Method for selectively catalyzing and synthesizing anthracene formic acid photo-dimerization product through nut macroring

Abstract

The invention provides a method for synthesizing an anthracene formic acid photo-dimerization product through selective catalysis of a nut macroring. A macrocyclic reactor is obtained by synthesizing a nut macrocyclic ring and is applied to anthracene formic acid photoreaction, and a new template is provided for catalyzing chiral photochemistry. The application conditions are simple, the operation is easy, the selectivity of head-to-tail photodimerization products in the anthracene formic acid photoreaction is obviously improved, and a new tool which is complementary with the traditional cyclodextrin in function and has unique advantages is provided for the control of the photochemical reaction.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic synthesis and photochemistry, and specifically relates to a method for selectively catalyzing synthesis of anthracene carboxylic acid photodimerization products by a screw cap macrocycle. BACKGROUND

[0002] Anthracene and its derivatives have rich photophysical and photochemical properties and are widely used in many fields, such as energy transfer probes in polymers, triplet state sensitizers, molecular fluorescent sensors, electron acceptor or donor chromophores, and photochromic materials. Under light conditions, anthracene derivatives can undergo [4+4] cycloaddition to form dimers, but the selectivity of the dimer product produced by 2-anthracene carboxylic acid is low. To improve the chemical selectivity of anthracene dimerization products, the key is how to achieve efficient stereochemical control of the electronically excited state of the weakly interacting, short-lived and highly reactive organic photo-substrate. In 2022, Yang Cheng's research group published "Synthesis of cyclodextrin derivatives for enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate", which synthesized a series of cyclodextrin derivatives and achieved control of the region and enantioselectivity of the photodimerization reaction product of 2-anthracene carboxylic acid through supramolecular regulation. In addition, patent CN120504601A discloses a preparation method of water-soluble screw cap arene macrocycle, and proves that it has good guest inclusion ability, but does not involve its application potential in photocatalysis. Therefore, the present application synthesizes a new container and finds that it can regulate the photodimerization of 2-anthracene carboxylic acid, significantly improving the selectivity of a group of dimerization products, providing a new tool complementary to traditional cyclodextrin and having unique advantages for the control of photochemical reactions. SUMMARY

[0003] In view of the deficiencies in the prior art, the purpose of the present application is to synthesize a screw cap macrocycle and apply it to the catalytic photodimerization product in water, to provide a new template for catalytic chiral photochemistry, and the control of the macrocycle on the photocatalytic reaction can be used for light-responsive materials.

[0004] In order to achieve the above-mentioned purpose of the application, the following technical means are used: The present application provides a method for selectively catalyzing synthesis of anthracene carboxylic acid photodimerization products by a screw cap macrocycle, comprising the following steps: (a) sealing a quartz glass tube containing a rotor with a rubber plug, injecting anthracene carboxylic acid solution and screw cap macrocycle solution into the tube, and performing degassing by air displacement method; (b) After exhausting the air, nitrogen is filled in, the quartz glass tube is clamped on the iron stand, the light source is aimed at the quartz glass tube, the ultraviolet lamp is covered with a black plastic bag to shield the light from the iron stand, and the catalytic synthesis of the anthracene carboxylic acid photodimerization product is carried out under stirring.

[0005] Preferably, in step (a), the screw cap macrocycle structure has the following general formula:

[0006] Further preferably, the screw cap macrocycle has a large cavity with 12 positive charges outside the cavity and can be dissolved in water.

[0007] Further preferably, the preparation method of the screw cap macrocycle has the following synthesis route: ; (1) Under the conditions of inert gas protection and ice water bath, compound 1 is added to a container containing an organic solvent, pyridine and trifluoromethyl sulfonic anhydride are added, stirring is carried out, water is added to quench the reaction after the reaction is completed, extraction and separation are carried out, the organic phase is collected and dried, concentrated, separated and purified to obtain a white transparent oily product, i.e. compound 2; (2) Under the protection of inert gas, compound 2, 2,5-dimethoxyphenylboronic acid, anhydrous potassium carbonate and tetrakis(triphenylphosphine)palladium are added to a mixed solution of toluene, ethanol and water (Vtoluene:Vethanol:Vwater = 5:4:2), and the reaction is carried out under reflux at 85-90°C, after the reaction is completed, the temperature is lowered to room temperature, washing and separation are carried out, the organic phase is collected and dried with anhydrous sodium sulfate, and concentrated to obtain a white product, i.e. compound 3.

[0008] (3) Under the protection of inert gas, compound 3 is dissolved in chloroform solution to obtain a chloroform solution of compound 3, and under the condition of ice water bath, boron tribromide is added, stirring is carried out at room temperature for 10-12h, after the reaction is completed, 100-120mL of ice water mixture is quickly added to the reaction solution, stirring is continued at room temperature for 1-2h, then quick filtration is carried out, the filter cake is collected and washed with water and chloroform for several times; the filter cake is dried to obtain a light brown solid, i.e. compound 4; (4) Under the protection of inert gas, anhydrous potassium carbonate and 1,4-dibromobutane are dissolved in 120-150mL of acetone solution, the acetone solution of compound 4 is added dropwise, and the solution is refluxed at 60-65°C for 20-24h, and the solution gradually turns into red brown; after the reaction is completed, the reaction solution is cooled to room temperature, washing and separation are carried out, the organic phase is collected and dried with anhydrous sodium sulfate, and concentrated to obtain a crude product, which is separated and purified to obtain a light yellow oily liquid product, i.e. compound 5; (5) under inert gas protection, compound 5 is dissolved in chloroform solution to obtain a chloroform solution of compound 5, and then methylal and boron trifluoride ether are added, and stirring is carried out at room temperature, after the reaction is completed, a small amount of water is added to quench the reaction, and then washing, separation, collection of the organic phase and drying with anhydrous sodium sulfate are carried out, and then concentration, separation and purification are carried out to obtain a white oily product, i.e. compound 6; (6) under inert gas protection, compound 6 and trimethylamine are added to anhydrous ethanol, and refluxing is carried out at 80-85℃ for 12-18h, after the reaction is completed, the solution is cooled to room temperature, and the solvent is removed by rotary evaporation to obtain a crude product, a small amount of deionized water is added to dissolve the crude product, and then a proper amount of acetone solution is added to precipitate a white solid, and the white solid is obtained by centrifugation; the re-precipitation treatment is repeated for 4-5 times, and the white solid, i.e. compound 7, is obtained by drying at 65-70℃.

[0009] (7) compound 7 is dissolved in deionized water solution to obtain a water-soluble cationic screw cap

[12] arene solution.

[0010] Preferably, in step (a), the screw cap macrocycle is added in an amount of 0.1-1mM, and anthracene carboxylic acid is added in an amount of 0.2-2mM.

[0011] Preferably, in step (a), when the anthracene carboxylic acid solution is prepared, the solubility of anthracene carboxylic acid in the aqueous solution is poor, and the pH is adjusted to 6.0-7.0 by adding a standard NaOH solution.

[0012] Preferably, in step (b), the light reaction for synthesizing the anthracene carboxylic acid photodimerization product is as follows:

[0013] Further preferably, the head-to-tail photodimerization products anti-HT and syn-HT are selectively catalyzed by the screw cap macrocycle, and the yield is improved.

[0014] Preferably, in step (b), the reaction light source is a 365nm ultraviolet lamp.

[0015] Preferably, in step (b), the distance between the ultraviolet curing lamp light source and the test tube is 5-10cm.

[0016] Preferably, in step (b), the light irradiation time is 30-35min.

[0017] Compared with the prior art, the present application has the following advantages: (1) Compared with other macrocycles used for catalyzing anthracene carboxylic acid dimerization products, the screw cap macrocycle used in the present application has the advantages of low synthesis cost and derivatization, etc. (2) The application provides a method for selectively catalytically synthesizing anthracene formic acid photodimerization products by using a screw cap macrocycle, which is applied to catalytic anthracene formic acid photoreaction, has simple experimental conditions, is easy to operate and easy to build, widens the application field of the screw cap macrocycle and provides a new template for photodimerization catalytic reaction. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 is a UV absorption spectrum (a) and a fluorescence emission spectrum (b) of a screw cap macrocycle, anthracene formic acid and a mixed solution of the two.

[0019] Figure 2 is a fluorescence emission spectrum (a) of a mixed solution of anthracene formic acid and a screw cap macrocycle with different concentration ratios and a combined model fitting curve (b).

[0020] Figure 3 is a UV absorption spectrum of anthracene formic acid solution under 365 nm light irradiation with time.

[0021] Figure 4 is a high performance liquid chromatogram of a photodimerization product before (lower) and after 30 min of reaction (upper) of anthracene formic acid without adding a screw cap macrocycle in the comparative example 1.

[0022] Figure 5 is a high performance liquid chromatogram of a photodimerization product before (b) and after 30 min of reaction (a) of anthracene formic acid without adding a screw cap macrocycle in the comparative example 2.

[0023] Figure 6 is a high performance liquid chromatogram of a photodimerization product after 30 min of reaction of anthracene formic acid without adding a screw cap macrocycle in the comparative example 3. DETAILED DESCRIPTION

[0024] The specific examples of the application are further described below in combination with the drawings and examples, but the scope of the application claimed is not limited to the scope expressed by the examples.

[0025] The specific synthesis route of the screw cap macrocycle is as follows:

[0026] The specific preparation steps are as follows: Step one, compound 1-1 (2 g, 10 mmol) was added to 200 ml of dichloromethane, and the reaction bottle was placed in an ice bath under nitrogen protection and stirred for 10 min. Pyridine (20 ml, 250 mmol) and triflic anhydride (8.5 ml, 50 mmol) were injected into the reaction solution in sequence using a syringe, and the reaction was carried out in an ice bath for 5 h. After the reaction was completed, water was added to quench the reaction, and the reaction solution was extracted and separated. The organic phase was collected and dried with anhydrous sodium sulfate, and concentrated. Petroleum ether and dichloromethane mixed solution (V petroleum ether: V dichloromethane = 1 :1) was used as the eluent for column chromatography separation and purification. The white oily product 1-2 (4.45 g, yield 95.9%) was obtained.

[0027] Step two, the product 1-2 (1.6 g, 3.4 mmol) of the previous step was added to a mixture of toluene, ethanol and water in a volume ratio of 4:2:1, and stirred under nitrogen atmosphere for 10 min. After adding the catalyst palladium tetrakis (triphenylphosphine) (120 mg, 0.1 mmol), nitrogen was quickly charged, and the reaction was carried out at 90°C overnight. After the reaction was completed, the reaction solution was extracted and separated, and the organic phase was collected and dried with anhydrous sodium sulfate, and concentrated. Petroleum ether and dichloromethane mixed solution (V petroleum ether: V dichloromethane = 1 :1) was used as the eluent for column chromatography separation and purification, and the white product 1-3 (1.36 g, yield 89.3%) was obtained.

[0028] Step three, under nitrogen protection, the product 1-3 (1 g, 2.3 mmol) was dissolved in chloroform solution. After adding boron tribromide (5 ml, 36 mmol) under ice water bath conditions, it was stirred for 12 h. After the reaction was completed, an ice water mixture was quickly added to the solution, and stirring was continued at room temperature for 1 h. White solid gradually appeared, which was observed. After stirring was completed, rapid filtration was carried out, and the filter cake was washed with water and chloroform several times. The filter cake was collected to obtain the product 1-4 (801 mg, yield 90.5%).

[0029] Step four, under nitrogen atmosphere, dissolve the product of step three 1-4 (200 mg, 0.5 mmol) in 60 ml acetone in a constant pressure dropping funnel, dissolve anhydrous potassium carbonate (1.6 g, 10 mmol), 1,4-dibromobutane (1.4 ml, 10 mmol) in 60 ml acetone solution. Slowly drop the acetone solution of 1-4 in 1 h, reflux at 60 °C for 16 h, the solution turns to brown red, monitor the reaction progress by TLC, after the reaction is completed, cool to room temperature. Then extract with water and dichloromethane to obtain the organic phase, concentrate. The obtained crude product is column chromatographed with a mixture of petroleum ether and dichloromethane (V petroleum ether: V dichloromethane = 1:1) to separate and purify, to obtain compound 1-5 (368 mg, yield 79.6%) as yellow oil.

[0030] Step five, first dissolve compound 1-5 (491.3 mg, 0.5 mmol) in 150 ml chloroform solution. Under nitrogen atmosphere, inject acetal (0.24 ml, 2.5 mmol) with a syringe, after stirring for 10 min, inject boron trifluoride etherate (0.74 ml, 5.5 mmol) again, monitor the reaction progress by TLC while stirring at room temperature. After the reaction is completed, quickly add water to quench the reaction, extract the reaction solution to separate the organic phase and dry with anhydrous sodium sulfate, concentrate. Column chromatography is carried out with a mixture of petroleum ether and dichloromethane (V petroleum ether: V dichloromethane = 2:1) as eluent to separate and purify, to obtain product 1-6 (114 mg, yield 22.8%) as white oil.

[0031] Step six, dissolve the product 1-6 (226.2 mg, 0.08 mmol) of the previous step in 60 ml ethanol, inject trimethylamine (1.5 ml, 2 mmol) into the solution under nitrogen atmosphere, gradually increase the temperature to 80 °C and react for 10 h. After the reaction is completed, the reaction solution becomes clear and transparent, rotary evaporation, concentrate the reaction solution, then gradually add acetone to observe the precipitation of white solid, centrifuge to obtain white solid, repeat the addition of acetone and centrifugation several times, finally dry the obtained solid at 65 °C to obtain the product spiro macrocycle (231 mg, yield 82%).

[0032] Test method of UV absorption spectrum and fluorescence emission spectrum of spiro macrocycle and anthracene carboxylic acid.

[0033] Prepare the prepared spiro macrocycle to a solution of 1×10 -5 mol / L with pure water, prepare a solution of anthracene carboxylic acid with pure water and standard NaOH solution to a concentration of 5×10 -5 mol / L at pH 6, and prepare a solution containing 1×10 -5 mol / L spiro macrocycle and 5×10-5 mol / L anthracene carboxylic acid solution. The UV absorption spectrum and fluorescence emission spectrum of the macrocycle, anthracene carboxylic acid and the mixed solution were tested respectively, and the results are shown in Figure 1 , wherein AC is anthracene carboxylic acid and H is the screw cap macrocycle.

[0034] Fluorescence titration test of the screw cap macrocycle and anthracene carboxylic acid.

[0035] Prepare 5*10 -5 mol / L anthracene carboxylic acid solution and 1*10 -3 mol / L screw cap macrocycle solution, gradually add the screw cap macrocycle solution to the anthracene carboxylic acid solution, so that the concentration of the screw cap macrocycle solution in the mixed solution is from 0-69*10 - 6 According to the results of the UV spectrum, select the wavelength at which the anthracene carboxylic acid AC has maximum absorption and the screw cap macrocycle H does not absorb, and perform fluorescence test. In this example, the fluorescence emission spectrum was tested in turn at an excitation wavelength of 363 nm, the half-peak high region of the characteristic fluorescence peak was selected for integral calculation, the relative fluorescence intensity change value was calculated according to the formula: (I-I0) / I0, then the scientist3.0 was used for fitting, and the 1:1, 1:2 and 1:3 binding models were used. It was found that the model H and AC had better fitting effect in the 1:3 model, and the macrocycle and anthracene carboxylic acid were combined by 1:3, and the complexation constant K=1.69*10 5 M -1 . The results are shown in Figure 2 .

[0036] Comparative Example 1 The anthracene carboxylic acid photo-reaction process includes the following steps: prepare 2*10 - 3 mol / L anthracene carboxylic acid solution with pure water and standard NaOH at pH=6, add it to a quartz glass tube containing a rotor, seal the quartz glass tube with a rubber plug of appropriate size, insert a long and short glass tube into the rubber plug, insert the long glass tube into the bottom of the liquid surface to exhaust, exhaust the air in the test tube for 15 min by the air exhaust method, fill in nitrogen, clamp the quartz glass tube on the iron stand, irradiate with a 365 nm ultraviolet lamp, the distance between the light source and the quartz glass tube is 10 cm, cover the ultraviolet lamp and the iron stand with a black plastic bag, and stir to perform photo-reaction.

[0037] The reaction solution irradiated for 0-50 min was tested for UV absorption every 5 min, and the results are shown in Figure 3, 388 nm, which is the characteristic absorption peak of anthracene carboxylic acid monomer, with the light irradiation, anthracene carboxylic acid monomer is continuously converted into dimer, the conjugated system of the molecule is destroyed, and the absorption of anthracene carboxylic acid dimer at 388 nm is very weak and can be ignored, so it can be seen that the absorbance at 388 nm decreases to remain unchanged after irradiation for 35-40 min, indicating that most of the anthracene carboxylic acid monomer is converted into anthracene carboxylic acid dimer. In order to prevent the occurrence of oxidation products and other by-products due to the prolongation of the reaction time, the optimal reaction time is selected to be 30-35 min.

[0038] The solutions of anthracene carboxylic acid before reaction (b) and after reaction for 30 min (a) were subjected to high performance liquid separation to obtain the chromatograms as shown in Figure 4 The figure before reaction (lower figure) only has anthracene carboxylic acid monomer, i.e. AC, and four dimer product peaks appear after reaction (upper figure), indicating that the photo-reaction is good and is not oxidized, and the product distribution is as shown in Table of Example 1 without WHN

[12] .

[0039] Comparative Example 2 A pH = 3.7 anthracene carboxylic acid solution with a concentration of 2 x 10 -4 mol / L was prepared using pure water and standard HCl, added to a quartz glass tube containing a rotor, and the opening of the quartz glass tube was sealed with a rubber plug. A long and a short glass tube were inserted into the rubber plug, the long glass tube was inserted into the bottom of the liquid surface for air exhaust, the air in the test tube was exhausted for 15 min by the air exhaust method, nitrogen was filled, the quartz glass tube was clamped on the iron stand, and the photo-reaction was carried out by irradiation with a 365 nm ultraviolet lamp, the distance between the light source and the quartz glass tube was 10 cm, and the ultraviolet lamp and the iron stand were covered with a black plastic bag.

[0040] The solutions of anthracene carboxylic acid before reaction (b) and after reaction for 30 min (a) were subjected to high performance liquid separation to obtain the chromatograms as shown in Figure 5 Due to the fact that the pH is not adjusted to the required 6.0-7.0, the solubility of anthracene carboxylic acid is poor, and the photo-dimerization product separation cannot be achieved.

[0041] Comparative Example 3 A pH = 7 anthracene carboxylic acid solution with a concentration of 2 x 10 -4 mol / L was prepared using pure water and standard HCl, added to a quartz glass tube containing a rotor, and the opening of the quartz glass tube was sealed with a rubber plug. A long and a short glass tube were inserted into the rubber plug, the long glass tube was inserted into the bottom of the liquid surface for air exhaust, the air in the test tube was exhausted for 15 min by the air exhaust method, nitrogen was filled, the quartz glass tube was clamped on the iron stand, and the photo-reaction was carried out by irradiation with a 365 nm ultraviolet lamp, the distance between the light source and the quartz glass tube was 10 cm, and the ultraviolet lamp and the iron stand were covered with a black plastic bag.

[0042] The solution after reacting anthracene carboxylic acid for 30 min was separated by high performance liquid chromatography to obtain a chromatogram as shown in Figure 6 .

[0043] Comparative Example 4 Two anthracene carboxylic acid solutions with a concentration of 2×10 -3 mol / L and pH=6 were prepared using pure water and standard HCl, and were added to a quartz glass tube containing a rotor. The opening of the quartz glass tube was sealed with a rubber plug of appropriate size, and a long and a short glass tube were inserted into the rubber plug. The long glass tube was inserted into the bottom of the liquid surface to exhaust air. The air in the test tube was exhausted for 15 min by the air exhaust method, and was filled with nitrogen. The quartz glass tube was clamped on an iron stand, and was irradiated with a 365 nm ultraviolet lamp.

[0044] Reaction solution ①: the distance between the light source and the quartz glass tube was 5 cm. The ultraviolet lamp and the iron stand were covered with a black plastic bag. The light reaction was carried out for 30 min with stirring.

[0045] Reaction solution ②: the distance between the light source and the quartz glass tube was 10 cm. The ultraviolet lamp and the iron stand were covered with a black plastic bag. The light reaction was carried out for 35 min with stirring.

[0046] After the reaction was completed, separation was carried out. The liquid chromatogram is shown in Comparative Example 1. The specific relative yield distribution is shown in the following table. Product 1 is anti-HT, product 2 is syn-HT, product 3 is anti-HH, and product 4 is syn-HH.

[0047]

[0048] Example 1 The present example provides an application of the screw cap macrocycle catalytic anthracene carboxylic acid photoreaction. The method for selectively catalyzing anthracene carboxylic acid photodimerization products is as follows: Two anthracene carboxylic acid solutions with a concentration of 2×10 -3 mol / L and pH=6 were prepared using pure water and standard NaOH, and were added to a quartz glass tube containing a rotor. The corresponding concentration of the screw cap macrocycle (WHN

[12] ) was added to the reaction solution. The opening of the quartz glass tube was sealed with a rubber plug of appropriate size, and a long and a short glass tube were inserted into the rubber plug. The long glass tube was inserted into the bottom of the liquid surface to exhaust air. The air in the test tube was exhausted for 15 min by the air exhaust method, and was filled with nitrogen. The quartz glass tube was clamped on an iron stand, and was irradiated with a 365 nm ultraviolet lamp. The distance between the light source and the quartz glass tube was 10 cm. The ultraviolet lamp and the iron stand were covered with a black plastic bag. The light reaction was carried out with stirring. The reaction was carried out for 30 min. After the reaction was completed, separation was carried out to obtain the relative yield distribution. Product 1 is anti-HT, product 2 is syn-HT, product 3 is anti-HH, and product 4 is syn-HH.

[0049]

[0050] The experimental results show that the yield of the head-to-tail photodimerization product in the anthracene formic acid photoreaction is significantly improved in the presence of the screw cap macrocycle, and the head-to-tail product yield: head-to-head product yield ratio is increased from 2.09 without the screw cap macrocycle to 6.35.

[0051] In summary, compared with the prior art, the present application has the following advantages: (1) Compared with other screw cap macrocycles used for catalyzing anthracene formic acid dimerization products, the screw cap macrocycle used in the present application has the advantages of low synthesis cost and derivatization; (2) The present application applies the screw cap macrocycle to the catalysis of anthracene formic acid photodimerization reaction, and the experimental conditions are simple, the operation is easy, and the application field of the screw cap macrocycle is widened, thereby providing a new template for the photodimerization catalysis reaction.

Claims

1. A method for selectively catalyzing the synthesis of anthracene carboxylic acid photodimers using a nut-shaped macrocyclic ring, characterized in that, Includes the following steps: (a) Seal the quartz glass tube containing the rotor with a rubber stopper, inject anthracenic acid solution and screw cap macroring solution into it, and vent the air by air removal method; (b) After venting, nitrogen gas is introduced, the quartz glass tube is clamped on the iron stand, the light source is aimed at the quartz glass tube, the ultraviolet lamp and the iron stand are covered with a black plastic bag, and the mixture is stirred to carry out the photocatalytic synthesis of anthracene photodimer.

2. The method for selectively catalytically synthesizing anthracitic acid photodimer products using a nut-shaped macrocyclic ring according to claim 1, characterized in that, In step (a), the large ring of the nut has the following general structural formula: 。 3. The method for selectively catalytically synthesizing anthracene carboxylic acid photodimer according to claim 2, characterized in that, The large ring of the nut has a large cavity with 12 positive charges on the outside of the cavity, making it soluble in water.

4. The method for selectively catalytically synthesizing anthracitic acid photodimer products using a nut-shaped macrocyclic ring according to claim 1, characterized in that, In step (a), the amount of the nut macroring added is 0.1-1 mM, and the amount of anthracene acid added is 0.2-2 mM.

5. The method for selectively catalytically synthesizing anthracitic acid photodimer products using a nut-shaped macrocyclic ring according to claim 1, characterized in that, In step (a), when preparing the anthracitic acid solution, since anthracitic acid has poor solubility in aqueous solution, NaOH standard solution is added to adjust the pH to 6.0-7.

0.

6. The method for selectively catalytically synthesizing anthracitic acid photodimer products using a nut-shaped macrocyclic ring according to claim 1, characterized in that, In step (b), the photoreaction for synthesizing the anthracite photodimer product follows the following synthetic route: 。 7. The method for selectively catalytically synthesizing anthracene carboxylic acid photodimer according to claim 6, characterized in that, The head-to-tail photodimers anti-HT and syn-HT are selectively catalyzed by a nut-shaped macrocycle, resulting in increased yield.

8. The method for selectively catalytically synthesizing anthracitic acid photodimer products using a nut-shaped macrocyclic ring according to claim 1, characterized in that, In step (b), the reaction light source is a 365nm ultraviolet lamp.

9. The method for selectively catalytically synthesizing anthracene carboxylic acid photodimer according to claim 1, characterized in that, In step (b), the distance between the UV curing lamp light source and the test tube is 5~10cm.

10. The method for selectively catalytically synthesizing anthracene carboxylic acid photodimer according to claim 1, characterized in that, In step (b), the illumination time is 30-35 minutes.

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