectroscopy identified it as the target compound DBTP, with a yield of 50%.

[0044] Comparative Example 1: Compared with Example 5, the reaction time was too long. At room temperature (25°C), o-o-o'-diazisazobenzene (DAZB) was dissolved in acetone to prepare a 0.0018 M solution. The solution was placed in a photochemical reactor and irradiated with an LED light source of 10 W at a center wavelength of 340 nm for 240 min under continuous purging of inert gas (nitrogen) or air. After the reaction, the product was concentrated under reduced pressure and separated by column chromatography (eluting solvents were petroleum ether and ethyl acetate, with a volume ratio of 20:1) to obtain a white solid product. Nuclear magnetic resonance (NMR) spectroscopy identified it as the target compound DBTP, with a yield of 20.8%.

[0045] Comparative Example 2 At room temperature (25°C), o-o-o'-diazisazobenzene (DAZB) was dissolved in dichloromethane to prepare a 0.0072 M solution. The solution was placed in a photochemical reactor and irradiated with an LED light source of 10 W at a center wavelength of 255 nm for 30 min under continuous purging of inert gas (nitrogen) or air. After the reaction, the product was concentrated under reduced pressure and separated by column chromatography (eluting solvents were petroleum ether and ethyl acetate, with a volume ratio of 20:1) to obtain a white solid product. Nuclear magnetic resonance (NMR) spectroscopy identified the product as the target compound DBTP, with a yield of 0%. This indicates that no reaction occurs at a center wavelength of 255 nm.

[0046] Comparative Example 3 At room temperature (25°C), o-o-o'-diazisazobenzene (DAZB) was dissolved in dichloromethane to prepare a 0.0072 M solution. The solution was placed in a photochemical reactor and irradiated with an LED light source of 10 W at a center wavelength of 470 nm for 30 min under continuous purging of inert gas (nitrogen) or air. After the reaction, the product was concentrated under reduced pressure and separated by column chromatography (eluting solvents were petroleum ether and ethyl acetate, with a volume ratio of 20:1) to obtain a white solid product. Nuclear magnetic resonance (NMR) spectroscopy identified the product as the target compound DBTP, with a yield of 0%. This indicates that no reaction occurs at a center wavelength of 470 nm.

[0047] As can be seen from the above examples and comparative examples, the preparation method provided by the present invention has been systematically optimized by adjusting conditions such as wavelength, solvent, irradiation time, power, and reaction temperature to obtain a satisfactory yield of the target product. The yields under all reaction conditions were determined by quantitative nuclear magnetic resonance using 1,3,5-triacetylbenzene as an internal standard. To improve overall experimental efficiency, the reaction time was first optimized. Under the initial conditions (25°C, DAZB acetone solution concentration of 0.0018 M, irradiation wavelength of 340 nm, and power of 10 W), thin-layer chromatography (TLC) showed that the starting material was completely consumed within 15 minutes. Therefore, the reaction yield was evaluated over a time span of 240 minutes. 1 ¹H NMR analysis showed that the reaction reached its highest yield of 58.2% at 30 min. The yield then gradually decreased, remaining above 50% for 60 min, but the yield was only 20.8% after continuous irradiation up to 240 min. Therefore, 30 min was determined to be the optimal irradiation time.

[0048] Wavelength is one of the key factors affecting the reaction. This invention selected different wavelengths from near-ultraviolet (255 nm) to blue light (470 nm) to evaluate the reaction yield. Experimental results showed that 340 nm was the optimal irradiation wavelength, with a significantly higher yield than other wavelengths. Furthermore, DAZB did not convert in complete darkness. After determining the irradiation time and wavelength, this invention evaluated the types of solvents. Protic solvents methanol (MeOH) and ethanol (EtOH) performed worse than aprotic solvents, with yields ≤50%, while other solvents all yielded yields higher than 55%. Acetonitrile (MeCN), dichloromethane (DCM), and trichloromethane (TCM) yielded yields exceeding 65%. DCM performed best and was therefore selected as the solvent for subsequent condition screening. Considering the principle of green solvents, acetonitrile is also a feasible and effective alternative.

[0049] Finally, the effects of irradiation power and reaction temperature were investigated. The results showed that the yield decreased with decreasing power but increased with decreasing temperature. Considering both efficiency and energy consumption, a power of 10 W and a reaction temperature of 25 °C were ultimately adopted. In summary, the optimal reaction conditions for the preparation method provided by this invention are: dichloromethane as solvent, reaction temperature 25 °C, irradiation power 10 W, and irradiation at a wavelength of 340 nm for 30 min. To scale up the reaction, the DAZB concentration in the dichloromethane solvent was increased. The results showed that the yield reached 70.5% when the DAZB concentration increased to 0.0054 M; the yield reached 73.4% when the DAZB concentration increased to 0.0072 M; however, when the DAZB concentration was further increased to 0.0108 M, the yield only slightly decreased to 68.4%.

[0050] As can be seen from the above embodiments, the preparation method provided by the present invention, through repeated quantitative nuclear magnetic resonance (qNMR) experiments, determined the optimal conditions for photochemical synthesis of DBTP within 30 min at room temperature. The preparation method provided by the present invention makes the synthesis of DAZB faster (reduced from 2-3 hours to 30 min), milder (reduced from 170℃ to 25℃), and more economical (replacing decahydronaphthalene with dichloromethane), achieving environmentally friendly and green synthesis (e.g., Figure 1 (As shown).

[0051] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. Other embodiments can be obtained based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A photo-driven preparation method for dibenzo-1,3a,4,6a-tetraazapentaene compounds, characterized in that, Includes the following steps: Dissolving o-o-'-diazidoazobenzene compounds in an organic solvent yields an o-o-'-diazidoazobenzene compound solution; The solution of the ortho- ortho-diazidoazobenzene compound was irradiated with visible light to produce the dibenzo-1,3a,4,6a-tetraazapentaene compound. The wavelength of the visible light was 300-400 nm, the reaction temperature was 15-40°C, and the reaction time was 15-60 min. The structural formulas of the ortho-ortho-diazidoazobenzene compounds and the dibenzo-1,3a,4,6a-tetraazapentaene compounds are shown in Formula 1 and Formula 2: Formula 1 Formula 2; In Formulas 1 and 2: R is selected from one or more of H, C1-10 alkyl, halogen and C1-10 alkoxy, and the number of R is 1 to 4.

2. The optically driven fabrication method according to claim 1, characterized in that, The dibenzo-1,3a,4,6a-tetraazapentaene compounds are selected from any of the following structures: 、 、 、 、 。 3. The optically driven fabrication method according to claim 1, characterized in that, The organic solvent includes methanol, ethanol, or aprotic organic solvents.

4. The optically driven fabrication method according to claim 3, characterized in that, The aprotic organic solvent includes acetonitrile and / or halogenated hydrocarbon solvents; the halogenated hydrocarbon solvents include dichloromethane and / or trichloromethane.

5. The optically driven fabrication method according to claim 1, characterized in that, The molar concentration of the o-o-diazidoazobenzene compound in the o-o-diazidoazobenzene compound solution is 0.0001~0.02 mol / L.

6. The optically driven fabrication method according to claim 1, characterized in that, The wavelength of the visible light is 340 nm.

7. The optically driven fabrication method according to claim 1, characterized in that, The visible light irradiation power is 5~20W.

8. The optically driven fabrication method according to claim 7, characterized in that, The visible light irradiation power is 10W.

9. The optically driven fabrication method according to claim 1, characterized in that, The reaction temperature is 20~30℃.

10. The optically driven fabrication method according to claim 1 or 9, characterized in that, The reaction time is 20-40 minutes; the reaction is carried out in an inert gas atmosphere or air, the inert gas including nitrogen and / or rare gases.

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