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CN-122010952-A - Light-driven preparation method of dibenzo-1, 3a,4,6 a-tetraazapentalene compound

CN122010952ACN 122010952 ACN122010952 ACN 122010952ACN-122010952-A

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to an optical drive preparation method of a dibenzo-1, 3a,4,6 a-tetraazapentalene compound. The method comprises the steps of dissolving an o-o ' -diazidoazobenzene compound in an organic solvent to obtain an o-o ' -diazidoazobenzene compound solution, and carrying out irradiation reaction on the o-o ' -diazidoazobenzene compound solution by adopting visible light to obtain the dibenzo-1, 3a,4,6 a-tetraazapentalene compound, wherein the wavelength of the visible light is 300-400 nm, the reaction temperature is 15-40 ℃, and the reaction time is 15-60 min. The preparation method provided by the invention has the characteristics of mild condition, high yield, environmental friendliness and safe operation, overcomes the defects of the traditional thermal synthesis process, can realize industrial mass production, and has remarkable economic value.

Inventors

  • ZHANG WENQUAN
  • LIAO SICHENG
  • SHI JUNHAO
  • TIAN TIAN

Assignees

  • 中国工程物理研究院化工材料研究所

Dates

Publication Date
20260512
Application Date
20260204

Claims (10)

  1. 1. A light-driven preparation method of dibenzo-1, 3a,4,6 a-tetraazapentalene compound, which is characterized by comprising the following steps: Dissolving an o-o '-diazidoazobenzene compound in an organic solvent to obtain an o-o' -diazidoazobenzene compound solution; the o-o' -diazidoazobenzene compound solution is irradiated by visible light to react to obtain the dibenzo-1, 3a,4,6 a-tetraazapentalene 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; the structural formulas of the o-o' -diazidoazobenzene compound and the dibenzo-1, 3a,4,6 a-tetraazapentalene compound are shown as formula 1 and formula 2: A formula 1, Formula 2; In the formula 1 and the formula 2, R is selected from one or more of H, C-10 alkyl, halogen and C1-10 alkoxy, and the number of R is 1-4.
  2. 2. The method of claim 1, wherein the dibenzo-1, 3a,4,6 a-tetraazapentalene compound is selected from any one of the following structures: 、 、 、 、 。
  3. 3. the method of claim 1, wherein the organic solvent comprises methanol, ethanol, or an aprotic organic solvent.
  4. 4. The method of claim 3, wherein the aprotic organic solvent comprises acetonitrile and/or halogenated hydrocarbon solvents, and the halogenated hydrocarbon solvents comprise dichloromethane and/or chloroform.
  5. 5. The method according to claim 1, wherein the molar concentration of the o-o '-diazidoazobenzene compound in the o-o' -diazidoazobenzene compound solution is 0.0001-0.02 mol/L.
  6. 6. The method of claim 1, wherein the wavelength of the visible light is 340 nm.
  7. 7. The method of claim 1, wherein the irradiation power of the visible light is 5-20W.
  8. 8. The method of claim 7, wherein the irradiation power of the visible light is 10W.
  9. 9. The method of claim 1, wherein the reaction temperature is 20-30 ℃.
  10. 10. The method for preparing the light-driven material according to claim 1 or 9, wherein the reaction time is 20-40 min, and the reaction is performed in an inert gas atmosphere or air, wherein the inert gas comprises nitrogen and/or rare gas.

Description

Light-driven preparation method of dibenzo-1, 3a,4,6 a-tetraazapentalene compound Technical Field The invention belongs to the technical field of organic synthesis, and particularly relates to an optical drive preparation method of a dibenzo-1, 3a,4,6 a-tetraazapentalene compound. Background Currently, heat resistant explosives are characterized by their excellent thermal stability and are critical for applications in the military and civilian fields where reliability needs to be maintained under extreme conditions. This includes military applications such as Flexible Linear Shaped Charges (FLSCs) and sheet explosives, and civil applications such as well perforating operations. A representative example is tetranitrodibenzo-1, 3a,4,6 a-tetraazapentalene (TACOT), which has an ultra-high decomposition temperature. However, the synthesis of such advanced energetic compounds often depends on the availability of their key heterocyclic precursors. For example, dibenzo-1, 3a,4,6 a-tetraazapentalene (DBTP) is a key intermediate for synthesizing materials such as heat resistant explosive TACOT. Since the first report, the synthesis of DBTP has been dependent on the thermal denitrification of ortho-ortho' -Diazidobenzene (DAZB) requiring prolonged heating at about 170 ℃ in expensive high boiling solvents such as decalin. This high energy process not only raises safety concerns but also limits scalability and functional group tolerance, making it difficult to meet green, safe, sustainable synthesis requirements. Disclosure of Invention The invention aims to provide the light-driven preparation method of the dibenzo-1, 3a,4,6 a-tetraazapentylene compound, which has the characteristics of mild condition, high yield, environmental friendliness and safe operation, overcomes the defects of the traditional thermal synthesis process, can realize industrialized mass production, and has remarkable economic value. In order to achieve the above object, the present invention provides the following technical solutions: the invention provides a preparation method of a dibenzo-1, 3a,4,6 a-tetraazapentalene compound, which comprises the following steps: Dissolving an o-o '-diazidoazobenzene compound in an organic solvent to obtain an o-o' -diazidoazobenzene compound solution; the o-o' -diazidoazobenzene compound solution is irradiated by visible light to react to obtain the dibenzo-1, 3a,4,6 a-tetraazapentalene 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; the structural formulas of the o-o' -diazidoazobenzene compound and the dibenzo-1, 3a,4,6 a-tetraazapentalene compound are shown as formula 1 and formula 2: A formula 1, Formula 2; In the formula 1 and the formula 2, R is selected from one or more of H, C-10 alkyl, halogen and C1-10 alkoxy, and the number of R is 1-4. Preferably, the dibenzo-1, 3a,4,6 a-tetraazapentalene compound is selected from any one of the following structures: 、、、、。 preferably, the organic solvent includes methanol, ethanol or aprotic organic solvents. Preferably, the aprotic organic solvent comprises acetonitrile and/or halogenated hydrocarbon solvents, and the halogenated hydrocarbon solvents comprise dichloromethane and/or chloroform. Preferably, the molar concentration of the o-o '-diazidoazobenzene compound in the o-o' -diazidoazobenzene compound solution is 0.0001-0.02 mol/L. Preferably, the wavelength of the visible light is 340 nm. Preferably, the irradiation power of the visible light is 5-20W. Preferably, the irradiation power of the visible light is 10W. Preferably, the reaction temperature is 20-30 ℃. Preferably, the reaction is carried out in an inert gas atmosphere or air for 20-40min, wherein the inert gas comprises nitrogen and/or rare gas. The invention provides a preparation method of a dibenzo-1, 3a,4,6 a-tetraazapentalene compound, which comprises the following steps of dissolving an o-o '-diazidoazobenzene compound in an organic solvent to obtain an o-o' -diazidoazobenzene compound solution, carrying out irradiation reaction on the o-o '-diazidoazobenzene compound solution by adopting visible light to obtain the dibenzo-1, 3a,4,6 a-tetraazapentalene compound, wherein the wavelength of the visible light is 300-400 nm, the reaction temperature is 15-40 ℃, the reaction time is 15-60 min, the structural formulas of the o-o' -diazidoazobenzene compound and the dibenzo-1, 3a,4,6 a-tetraazapentalene compound are shown as formula 1 and formula 2, R in the formulas 1 and 2 is selected from one or more of H, C-10 alkyl groups, halogen and C1-10 alkoxy groups, and R is 1-4. The invention takes an o-o' -diazidoazobenzene compound (a compound with a structure shown in a formula 1 and DAZB) as a reaction substrate, and successfully synthesizes a nitrogen-rich compound with a complex structure (namely a dibenzo-1, 3a,4,6 a-tetraazapentalene compound) under visible light irradiation. Compared with the traditional multi