A preparation method and application of a fused ring aromatic hydrocarbon embedding pyrrole and pyridine into perylene

Abstract

The application discloses a preparation method and application of a fused ring aromatic hydrocarbon with pyrrole and pyridine embedded in perylene. A five-membered pyrrole ring and a six-membered pyridine ring are introduced into two side bay positions of perylene respectively, so that a new derivative PerNN of perylene with two different nitrogen atom doping types of pyrrole type and pyridine type existing in one molecule is obtained; the PerNN can be easily derived into acidified PerNN-H, oxidized PerNN-O, alkylated PerNN-MeCl and PerNN-MeI. The PerNN-MeCl and the PerNN-MeI show reverse Karast's short-wavelength double emission. Moreover, the PerNN-MeCl and the PerNN-MeI both have high efficient ROS properties, and these findings greatly enrich the possible application fields of nitrogen-doped fused ring aromatic hydrocarbons. The application has mild reaction conditions, simple process, and the product has unique photoelectric properties, and therefore has good application prospect.

Description

Technical Field

[0001] This invention relates to a method for preparing fused-ring aromatic hydrocarbons by intercalating pyrrole and pyridine into perylene and its applications. The method of this invention has the advantages of mild reaction conditions, short reaction time, and simple process. It belongs to the field of organic functional molecule synthesis technology. Background Technology

[0002] From the perspective of the electronic structure of nitrogen-doped fused-ring aromatic hydrocarbons (FRAs), they can be divided into three categories: pyridine-type, pyrrole-type, and graphene-type. These three different doping forms produce drastically different properties. For example, pyridine-type doping leads to electron deficiency (pyridine salts have significant electron acceptor properties), while pyrrole-type doping makes the compound electron-rich. Most reported nitrogen-doped FRAs contain only one type of nitrogen doping, and molecules incorporating two or more different nitrogen doping forms into a single FRA framework are few and far between, existing only in very simple structures. Furthermore, their synthesis methods and photoelectric properties are still in their early stages. The few preliminary studies have already demonstrated the application value of these compounds in the field of organic functional materials. Therefore, further expanding the variety of these compounds and conducting more thorough performance studies are of great significance and value. In this invention, we can obtain a novel perylene derivative, PerNN, in which both pyrrole-type and pyridine-type nitrogen doping forms coexist in a single molecule through a one-step reaction. Due to the electrostatic interaction between the electron-donating pyrrole and the electron-accepting pyridine in the PerNN structure, its crystals exhibit a dense columnar packing. With external nitrogen doping, PerNN readily derives into acidified PerNN-H, oxidized PerNN-O, alkylated PerNN-MeCl, and PerNN-MeI. PerNN-MeCl and PerNN-MeI exhibit anti-Kasha dual emission at short wavelengths, and both PerNN-MeCl and PerNN-MeI efficiently generate reactive oxygen species. These new findings greatly expand the potential application areas of nitrogen-doped polycyclic aromatic hydrocarbons. Summary of the Invention

[0003] This invention provides a method for preparing fused-ring aromatic hydrocarbons in which pyrrole and pyridine are intercalated into perylene, and their applications. These derivatives are abbreviated as PerNN, PerNN-H, PerNN-O, PerNN-MeCl, and PerNN-MeI, respectively.

[0004] This invention uses NP-CHO as a raw material to synthesize PerNN via the following synthetic route. Furthermore, using PerNN as a raw material, PerNN-H, PerNN-O, PerNN-MeCl, and PerNN-MeI were synthesized via the following synthetic routes:

[0005]

[0006] The above-mentioned method for preparing PerNN specifically includes the following steps:

[0007] Under argon protection, a certain amount of NP-CHO, azide-trimethylsilane, trifluoromethanesulfonic acid, and trifluoroacetic acid were added to a double-necked flask, and the mixture was stirred at a certain temperature for a certain time. After the reaction was completed, a certain amount of 20% sodium hydroxide solution was added to the reaction solution, followed by extraction with a certain amount of ethyl acetate. The extraction was repeated three times, and the organic phases were combined. The organic phase was dried with an appropriate amount of anhydrous sodium sulfate for a certain time, filtered, and the solvent was recovered by vacuum distillation to obtain the crude product. The crude product was separated by 200-300 mesh neutral silica gel column chromatography, using a mixed solvent of petroleum ether and ethyl acetate at a volume ratio of 6:1 as the eluent. The fifth light yellow band was collected to obtain a solution of the target product PerNN. The solvent was then recovered by vacuum distillation, and the residue was dried under vacuum to obtain a pale yellow solid, which was the compound PerNN.

[0008] The preparation method of the above PerNN-O specifically includes the following steps:

[0009] Under argon protection and at a certain temperature, a certain amount of m-chloroperoxybenzoic acid was added to a certain amount of a dichloromethane solution of PerNN. The reaction mixture was stirred at a certain temperature for a certain time. After the reaction was completed, the solvent was recovered by vacuum distillation, and the residue was separated by 200-300 mesh neutral silica gel column chromatography. A mixed solvent of dichloromethane and methanol with a volume ratio of 30:1 was used as the eluent. The fourth yellow-green band was collected to obtain a solution of the target product PerNN-O. The solvent was then recovered by vacuum distillation, and the residue was dried under vacuum to obtain a yellow solid, which was the compound PerNN-O.

[0010] The preparation method of the above PerNN-H specifically includes the following steps:

[0011] A certain amount of PerNN was dissolved in a certain amount of dichloromethane, and a certain amount of 12 M hydrochloric acid was added dropwise. The mixture was stirred and reacted for a certain period of time. After the reaction was completed, the solvent was recovered by vacuum distillation, and the product was washed with n-hexane to obtain a yellow solid, which was the compound PerNN-H.

[0012] The preparation method of the above PerNN-MeI specifically includes the following steps:

[0013] Under argon protection, a certain amount of acetonitrile and PerNN were added to a double-necked flask and stirred at a certain temperature for a certain time to dissolve. Then, a certain amount of iodomethane was added dropwise and stirred at a certain temperature for a certain time. After the reaction was completed, the solvent was recovered by vacuum distillation to obtain the crude product. The crude product was separated by 200-300 mesh neutral silica gel column chromatography with a mixed solvent of dichloromethane and methanol at a volume ratio of 20:1 as the eluent. The third yellow band was collected to obtain a solution of the target product PerNN-MeI. The solvent was then recovered by vacuum distillation, and the residue was dried under vacuum to obtain a yellow solid, which was the compound PerNN-MeI.

[0014] The preparation method of the above PerNN-MeCl specifically includes the following steps:

[0015] A certain amount of PerNN-MeI was dissolved in a certain amount of methanol. Then, a certain amount of aqueous solution of ammonium hexafluorophosphate was added, followed by a certain amount of water. The resulting precipitate was filtered, dried, and dissolved in a certain amount of acetonitrile. A certain amount of tetrabutylammonium chloride was added to a certain amount of acetonitrile, and then the tetrabutylammonium chloride solution was added to the above acetonitrile solution. The mixture was stirred and reacted for a certain period of time. After the reaction was completed, the solvent was recovered by vacuum distillation to obtain a crude product. The crude product was separated by 200-300 mesh neutral silica gel column chromatography, using a mixed solvent of dichloromethane and methanol at a volume ratio of 20:1 as the eluent. The third yellow band was collected to obtain a solution of PerNN-MeCl. The solvent was then recovered by vacuum distillation, and the residue was dried under vacuum to obtain a yellow solid product, which was the compound PerNN-MeCl.

[0016] The advantages of this invention are:

[0017] The present invention provides a method for preparing a polycyclic aromatic hydrocarbon by embedding pyrrole and pyridine into perylene and its application. The synthesis process of the present invention is simple and has low cost.

[0018] In the structure of the product of the present invention, two different nitrogen atom doping types, pyrrole type and pyridine type, coexist. The different nitrogen atom doping forms will bring about strong intermolecular charge transfer, thereby giving the product molecule unique photoelectric properties. Therefore, the product of the present invention is expected to play a unique role in the preparation of functional materials such as organic light-emitting diodes, fluorescence imaging and charge transport.

[0019] PerNN has been derived into acidified PerNN-H, oxidized PerNN-O, alkylated PerNN-MeCl, and PerNN-MeI. Among these, PerNN-MeCl and PerNN-MeI exhibit anti-Kasha dual emission at short wavelengths. Furthermore, both PerNN-MeCl and PerNN-MeI can efficiently generate reactive oxygen species, showing potential application value in phototherapy. Attached Figure Description

[0020] Figure 1 This is the proton NMR spectrum of NP-CHO.

[0021] Figure 2 This is the carbon NMR spectrum of NP-CHO.

[0022] Figure 3 This is the hydrogen NMR spectrum of PerNN.

[0023] Figure 4 This is the carbon NMR spectrum of PerNN.

[0024] Figure 5 This is a high-resolution mass spectrum of PerNN.

[0025] Figure 6 This is a single-crystal structure diagram of PerNN.

[0026] Figure 7 The graphs show the UV absorption (a) and fluorescence emission (b) of PerNN in different solvents.

[0027] Figure 8 The image shows the proton NMR spectrum of PerNN-O.

[0028] Figure 9 This is the carbon NMR spectrum of PerNN-O.

[0029] Figure 10 This is a high-resolution mass spectrum of PerNN-O.

[0030] Figure 11 The graphs show the UV absorption (a) and fluorescence emission (b) of PerNN-O in different solvents.

[0031] Figure 12 This is the hydrogen NMR spectrum of PerNN-H.

[0032] Figure 13 This is the carbon NMR spectrum of PerNN-H.

[0033] Figure 14 This is a high-resolution mass spectrum of PerNN-H.

[0034] Figure 15 The graphs show the UV absorption (a) and fluorescence emission (b) of PerNN-H in different solvents.

[0035] Figure 16 This is the hydrogen NMR spectrum of PerNN-MeI.

[0036] Figure 17 This is the carbon NMR spectrum of PerNN-MeI.

[0037] Figure 18 This is a high-resolution mass spectrum of PerNN-MeI.

[0038] Figure 19 The graphs show the UV absorption (a) and fluorescence emission (b) of PerNN-MeI in different solvents.

[0039] Figure 20 The image shows the proton NMR spectrum of PerNN-MeCl.

[0040] Figure 21 This is the carbon NMR spectrum of PerNN-MeCl.

[0041] Figure 22 This is a high-resolution mass spectrum of PerNN-MeCl.

[0042] Figure 23 The graphs show the UV absorption (a) and fluorescence emission (b) of PerNN-MeCl in different solvents.

[0043] Figure 24 The graph shows the fluorescence intensity of PerNN-H, PerNN-O, PerNN-MeCl, and PerNN-MeI versus DCFH over time. Implementation

[0044] The raw material NP-CHO used in this invention is synthesized according to the patent application entitled "A Method for Preparing Polycyclic Aromatic Hydrocarbons with Aldehyde Groups Introduced into the Bay Region of Pyrrole Perylene". Its 1H and 1C NMR spectra are as follows: Figure 1 The hydrogen nuclear magnetic resonance spectrum of NP-CHO; 1 H NMR (600 MHz, CDCl3) δ 11.06 (s, 1H), 8.50 (d, J = 7.3 Hz, 1H), 8.35 (d, J = 8.5 Hz, 1H), 8.04 (s, 1H), 7.99 – 7.93 (m, 3H), 7.87 (d, J = 8.6Hz, 1H), 4.83 (t, J = 7.1 Hz, 2H), 2.19 – 2.14 (m, 2H), 1.47 – 1.42 (m, 2H), 1.38 – 1.33 (m, 2H), 1.30 – 1.24 (m, 2H), 0.83 (t, J = 7.3 Hz, 3H); Figure 2 The image shows the carbon NMR spectrum of NP-CHO.13 C NMR (151 MHz, CDCl3) δ 192.06, 141.18 (d, J F-C = 255.4Hz), 141.18 (d, J F-C = 255.4 Hz), 138.01 (d, J F-C = 251.0 Hz), 132.93, 132.78,132.52, 131.89, 130.54, 129.59, 128.38, 127.26, 125.78, 125.00, 124.95,124.69, 123.04, 121.88, 120.37, 118.06, 117.98, 117.79, 116.52, 114.84 (dd, J F-C = 38.7, 18.9 Hz), 46.24, 31.37, 31.25, 26.94, 22.48, 13.85.

[0045] Example 1. Synthesis of compound PerNN

[0046] Under argon protection, 50 mg (0.071 mmol) of NP-CHO was added to a 25 ml double-necked flask containing a magnetic magnet. After evacuating for 3 min, nitrogen was introduced, and this process was repeated three times. 1 ml of trifluoroacetic acid was added, and the mixture was stirred to dissolve the starting material. Then, 1.3 ml (9.89 mmol) of tris(hydroxymethyl)-azidosilane was added dropwise while stirring, followed by 0.4 ml (4.52 mmol) of trifluoromethanesulfonic acid. The mixture was heated to 60 °C and stirred at this temperature for 1 hour. After the reaction was complete, 5 ml of 20% sodium hydroxide solution was added to the reaction solution, followed by extraction with 5 ml of ethyl acetate each time, for a total of three extractions. The organic phases were combined, dried over anhydrous sodium sulfate for 2 hours, filtered, and the solvent was recovered by vacuum distillation to obtain a brown, oily crude product. The crude product was then subjected to 200 ~ Separation was performed by neutral silica gel column chromatography with a 300-mesh filter. The eluent was a mixture of petroleum ether and ethyl acetate in a volume ratio of 6:1. The fifth eluent, which was light yellow, was collected. The solvent was recovered by vacuum distillation, and a light yellow solid was obtained. After vacuum drying, the mass of the solid was 19.92 mg, which was identified as compound PerNN, with a yield of 40%.

[0047] Figure 3 The image shows the proton NMR spectrum of the compound PerNN. 1H NMR (600 MHz, CDCl3) δ 10.28 (s,1H), 8.86 (d, J = 8.4 Hz, 1H), 8.71 (d, J = 8.8 Hz, 1H), 8.51 (d, J = 8.5 Hz,1H), 8.48 (s, 1H), 8.41 (s, 1H), 8.39 (d, J = 9.1 Hz, 1H), 5.06 (t, J = 6.8Hz, 2H), 2.35 – 2.30 (m, 2H), 1.56 – 1.51 (m, 2H), 1.42 – 1.37 (m, 2H), 1.31– 1.28 (m, 2H), 0.84 (t, J = 7.2 Hz, 3H).

[0048] Figure 4 The image shows the carbon NMR spectrum of the compound PerNN. 13 C NMR (151 MHz, CDCl3) δ 149.82,144.98 (d, J F-C = 246.5 Hz), 143.98, 141.21 (d, J F-C = 256.7 Hz), 138.09 (d, J F-C = 252.7 Hz), 135.89, 135.47, 126.39, 125.99, 124.90, 124.02, 123.72,122.89, 121.71, 120.70, 120.45, 119.66, 118.70, 118.33, 116.22, 115.30 (d, J F-C = 15.9 Hz), 114.85, 47.03, 31.43, 31.22, 27.01, 22.48, 13.88.

[0049] Performance testing: (attached) Figure 6The image shows the single-crystal structure of compound PerNN at 193K using a Bruker D8 VENTURE MetaljetPHOTON II diffractometer. The results indicate that PerNN crystals exhibit a dense columnar packing structure, which is beneficial for charge transport. Therefore, this compound has the potential for application in charge transport materials. The UV absorption and fluorescence emission spectra of compound PerNN in different solvents are attached. Figure 7 As shown; the fluorescence quantum yield of compound PerNN in dimethyl sulfoxide is 30.64%; we selected 2',7'-dichlorodihydrofluorescein (DCFH), which can be converted into green fluorescent 2',7'-dichlorofluorescein (DCF) after activation by reactive oxygen species, as an indicator of reactive oxygen species. The efficiency of PerNN in generating reactive oxygen species in a solution of H₂O:tetrahydrofuran = 1:1 was investigated. After 9 minutes of white light irradiation, the fluorescence intensity of PerNN increased by 3 times compared to DCFH, as shown in the attached figure. Figure 24 As shown.

[0050] Example 2. Synthesis of compound PerNN-O

[0051] Under argon protection and at 0°C, 19.55 mg (0.113 mmol) of m-chloroperoxybenzoic acid was added to a 2.3 mL dichloromethane solution containing 20 mg (0.028 mmol) of PerNN. The reaction mixture was stirred at 0°C for 90 minutes, then restored to 25°C, and stirred for another 12 hours at this temperature. After the reaction was complete, the solvent was recovered by vacuum distillation, and the residue was separated by 200-300 mesh neutral silica gel column chromatography. A mixture of dichloromethane and methanol (30:1 v / v) was used as the eluent, and the fourth yellow-green band was collected to obtain a solution of the target product PerNN-O. The solvent was then recovered by vacuum distillation, and the residue was dried under vacuum to obtain a yellow solid of 11.25 mg, which was the compound PerNN-O, with a yield of 55%.

[0052] Figure 8 The hydrogen NMR spectrum of PerNN-O; 1 H NMR (600 MHz, CDCl3) δ 9.78 (s, 1H),9.22 (d, J = 9.2 Hz, 1H), 8.50 (d, J = 9.2 Hz, 1H), 8.44 (s, 1H), 8.43 – 8.42(m, 2H), 8.35 (d, J = 8.8 Hz, 1H), 5.06 (t, J= 7.1 Hz, 2H), 2.34 – 2.29 (m,2H), 1.56 – 1.50 (m, 2H), 1.42 – 1.39 (m, 2H), 1.31 – 1.29 (m, 2H), 0.84 (t, J = 7.3 Hz, 3H).

[0053] Figure 9 The carbon NMR spectrum of PerNN-O; 13 C NMR (151 MHz, CDCl3) δ 144.91 (d, J F-C = 247.3 Hz), 141.32 (d, J F-C = 245.6 Hz), 137.85 (d, J F-C = 125.9 Hz), 137.35,135.80, 135.75, 135.44, 126.63, 125.81, 124.68, 123.87, 123.79, 121.77,121.65, 121.46, 119.81, 119.54, 119.37, 119.23, 118.31, 117.78, 116.89,116.24, 115.92, 114.90 (d, J F-C = 17.4 Hz), 47.15, 31.40, 31.25, 29.70, 22.47,13.87.

[0054] Performance testing: The UV absorption and fluorescence emission spectra of compound PerNN-O in different solvents are attached. Figure 11 As shown; the fluorescence quantum yield of compound PerNN-O in tetrahydrofuran was 8.00%; we selected 2',7'-dichlorodihydrofluorescein (DCFH), which can be converted into green fluorescent 2',7'-dichlorofluorescein (DCF) after activation by reactive oxygen species, as an indicator of reactive oxygen species. The efficiency of PerNN-O in generating reactive oxygen species in a solution of H2O:tetrahydrofuran = 1:1 was investigated. After 9 minutes of white light irradiation, the fluorescence intensity of PerNN-O increased by 5 times compared to DCFH. The results are shown in the attached figure. Figure 24 As shown.

[0055] Example 4. Synthesis of compound PerNN-H

[0056] 20 mg (0.028 mmol) of PerNN was dissolved in 1 mL of dichloromethane, and 2.6 μL (0.031 mmol) of 12 M hydrochloric acid was added dropwise. The mixture was stirred at room temperature for 30 min. After the reaction was complete, the solvent was recovered by vacuum distillation, and the residue was washed with n-hexane, filtered, and air-dried to give 19.63 mg of a yellow solid, which was compound PerNN-H, with a yield of 98%.

[0057] Figure 12 The image shows the proton NMR spectrum of PerNN-H. 1 H NMR (600 MHz, CDCl3) δ 10.43 (s, 1H),9.00 (d, J = 8.9 Hz, 1H), 8.78 (d, J = 8.9 Hz, 1H), 8.67 (s, 1H), 8.63 (d, J = 8.9 Hz, 1H), 8.56 (s, 1H), 8.53 (d, J = 8.8 Hz, 1H), 5.15 (t, J = 6.9 Hz,2H), 2.38 – 2.32 (m, 2H), 1.56 – 1.51 (m, 2H), 1.43 – 1.38 (m, 2H), 1.32 –1.28 (m, 2H), 0.84 (t, J = 7.2 Hz, 3H).

[0058] Figure 13 The image shows the carbon NMR spectrum of PerNN-H. 13 C NMR (151 MHz, CDCl3) δ 160.41 (d, J F-C = 41.3 Hz), 144.94 (d, J F-C = 243.7 Hz), 142.37, 138.11 (d, J F-C= 125.2Hz), 137.78, 136.46, 133.81, 131.25, 129.73, 127.50, 127.31, 124.70, 124.62,123.15, 122.75, 122.09, 119.97, 118.58, 118.29, 117.89, 117.57, 117.23,115.39, 113.50, 112.97 (d, J F-C = 165.2 Hz), 47.62, 31.33, 27.01, 22.43,13.80.

[0059] Performance testing: The UV absorption and fluorescence emission spectra of compound PerNN-H in different solvents are attached. Figure 15 As shown, the fluorescence quantum yield of compound PerNN-H in tetrahydrofuran is 8.00%.

[0060] Example 5. Synthesis of compound PerNN-MeI

[0061] Under argon protection, 20 mg (0.028 mmol) of PerNN was added to a 25 ml double-necked flask containing a magnetic magnet. After evacuation for 3 min, nitrogen was introduced, and this operation was repeated three times. Then, 1 ml of acetonitrile was added, the temperature was raised to 90 °C, and the mixture was stirred at 90 °C for 0.5 h to completely dissolve PerNN. Then, 1 ml (16.1 mmol) of iodomethane was added dropwise, and the reaction was stirred at 90 °C for 12 h. After the reaction was completed, the solvent was recovered by vacuum distillation to obtain a mixture of the target products. The mixture was separated by 200-300 mesh neutral silica gel column chromatography using a 20:1 volume ratio of dichloromethane and methanol as the eluent. The third yellow band was collected to obtain a solution of the target product PerNN-MeI. The solvent was then recovered by vacuum distillation, and the residue was dried under vacuum to obtain 16.14 mg of yellow solid, which was the compound PerNN-MeI, with a yield of 79%.

[0062] Figure 16 The 1H NMR spectrum of PerNN-MeI: 1 H NMR (600 MHz, MeOD) δ 10.69 (s,1H), 9.24 (s, 1H), 9.13 (m, 3H), 9.05 (d, J = 8.9 Hz, 1H), 8.86 (d, J = 8.7Hz, 1H), 5.35 (t, J= 6.6 Hz, 2H), 5.29 (s, 3H), 2.40 – 2.35 (m, 2H), 1.50 –1.44 (m, 2H), 1.40 – 1.35 (m, 2H), 1.30 – 2.70 (m, 2H), 0.77 (t, J = 7.2 Hz, 3H).

[0063] Figure 17 The carbon NMR spectrum of PerNN-MeI: 13 C NMR (151 MHz, MeOD) δ 147.57,145.11 (d, J F-C = 240.0 Hz), 141.75 (d, J F-C = 262.0 Hz), 138.12 (t, J F-C =127.4 Hz), 137.81, 136.21, 135.02, 131.03, 128.26, 127.17, 127.13, 124.22,122.83, 122.52, 122.14, 120.86, 118.58, 118.24, 118.08, 117.50, 117.01,116.74, 114.89, 114.03 (t, J F-C = 18.6 Hz), 114.03, 45.13, 31.09, 30.92,26.46, 22.09, 12.69.

[0064] Performance testing: The UV absorption and fluorescence emission spectra of compound PerNN-MeI in different solvents are attached. Figure 19 As shown, the results indicate that compound PerNN-MeI exhibits anti-Kasha dual emission; the fluorescence quantum yield of compound PerNN-MeI in tetrahydrofuran is 62.28%; we selected 2',7'-dichlorodihydrofluorescein (DCFH), which can be converted into green fluorescent 2',7'-dichlorofluorescein (DCF) after activation by reactive oxygen species, as a reactive oxygen species indicator. The efficiency of reactive oxygen species generation by compound PerNN-MeI in a solution of H2O:tetrahydrofuran = 1:1 was investigated. After 9 minutes of white light irradiation, the fluorescence intensity of PerNN-MeI increased by 228 times compared to DCFH, indicating that the product PerNN-MeI can efficiently generate reactive oxygen species and has the potential for application in photodynamic therapy. (See attached image.) Figure 24 As shown.

[0065] Example 6. Synthesis of compound PerNN-MeCl

[0066] Dissolve 16.14 mg (0.022 mmol) of PerNN-MeI in 3 ml of methanol, then add a solution of 17.93 mg (0.11 mmol) of ammonium hexafluorophosphate dissolved in 0.5 ml of water, then add 5 ml of water and stir for 1 minute to produce a yellow precipitate. Filter and dry the precipitate, and dissolve the product obtained above in 1.2 ml of acetonitrile. 30.57 mg (0.11 mmol) of tetrabutylammonium chloride was added to 0.5 ml of acetonitrile. Then, the tetrabutylammonium chloride solution was added to the acetonitrile solution of the above-obtained reactants. The mixture was stirred for 1 minute. After the reaction was completed, the solvent was recovered by vacuum distillation to obtain the crude product. The crude product was separated by 200-300 mesh neutral silica gel column chromatography. A mixed solvent of dichloromethane and methanol with a volume ratio of 20:1 was used as the eluent. The third yellow band was collected to obtain a solution of PerNN-MeCl. The solvent was then recovered by vacuum distillation. The residue was dried under vacuum to obtain 12.11 mg of yellow solid, which was the compound PerNN-MeCl, with a yield of 75%.

[0067] Figure 20 The 1H NMR spectrum of PerNN-MeCl: 1 H NMR (600 MHz, CDCl3) δ 12.52 (s,1H), 9.42 (d, J = 8.4 Hz, 1H), 8.96 (m, 2H), 8.81 (s, 1H), 8.72 (s, 1H), 8.69(d, J = 8.1 Hz, 1H), 5.66 (s, 3H), 5.20 (t, J = 6.8 Hz, 2H), 2.43 – 2.35 (m,2H), 1.66 – 1.61 (m, 2H), 1.44 – 1.39 (m, 2H), 1.31 – 1.29 (m, 2H), 0.84 (d, J = 7.2 Hz, 3H).

[0068] Figure 21 The carbon NMR spectrum of PerNN-MeCl: 13 C NMR (126 MHz, CDCl3) δ 150.32,144.86 (d, J F-C = 243.6 Hz), 141.80 (d,J F-C = 252.7 Hz), 138.22 (d, J F-C =255.8 Hz), 137.59, 135.97, 134.55, 130.97, 128.43, 127.56, 127.18, 126.23,124.14, 122.91, 122.81, 122.61, 119.90, 118.87, 118.57, 118.18, 117.80,117.62, 117.41, 114.61, 113.79 (d, J F-C = 2.1 Hz), 45.84, 31.38, 31.34, 27.02,22.44, 13.86.

[0069] Performance testing: The UV absorption and fluorescence emission spectra of compound PerNN-MeCl in different solvents are attached. Figure 23 As shown, the results indicate that compound PerNN-MeCl exhibits anti-Kasha dual emission; the fluorescence quantum yield of compound PerNN-MeCl in n-hexane is 55.00%; we selected 2',7'-dichlorodihydrofluorescein (DCFH), which can be converted into green fluorescent 2',7'-dichlorofluorescein (DCF) after activation by reactive oxygen species (ROS) as an ROS indicator. The efficiency of ROS generation by compound PerNN-MeCl in a H2O:tetrahydrofuran = 1:1 solution was investigated. After 9 minutes of white light irradiation, the fluorescence intensity of PerNN-MeCl increased by 150 times compared to DCFH, indicating that this compound possesses highly efficient ROS properties. This suggests that the product PerNN-MeCl can efficiently generate ROS and has the potential for application in photodynamic therapy. The results are attached. Figure 24 As shown.

Claims

1. A method for preparing a fused-ring aromatic hydrocarbon by intercalating pyrrole and pyridine into perylene, characterized in that, The compounds PerNN, PerNN-O, PerNN-MeCl, and PerNN-MeI were obtained via the following synthetic routes.

2. In the method for preparing pyrrole and pyridine intercalated into perylene according to claim 1, the mass ratio of each reactant in the synthesis reaction of compound PerNN is NP-CHO: azidetrimethylsilane: trifluoromethanesulfonic acid = 1:22.78:13.57; the solvent used in the reaction is trifluoroacetic acid, and the amount of trifluoroacetic acid used is 20 ml / g NP-CHO.

3. The method for preparing fused-ring aromatic hydrocarbons by embedding pyrrole and pyridine into perylene according to claim 1, wherein the synthesis reaction of compound PerNN is carried out under argon protection, the reaction temperature is 60°C, and the reaction time is 1 hour.

4. In the method for preparing a polycyclic aromatic hydrocarbon by embedding pyrrole and pyridine into perylene according to claim 1, the mass ratio of each reactant in the synthesis reaction of compound PerNN-O is PerNN: m-chloroperoxybenzoic acid = 1:0.98; the solvent used in the reaction is dichloromethane, and the amount of dichloromethane used is 115 ml / g PerNN.

5. The method for preparing a polycyclic aromatic hydrocarbon by embedding pyrrole and pyridine into perylene according to claim 1, wherein the synthesis reaction of compound PerNN-O is carried out under argon protection, the first stage reaction temperature is 0°C, and the reaction time is 90 minutes; The second stage reaction temperature is 25℃, and the reaction time is 12 hours.

6. In the method for preparing a polycyclic aromatic hydrocarbon by intercalating pyrrole and pyridine into perylene according to claim 1, the mass ratio of each reactant in the synthesis reaction of compound PerNN-MeI is PerNN: iodomethane = 1:114; the solvent used in the reaction is acetonitrile, and the amount of acetonitrile used is 50 ml / g PerNN.

7. The method for preparing a fused-ring aromatic hydrocarbon by intercalating pyrrole and pyridine into perylene according to claim 1, wherein the synthesis reaction of compound PerNN-MeI is carried out under argon protection, the reaction temperature is 90°C, and the reaction time is 12 hours.

8. In the method for preparing pyrrole and pyridine intercalated into perylene according to claim 1, the mass ratio of each reactant in the synthesis reaction of compound PerNN-MeCl is PerNN-MeI:ammonium hexafluorophosphate:tetrabutylammonium chloride = 1:1.11:1.89; the solvent used in the first stage reaction is methanol, and the amount of methanol used is 185.87 ml / g PerNN-MeI; The solvent used in the second stage reaction was acetonitrile, and the amount of acetonitrile used was 74.35 ml / g PerNN-MeI.

9. The method for preparing a fused-ring aromatic hydrocarbon by intercalating pyrrole and pyridine into perylene according to claim 1, wherein the synthesis reaction temperature of compound PerNN-MeCl is 25°C, the reaction time of the first stage is 1 minute, and the reaction time of the second stage is 1 minute.

10. The application of compounds PerNN-MeI and PerNN-MeCl in the preparation of photodynamic therapeutic drugs, characterized in that... The compound PerNN-MeI has the following structural formula: The structural formula of the compound PerNN-MeCl is: The compounds PerNN-MeI and PerNN-MeCl generate reactive oxygen species.

Images