Electrochemical preparation of a class of polysubstituted phenol derivatives

Abstract

The application discloses a kind of polysubstituted phenol derivatives and electrochemical preparation method thereof, which uses 2-(benzo[d]thiazole-2-yl)-4-substituted phenol, substituted pyrazole or benzimidazole as raw material, tetrabutylammonium tetrafluoroborate as electrolyte, a mixture of hexafluoroisopropanol and dichloromethane (volume ratio 7:3) as solvent, direct electrolysis reaction under air atmosphere at room temperature to obtain the target product shown in formula one or formula two. Research has found that such products have good solid fluorescence and exhibit aggregation-induced emission properties in tetrahydrofuran and water systems. The method of the application has the advantages of simple operation, good compatibility of substrate functional groups, mild conditions, low production process cost and environmental friendliness.

Description

Technical Field

[0001] This invention belongs to the field of chemical synthesis, specifically relating to an electrochemical preparation method for a class of polysubstituted phenol derivatives, which prepares polysubstituted phenol derivatives with novel structures. Background Technology

[0002] In recent years, electrochemical synthesis has attracted increasing attention as a sustainable synthetic method, driving redox processes by using electric current instead of chemical oxidants. On the other hand, dehydrogenation cross-coupling is a process that forms CX bonds through the cleavage of carbon / heteroatom hydrogen bonds under oxidative conditions, avoiding the limitation of pre-functionalized starting materials often required in classical coupling reactions. Applying electrochemical reactions to dehydrogenation cross-coupling can significantly improve the efficiency of such reactions because: 1) electrochemistry allows for continuous oxidation of starting materials and intermediate products, thus enabling the development of tandem cross-coupling reactions; 2) electrochemical methods can directly oxidize and activate electron-rich aromatic rings, avoiding the use of oxidants and catalysts. Simultaneously, the cathode can directly reduce the removed hydrogen atoms to hydrogen gas, allowing for subsequent utilization and improving the atom economy of the reaction. Currently, electrochemically mediated tandem dehydrogenation-hydrogen coupling has not been reported.

[0003] Polysubstituted phenols are an important class of organic synthetic intermediates, and their structurally related compounds are frequently used in pharmaceutical chemistry and materials chemistry. The synthesis of these compounds often originates from halogenation, followed by metal-catalyzed coupling reactions to prepare polysubstituted phenol derivatives. Based on the fact that phenols typically exhibit low oxidation potentials and readily oxidize cationic radical intermediates under electrochemical conditions, followed by reactions with various nucleophiles, we discovered a class of tandem oxidative dehydrogenation coupling reactions that can smoothly generate CO and CN bonds in a one-pot reaction, constructing complex polysubstituted phenol derivatives with abundant fluorescent properties. Summary of the Invention

[0004] The purpose of this invention is to provide an electrochemical preparation method for a class of polysubstituted phenol derivatives, and another purpose is to provide the above-mentioned polysubstituted phenol derivatives with abundant fluorescent properties.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows:

[0006] 1. A method for preparing a target polysubstituted phenol derivative by electrochemical synthesis, specifically comprising the following steps:

[0007] Step (1): Dissolve the reactants 2-(benzo[d]thiazol-2-yl)-4-substituted phenol, substituted pyrazole or benzimidazole, and the electrolyte tetrabutylammonium tetrafluoroborate in a mixed solvent of hexafluoroisopropanol and dichloromethane (volume ratio 7:3), and stir with a magnetic stir bar in a round-bottom flask. The molar ratio of the two reactants and the electrolyte is 1:1:2, and the molar concentration of the reaction solution relative to a certain reactant is 0.25 mol / L.

[0008] Step (2): The entire mixture was stirred in air at room temperature with a platinum plate as the anode and a platinum plate electrode as the cathode. The reaction mixture was stirred and electrolyzed at room temperature under a constant battery potential. When the reaction was monitored with a thin-layer chromatography plate and the 2-(benzo[d]thiazol-2-yl)-4-substituted phenol was completely consumed, the reaction solution was directly concentrated under vacuum. The concentrate was separated and purified by a chromatography column to obtain the polysubstituted phenol derivative.

[0009] Preferably, the solvent in step (1) is hexafluoroisopropanol and dichloromethane after drying with activated 4A molecular sieve, and the purity of the two solvents is analytical grade.

[0010] Preferably, the anode and cathode in step (2) are platinum sheets with dimensions of (1.0cm×1.0cm×0.1mm).

[0011] Preferably, the constant voltage reaction voltage in step (2) is 2.50V.

[0012] Preferably, the chromatography in step (2) is performed using a silica gel column, wherein the silica gel used in the silica gel column is 200-300 mesh, and the eluent of the silica gel column is a mixture of petroleum ether and ethyl acetate.

[0013] The polysubstituted phenol derivatives prepared by the above method are characterized by having the following structural formula as shown in Formula 1 or Formula 2:

[0014]

[0015] In Formula 1, when R2 is hydrogen, R1 is selected from any of the following groups: fluorine, chlorine, bromine, iodine, hydrogen, methyl, nitro, cyano, ester; in Formula 2, R3 is selected from methoxy, thiomethyl, dimethyl tert-butylsilyl ether.

[0016] 2. A class of polysubstituted phenol derivatives prepared according to the above method are characterized by solid-state fluorescence and aggregation-induced emission in a tetrahydrofuran and water system. Solid-state fluorescence can be observed directly by placing the solid under a 254 nm UV lamp, while aggregation-induced emission requires testing with a fluorescence spectrophotometer after dissolving the solid in a solution of a certain proportion of water and tetrahydrofuran. Attached Figure Description

[0017] Figure 1 It is the reaction formula for preparing a compound with a specific structure;

[0018] Figure 2 It is the reaction formula for preparing a binary compound;

[0019] Figure 3 These are the solid-state fluorescence of compounds 14b, 11b, 10b, 5b, and 8b under a 254 nm UV lamp;

[0020] Figure 4 This is an aggregation-induced emission fluorescence spectrum of compound 12b. Detailed Implementation

[0021] To enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

[0022] The present invention will be further described below with reference to specific embodiments.

[0023] Example 1: Preparation method of 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-4-methoxy-3-(1H-pyrazol-1-yl)phenol

[0024] Step 1: Add 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol (0.25 mmol, 64 mg, 1.0 equiv), 1H-pyrazole (0.25 mmol, 17 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) sequentially to a dry 40 mL reaction tube. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solids are completely dissolved.

[0025] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of silica gel (200-300 mesh) to the round-bottom flask; evaporating the solution by rotary evaporation; and passing the solution through a silica gel column using a mixture of petroleum ether and ethyl acetate as the eluent. The product, a yellow solid 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-4-methoxy-3-(1H-pyrazole-1-yl)phenol, was obtained. Yellow solid (0.051 g, 0.088 mmol, 70% yield); R f =0.5 (petroleum ether / ethyl acetate = 5:1 (v / v)). (See structural formula 1b).

[0026]

[0027] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1 H NMR (300MHz, CDCl3, 25℃, δ): 14.01 (s, 1H), 8.17 (d, J = 1.8Hz, 1H), 8.13 (d, J = 8.1Hz, 1H), 7.97-7.88 (m, 3H), 7.75 (d, J = 7.5Hz, 1H), 7.60 (d ,J=2.4Hz,1H),7.53-7.44(m,2H),7.37(t,J=7.8Hz,2H),7.07-7.00(m,2H),6.86(s,1H),6.86(t,J=2.1Hz,1H),3.96(s,3H),3.59(s,3H). 13 C10 NMR (75MHz, CDCl3, 25℃, δ): 164.9, 162.5, 156.1, 152.3, 149.3, 149.1, 148.7, 146.3, 145.3, 142.1, 136.5, 134.1, 133.8, 126.8, 126.2, 126.0, 125.2, 125.1, 123.1, 122.9, 122.2, 121.6, 121.3, 119.8, 119.3, 116.7, 112.7, 108.1, 107.5, 57.3, 56.1. Mass spectrometry: calcd for C10 31 H 22 N4O4S2 + ([M+H))+ ),579.1155,found,579.1170. The synthesized compound, after structural identification, is indeed the target compound 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-4-methoxy-3-(1H-pyrazol-1-yl)phenol.

[0028] Example 2: Method for synthesizing 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-fluoro-1H-pyrazole-1-yl)-4-methoxyphenol

[0029] Step 1: Add 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol (0.25 mmol, 64 mg, 1.0 equiv), 4-fluoro-1H-pyrazole (0.25 mmol, 22 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) sequentially to a dry 40 mL reaction tube. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solids are completely dissolved.

[0030] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of silica gel (200-300 mesh) to the round-bottom flask; evaporating the solution by rotary evaporation; and passing the solution through a silica gel column using a mixture of petroleum ether and ethyl acetate as the eluent. The product, a yellow solid 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-fluoro-1H-pyrazole-1-yl)-4-methoxyphenol, was obtained. Yellow solid (0.017 g, 0.029 mmol, 23% yield); R f =0.25 (petroleum ether / ethyl acetate = 10:1 (v / v)). (See structural formula 2b).

[0031]

[0032] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1H NMR (300MHz, CDCl3, 25℃, δ): 13.95 (s, 1H), 8.17 (d, J = 0.9Hz, 1H), 8.13 (d, J = 8.1Hz, 1H), 7.97 (d, J = 8.1Hz, 1H), 7.89 (d, J = 8.1Hz, 1H), 7.8 1(d,J=7.8Hz,1H),7.77(d,J=3.9Hz,1H),7.52-7.47(m,3H),7.43-7.34(m,2H),7.07-7.00(m,2H),6.82(s,1H),3.96(s,3H),3.61(s,3H). 13 C NMR (75MHz, CDCl3, 25℃, δ): 164.5, 162.4, 156.2, 152.8, 152.3, 149.3, 149.2, 148.5, 146.7, 145.2, 136.5, 133.9, 129.9 (d, J=13. 5Hz,1C),126.9,126.2,125.3,125.2,123.1,122.6,122.3,121.6,121.3,119.9,119.5,119.3,116.6,112.7,107.1,57.2,56.1. 19 F NMR (282MHz, CDCl3, 25℃, δ): -174.8(s). Mass spectrometry: HRMS (ESI-TOF) (m / z): calcd for C 31 H 21 FN4O4S2 + ([M+H)) + ),597.1061,found,597.1070.

[0033] The synthesized compound was identified by structural analysis as the target compound 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-fluoro-1H-pyrazole-1-yl)-4-methoxyphenol.

[0034] Example 3: Method for synthesizing 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-chloro-1H-pyrazole-1-yl)-4-methoxyphenol

[0035] Step 1: Add 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol (0.25 mmol, 64 mg, 1.0 equiv), 4-chloro-1H-pyrazole (0.25 mmol, 26 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) sequentially to a dry 40 mL reaction tube. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solids are completely dissolved.

[0036] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of (200-300 mesh) silica gel to the round-bottom flask; evaporating the solution by rotary evaporation; and passing the solution through a silica gel column using a mixture of petroleum ether and ethyl acetate as the eluent. The product, a yellow solid 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-chloro-1H-pyrazole-1-yl)-4-methoxyphenol, was obtained. Yellow solid (0.032 g, 0.053 mmol, 42% yield); R f =0.2 (petroleum ether / ethyl acetate = 10:1 (v / v)). (See structural formula 3b).

[0037]

[0038] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1 H NMR (300MHz, CDCl3, 25℃, δ): 13.86(s,1H),8.16(d,J=1.5Hz,1H),8.12(d,J=8.1Hz,1H),7.96(d,J=8.1Hz,1H),7.89(d,J=8.1Hz,1H),7.84( s,1H),7.80(d,J=7.8Hz,1H),7.62(s,1H),7.51-7.46(m,3H),7.42-7 .34(m,2H),7.07-7.03(m,2H),6.83(s,1H),3.95(s,3H),3.60(s,3H). 13C10 NMR (75MHz, CDCl3, 25℃, δ): 164.3, 162.4, 156.2, 152.3, 149.1, 148.5, 146.8, 145.1, 140.7, 136.5, 133.9, 131.7, 126.9, 126.2, 125.3, 125.2, 123.1, 122.3, 122.0, 121.6, 121.4, 119.9, 119.3, 116.5, 112.7, 112.4, 106.9, 57.1, 56.1. Mass spectrometry: calcd for C10 31 H 21 ClN4O4S2 + ([M+H)) + ),613.0766,found,613.0775.

[0039] The synthesized compound was identified by structural analysis as the target compound 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-chloro-1H-pyrazole-1-yl)-4-methoxyphenol.

[0040] Example 4: Method for synthesizing 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-bromo-1H-pyrazol-1-yl)-4-methoxyphenol

[0041] Step 1: Add 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol (0.25 mmol, 64 mg, 1.0 equiv), 4-bromo-1H-pyrazole (0.25 mmol, 37 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) to a dry 40 mL reaction tube in sequence. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solids are completely dissolved.

[0042] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of silica gel (200-300 mesh) to the round-bottom flask; evaporating the solution by rotary evaporation; and passing the solution through a silica gel column using a mixture of petroleum ether and ethyl acetate as the eluent. The product, a yellow solid 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-bromo-1H-pyrazole-1-yl)-4-methoxyphenol, was obtained. Yellow solid (0.072 g, 0.110 mmol, 88% yield); R f =0.17 (petroleum ether / ethyl acetate = 10:1 (v / v)). (See structural formula 4b).

[0043]

[0044] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1 H NMR (300MHz, CDCl3, 25℃, δ): 13.95(s,1H),8.18–8.17(m,1H),8.13(d,J=8.1Hz,1H),7.97(d,J=7.8Hz,1H),7.89(d,J=8.1Hz,1H),7.86(s ,1H),7.81(d,J=8.1Hz,1H),7.63(s,1H),7.53-7.47(m,2H),7.43-7.34(m,2H),7.07-7.00(m,2H),6.82(s,1H),3.97(s,3H),3.61(s,3H). 13 C10 NMR (75MHz, CDCl3, 25℃, δ): 164.3, 162.4, 156.2, 152.3, 149.1, 149.1, 148.5, 146.8, 145.2, 142.7, 136.5, 133.9, 133.8, 126.9, 126.2, 125.3, 125.2, 123.1, 122.3, 121.9, 121.6, 121.4, 119.9, 119.3, 116.4, 112.7, 106.9, 95.5, 57.1, 56.1. Mass spectrometry: calcd for C10 31 H 21 BrN4O4S2 + ([M+H))+ ),657.0260,found,657.0248.

[0045] The synthesized compound was identified by structural analysis as the target compound 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-bromo-1H-pyrazole-1-yl)-4-methoxyphenol.

[0046] Example 5: Method for synthesizing 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-iodo-1H-pyrazol-1-yl)-4-methoxyphenol

[0047] Step 1: Add 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol (0.25 mmol, 64 mg, 1.0 equiv), 4-iodo-1H-pyrazole (0.25 mmol, 49 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) to a dry 40 mL reaction tube in sequence. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solids are completely dissolved.

[0048] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of (200-300 mesh) silica gel to the round-bottom flask; evaporating the solution by rotary evaporation; and passing the solution through a silica gel column using a mixture of petroleum ether and ethyl acetate as the eluent. The product, a yellow solid 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-iodo-1H-pyrazole-1-yl)-4-methoxyphenol, was obtained. Yellow solid (0.038 g, 0.054 mmol, 43% yield); R f =0.35 (petroleum ether / ethyl acetate = 3:1 (v / v)). (See structural formula 5b).

[0049]

[0050] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1HNMR (300MHz, CDCl3, 25℃, δ): 13.96 (s, 1H), 8.17 (d, J = 1.8Hz, 1H), 8.12 (d, J = 8.1Hz, 1H), 7.95 (d, J = 7.8Hz, 1H), 7.91–7.87 (m, 2H), 7.79(d,J=8.1Hz,1H),7.66(s,1H),7.52-7.45(m,2H),7.41-7.33(m,2H),7.06–6.99(m,2H),6.84(s,1H),3.95(s,3H),3.59(s,3H). 13 CNMR (75MHz, CDCl3, 25℃, δ): 164.4, 162.4, 156.2, 152.3, 149.1, 149.0, 148.5, 147.1, 146.7, 145.2, 138.0, 136.5, 133.9, 126.9, 126.2, 125.3, 125.2, 123.1, 122.3, 121.9, 121.6, 121.4, 119.9, 119.3, 116.4, 112.7, 107.0, 57.1, 56.1. Mass spectrometry: calcd for C 31 H 21 IN4O4S2 + ([M+H)) + ),705.0122,found,705.0131.

[0051] The synthesized compound was identified by structural analysis as the target compound 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-iodo-1H-pyrazole-1-yl)-4-methoxyphenol.

[0052] Example 6: Method for preparing 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-4-methoxy-3-(4-methyl-1H-pyrazole-1-yl)phenol

[0053] Step 1: Add 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol (0.25 mmol, 64 mg, 1.0 equiv), 4-methyl-1H-pyrazole (0.25 mmol, 21 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) sequentially to a dry 40 mL reaction tube. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solids are completely dissolved.

[0054] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of 200-300 mesh silica gel to the round-bottom flask; evaporating the solution by rotary evaporation; and passing the solution through a silica gel column using a mixture of petroleum ether and ethyl acetate as the eluent. The product, a yellow solid 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-methyl-1H-pyrazole-1-yl)-4-methoxyphenol, was obtained. Yellow solid (0.049 g, 0.084 mmol, 67% yield); R f =0.21 (petroleum ether / ethyl acetate = 5:1 (v / v)). (See structural formula 6b).

[0055]

[0056] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1 HNMR (300MHz, CDCl3, 25℃, δ): 13.96 (s, 1H), 8.18–8.17 (m, 1H), 8.13 (d, J = 7.8Hz, 1H), 7.94 (d, J = 8.1Hz, 1H), 7.89 (d, J = 7.5Hz, 1H), 7.77 (d . 13 C10 NMR (75MHz, CDCl3, 25℃, δ): 164.9, 162.5, 155.9, 152.3, 149.3, 149.1, 148.8, 145.9, 145.2, 142.9, 136.5, 134.2, 132.0, 126.7, 126.1, 125.9, 125.1, 123.3, 123.1, 122.1, 121.6, 121.3, 119.6, 119.2, 118.6, 116.8, 112.6, 107.6, 57.3, 56.1, 9.3. Mass spectrometry: calcd for C10 32 H 24 N4O4S2 +([M+H)) + ),593.1312,found,593.1327.

[0057] The synthesized compound was identified by structural analysis as the target compound 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-methyl-1H-pyrazole-1-yl)-4-methoxyphenol.

[0058] Example 7: Method for preparing 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-4-methoxy-3-(4-nitro-1H-pyrazole-1-yl)phenol

[0059] Step 1: Add 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol (0.25 mmol, 64 mg, 1.0 equiv), 4-nitro-1H-pyrazole (0.25 mmol, 28 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) sequentially to a dry 40 mL reaction tube. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solids are completely dissolved.

[0060] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of (200-300 mesh) silica gel to the round-bottom flask; evaporating the solution by rotary evaporation; and passing the solution through a silica gel column using a mixture of petroleum ether and ethyl acetate as the eluent. The product, a yellow solid 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-nitro-1H-pyrazole-1-yl)-4-methoxyphenol, was obtained. Yellow solid (0.050 g, 0.080 mmol, 64% yield); R f =0.16 (petroleum ether / ethyl acetate = 3:1 (v / v)). (See structural formula 7b).

[0061]

[0062] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1HNMR (300MHz, CDCl3, 25℃, δ): 13.80 (s, 1H), 8.42 (d, J = 3.3Hz, 2H), 8.14 (d, J = 2.7Hz, 1H), 8.11 (d, J = 8.1Hz, 1H), 7.96 (d, J = 7.8Hz, 1H), 7.8 7(d,J=7.8Hz,1H),7.79(d,J=7.8Hz,1H),7.52-7.41(m,3H),7.39-7.31(m,1H),7.07–6.98(m,2H),6.84(s,1H),3.93(s,3H),3.59(s,3H). 13 C10 NMR (75MHz, CDCl3, 25℃, δ): 163.4, 162.2, 156.3, 152.2, 149.1, 148.6, 147.9, 147.1, 145.0, 137.7, 136.3, 133.8, 133.3, 127.2, 126.5, 126.2, 125.5, 125.2, 123.1, 122.4, 121.5, 121.4, 120.2, 119.2, 115.8, 112.7, 106.3, 56.9, 56.0. Mass spectrometry: calcd for C10 31 H 21 N5O6S2 + ([M+H)) + ),624.1006,found,624.1005.

[0063] The synthesized compound was identified by structural analysis as the target compound 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(4-nitro-1H-pyrazole-1-yl)-4-methoxyphenol.

[0064] Example 8. Method for synthesizing 1-(2-(benzo[d]thiazol-2-yl)-4-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-hydroxy-6-methoxyphenyl)-1H-pyrazole-4-nitrile

[0065] Step 1: Add 2-(benzo[d]thiazolyl)-4-methoxyphenol (0.25 mmol, 64 mg, 1.0 equiv), 1H-pyrazole-4-onitrile (0.25 mmol, 23 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) sequentially to a dry 40 mL reaction tube. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solids are completely dissolved.

[0066] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of silica gel (200-300 mesh) to the round-bottom flask; evaporating the solution by rotary evaporation; and passing the solution through a silica gel column using a mixture of petroleum ether and ethyl acetate as the eluent. The product 1-(2-(benzo[d]thiazol-2-yl)-4-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-hydroxy-6-methoxyphenyl)-1H-pyrazole-4-nitrile was obtained. Yellow solid (0.052 g, 0.085 mmol, 68% yield); R f =0.10 (petroleum ether / ethyl acetate = 3:1 (v / v)). (See structural formula 8b).

[0067]

[0068] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1 HNMR (300MHz, CDCl3, 25℃, δ): 13.86 (s, 1H), 8.15 (s, 2H), 8.12 (d, J = 8.1Hz ,1H),8.08(s,1H),7.98(d,J=8.1Hz,1H),7.88(d,J=7.8Hz,1H),7.81(d,J= 7.5Hz,1H),7.79(d,J=7.8Hz,1H),7.54-7.46(m,2H),7.45-7.40(m,1H),7. 38-7.33(m,1H),7.07-6.99(m,2H),6.80(s,1H),3.95(s,3H),3.58(s,3H). 13 CNMR (75MHz, CDCl3, 25℃, δ): 163.6, 162.3, 156.4, 152.3, 149.2, 148.8, 148.0, 147.6, 145.1, 144.1, 139.6, 136.4, 133.4, 127.2, 126.5, 126.3, 125.5, 125.2, 123.2, 122.4, 121.6, 121.4, 120.3, 120.2, 119.3, 116.1, 113.2, 112.8, 106.4, 94.9, 57.0, 56.1. Mass spectrometry: calcd for C 32 H 21N5O4S2 + ([M+H)) + ),604.1108,found,604.1120.

[0069] The synthesized compound was identified by structural analysis as the target compound 1-(2-(benzo[d]thiazol-2-yl)-4-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-hydroxy-6-methoxyphenyl)-1H-pyrazole-4-nitrile.

[0070] Example 9. Method for synthesizing ethyl 1-(2-(benzo[d]thiazol-2-yl)-4-(2-(benzo[d]azol-2-yl)-4-methoxyphenoxy)-3-hydroxy-6-methoxyphenyl)-1H-pyrazole-4-carboxylate

[0071] Step 1: Add 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol (0.25 mmol, 64 mg, 1.0 equiv), ethyl 1H-pyrazole-4-carboxylate (0.25 mmol, 35 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) to a dry 40 mL reaction tube in sequence. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solid is completely dissolved.

[0072] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of (200-300 mesh) silica gel to the round-bottom flask; evaporating the solution by rotary evaporation; and passing the solution through a silica gel column using a mixture of petroleum ether and ethyl acetate as the eluent. The product 1-(2-(benzo[d]thiazol-2-yl)-4-(2-(benzo[d]azol-2-yl)-4-methoxyphenoxy)-3-hydroxy-6-methoxyphenyl)-1H-pyrazole-4-carboxylic acid ethyl ester was obtained. Yellow solid (0.037 g, 0.058 mmol, 46% yield); R f =0.32 (petroleum ether / ethyl acetate = 5:1 (v / v)). (See structural formula 9b).

[0073]

[0074] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1HNMR (300MHz, CDCl3, 25℃, δ): 13.93 (s, 1H), 8.29 (s, 1H), 8.16 (d, J = 2.1Hz, 1H), 8.1 2(d,J=8.4Hz,2H),7.95(d,J=8.1Hz,1H),7.95(d,J=7.5Hz,1H),7.88(d,J=7.5Hz,1H ),7.77(d,J=7.8Hz,1H),7.51-7.45(m,2H),7.41-7.33(m,2H),7.07-6.99(m,2H),6 .84(s,1H),4.41-4.34(q,J=9Hz,2H),3.95(s,3H),3.59(s,3H),1.39(t,J=9Hz,3H). 13 C10 NMR (75MHz, CDCl3, 25℃, δ): 164.2, 162.9, 162.3, 156.2, 152.3, 149.1, 148.9, 148.4, 146.9, 145.1, 143.1, 137.6, 136.4, 133.7, 126.9, 126.2, 126.1, 125.3, 125.1, 123.1, 122.2, 121.6, 121.5, 121.3, 119.9, 117.5, 116.2, 112.6, 106.9, 60.7, 57.1, 56.0, 14.5. Mass spectrometry: calcd for C10 34 H 26 N4O6S2 + ([M+H)) + ),651.1367,found,651.1351.

[0075] The synthesized compound was identified by structural analysis as the target compound ethyl 1-(2-(benzo[d]thiazol-2-yl)-4-(2-(benzo[d]azol-2-yl)-4-methoxyphenoxy)-3-hydroxy-6-methoxyphenyl)-1H-pyrazole-4-carboxylic acid.

[0076] Example 10: Method for synthesizing 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(3,5-dimethyl-1H-pyrazol-1-yl)-4-methoxyphenol

[0077] Step 1: Add 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol (0.25 mmol, 64 mg, 1.0 equiv), 3,5-dimethyl-1H-pyrazole (0.25 mmol, 24 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) to a dry 40 mL reaction tube in sequence. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solids are completely dissolved.

[0078] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of 200-300 mesh silica gel to the round-bottom flask; evaporating the solution by rotary evaporation; and passing the solution through a silica gel column using a mixture of petroleum ether and ethyl acetate as the eluent. The product 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(3,5-dimethyl-1H-pyrazole-1-yl)-4-methoxyphenol was obtained. Yellow solid (0.041 g, 0.068 mmol, 54% yield); R f =0.27 (petroleum ether / ethyl acetate = 3:1 (v / v)). (See structural formula 10b).

[0079]

[0080] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1 HNMR (300MHz, CDCl3, 25℃, δ): 14.16 (s, 1H), 7.18 (t, J = 1.5Hz, 1H), 8.13 (d, J = 8.1Hz, 1H), 7.94 (d, J = 8.1Hz, 1H), 7.89 (d, J = 7.8Hz, 1H), 7.79 (d, J = 7. 8Hz,1H),7.52-7.43(m,2H),7.39-7.34(m,2H),7.02(d,J=1.5Hz,2H),6.8 8(s,1H),6.18(s,1H),3.95(s,3H),3.62(s,3H),2.37(s,3H),2.06(s,3H). 13C10 NMR (75MHz, CDCl3, 25℃, δ): 165.1, 162.5, 155.9, 152.3, 151.3, 149.2, 149.1, 148.9, 145.8, 145.5, 143.0, 136.5, 134.2, 126.7, 126.1, 125.9, 125.0, 124.8, 123.0, 122.1, 121.6, 121.3, 119.4, 119.1, 117.0, 112.6, 107.7, 107.0, 57.0, 56.0, 14.0, 11.2. Mass spectrometry: calcd for C10 33 H 26 N4O4S2 + ([M+H)) + ),607.1468,found,607.1477.

[0081] The synthesized compound was identified by structural analysis as the target compound 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(3,5-dimethyl-1H-pyrazol-1-yl)-4-methoxyphenol.

[0082] Example 11: Method for synthesizing 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(3,5-diphenyl-1H-pyrazol-1-yl)-4-methoxyphenol

[0083] Step 1: Add 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol (0.25 mmol, 64 mg, 1.0 equiv), 3,5-diphenyl-1H-pyrazole (0.25 mmol, 24 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) sequentially to a dry 40 mL reaction tube. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solids are completely dissolved.

[0084] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of (200-300 mesh) silica gel to the round-bottom flask; evaporating the solution by rotary evaporation; and using a mixture of petroleum ether and ethyl acetate as the eluent for silica gel column chromatography. The product 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(3,5-diphenyl-1H-pyrazole-1-yl)-4-methoxyphenol was obtained. Yellow solid (0.082 g, 0.113 mmol, 90% yield); R f =0.23 (petroleum ether / ethyl acetate = 5:1 (v / v)). (See structural formula 11b).

[0085]

[0086] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1 HNMR (300MHz, CDCl3, 25℃, δ): 14.25 (s, 1H), 8.16-8.12 (m, 2H), 7.98-7.91 (m, 4H), 7.75 (d, J=7.8Hz, 1H), 7.51-7.44 (m, 3H) ,7.41-7.36(m,3H),7.33-7.29(m,2H),7.26-7.22(m,4H),7.09(s,1H),7.01(s,2H),6.77(s,1H),3.96(s,3H),3.42(s,3H). 13 C NMR (75MHz, CDCl3, 25℃, δ): 165.1, 162.6, 156.0, 154.0, 152.4, 149.2, 149.0 ,148.9,147.8,146.1,145.8,136.6,134.2,133.1,129.9,128.8,128.7,128. 6,128.4,127.6,126.9,126.2,126.0,125.1,124.9,123.2,122.7,122.2,121.7,121.5,119.5,119.2,117.1,112.8,108.1,104.9,57.0,56.1. Mass spectrometry: calcd for C 43 H 30N4O4S2 + ([M+H)) + ),731.1781,found,731.1791.

[0087] The synthesized compound was identified by structural analysis as the target compound 2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-3-(3,5-diphenyl-1H-pyrazole-1-yl)-4-methoxyphenol.

[0088] Example 12: Method for synthesizing 3-(1H-benzo[d]imidazol-1-yl)-2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-4-methoxyphenol

[0089] Step 1: Add 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol (0.25 mmol, 64 mg, 1.0 equiv), 1H-benzo[d]imidazole (0.25 mmol, 30 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) sequentially to a dry 40 mL reaction tube. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solids are completely dissolved.

[0090] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-methoxyphenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of (200-300 mesh) silica gel to the round-bottom flask; evaporating the solution by rotary evaporation; and passing the solution through a silica gel column using a mixture of petroleum ether and ethyl acetate as the eluent. The product 3-(1H-benzo[d]imidazol-1-yl)-2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-4-methoxyphenol was obtained. Yellow solid (0.077 g, 0.123 mmol, 98% yield); R f =0.19 (petroleum ether / ethyl acetate = 5:1 (v / v)). (See structural formula 21b).

[0091]

[0092] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1HNMR (300MHz, CDCl3, 25℃, δ): 14.07 (s, 1H), 8.19 (d, J = 3Hz, 1H), 8.14 (d, J = 8.1Hz, 1H), 7.97-7.89 (m, 4H), 7.57 (d, J = 6Hz, 1H), 7.52-7.49 (m, 1 H),7.46(d,J=9Hz,1H),7.42-7.33(m,3H),7.29(d,J=9Hz,1H),7.24(d,J=9Hz,1H),7.13-7.03(m,3H),6.91(s,1H),3.96(s,3H),3.49(s,3H). 13 C10 NMR (75MHz, CDCl3, 25℃, δ): 164.2, 162.4, 156.2, 152.3, 149.2, 148.9, 148.5, 146.6, 145.4, 144.3, 143.9, 136.5, 134.9, 133.4, 127.0, 126.2, 125.3, 125.2, 124.2, 123.2, 123.1, 122.1, 121.6, 121.5, 120.6, 119.9, 119.3, 116.9, 116.8, 112.7, 110.4, 107.1, 56.8, 56.1. Mass spectrometry: calcd for C10 35 H 24 N4O4S2 + ([M+H)) + ),629.1312,found,629.1329.

[0093] The synthesized compound was identified by structural analysis as the target compound 3-(1H-benzo[d]imidazol-1-yl)-2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-methoxyphenoxy)-4-methoxyphenol.

[0094] Example 13: Method for synthesizing 3-(1H-benzo[d]imidazol-1-yl)-2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-((tert-butyldimethylsilyl)oxy)phenoxy)-4-((tert-butyldimethylsilyl)oxy)phenol

[0095] Step 1: Add 2-(benzo[d]thiazolyl-2-yl)-4-((tert-butyldimethylsilyl)oxy)phenol (0.25 mmol, 89 mg, 1.0 equiv), 1H-benzo[d]imidazole (0.25 mmol, 30 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) to a dry 40 mL reaction tube in sequence. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solid is completely dissolved.

[0096] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-((tert-butyldimethylsilyl)oxy)phenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of (200-300 mesh) silica gel to the round-bottom flask; evaporating the solution by rotary evaporation; and passing the solution through a silica gel column using a mixture of petroleum ether and ethyl acetate as the eluent. The product 3-(1H-benzo[d]imidazol-1-yl)-2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-((tert-butyldimethylsilyl)oxy)phenoxy)-4-((tert-butyldimethylsilyl)oxy)phenol was given as a pale yellow solid (0.036 g, 0.044 mmol, 35% yield). f =0.17 (petroleum ether / ethyl acetate = 3:1 (v / v)). (See structural formula 13b).

[0097]

[0098] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1 HNMR (300MHz, CDCl3, 25℃, δ): 14.18 (s, 1H), 8.14-8.12 (m, 2H), 7.98-7.89 (m, 4H), 7.59 (d, J=7 .8Hz,1H),7.52-7.43(m,2H),7.39-7.28(m,3H),7.22(d,J=7.2Hz,1H),7.11-7.07(m,2H),7.02

[0099] -6.98(m,1H),6.70(s,1H),1.05(d,J=3Hz,9H),0.43(s,9H),0.29(s,6H),-0.13(s,3H),-0.3(s,3H). 13 C NMR (75MHz, CDCl3, 25℃, δ): 164.6,162.1,152.6,152.5,149.1,148.2,147.2,1 45.7,145.2,144.1,144.0,136.5,134.9,133.4,127.0,126.3,126.2,126.1,1 25.2, 124.1, 123.5, 123.3, 123.1, 122.1, 121.6, 121.5, 120.8, 120.7, 120.6, 118.5, 116.4, 112.2, 110.6, 25.9, 24.9, 18.4, 17.5, -4.2, -4.4, -4.8. Mass spectrometry: calcd for C 45 H 48 N4O4S2Si2 + ([M+H)) + ),829.2728,found,829.2739.

[0100] The synthesized compound was identified by structural analysis as the target compound 3-(1H-benzo[d]imidazol-1-yl)-2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-((tert-butyldimethylsilyl)oxy)phenoxy)-4-((tert-butyldimethylsilyl)oxy)phenol.

[0101] Example 14: Method for synthesizing 3-(1H-benzo[d]imidazol-1-yl)-2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-(methylthio)phenoxy)-4-(methylthio)phenol

[0102] Step 1: Add 2-(benzo[d]thiazolyl)-4-(methylthio)phenol (0.25 mmol, 68 mg, 1.0 equiv), 1H-benzo[d]imidazole (0.25 mmol, 30 mg, 1.0 equiv), and tetrabutylammonium tetrafluoroborate (0.5 mmol, 1.0 eq., 165 mg) to a dry 40 mL reaction tube in sequence. Then add 1.5 mL of dry dichloromethane and 3.5 mL of hexafluoroisopropanol, and stir until the solids are completely dissolved.

[0103] Step 2: The entire mixture was stirred in air at room temperature. Two platinum plates, each 1.0 cm × 1.0 cm × 1.0 mm in length, width, and thickness, were used as the anode and cathode, respectively. The reaction mixture was stirred and electrolyzed at a battery potential of 2.5 V at room temperature. The reaction progress was monitored by TLC. The reaction was stopped when all 2-(benzo[d]thiazol-2-yl)-4-(methylthio)phenol was detected to have reacted completely. The experimental treatment involved drying the solution in the reaction tube; dissolving the solute in the reaction tube with dichloromethane and transferring it to a 100 mL round-bottom flask; adding 2 mL of silica gel (200-300 mesh) to the round-bottom flask; evaporating the solution by rotary evaporation; and passing the solution through a silica gel column using a mixture of petroleum ether and ethyl acetate as the eluent. The product 3-(1H-benzo[d]imidazol-1-yl)-2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-(methylthio)phenoxy)-4-(methylthio)phenol was given as a pale yellow solid (0.039 g, 0.059 mmol, 47% yield); R f =0.21 (petroleum ether / ethyl acetate = 3:1 (v / v)). (See structural formula 14b).

[0104]

[0105] The structure was confirmed as follows: Nuclear magnetic resonance spectroscopy: 1 HNMR (300MHz, CDCl3, 25℃, δ): 14.59 (s, 1H), 8.15 (d, J = 8.1Hz, 1H), 8.00 (d, J = 8.0Hz, 2H), 7.91 (d, J = 8.1Hz, 2H), 7.59 ( d,J=7.9Hz,1H),7.54-7.45(m,2H),7.43-7.38(m,2H),7.37-7.35(m,1H),7.32-7.28(m,1H),2.61(s,3H),2.19(s,3H). 13 C10 NMR (75MHz, CDCl3, 25℃, δ): 164.1, 162.0, 152.9, 152.4, 150.3, 148.7, 145.8, 143.9, 143.3, 136.4, 134.1, 133.2, 130.7, 130.4, 128.8, 128.2, 127.2, 126.4, 126.3, 125.2, 124.6, 123.5, 123.3, 122.1, 121.5, 121.4, 120.9, 117.9, 117.8, 110.3, 16.9, 16.6. Mass spectrometry: calcd for C10 35 H 24 N4O2S4 + ([M+H)) +),661.0855,found,661.0855.

[0106] The synthesized compound was identified by structural analysis as the target compound 3-(1H-benzo[d]imidazol-1-yl)-2-(benzo[d]thiazol-2-yl)-6-(2-(benzo[d]thiazol-2-yl)-4-(methylthio)phenoxy)-4-(methylthio)phenol.

[0107] Example 15: The solid products obtained in Examples 14, 11, 10, 5, and 8 were placed in a 20 ml glass bottle and placed under a 254 nm ultraviolet lamp in a dark room to observe their luminescence properties. A photograph was taken with a mobile phone, revealing that different structures emitted different colors of solid fluorescence. Figure 3 The aggregation-induced emission fluorescence properties of compound 12b in Examples 16 and 12 were tested. The results are as follows: Figure 4 As shown. The specific operating method is to first prepare liquid solutions of compound 12b at equal concentrations in different mixtures, and then use them for fluorescence testing. Solution preparation method:

[0108] ①H2O / THF=95 / 5: Take 0.5mL of a pre-prepared 0.0002mol / L 21b THF solution and add 9.5mL of H2O;

[0109] ②H2O / THF=9 / 1: Take 1 mL of a pre-prepared 0.0001 mol / L 21b THF solution and add 9 mL of H2O;

[0110] ③H2O / THF=85 / 15: Take 1 mL of 0.0001 mol / L 21b THF solution prepared in advance, and add 8.5 mL of H2O and 0.5 mL of THF;

[0111] ④H2O / THF=8 / 2: Take 1 mL of a pre-prepared 0.0001 mol / L 21b THF solution, then add 8 mL of H2O and 1 mL of THF;

[0112] ⑤H2O / THF=75 / 25: Take 1 mL of 0.0001 mol / L 21b THF solution prepared in advance, and add 7.5 mL of H2O and 1.5 mL of THF;

[0113] ⑥H2O / THF=7 / 3: Take 1 mL of a pre-prepared 0.0001 mol / L 21b THF solution, then add 7 mL of H2O and 2 mL of THF;

[0114] ⑦H2O / THF=6 / 4: Take 1 mL of a pre-prepared 0.0001 mol / L 21b THF solution, then add 6 mL of H2O and 3 mL of THF;

[0115] ⑧H2O / THF=3 / 7: Take 1 mL of a pre-prepared 0.0001 mol / L 21b THF solution, then add 3 mL of H2O and 6 mL of THF;

[0116] ⑨H2O / THF=5 / 95: Take 1 mL of a pre-prepared 0.0001 mol / L 21b THF solution, then add 0.5 mL of H2O and 8.5 mL of THF;

[0117] ⑩H2O / THF=0 / 10: Take 1 mL of a pre-prepared 0.0001 mol / L 21b THF solution and add 9 mL of THF.

[0118] Test method: Take a small amount of solution each time and add it to the cuvette. Then place the cuvette in the fluorescence spectrometer, adjust the instrument parameters, and start the test.

[0119] The embodiments of the present invention are not limited thereto. Based on the above description of the present invention, and using common technical knowledge and conventional means in the field, the present invention can be modified, replaced or changed in various other forms without departing from the basic technical idea of ​​the present invention, and all such modifications or changes fall within the scope of protection of the present invention.

Claims

1. An electrochemical preparation method for a class of polysubstituted phenol derivatives, characterized in that, Its structural formula is shown in Formula 1 or Formula 2 below, and the structural characteristics of the raw materials are shown in Formula 3 and Formula 4 below; in Formula 1 and Formula 3, when R2 is hydrogen, R1 is selected from any of the following groups: fluorine, chlorine, bromine, iodine, hydrogen, methyl, nitro, cyano, ester; in Formula 2 and Formula 4, R3 is selected from methoxy, thiomethyl, dimethyl tert-butylsilyl ether. These compounds were synthesized using the following electrochemical synthesis steps: The synthesis steps include: Step (1): Dissolve the reaction raw material 2-(benzo[d]thiazol-2-yl)-4-substituted phenol (formula tetra), substituted pyrazole (formula tri) or benzimidazole, and the electrolyte tetrabutylammonium tetrafluoroborate in a mixed solvent of hexafluoroisopropanol and dichloromethane in a volume ratio of 7:

3. Place the solution in a round-bottom flask and stir with a magnetic stirrer. The molar ratio of the two reaction raw materials and the electrolyte is 1:1:2, and the molar concentration of the reaction solution relative to a certain reactant is 0.25 mol / L. Step (2): The entire mixture is stirred in air at room temperature with a platinum plate as the anode and a platinum plate electrode as the cathode. The reaction mixture is stirred and electrolyzed at room temperature under a constant battery potential. When the reaction is monitored with a thin-layer chromatography plate and 2-(benzo[d]thiazol-2-yl)-4-substituted phenol (formula tetra) is completely consumed, the reaction solution is directly concentrated under vacuum. The concentrate is separated and purified by a chromatography column to obtain polysubstituted phenol derivatives.

2. The preparation method according to claim 1, characterized in that, The solvents in step (1) are hexafluoroisopropanol and dichloromethane after the activation of 4A molecular sieve and drying. The purity of the two solvents is analytical grade.

3. The preparation method according to claim 1, characterized in that, In step (2), the anode is a platinum plate with dimensions of 1.0 cm × 1.0 cm × 0.1 mm, and the cathode is a platinum plate electrode with dimensions of 1.0 cm × 1.0 cm × 0.1 mm.

4. The preparation method according to claim 1, characterized in that, The constant voltage reaction voltage in step (2) is 2.50 V.

5. The preparation method according to claim 1, characterized in that, The reaction time in step (2) is determined based on the results of thin-layer chromatography plate monitoring.

6. The preparation method according to claim 1, characterized in that, The chromatography in step (2) uses a silica gel column. The silica gel used in the silica gel column is 200-300 mesh, and the eluent for the silica gel column is petroleum ether.

7. A class of polysubstituted phenol derivatives prepared by the method according to any one of claims 1-6, characterized by having solid-state fluorescence and exhibiting aggregation-induced emission properties in a tetrahydrofuran and aqueous system.

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