Dual-band dianthracene photocatalyst as well as preparation method and application thereof

Abstract

The invention discloses a dual-band dianthracene photocatalyst as well as a preparation method and application thereof, and belongs to the field of heterocyclic compounds. The novel 2, 9 '-dianthracene photocatalyst is designed and synthesized, the compatibility at the two wavebands of 365 nm and 405 nm is good, the tetrahydroisoquinoline phosphoramidite can be induced by light, and a new thought is provided for preparing an alpha-phosphoramidate compound; the reaction conditions are mild, the reaction time is short, the photocatalyst can be recycled, the circulation loss is low, the circulation efficiency is high, the production efficiency is greatly improved, and the production period and cost are reduced; the product is free of transition metal residues and high in yield.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of heterocyclic compounds, and particularly relates to a dual-band binaphthyl photocatalyst as well as a preparation method and application thereof. BACKGROUND

[0002] As an analogue of natural amino acid, α-amino phosphates play a crucial role in the fields of materials, agriculture, medicine and even life science, and have attracted extensive attention due to their functions such as anti-tumor, anti-plant virus, plant growth regulation, herbicide, bactericide, enzyme activity inhibition, antioxidant, radiation protection and biological cell membrane destruction.

[0003] Many methods for synthesizing α-amino phosphates have been reported, and the most classic synthesis process is achieved through Kabachnik-Fields reaction and Pudovik reaction. In addition, there are also many reports on transition metal catalytic systems, such as iridium catalytic system (Green Chem., 2014, 16, 2438-2442), palladium catalytic system (Chem. Eur. J., 2013, 19, 5654-5664), gold catalyst system (Adv. Synth. Catal. 2012, 354, 1646-1650; Org. Biomol. Chem., 2013, 11, 1606-1609), silver catalytic system (CN201710063566.2), copper catalytic system (Chem. Commun. 2009, 0, 4124-4126), iron catalytic system (Org. Chem. 2014, 34, 2249-2254), ruthenium catalytic system (CN201210171571.2), tungsten catalytic system (Org. Biomol. Chem., 2023, 21, 9049-9053), antimony catalytic system (Chem. Asian J. 2022, 17, e202200656), cobalt catalytic system (CN202210409165.9) and molybdenum catalytic system (Tetrahedron Lett., 2012, 53, 1456-1459), which can all achieve the α-amino phosphorization of tertiary amines. However, the above methods still have many shortcomings, such as substrates containing special functional groups, expensive or toxic transition metal catalysts, and the need for metering or even excess oxidants in some reaction conditions; all the above defects limit the large-scale application of such reactions.

[0004] The photocatalytic method is more efficient and has mild reaction conditions, but it needs to use rare metal catalysts, which are high in cost. Although a photocatalytic system is used, it is still carried out under the participation of a transition metal photocatalyst, so the disadvantages of noble metal catalysts cannot be completely avoided. In summary, it is essential to develop a low-cost method that can efficiently achieve such conversions. Chinese invention patent CN202211392739.2 discloses a method for preparing alkynyl tetrahydroisoquinoline derivatives using insoluble poly-porphyrin P as a photosensitizer under visible light conditions. The obvious advantage of this system is that the reaction conditions are mild, but the reaction time is long and the yield is poor.

[0005] In addition, in the existing reported cases of photocatalysts, most of them are single-waveband light sources or directly use white light sources, but photocatalysts that are compatible with both light sources, especially the photolithography light sources commonly used in the industry at this stage, such as 365 nm and 405 nm, are not common. Therefore, developing a dual-waveband compatible photocatalytic system without the participation of transition metal catalysts is still a hot research and development issue. SUMMARY

[0006] To solve the problems in the background art, the present application provides a dual-waveband binaphthyl photocatalyst, its preparation method and application. A new type of 2,9'-binaphthyl photocatalyst is designed and synthesized, which overcomes the defects of existing catalysts and catalytic systems and effectively reduces the production cost.

[0007] The present application provides a dual-waveband 2,9'-binaphthyl photocatalyst, which has the following structure: ; wherein R1 and R2 are independently selected from one of hydrogen, halogen, C1-C12 alkyl, C1-C12 alkoxy, C6-C12 aryl, C6-C12 aryl substituted by one or more halogens, C6-C12 aryl substituted by one or more C1-C12 alkyl groups, C6-C12 aryl substituted by one or more C1-C12 alkoxy groups, C6-C12 aryloxy, C6-C12 aryloxy substituted by one or more halogens, C6-C12 aryloxy substituted by one or more C1-C12 alkyl groups, and C6-C12 aryloxy substituted by one or more C1-C12 alkoxy groups.

[0008] As a preferred embodiment, the dual-waveband 2,9'-binaphthyl photocatalyst has the following specific structure: , , , , , , .

[0009] The application also provides a preparation method of the above-mentioned dual-band 2,9'-bianthracene photocatalyst, comprising the following steps: S1, under a nitrogen atmosphere, an anthryl boronic acid, anthracene bromide, a catalyst, a base and an organic solvent are added into a reactor; S2, temperature is raised for stirring, and the reaction is monitored by TLC; S3, after the reaction is completed, the solvent is removed, and the target 2,9'-bianthracene photocatalyst is obtained through column chromatography.

[0010] As a preferred embodiment, the catalyst in S1 is palladium tetraphenylphosphine; the equivalent ratio of the anthryl boronic acid, the anthracene bromide, the base and the palladium tetraphenylphosphine is (1-2):1:(1-3):(0.01-0.1), and preferably 1.5:1:2:0.05.

[0011] As a preferred embodiment, the base in S1 is potassium carbonate, and the organic solvent is dimethyl sulfoxide (DMSO).

[0012] As a preferred embodiment, the reaction temperature for stirring in S2 is 80-85℃, and preferably 83℃.

[0013] As a preferred embodiment, the eluent used in the column chromatography in S3 is a mixed solvent of petroleum ether and dichloromethane, and the volume ratio is 1:(1-10).

[0014] The application also provides an application of the above-mentioned dual-band 2,9'-bianthracene photocatalyst in catalyzing the phosphinoylation of tetrahydroisoquinoline to prepare an α-amino phosphate compound under the irradiation of a wavelength 365 nm and 405 nm light source.

[0015] As a preferred embodiment, the catalyzing the phosphinoylation of tetrahydroisoquinoline comprises the following steps: a tetrahydroisoquinoline compound, a phosphite, a 2,9'-bianthracene photocatalyst and an organic solvent are added into a reaction container, and are respectively placed under the irradiation of a wavelength 365 nm and 405 nm light source and in an oxygen atmosphere, and are stirred at room temperature for reaction, the reaction is monitored by TLC, after the reaction is completed, the solvent is removed, and the target product is obtained through column chromatography.

[0016] As a preferred embodiment, the structure of the tetrahydroisoquinoline compound is , and the structure of the phosphite is ; wherein, R a , R bone or a combination of two selected from alkyl, alkoxy, alkylamine, halogen, nitro, cyano, amine group, R c one selected from aryl or alkoxy with carbon number of 1-6.

[0017] As a preferred embodiment, the reaction formula of photocatalytic tetrahydroisoquinoline phosphinyl preparation of alpha-amino phosphate compound is as follows: .

[0018] Compared with the prior art, the present application has the following beneficial effects: 1、The photocatalytic system of the present application does not need the participation of a transition metal catalyst, and a new 2,9'-linked anthracene photocatalyst is designed and synthesized, which provides a new idea for preparing alpha-amino phosphate compounds.

[0019] 2、The 2,9'-linked anthracene photocatalyst prepared by the present application has good compatibility at 365 nm and 405 nm.

[0020] 3、The 2,9'-linked anthracene photocatalyst prepared by the present application can be recycled, and the recycling loss is low. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 The H-NMR spectrum of the TM-1 photocatalyst prepared in Example 1 1 .

[0022] Figure 2 The C-NMR spectrum of the TM-1 photocatalyst prepared in Example 1 13 .

[0023] Figure 3 The H-NMR spectrum of the TM-2 photocatalyst prepared in Example 2 1 .

[0024] Figure 4 The C-NMR spectrum of the TM-2 photocatalyst prepared in Example 2 13 .

[0025] Figure 5 The H-NMR spectrum of the TM-3 photocatalyst prepared in Example 3 1 .

[0026] Figure 6 The C-NMR spectrum of the TM-3 photocatalyst prepared in Example 3 13 .

[0027] Figure 7 The H-NMR spectrum of the TM-4 photocatalyst prepared in Example 4 1 .

[0028] Figure 8 UV-Visible spectrum of TM-1 photocatalyst prepared for Example 1. 13 H-NMR spectrum.

[0029] Figure 9 UV-Visible spectrum of TM-5 photocatalyst prepared for Example 5. 1 H-NMR spectrum.

[0030] Figure 10 UV-Visible spectrum of TM-5 photocatalyst prepared for Example 5. 13 C-NMR spectrum.

[0031] Figure 11 UV-Visible spectrum of TM-6 photocatalyst prepared for Example 6. 1 H-NMR spectrum.

[0032] Figure 12 UV-Visible spectrum of TM-6 photocatalyst prepared for Example 6. 13 C-NMR spectrum.

[0033] Figure 13 UV-Visible spectrum of TM-7 photocatalyst prepared for Example 7. 1 H-NMR spectrum.

[0034] Figure 14 UV-Visible spectrum of TM-7 photocatalyst prepared for Example 7. 13 C-NMR spectrum.

[0035] Figure 15 UV-Visible spectrum of TM-1 photocatalyst prepared for Example 1.

[0036] Figure 16 UV-Visible spectrum of TM-2 photocatalyst prepared for Example 2.

[0037] Figure 17 UV-Visible spectrum of TM-3 photocatalyst prepared for Example 3.

[0038] Figure 18 UV-Visible spectrum of TM-4 photocatalyst prepared for Example 4.

[0039] Figure 19 UV-Visible spectrum of TM-5 photocatalyst prepared for Example 5.

[0040] Figure 20 UV-Visible spectrum of TM-6 photocatalyst prepared for Example 6.

[0041] Figure 21 UV-Visible spectrum of TM-7 photocatalyst prepared for Example 7.

[0042] Figure 22An electron paramagnetic resonance spectrum (EPR). DETAILED DESCRIPTION

[0043] In order to make the objectives, technical solutions and advantages of the present application clearer, the technical solutions of the present application will be described clearly and completely below in conjunction with embodiments. If specific conditions are not indicated in the embodiments, conventional conditions or conditions suggested by the manufacturers are used. If the manufacturers of the reagents or instruments are not indicated, they are all conventional products that can be purchased on the market.

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0045] Example 1 A preparation method of a dual-band 2,9'-bianthracene photocatalyst, comprising the following steps: 1. A 50 mL single-neck flask equipped with a magnetic stirrer was charged with 9-boronic acid anthracene (1.5 eq, 1.5 mmol, 333 mg), 2-bromoanthracene (1 eq, 1 mmol, 257 mg), potassium carbonate (2 eq, 2 mmol, 276 mg), tetrakis(triphenylphosphine)palladium (0.05 eq, 0.05 mmol, 58 mg), and nitrogen was replaced for 3 times; 5 mL of DMSO was added.

[0046] 2. The stirring was started, and the temperature was raised to 83°C for reaction, and during the reaction, sampling was performed for TLC monitoring.

[0047] 3. After the raw materials were substantially completely reacted, the reaction solution was cooled to room temperature, 10 mL of water was added, the reaction solution was transferred to a separatory funnel, extracted with DCM twice, the organic phase was back-extracted with water twice, dried with anhydrous Na2SO4, and the solvent was removed by reduced pressure distillation. The crude product was separated by column chromatography to obtain white solid TM-1 (283 mg, yield 80%).

[0048] The reaction formula is:

[0049] Figure 1 The H-NMR spectrum of TM-1 photocatalyst is: 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3): delta 8.59 (s, 1H), 8.56 (s, 1H), 8.48 (s, 1H), 8.21 (d,J = 8.59 Hz, 1H), 8.13 – 8.07 (m, 4H),8.04 (d, J = 9.21 Hz, 1H), 7.78 (d, J = 7.71 Hz, 2H), 7.59 – 7.44 (m, 5H), 7.35(t, J = 8.72 Hz, 2H). Figure 2 is TM-1 photocatalyst 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 136.9, 135.9,132.3, 132.1, 131.7, 131.6, 131.1, 130.5, 130.3, 129.5, 128.6, 128.4, 128.3,128.3, 127.0, 126.9, 126.6, 126.4, 125.7, 125.7, 125.6, 125.3. Example 2 A method for preparing a dual-band 2,9'-bianthracene photocatalyst, comprising the following steps: 1. Into a 50 mL single-necked flask equipped with a magnetic stirrer, 9-boronic acid anthracene (1.5 eq, 1.5 mmol, 333 mg), 2-bromo-9,10-diphenylanthracene (1 eq, 1 mmol, 409 mg), potassium carbonate (2 eq, 2 mmol, 276 mg), tetrakis(triphenylphosphine)palladium (0.05 eq, 0.05 mmol, 58 mg) were added, and nitrogen was replaced for 3 times; and 5 mL of DMSO was added.

[0050] 2. Stirring was started, and the temperature was raised to 83°C for reaction, during which sampling was performed for TLC monitoring.

[0051] 3. After the raw materials were substantially completely reacted, the reaction solution was cooled to room temperature, 10 mL of water was added, the reaction solution was transferred to a separatory funnel, and extraction was performed twice with DCM; after the organic phase was back-extracted twice with water, drying was performed with anhydrous Na2SO4, and the solvent was removed by reduced pressure distillation. The crude product was separated by column chromatography to obtain yellow-white solid TM-2 (379 mg, yield 75%).

[0052] The reaction formula is:

[0053] Figure 3 is TM-2 photocatalyst 1H-NMR spectrum; 1 H NMR (400 MHz, CDC13): delta 8.47 (s, 1H), 8.02 (d, J = 8.48 Hz, 2H), 7.90 (d, J = 8.87 Hz, 1H), 7.83 (s, 1H), 7.81 - 7.56 (m, 9H), 7.54 - 7.28 (m, 12H). Figure 4 is a TM-2 photocatalyst 13 C-NMR spectrum; 13 C NMR (100 MHz, CDC13): delta 139.2, 138.9, 137.5, 137.3, 137.2, 135.4, 131.6, 131.5, 131.4, 130.5, 130.4, 130.3, 129.9, 129.3, 129.2, 129.1, 128.7, 128.5, 128.5, 127.8, 127.5, 127.2, 127.1, 127.0, 126.7, 125.5, 125.3, 125.3, 125.2. Example 3 A method for preparing a dual-band 2,9'-bianthracene photocatalyst, comprising the following steps: 1. A 50 mL single-necked flask equipped with a magnetic stirrer was charged with 9-boronic acid anthracene (1.5 eq, 1.5 mmol, 333 mg), 2-bromo-9,10-dinaphthyl anthracene (1 eq, 1 mmol, 509 mg), potassium carbonate (2 eq, 2 mmol, 276 mg), and tetrakis(triphenylphosphine)palladium (0.05 eq, 0.05 mmol, 58 mg), and nitrogen was replaced for 3 times; and 5 mL of DMSO was added.

[0054] 2. The stirring was started, and the temperature was raised to 83°C for reaction, and TLC was used to monitor the reaction during the sampling.

[0055] 3. After the raw materials were substantially reacted, the reaction solution was cooled to room temperature, 10 mL of water was added, the reaction solution was transferred to a separatory funnel, and extracted with DCM twice, and the organic phase was back-extracted with water twice, dried with anhydrous Na2SO4, and the solvent was removed by reduced pressure distillation. The crude product was separated by column chromatography to obtain a light yellow solid TM-3 (455 mg, yield 75%).

[0056] The reaction formula is:

[0057] Figure 5 It is a TM-3 photocatalyst 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3): delta 8.42 (s, 1H), 8.20 – 8.13 (m, 2H), 8.11 – 8.04 (m, 1H), 8.05 – 7.91 (m, 6H), 7.90 – 7.76(m, 6H), 7.73 (d, J = 8.77 Hz, 2H), 7.69 – 7.60 (m, 3H), 7.50 – 7.44 (m, 2H), 7.43 – 7.29 (m, 7H). Figure 6 It is a TM-3 photocatalyst 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 137.4, 137.3,137.0, 136.7, 136.4, 135.6, 133.6, 133.4, 133.0, 132.8, 131.4, 130.7, 130.5,130.4, 130.3(3), 130.3(1), 130.1, 129.8, 129.6, 129.6, 129.3, 129.2, 128.4(9), 128.4(5), 128.3, 128.3, 128.2, 128.1, 128.1, 127.9, 127.3, 127.2, 126.9,126.9, 126.8, 126.7, 126.4(5), 126.4(2), 126.2, 125.5, 125.4, 125.2. Example 4 A method for preparing a dual-band 2,9'-bianthracite photocatalyst includes the following steps: 1. Add 9-borate anthracene (1.5 eq, 1.5 mmol, 333 mg), 2-bromo-9,10-dibutoxyanthracene (1 eq, 1 mmol, 401 mg), potassium carbonate (2 eq, 2 mmol, 276 mg), and tetrakis(triphenylphosphine)palladium (0.05 eq, 0.05 mmol, 58 mg) to a 50 mL single-necked flask equipped with a magnetic stirrer, and purge with nitrogen three times; then add 5 mL of DMSO.

[0058] 2. Start stirring and heat to 83°C for reaction, during which sampling for TLC monitoring.

[0059] 3. After the raw materials are substantially reacted, the reaction solution is cooled to room temperature, 10 mL of water is added, the reaction solution is transferred to a separatory funnel and extracted twice with DCM, the organic phase is back-extracted twice with water and then dried over anhydrous Na2SO4, and the solvent is removed by reduced pressure distillation. The crude product is separated by column chromatography to obtain a light yellow solid TM-4 (300 mg, yield 60%).

[0060] The reaction formula is:

[0061] Figure 7 TM-4 photocatalyst is 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3): delta 8.57 (s, 1H), 8.49 (d, J = 8.81 Hz, 1H), 8.42 – 8.31 (m, 3H), 8.11 (d, J = 8.50 Hz, 2H), 7.82(d, J = 8.84 Hz, 2H), 7.61 – 7.46 (m, 5H), 7.37 (t, J = 8.14 Hz, 2H), 4.33 (t, J = 6.66 Hz, 2H), 4.18 (t, J = 6.79 Hz, 2H), 2.13 (dt, J = 14.37, 6.80 Hz, 2H), 1.89(dt, J = 14.55, 6.95 Hz, 2H), 1.78 (h, J = 7.40 Hz, 2H), 1.51 (h, J = 7.41 Hz, 2H), 1.13 (t, J = 7.38 Hz, 3H), 0.90 (t, J = 7.38 Hz, 3H). Figure 8 TM-4 photocatalyst is 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta147.8, 137.2, 135.5, 131.6, 130.5, 129.3, 128.6, 127.0, 126.9, 125.8, 125.6 (bs), 125.5, 125.4, 125.3, 125.2, 125.0, 124.6, 123.0, 122.9 (3), 122.9 (1), 76.3, 76.2, 33.0, 32.7, 19.7, 19.4, 14.3, 14.1. Example 5 A method for preparing a dual-band 2,9'-bianthracene photocatalyst, comprising the following steps: 1. A 50 mL single-necked flask equipped with magnetic stirring was charged with 10-phenyl-9-anthracene boronic acid (1.5 eq, 1.5 mmol, 447 mg), 2-bromoanthracene (1 eq, 1 mmol, 257 mg), potassium carbonate (2 eq, 2 mmol, 276 mg), tetrakis(triphenylphosphine)palladium (0.05 eq, 0.05 mmol, 58 mg), and nitrogen was replaced for 3 times; 5 mL of DMSO was added.

[0062] 2. Start stirring and heat to 83°C for reaction, and take samples for TLC monitoring during the reaction.

[0063] 3. After the raw materials are substantially completely reacted, the reaction solution is cooled to room temperature, 10 mL of water is added, the reaction solution is transferred to a separatory funnel, extracted with DCM twice, the organic phase is back-extracted with water twice, dried with anhydrous Na2SO4, and the solvent is removed under reduced pressure. The crude product is separated by column chromatography to obtain a light yellow solid TM-5 (258 mg, yield 60%).

[0064] The reaction formula is:

[0065] Figure 9 TM-5 photocatalyst is 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3): delta 8.61 (s, 1H), 8.51 (s, 1H), 8.24 (d, J = 8.62 Hz, 1H), 8.16 (s, 1H), 8.11 (d, J = 9.38 Hz, 1H), 8.06 (d, J = 9.29 Hz, 1H), 7.82 (d, J= 8.23 Hz, 1H), 7.75 (d, J = 8.32 Hz, 2H),7.68 – 7.56 (m, 4H), 7.58 – 7.49 (m, 4H), 7.39 – 7.30 (m, 4H). Figure 10 is a TM-5 photocatalyst 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 139.2, 137.5,137.0, 136.1, 132.3, 132.1, 131.7, 131.5, 131.1, 130.4, 130.1, 130.1, 129.6,128.6, 128.4, 128.4, 127.7, 127.2, 127.1, 126.6, 126.4, 125.8, 125.7, 125.3,125.2. Example 6 A method for preparing a dual-band 2,9'-bianthracene photocatalyst, comprising the following steps: 1. A 50 mL single-necked flask equipped with a magnetic stirrer was charged with 2-anthracene boronic acid (1.5 eq, 1.5 mmol, 333 mg), 9-bromo-10-methoxyanthracene (1 eq, 1 mmol, 287 mg), potassium carbonate (2 eq, 2 mmol, 276 mg), tetrakis(triphenylphosphine)palladium (0.05 eq, 0.05 mmol, 58 mg), and nitrogen was replaced for 3 times; 5 mL of DMSO was added.

[0066] 2. Start stirring and heat to 83°C for reaction, and take samples for TLC monitoring during the period.

[0067] 3. After the raw materials were substantially reacted, the reaction solution was cooled to room temperature, 10 mL of water was added, and the reaction solution was transferred to a separatory funnel and extracted with DCM twice, and the organic phase was back-extracted with water twice, then dried with anhydrous Na2SO4, and the solvent was removed by reduced pressure distillation. The crude product was separated by column chromatography to obtain a light yellow solid TM-6 (230 mg, yield 60%).

[0068] The reaction formula is:

[0069] Figure 11 is a TM-6 photocatalyst 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3):delta 8.58 (s, 1H),8.47 (s, 1H), 8.42 (d, J = 8.71 Hz, 2H), 8.20 (d, J = 8.59 Hz, 1H), 8.11 – 8.08(m, 2H), 8.04 (d, J = 9.18 Hz, 1H), 7.78 (d, J = 8.83 Hz, 2H), 7.57 – 7.48 (m,5H), 7.35 (t, J = 8.46 Hz, 2H), 4.25 (s, 3H). Figure 12 is a TM-6 photocatalyst 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 152.4, 135.9,133.1, 132.3, 132.2, 131.8, 131.3, 131.1, 130.6, 129.7, 128.4, 128.3(5),128.3(1), 127.4, 126.5, 126.4, 125.8(bs), 125.7, 125.2, 124.3, 122.5, 63.4. Example 7 A method for preparing a dual-band 2,9'-bianthracene photocatalyst, comprising the following steps: 1. Into a 50 mL single-necked flask equipped with a magnetic stirrer, 2-anthracene boronic acid (1.5 eq, 1.5 mmol, 333 mg), 9-bromo-10-butoxyanthracene (1 eq, 1 mmol, 329 mg), potassium carbonate (2 eq, 2 mmol, 276 mg), tetrakis(triphenylphosphine)palladium (0.05 eq, 0.05 mmol, 58 mg) were added, and nitrogen was replaced for 3 times; and 5 mL of DMSO was added.

[0070] 2. Stirring was started, and the temperature was raised to 83°C for reaction, during which sampling was performed for TLC monitoring.

[0071] 3. After the raw materials were substantially completely reacted, the reaction solution was cooled to room temperature, 10 mL of water was added, the reaction solution was transferred to a separatory funnel, and extraction was performed twice with DCM; after the organic phase was back-extracted twice with water, drying was performed with anhydrous Na2SO4, and the solvent was removed by reduced pressure distillation. The crude product was separated by column chromatography to obtain a light yellow solid TM-7 (256 mg, yield 60%).

[0072] The reaction formula is:

[0073] Figure 13 is a TM-7 photocatalyst 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3): delta 8.58 (s, 1H), 8.47 (s, 1H), 8.42 (d, J = 8.73 Hz, 2H), 8.20 (d, J = 8.61 Hz, 1H), 8.13 – 8.07 (m, 2H), 8.04 (d, J = 9.33 Hz, 1H), 7.77 (d, J = 8.83 Hz, 2H), 7.60 – 7.46 (m, 5H), 7.35 (t, J = 7.22 Hz, 2H), 4.31 (t, J = 6.63 Hz, 2H), 2.13 (p, J = 6.81 Hz, 2H), 1.78 (h, J = 7.40 Hz, 2H), 1.14 (t, J = 7.36 Hz, 3H). Figure 14 is a TM-7 photocatalyst 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 151.7, 135.9, 132.8, 132.2, 132.1, 131.7, 131.2, 131.1, 130.6, 129.7, 128.4, 128.3(4), 128.2(6), 127.3, 126.5, 126.4, 125.7(2), 125.6(9), 125.6(5), 125.0, 124.6, 122.6, 76.2, 33.0, 19.7, 14.3. Example 8 UV-Vis spectrum The UV-Vis spectrum was tested on a Shimadzu UV-1900 UV-Vis spectrophotometer, with toluene as the solvent (photosensitizer concentration: 4×10 -5 mol / L).

[0074] Figures 15-21 The UV-Vis spectra of the TM-1 photocatalyst to the TM-7 photocatalyst prepared in Examples 1-7 are shown respectively.

[0075] This indicates that the newly synthesized 2,9'-bianthracite compounds exhibit very high absorption intensities in the light regions near 365 nm and 405 nm, meaning that these compounds possess excellent photo-radical conversion capabilities under these two light sources, thus fulfilling the prerequisites for catalyzing / initiating photo-induced radical reactions.

[0076] Example 9 Electron spin resonance (EPR) characterization ESR-ST experiments were performed on a Bruker-BioSpin ESR5000 electron spin resonance spectrometer with a field strength of 0-650 mT, a power of 9.5 GHz, and a frequency modulation of 100 kHz. Under stirring conditions, anthracene-based photocatalyst (0.01 mmol) and radical scavenger methylpyridine N-oxide (DMPO, 0.02 mmol) were sequentially added to a solution of THF (1.0 mL). In the dark, the sample was irradiated for 1-3 min using handheld 365 nm and 405 nm LEDs, respectively. 25 μL of the sample was placed in an EPR test tube, nitrogen gas was introduced to purge oxygen, and then the tube was placed in the test chamber.

[0077] Figure 22 Here is the EPR spectrum: As can be seen from the spectrum, the same free radical signal was generated under irradiation by light sources at 365 nm and 405 nm, that is, the same free radical species were generated, which can initiate the same synthetic reaction mechanism.

[0078] Example 10 Catalytic performance characterization

[0079] 1. Yield: Yield = [(Actual product yield) ÷ (Theoretical product yield)] × 100%.

[0080] 2. Purity: NMR spectroscopy was performed. 1 H NMR and 13 All C NMR measurements were performed using a Bruker AM-400 instrument. The test temperature was room temperature, and the solvent was deuterated chloroform. (Reference selection follows.) 1 ¹H NMR: CHCl₃ was 7.26 ppm; 13 C10 NMR: CHCl3 was 77.2 ppm. The NMR spectra of Examples 1-7 are shown below. Figures 1-14 .

[0081] The results of the yield and purity tests are shown in Table 1.

[0082] Table 1. Yield and purity test results

[0083] Example 11 Catalyst recycle test

[0084] The catalyst recycle activity was tested using TM4 of Example 4, after the first reaction was completed, the catalyst was recycled and the steps 1-3 were repeated, the product yield of the second reaction was tested, then the catalyst was recycled again, the product yield of the recycling 0-7 times was tested, the test results are shown in Table 2.

[0085] Table 2. Recycle test results

[0086] It can be seen that the 2,9'-bianthracene photocatalyst of the present application can be separated and purified and recycled, and the recycling number is as high as seven times, and there is no obvious decrease in catalytic efficiency.

[0087] The above described embodiments only express several preferred embodiments of the present application, the description is more specific and detailed, but is not used to limit the present application. It should be pointed out that for those skilled in the art, the present application can also have various changes and modifications, any modification, equivalent replacement, improvement, etc. within the concept and principle of the present application, should be included in the protection scope of the present application.

Claims

1. A dual-band 2,9'-bianthracite photocatalyst, characterized in that, The structure is as follows: ； R1 and R2 are each independently selected from one of hydrogen, halogen, C1-C12 alkyl, C1-C12 alkoxy, C6-C12 aryl, C6-C12 aryl substituted with one or more halogens, C6-C12 aryl substituted with one or more C1-C12 alkyls, C6-C12 aryl substituted with one or more C1-C12 alkoxys, C6-C12 aryloxy, C6-C12 aryloxy substituted with one or more halogens, C6-C12 aryloxy substituted with one or more C1-C12 alkyls, and C6-C12 aryloxy substituted with one or more C1-C12 alkoxys.

2. The dual-band 2,9'-bianthracite photocatalyst according to claim 1, characterized in that, Its specific structure is as follows: ， ， ， ， ， ， 。 3. The method for preparing the dual-band 2,9'-bianthracite photocatalyst according to claim 1 or 2, characterized in that, Includes the following steps: S1. Under a nitrogen atmosphere, anthraquinone, anthraquinone bromide, catalyst, base and organic solvent are added to the reactor; S2. Heat and stir, and monitor the reaction by TLC thin-layer chromatography; S3. After the reaction is complete, the solvent is removed, and the target 2,9'-bianthracite photocatalyst is obtained by column chromatography.

4. The preparation method of the dual-band 2,9'-bianthracite photocatalyst according to claim 3, characterized in that, The catalyst described in S1 is tetrakis(triphenylphosphine)palladium; the equivalent ratio of anthracene boronic acid, anthracene bromide, base, and tetrakis(triphenylphosphine)palladium is (1-2):1:(1-3):(0.01-0.1).

5. The preparation method of the dual-band 2,9'-bianthracite photocatalyst according to claim 3, characterized in that, The base in S1 is potassium carbonate, and the organic solvent is dimethyl sulfoxide.

6. The preparation method of the dual-band 2,9'-bianthracite photocatalyst according to claim 3, characterized in that, The reaction temperature in S2, with heating and stirring, is 80-85℃.

7. The application of the dual-band 2,9'-bianthracite photocatalyst described in claim 1 or 2 in the catalytic tetrahydroisoquinoline phosphonacylation preparation of α-aminophosphate compounds under irradiation with light sources at wavelengths of 365 nm and 405 nm.

8. The application according to claim 7, characterized in that, The catalytic tetrahydroisoquinoline phosphonylation includes the following steps: Tetrahydroisoquinoline compound, phosphite, 2,9'-bianthracite photocatalyst and organic solvent were added to a reaction vessel and placed under light sources with wavelengths of 365 nm and 405 nm respectively, in an oxygen atmosphere. The reaction was stirred at room temperature and monitored by TLC thin-layer chromatography. After the reaction was completed, the solvent was removed and the product was obtained by column chromatography.

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