Lactone unit embedded bisanthene compound, synthetic method and application thereof
By embedding lactone groups on both sides of bisanthene, compound A was synthesized and made into nanoparticles, solving the problem of the scarcity of oxygen atoms embedded in fused-ring aromatic hydrocarbons and achieving high stability and efficient photothermal conversion of the compound.
Patent Information
- Application Number
- CN202511521347.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-23
- Publication Date
- 2025-12-26
- Estimated Expiration
- 2045-10-23
AI Technical Summary
There are few existing technologies that incorporate oxygen atoms into the framework of polycyclic aromatic hydrocarbons, especially in two-dimensional nano-polycyclic aromatic hydrocarbons. Furthermore, there are few reports on the introduction of lactone groups into two-dimensional nano-polycyclic aromatic hydrocarbons, which affects the improvement of their optical and solid-state properties.
Compound A, which incorporates lactone groups on both sides of a bisanthene, was synthesized using the Vilsmeier–Haack reaction and an oxidation reaction involving K2S2O8. The specific steps included the separation and purification of the compound in multiple steps.
The synthesized compound A improved the chemical stability of bisanthene and exhibited high stability and a photothermal conversion efficiency of 65% as a nanoparticle photothermal agent.
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Figure CN120987966B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a lactone unit embedded bisanthene compound and a synthesis method and application, and belongs to the technical field of organic functional molecule synthesis. BACKGROUND
[0002] Nanometer fused ring aromatic hydrocarbons have great potential in the fields of electronic devices, biological imaging and energy technology due to their excellent two-dimensional pi-conjugated structure. By precisely doping heteroatoms, the skeleton and electron cloud distribution can be reconstructed at the molecular level, thereby systematically regulating key properties such as redox activity, energy band gap, charge transfer and photo-thermal conversion. However, compared with nitrogen, boron, sulfur, silicon and other heteroatoms, the case of oxygen atom embedded in the skeleton of fused ring aromatic hydrocarbons is still rare. So far, the oxygen-containing fused ring systems reported in the literature are mainly limited to furan or pyran structures, and their mixed valence cations exhibit excellent semiconductor properties. Therefore, it is of great value to develop more types of oxygen-doped fused ring aromatic hydrocarbons.
[0003] Lactone groups are stable and strong electron-deficient oxygen-doped units, which are favored in the field of polymer semiconductors due to their high electron mobility, but there are few reports on their introduction into two-dimensional nanometer fused ring aromatic hydrocarbons. This strategy also has multiple advantages: first, it can solve the low stability of extended pi-conjugated systems while retaining the inherent aromaticity of the molecule, thereby improving overall optical absorption, emission and solid-state performance. In addition, the unique Diels-Alder reactivity of lactones gives them modular expansion capabilities, which can be used to precisely construct more complex functional molecules.
[0004] In the present application, by embedding lactone groups in the bay region on both sides of bisanthene, compound A is successfully synthesized. This molecule not only enhances the stability of the functional molecule, but also uses the synthesized compound A to prepare nanoparticles as a photothermal agent. In the photothermal performance test, it shows high stability and a photo-thermal conversion efficiency of 65%. SUMMARY
[0005] To solve the above problems, the present application provides a lactone unit embedded bisanthene compound and a synthesis method and application, which has the advantages of simple operation, high atom economy, high chemical selectivity and high yield.
[0006] In order to achieve the above purpose, the technical scheme of the present application is as follows:
[0007] A lactone unit embedded bisanthene compound, the structure is as follows:
[0008]
[0009] A method for synthesizing a lactone unit embedded bisanthene compound, comprising the following steps: using compound 1 as a raw material, obtaining compound A through Vilsmeier-Haack reaction and K2S2O8 involved oxidation reaction. The compound synthesis steps are as follows:
[0010] The synthesis method of the above A specifically comprises the following steps:
[0011] Step one, according to the mass ratio, compound 1: potassium persulfate: tetraethyl ammonium bromide = 1:1.32:0.10, dissolved in 1,2-dichloroethane solvent, the reaction mixture was stirred at 80°C for 12 hours. After the reaction was completed, the reaction liquid was filtered through diatomite, the filtrate was collected, and the solvent was recovered by reduced pressure distillation; using a mixed solvent of petroleum ether and dichloromethane with a volume ratio of 5:1 as the eluent, a neutral silica gel column with a particle size of 200-300 was used for column chromatography separation, the first green band was collected to obtain a solution of compound 2, then the solvent was recovered by reduced pressure distillation, and blue-green solid compound 2 was obtained after vacuum drying.
[0012] Step two, according to the mass ratio, compound 2: phosphorus oxychloride: N,N-dimethylformamide = 1:0.36:5.82, dissolved in 1,2-dichloroethane solvent, the reaction mixture was stirred at 90°C for 2 hours. After the reaction was completed, it was cooled to room temperature, and 3 mL of 20 wt% sodium hydroxide solution was slowly added to quench the reaction. Extracted with ethyl acetate and water, the organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. A mixed solvent of petroleum ether and dichloromethane with a volume ratio of 2:1 was used as the eluent, and a neutral silica gel column with a particle size of 200-300 was used for column chromatography separation. The third blue-green band was collected to obtain a solution of compound 3, then the solvent was recovered by reduced pressure distillation, and black solid compound 3 was obtained after vacuum drying.
[0013] Step three, according to the mass ratio, compound 3: potassium persulfate: tetraethyl ammonium bromide = 1:1.32:0.10, dissolved in 1,2-dichloroethane solvent, the reaction mixture was stirred at 80°C for 8 hours. After the reaction was completed, the reaction liquid was filtered through diatomite, the filtrate was collected, and the solvent was recovered by reduced pressure distillation; using a mixed solvent of petroleum ether and dichloromethane with a volume ratio of 1:1 as the eluent, a neutral silica gel column with a particle size of 200-300 was used for column chromatography separation, the second green band was collected to obtain a solution of compound A, then the solvent was recovered by reduced pressure distillation, and blue-green solid compound A was obtained after vacuum drying.
[0014] The application of the lactone unit embedded bisanthene compound is that the synthesized compound A is prepared into nanoparticles for use as a photothermal agent, which shows high stability and a photothermal conversion efficiency of 65% in a photothermal performance test.
[0015] The application has the following beneficial effects:
[0016] (1) The synthesis method of the lactone unit embedded bisanthene compound is simple in operation and high in yield. The synthesized compound A effectively improves the chemical stability of bisanthene.
[0017] (2) The compound A synthesized by embedding the lactone unit into bisanthene is prepared into nanoparticles for use as a photothermal agent, which shows good stability and a photothermal conversion efficiency of 65% in a photothermal performance test. BRIEF DESCRIPTION OF DRAWINGS
[0018] Figure 1 It is a synthesis route map of the compound A.
[0019] Figure 2 It is a nuclear magnetic resonance hydrogen spectrum diagram of the compound 1.
[0020] Figure 3 It is a nuclear magnetic resonance hydrogen spectrum diagram of the compound 2.
[0021] Figure 4 It is a nuclear magnetic resonance hydrogen spectrum diagram of the compound 3.
[0022] Figure 5 It is a nuclear magnetic resonance hydrogen spectrum diagram of the compound A.
[0023] Figure 6 (A) is a single crystal structure diagram of the compound A; (B) is a stacking mode of the compound A in a unit cell.
[0024] Figure 7 (A) is an ultraviolet-visible absorption spectrum of the compound A in different solvents; (B) is a fluorescence emission spectrum of the compound A in a concentration-dependent manner.
[0025] Figure 8 It is a concentration-dependent photothermal heating curve of the A nanoparticle under 660 nm laser (0.5 W cm⁻²) irradiation.
[0026] Figure 9 It is a thermal conversion efficiency diagram of the compound A nanoparticle.
[0027] Figure 10 It is a photothermal stability experiment of the compound A nanoparticle. DETAILED DESCRIPTION
[0028] The raw material 1 used in the present application is synthesized according to the preparation method of the reference entitled: Synthesis and Properties of Aza-Ovalene with Six Zigzag Edges, and its nuclear magnetic resonance hydrogen spectrum data are as follows: Figure 2 is the nuclear magnetic resonance hydrogen spectrum of compound 1; 1 H NMR (600 MHz, CDCl3) δ (ppm) = 9.60 (s, 1H), 8.60 (dd, J = 12.7, 7.4 Hz, 2H), 7.92 (d, J = 9.1 Hz, 1H), 7.67 – 7.57 (m, 4H), 7.50 (d, J =8.6 Hz, 1H), 7.46 (d, J = 8.4 Hz, 1H), 7.39 (d, J = 8.8 Hz, 1H), 7.28 (d, J = 6.6Hz, 1H), 7.17 (s, 4H), 2.49 (d, J = 2.9 Hz, 6H), 1.88 (d, J = 3.5 Hz, 12H)。
[0029] Example 1. Synthesis of compound 2
[0030] 122.9 mg (0.2 mmol) of compound 1, 162.2 mg (0.6 mmol) of potassium persulfate, 19.3 mg (0.06 mmol) of tetraethylammonium bromide and 10 mL of 1,2-dichloroethane were added to a 50 mL two-necked flask, and the reaction mixture was stirred at 80°C for 12 hours; after the reaction was completed, the reaction solution was filtered through diatomite, the filtrate was collected, and the solvent was recovered by reduced pressure distillation; using a mixture of petroleum ether and dichloromethane with a volume ratio of 5:1 as the eluent, a neutral silica gel column with a mesh size of 200-300 was used for column chromatography separation, the first green band was collected to obtain a solution of compound 2, and then the solvent was recovered by reduced pressure distillation, and after vacuum drying, blue-green solid compound 2 was obtained, a total of 103.0 mg, with a yield of 82%.
[0031] Figure 3 is the nuclear magnetic resonance hydrogen spectrum of compound 2: 1H NMR (600 MHz, CDCl3) δ (ppm) = 8.73 (d , J = 7.4 Hz, 1H), 8.68 (d , J= 7.5 Hz, 1H), 8.13 (d , J = 9.3 Hz, 1H), 7.79–7.61 (m, 5H), 7.58 (d , J = 8.3 Hz, 1H), 7.44 (d , J = 8.9 Hz, 1H), 7.17 (s, 4H), 2.50 (s, 6H), 1.88 (d , J = 11.7 Hz, 12H).
[0032] Example 2. Synthesis of Compound 3
[0033] 125.7 mg (0.2 mmol) of compound 2, 45.3 mg (0.3 mmol) of phosphorus oxychloride, 731.6 mg (10 mmol) of N,N-dimethylformamide, and 8 mL of 1,2-dichloroethane were added to a 25 mL double-necked flask. The reaction mixture was stirred at 90 °C for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, and 3 mL of 20 wt% sodium hydroxide solution was slowly added dropwise to quench the reaction. The mixture was extracted with ethyl acetate and water. The resulting organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The solution was separated by 200-300 mesh neutral silica gel column chromatography using a 2:1 (v / v) mixture of petroleum ether and dichloromethane as eluent. The third blue-green band was collected to obtain a solution of compound 3. The solvent was then recovered by reduced pressure distillation, and the solution was dried under vacuum to obtain a black solid of compound 3, totaling 102.4 mg, with a yield of 78%.
[0034] Figure 4 The 1H NMR spectrum of compound 3 is shown below: ¹H NMR (600 MHz, CDCl3) δ (ppm) = 9.91 (s, 1H), 8.40 (d) , J = 9.1 Hz, 1H), 8.29 (d , J = 8.9 Hz, 1H), 8.04 (d , J = 8.4Hz, 1H), 8.00 (d , J = 9.3 Hz, 1H), 7.94 (t, J = 7.9 Hz, 1H), 7.87 (d , J = 9.3 Hz, 1H), 7.78 (d , J = 8.9 Hz, 1H), 7.74 (d , J = 7.3 Hz, 1H), 7.71 (d , J= 9.1 Hz,1H), 2.53 (s, 6H), 1.88 ( d, J = 4.1 Hz, 12H)。
[0035] Example 3. Synthesis of compound A
[0036] Into a 50 mL flask, 131.3 mg (0.2 mmol) of compound 3, 162.2 mg (0.6 mmol) of potassium persulfate, 19.3 mg (0.06 mmol) of tetraethylammonium bromide and 10 mL of 1,2-dichloroethane were added, and the reaction mixture was stirred at 80°C for 8 hours. After the reaction was completed, the reaction solution was filtered through diatomite, the filtrate was collected, and the solvent was recovered by reduced pressure distillation. Using a mixture of petroleum ether and dichloromethane (1:1 by volume) as the eluent, the compound A solution was separated by column chromatography using neutral silica gel with a particle size of 200-300 mesh, and the second green band was collected. The solvent was recovered by reduced pressure distillation, and the blue-green solid compound A was obtained after vacuum drying, with a total of 113.9 mg and a yield of 85%.
[0037] Figure 5 The nuclear magnetic resonance hydrogen spectrum of compound A is as follows: 1 H NMR (600 MHz, C6D6) δ (ppm) = 8.46 (d, J = 9.0 Hz, 2H), 7.75 (d, J = 9.3 Hz, 2H), 7.68 (d, J = 9.0 Hz, 2H), 7.37 (d, J =9.2 Hz, 2H), 7.10 – 7.06 (m, 4H), 2.40 (s, 6H), 1.91 (s, 6H), 1.81 (s, 6H).
[0038] Structural characterization of compound A in this example
[0039] Single crystal culture method of compound A in this example
[0040] The single crystal culture of compound A was performed by solvent diffusion method. The specific steps are as follows: first, 0.1 mL of compound A solution with a concentration of 10 -3The compound A solution of M in dichloromethane was filtered through an organic microporous filter membrane with a pore size of 0.45 μm, and then was added into a smooth glass tube with an inner diameter of 5 mm and a length of 10 mm; then, the glass tube was placed in a sealed glass bottle (outer diameter 20 mm, height 80 mm) containing 2 mL of n-hexane, ensuring that the mouth of the glass tube was higher than the liquid level of n-hexane; finally, the glass tube was inclined against the small glass bottle and placed in an environment at room temperature, away from light and vibration. After slow evaporation and diffusion for 3 days, a single crystal with regular morphology was finally obtained. Figure 6 (A) is a schematic diagram of a single crystal of compound A, Figure 6 (B) is the packing mode of compound A in the unit cell.
[0041] UV-visible near-infrared absorption spectrum of compound A in different solvents and emission spectrum performance of compound A in different concentrations of dichloromethane solution
[0042] The concentration of compound A was 1×10 -5 M was tested. The UV-visible near-infrared absorption spectrum in different solvents (n-hexane, toluene, dichloromethane, ethyl acetate and tetrahydrofuran) was determined by SHIMADZU UV-2600i UV-visible spectrophotometer, and the results are shown in FIG. Figure 7 (A). The maximum absorption wavelength of compound A is 703 nm. In addition, compound A shows a positive solvent effect in different solvents. The fluorescence emission spectrum of compound A under different concentrations (5×10 -6 M, 1×10 -5 M, 2.5×10 -5 M, 5×10 -5 M, 7.5×10 -5 M, 1×10 -4 M) was tested by HITACHI F-4700 fluorescence spectrophotometer, and the results are shown in FIG. Figure 7 (B). The fluorescence emission range of compound A is 715-1100 nm, and it shows self-absorption characteristics under different concentrations. With the increase of concentration, this self-absorption characteristic reaches the maximum at 1×10 -4 M.
[0043] Preparation of compound A nanoparticles
[0044] 2 mg of compound A and 10 mg of DSPE-PEG 2000The solution was dissolved in 2 mL of tetrahydrofuran solution, then poured into 10 mL of double distilled water for ultrasonic treatment (150 W). Then, the obtained dispersion was maintained under ultrasonic treatment (150 W) for 5 minutes. Subsequently, dialysis was performed for 12 hours to obtain a uniform and transparent dark blue or dark green micellar solution, and filtration was performed with a 0.45-micron polyvinylidene fluoride syringe. The obtained nanoparticle concentrated solution can be diluted with a phosphate buffered saline solution. Finally, the nanoparticles were stored at 4°C for subsequent use.
[0045] Evaluation of the photothermal performance and stability of the nanoparticles of the present embodiment A
[0046] Under 660 nm laser irradiation (power density of 0.5 W cm⁻², irradiation for 4 minutes), the temperature of the A nanoparticles rapidly rose to 81.22°C at a concentration of 200 µM. There was a positive correlation between the temperature rise of the A nanoparticles and their concentration and laser power density, and the results are shown in FIG. 6, which indicates that the generation of heat can be effectively controlled by adjusting these parameters. Figure 8 The photothermal conversion efficiency of the A nanoparticles was calculated to be 65% using the method reported in the literature (Highly Stable Near-Infrared II Luminescent Diradicaloids for Cancer Phototheranostics), and the specific results are shown in FIG. 7. Figure 9 In addition, the photothermal stability of the nanoparticles was verified by performing four heating-cooling cycles under continuous laser irradiation, and the results are shown in FIG. 8, which shows that the maximum temperature in each cycle remained consistent, indicating good photothermal stability. Figure 10
[0047] Obviously, the above embodiments are only illustrative of the present application and do not limit the embodiments of the present application. Based on the above description, other different forms of changes or adjustments can be made by those of ordinary skill in the art. It is impossible to enumerate all the embodiments here, and any obvious changes or adjustments that belong to the technical solutions of the present application are still within the protection scope of the present application.
Claims
1. An lactone unit embedded bisanthene compound, characterized in that, The structure is shown as follows: 。 2. A method of synthesizing a lactone unit-embedded bisanthene compound according to claim 1, characterized by, Compound A was synthesized by the following synthetic route 。 3. A method of synthesizing a lactone unit-embedded bisanthene compound according to claim 2, characterized by, In the reaction of compound 1 and K2S2O8 to generate compound 2, the mass ratio of compound 1 to potassium persulfate was 1:1.32, the mass ratio of compound 1 to tetraethylammonium bromide was 1:0.10, the solvent was 1,2-dichloroethane, the amount used was 50 L / mol of compound 1, the reaction temperature was 80℃, the reaction time was 12 hours, and after the reaction was completed, the reaction system was purified by extraction, drying, filtration, reduced pressure distillation, and silica gel column chromatography separation to obtain product 2.
4. A method of synthesizing a lactone unit-embedded bisanthene compound according to claim 2, characterized by, In the reaction of compound 2 and phosphorus oxychloride and N,N-dimethylformamide to generate compound 3, the mass ratio of compound 2 to phosphorus oxychloride was 1:0.36, the mass ratio of compound 2 to N,N-dimethylformamide was 1:5.82, the solvent was 1,2-dichloroethane, the amount used was 40 L / mol of compound 2, the reaction temperature was 90℃, the reaction time was 2 hours, and after the reaction was completed, the reaction system was purified by extraction, drying, filtration, reduced pressure distillation, and silica gel column chromatography separation to obtain product 3.
5. A method of synthesizing a lactone unit-embedded bisanthene compound according to claim 2, characterized by, In the reaction of compound 3 and K2S2O8 to generate compound A, the mass ratio of compound 3 to potassium persulfate was 1:1.32, the mass ratio of compound 3 to tetraethylammonium bromide was 1:0.10, the solvent was 1,2-dichloroethane, the amount used was 50 L / mol of compound 3, the reaction temperature was 80℃, the reaction time was 8 hours, and after the reaction was completed, the reaction system was purified by extraction, drying, filtration, reduced pressure distillation, and silica gel column chromatography separation to obtain product A.
6. Use of a lactone unit embedded in a bisanthene compound according to claim 1, characterized in that, The synthesized compound A was made into nanoparticles as a photothermal agent, which showed high stability and a photothermal conversion efficiency of 65% in the photothermal performance test.