A method for catalytic hydration carbonylation of arylacetylene by using the photothermal effect of gold nanoparticles

Abstract

The present invention relates to a method for catalytically hydrating carbonylation of arylacetylene by using the photothermal effect of gold nanoparticles, belonging to the technical field of catalysts. This method uses a photochemical synthesis method, with a xenon lamp as the light source, gold particles (AuNPs) as the photothermal material, tetrabutylammonium bromide and the selective fluorine reagent Selectfluor as additives, and under the action of Al, the hydration carbonylation of aryl alkynes is realized. When the reaction proceeds for 5 h, the separation yield of the carbonyl product is as high as 90.5%. This method uses photocatalysis to efficiently realize the carbonylation of alkynes under mild conditions without acid and strong oxidants.

Description

Technical Field

[0001] The present invention relates to a green chemical synthesis method, especially realizing the catalysis of the hydrocarboxylation reaction of arylacetylene under relatively mild conditions by using the photothermal effect of gold particles, belonging to the technical field of catalysts. Background Art

[0002] Carbonyl compounds and their derivatives widely exist in natural products and various drugs. In traditional organic methods for synthesizing carbonyl compounds, the catalytic addition (hydration) reaction of water with alkynes is relatively common. Using water as a reagent is relatively less harmful to the environment, and this method is simple and efficient. Adding water to alkynes is a 100% atom-economic reaction, and the carbonyl functional group can be obtained very simply. However, most of the catalysts used in the carbonylation reaction of alkynes in the literature are based on toxic or expensive transition metals. In 1860, Berthelot found that the hydration reaction of acetylene would occur under the condition of the coexistence of sulfuric acid and vinyl alcohol, but the actual products were a mixture of acetaldehyde and crotonaldehyde. In 1881, Kucherov discovered the reaction of Hg(II)-catalyzed hydration of alkynes. Under the catalysis of the catalyst, the alkyne undergoes a nucleophilic addition reaction with water to form an aldehyde or a ketone. Since then, this has become a classic textbook reaction. The conversion of terminal alkynes to aldehydes is usually achieved indirectly through hydroboration or hydrosilylation reactions, and subsequent oxidation. Although this reaction is relatively easy, the use of mercury salts is highly harmful to both humans and the environment. Therefore, scientists have been committed to developing safer and more easily operable alkyne carbonylation reactions. Summary of the Invention

[0003] The technical problem solved by the present invention is: to propose a method for the photothermal catalytic hydrocarboxylation of aryl alkynes, which does not use strong acids or strong bases, has mild conditions, can be carried out at normal temperature and pressure, and synthesizes carbonylated products in a green and efficient manner.

[0004] In order to solve the above technical problem, the technical solution proposed by the present invention is: a method for catalyzing the hydrocarboxylation reaction of arylacetylene by using the photothermal effect of gold nanoparticles, and the specific steps include:

[0005] Preparing gold particles with a size of 15 - 80 nm as the photothermal material, using a xenon lamp as the light source, in a mixed solvent of acetonitrile and water, using the fluorine reagent Selectfluor and tetrabutylammonium bromide TBAB as additives, and aluminum as the sacrificial agent to realize the catalysis of the hydrocarboxylation reaction of arylacetylene.

[0006] The specific reaction route is as follows:

[0007]

[0008] Wherein R is methoxy, methyl, fluorine or no group.

[0009] Preferably, the size of the gold nanoparticles can be 15nm, 40nm, 60nm or 80nm.

[0010] Preferably, the specific preparation steps of the 60nm gold nanoparticle aqueous solution are as follows:

[0011] Step (1): Under the condition of 115°C, add 25 mL of hot water and 0.25 mL of HAuCl4 solution to the flask and carry out condensation reflux; react for 30 min;

[0012] Step (2): Add 0.375 mL of sodium citrate solution. At this time, the color of the reaction solution changes from red to dark gray, then to black, then to purple, and finally to red within 10 min;

[0013] Step (3): After reflux reaction for 15 min, add 25 mL of hot water at 80°C, and dropwise add 50 μL of 6.6 mg / mL NaOH solution and 250 μL of sodium citrate solution, then quickly add 250 μL of HAuCl4 solution, and reflux and heat for 20 min;

[0014] Step (4): Add 50 ml of hot water, 0.1 mL of NaOH solution and 0.5 mL of sodium citrate solution, and quickly add 0.5 mL of HAuCl4 solution, and continue to heat and reflux for 20 min;

[0015] Step (5): Repeat this operation 4 times, and then naturally cool to room temperature to obtain a 60nm gold particle solution.

[0016] Preferably, the specific steps are as follows:

[0017] Weigh tetrabutylammonium bromide and an aluminum sheet and add them to a glass bottle, then add 4-methylphenylacetylene and acetonitrile to dissolve; dissolve Selectfluor in the 60nm Au particle solution, and then add it to the above mixed solution; carry out the reaction under the irradiation of a xenon lamp with stirring, and detect the reaction progress with a TLC plate; after the reaction is completed, rotary evaporate to remove acetonitrile, then add ethyl acetate for extraction, and wash the organic phase three times with water; dry with anhydrous sodium sulfate, collect the organic phase and concentrate it on a rotary evaporator to obtain the crude product; separate and purify with a silica gel chromatographic column using ethyl acetate / n-hexane as the eluent to obtain the pure target product

[0018] Preferably, the molar ratio of arylacetylene, TBAB, and Selectfluor is: 1:5:3, and the molar number of Au particles relative to arylacetylene is one ten-thousandth.

[0019] Preferably, the volume ratio of acetonitrile to water is 1:1.

[0020] Preferably, under normal temperature and pressure, the reaction can be completed within 5 h for the conversion of the reaction substrate.

[0021] Preferably, 0.644 g (2 mmol) of tetrabutylammonium bromide was weighed in a glove box, and together with a 1 cm × 1 cm aluminum sheet, they were added to a glass bottle. Then, 46.4 mg (0.4 mmol) of 4-methylphenylacetylene and 8 mL of acetonitrile were added and dissolved. 0.425 g (1.2 mmol) of Selectfluor was dissolved in 8 mL of a solution of 60 nm Au particles, and then added to the above mixed solution. The reaction was stirred under the irradiation of a xenon lamp, and the reaction progress was monitored by a TLC plate. After the reaction was completed, acetonitrile was removed by rotary evaporation, then ethyl acetate was added for extraction, and the organic phase was washed three times with water. After drying with anhydrous sodium sulfate, the organic phase was collected and concentrated on a rotary evaporator to obtain the crude product. The crude product was separated and purified by silica gel column chromatography (using ethyl acetate / n-hexane as the eluent) to obtain the pure target product, with a separation yield of 90.5% and an HPLC yield of 95.5%.

[0022]

[0023] Preferably, 0.644 g (2 mmol) of tetrabutylammonium bromide was weighed in a glove box, and together with a 1 cm × 1 cm aluminum sheet, they were added to a glass bottle. Then, 52.8 mg (0.4 mmol) of 4-methoxyphenylacetylene and 8 mL of acetonitrile were added and dissolved. 0.425 g (1.2 mmol) of Selectfluor was dissolved in 8 mL of a solution of 60 nm Au particles, and then added to the above mixed solution. The reaction was stirred under the irradiation of a xenon lamp, and the reaction progress was monitored by a TLC plate. After the reaction was completed, acetonitrile was removed by rotary evaporation, then ethyl acetate was added for extraction, and the organic phase was washed three times with water. After drying with anhydrous sodium sulfate, the organic phase was collected and concentrated on a rotary evaporator to obtain the crude product. The crude product was separated and purified by silica gel column chromatography (using ethyl acetate / n-hexane as the eluent) to obtain the pure target product, with a separation yield of 81% and an HPLC yield of 96.94%.

[0024]

[0025] A method for preparing gold nanoparticles. When light irradiates on gold nanoparticles, if the vibration frequency of the incident light is the same as the resonance frequency of the free electrons on the surface of gold nanoparticles, the coherent oscillation generated will trigger the collective excitation of electrons. The excited hot electrons resonate with the electromagnetic field of the incident light to generate heat energy. The specific steps include:

[0026] Preparation of AuNPs (15 nm): Add 99 mL of pure water and 1 mL of 10 mg / mL HAuCl4 solution into a 250 mL two-necked flask, heat under reflux at 130 °C, then add 3 mL of 1 w% sodium citrate solution. The color of the reaction solution turns purple in about 1 minute and then immediately turns red. Continue to heat under reflux for half an hour and then naturally cool to room temperature. 15 nm gold particles are obtained.

[0027] Preparation of AuNPs (40 nm): Add the prepared 15 nm gold particles into a two-necked flask and then add 45 mL of pure water. Heat under reflux at 130 °C, then add 250 μL of sodium citrate solution and 300 μL of HAuCl4 solution successively and reflux for half an hour. Repeat the above operation twice and naturally cool to room temperature to obtain 40 nm gold particles.

[0028] Preparation of AuNPs (60 nm): Under the condition of 115 °C, add 25 mL of hot water and 0.25 mL of HAuCl4 solution into the flask and carry out condensation reflux. React for 30 min. Then add 0.375 mL of sodium citrate solution. At this time, the color of the reaction solution changes from red to dark gray, then to black, then to purple, and finally to red within 10 min. After reflux reaction for 15 min, add 25 mL of 80 °C hot water, and dropwise add 50 μL of 6.6 mg / mL NaOH solution and 250 μL of sodium citrate solution, then quickly add 250 μL of HAuCl4 solution, and reflux and heat for 20 min. Then add 50 ml of hot water, 0.1 mL of NaOH solution and 0.5 mL of sodium citrate solution, and quickly add 0.5 mL of HAuCl4 solution, and continue to heat under reflux for 20 min. Repeat this operation 4 times and then naturally cool to room temperature to obtain a 60 nm gold particle solution.

[0029] Preparation of AuNPs (80 nm): Mix 250 μL of HAuCl4 solution with 25 mL of water, heat under reflux in an oil bath at 135 °C for 20 min, then add 375 μL of sodium citrate solution. After 10 min, it will be observed that the reaction system turns red. After 15 min, add 25 mL of boiling water and 50 μL of NaOH solution, and quickly add 250 μL of sodium citrate solution and 250 μL of HAuCl4 solution. After 20 min, continue to add 50 mL of boiling water, 100 μL of NaOH solution, 500 μL of sodium citrate solution and 500 μL of HAuCl4 solution into the reaction system. This step is repeated 6 times, with each reaction lasting 20 min. After naturally cooling to room temperature, an 80 nm gold particle solution can be obtained.

[0030] Advantages of the present invention:

[0031] (1) The method of the present invention is simple and easy to operate. Under normal temperature and pressure, directly using gold nanoparticles as the photothermal material to catalyze the hydrocarboxylation reaction of arylacetylenes. This method can obtain a separation yield of 90.5% of the target ketone product by using 4-methoxyphenylacetylene in a relatively short time.

[0032] (2) The method of the present invention is applicable to various types of alkyne substrates. Whether it is halogen group-substituted, alkoxy-substituted phenylacetylene, or alkyl, hydroxyl, ester group-substituted phenylacetylene, the corresponding carbonylation products can be obtained in good yields (56%-90.5%), showing good functional group tolerance. The present invention finally selects arylacetylenes where R is methoxy, methyl, fluorine or no group as described in claim 1, and the yield of the hydrocarboxylation reaction of arylacetylenes can reach more than 80%.

[0033] (3) The method of the present invention can directly use sunlight as the light source, and also has good yields under gram-scale reactions, providing the possibility for the future application of this method in large-scale production.

[0034] (4) The 60nm gold nanoparticles described in the method of the present invention have the best catalytic effect on the hydrocarboxylation reaction of arylacetylenes. For example, in Comparative Example 5, 80nm Au particles were used, and the conversion rates of the target products were greatly reduced to 70.7%, 73.2% and 68%. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] The following further describes the present invention with reference to the accompanying drawings.

[0036] Figure 1 It is the scanning electron microscope (SEM) image of the gold particles in Example 1;

[0037] Figure 2 It is the application (A), NMR spectrum (B) and high performance liquid chromatogram (C) of the photothermal catalysis of gold particles on the hydrocarboxylation reaction of 4-methylphenylacetylene, which respectively prove the structure of the product and the conversion rate of the product;

[0038] Figure 3 The application (A), NMR spectrum (B) and high performance liquid chromatogram (C) of the photothermal catalysis of gold particles on the hydrocarboxylation reaction of 4-methoxyphenylacetylene, which respectively prove the structure of the product and the conversion rate of the product.

[0039] Figure 4 It is the reaction expansion diagram of other alkyne substrates and their separation yields.

[0040] Figure 5 It is the TLC plate image of the hydrocarboxylation reaction of 4-methylphenylacetylene catalyzed by copper.

[0041] Figure 6 It is the TLC plate image of the hydrocarboxylation reaction of 4-methylphenylacetylene catalyzed by zinc. Detailed implementation mode

[0042] Example 1

[0043] Under the condition of 115 °C, 25 mL of hot water and 0.25 mL of HAuCl4 solution were added to a flask, and then condensed and refluxed. React for 30 min. Then 0.375 mL of sodium citrate solution was added. At this time, the color of the reaction solution changed from red to dark gray, then to black, then to purple, and finally to red within 10 min. After refluxing for 15 min, 25 mL of hot water at 80 °C was added, and 50 μL of 6.6 mg / mL NaOH solution and 250 μL of sodium citrate solution were added drop by drop. Then 250 μL of HAuCl4 solution was quickly added, and refluxed and heated for 20 min. Then 50 mL of hot water, 0.1 mL of NaOH solution and 0.5 mL of sodium citrate solution were added, and 0.5 mL of HAuCl4 solution was quickly added, and continued to reflux and heat for 20 min. Repeat this operation 4 times, and then naturally cool to room temperature to obtain a 60 nm gold particle solution.

[0044] Example 2

[0045] Weighed 2 mmol of tetrabutylammonium bromide in a glove box, added it together with a 1 cm × 1 cm aluminum sheet to a glass bottle, and then added 46.4 mmg of 4-methylphenylacetylene and 8 mL of acetonitrile to dissolve. Dissolved 0.425 g (1.2 mmol, 3 equiv) of Selectfluor in 8 mL of a 60 nm Au particle solution (where the content of Au particles is about 10 -12 mol), and then added it to the above mixed solution. The reaction was stirred under the irradiation of a xenon lamp, and the reaction progress was detected with a TLC plate. After the reaction was completed, the acetonitrile was removed by rotary evaporation, and then ethyl acetate was added for extraction, and the organic phase was washed three times with water. After drying with anhydrous sodium sulfate, the organic phase was collected and concentrated on a rotary evaporator to obtain the crude product. The crude product was separated and purified by silica gel column chromatography (using ethyl acetate / n-hexane as the eluent) to obtain the pure target product. The separation yield was 90.5%, and the HPLC yield was 95.5%. In addition to the target product, the by-products were mainly brominated products of aryl ketones.

[0046] Example 3

[0047] Weigh 2 mmol of tetrabutylammonium bromide in a glove box, add it together with a 1 cm × 1 cm aluminum sheet into a glass bottle, then add 52.8 mmol of 4-methoxyphenylacetylene and 8 mL of acetonitrile to dissolve. Take 0.425 g (1.2 mmol, 3 equiv) of Selectfluor and dissolve it in 8 mL of a solution of 60 nm Au particles, and then add it to the above mixed solution. Stir the reaction under the irradiation of a xenon lamp and monitor the reaction progress using a TLC plate. After the reaction is completed, remove acetonitrile by rotary evaporation, then add ethyl acetate for extraction, and wash the organic phase three times with water. Dry it with anhydrous sodium sulfate, collect the organic phase and concentrate it on a rotary evaporator to obtain the crude product. Separate and purify it using a silica gel chromatography column (using ethyl acetate / n-hexane as the eluent) to obtain the pure target product, with a separation yield of 81% and an HPLC yield of 96.94%.

[0048] Example 4

[0049] Weigh 2 mmol of tetrabutylammonium bromide in a glove box, add it together with a 1 cm × 1 cm aluminum sheet into a glass bottle, then add 0.4 mmol of other alkyne substrates and 8 mL of acetonitrile to dissolve. Take 0.425 g (1.2 mmol, 3 equiv) of Selectfluor and dissolve it in 8 mL of a solution of 60 nm Au particles, and then add it to the above mixed solution. Stir the reaction under the irradiation of a xenon lamp and monitor the reaction progress using a TLC plate. After the reaction is completed, remove acetonitrile by rotary evaporation, then add ethyl acetate for extraction, and wash the organic phase three times with water. Dry it with anhydrous sodium sulfate, collect the organic phase and concentrate it on a rotary evaporator to obtain the crude product. Separate and purify it using a silica gel chromatography column (using ethyl acetate / n-hexane as the eluent) to obtain the pure target product and calculate its separation yield.

[0050]

[0051] The specific reaction route is as follows:

[0052]

[0053]

[0054] Comparative Example 1

[0055] Weigh 2 mmol of tetrabutylammonium bromide in a glove box, add it together with a 1 cm × 1 cm aluminum sheet into a glass bottle, then add 58.8 mmol of 4-nitrophenylacetylene and 8 mL of acetonitrile and dissolve. Take 0.425 g (1.2 mmol, 3 equiv) of Selectfluor and dissolve it in 8 mL of a solution of 60 nm Au particles, then add it to the above mixed solution. Stir the reaction under the irradiation of a xenon lamp and detect the reaction progress with a TLC plate. It was found by TLC plate detection that the reaction did not occur and the target product was not obtained.

[0056] Comparative Example 2

[0057] Weigh 2 mmol of tetrabutylammonium iodide in a glove box, add it together with a 1 cm × 1 cm aluminum sheet into a glass bottle, then add 46.4 mmol of 4-methylphenylacetylene and 8 mL of acetonitrile and dissolve. Take 0.425 g (1.2 mmol, 3 equiv) of Selectfluor and dissolve it in 8 mL of a solution of 60 nm Au particles, then add it to the above mixed solution. Stir the reaction under the irradiation of a xenon lamp and detect the reaction progress with a TLC plate. By replacing tetrabutylammonium bromide with tetrabutylammonium iodide, it was found by TLC plate detection that the target product was not obtained.

[0058] Comparative Example 3

[0059] Weigh 2 mmol of tetrabutylammonium bromide and 0.01 g of copper powder in a glove box and add them together into a glass bottle, then add 46.4 mmol of 4-methylphenylacetylene and 8 mL of acetonitrile and dissolve. Take 0.425 g (1.2 mmol, 3 equiv) of Selectfluor and dissolve it in 8 mL of a solution of 60 nm Au particles, then add it to the above mixed solution. Stir the reaction under the irradiation of a xenon lamp and detect the reaction progress with a TLC plate. By replacing aluminum with copper powder, it was found by TLC plate detection that the reaction did not occur.

[0060] Comparative Example 4

[0061] Weigh 2 mmol of tetrabutylammonium bromide and 0.01 g of zinc powder in a glove box and add them together into a glass bottle, then add 46.4 mmol of 4-methylphenylacetylene and 8 mL of acetonitrile and dissolve. Take 0.425 g (1.2 mmol, 3 equiv) of Selectfluor and dissolve it in 8 mL of a solution of 60 nm Au particles, then add it to the above mixed solution. Stir the reaction under the irradiation of a xenon lamp and detect the reaction progress with a TLC plate. By replacing aluminum with zinc powder, it was found by TLC plate detection that the target product was not obtained and the product was 2,2-dibromo-1-aryl ethanone.

[0062] Comparative Example 5

[0063] Weigh 0.644 g (2 mmol) of tetrabutylammonium bromide in a glove box, add it together with a 1 cm × 1 cm aluminum sheet into a glass bottle, then add 52.8 mg (0.4 mmol) of 4-methoxyphenylacetylene and 8 mL of acetonitrile to dissolve. Dissolve 0.425 g (1.2 mmol) of Selectfluor in 8 mL of solutions of 15 nm, 40 nm, and 80 nm Au particles respectively, and then add them to the above mixed solution. Stir the reaction under the irradiation of a xenon lamp and monitor the reaction progress using a TLC plate. After the reaction is completed, the conversion rates of the target products are 70.7%, 73.2%, and 68% respectively.

Claims

1. A method for catalytically hydrating and carbonylating arylacetylene by using the photothermal effect of gold nanoparticles, characterized in that : The specific steps include: Prepare gold nanoparticles with a size of 15 - 80 nm as the photothermal material. Using a xenon lamp as the light source, in a mixed solvent of acetonitrile and water, with Selectfluor (a fluorine reagent) and tetrabutylammonium bromide (TBAB) as additives and aluminum as the sacrificial agent, to catalyze the hydrocarboxylation reaction of arylacetylene; The specific reaction route is as follows: ； Where R is methoxy, methyl, fluorine or no group.

2. The method for catalytic hydration carbonylation of arylacetylene by using the photothermal effect of gold nanoparticles according to claim 1, wherein: The size of the gold nanoparticles is 15 nm, 40 nm, 60 nm or 80 nm.

3. The method for catalytic hydrocarboxylation of arylacetylene by using the photothermal effect of gold nanoparticles according to claim 2, characterized in that: The specific preparation steps of the 60 - nm gold nanoparticle aqueous solution are as follows: Step (1): Under the condition of 115 °C, add 25 mL of hot water and 0.25 mL of HAuCl4 solution to a flask, and carry out condensation reflux; react for 30 min; Step (2): Add 0.375 mL of sodium citrate solution. At this time, the color of the reaction solution changes from red to dark gray, then to black, then to purple, and finally to red within 10 min; Step (3): After refluxing for 15 min, add 25 mL of hot water at 80 °C, and gradually add 50 μL of 6.6 mg / mL NaOH solution and 250 μL of sodium citrate solution, then quickly add 250 μL of HAuCl4 solution, and reflux and heat for 20 min; Step (4): Add 50 mL of hot water, 0.1 mL of NaOH solution and 0.5 mL of sodium citrate solution, and quickly add 0.5 mL of HAuCl4 solution, and continue to reflux and heat for 20 min; Step (5): Repeat this operation 4 times, and then naturally cool to room temperature to obtain a 60 - nm gold particle solution.

4. The method for catalytic hydration carbonylation of arylacetylene by using the photothermal effect of gold nanoparticles according to claim 2, characterized in that: The specific steps are as follows: Weigh tetrabutylammonium bromide and an aluminum sheet and add them together to a glass bottle, then add 4 - methylphenylacetylene and acetonitrile to dissolve; dissolve Selectfluor in the 60 - nm Au particle solution, and then add it to the above - mentioned mixed solution; carry out the reaction under the irradiation of a xenon lamp with stirring, and use a TLC plate to detect the reaction progress; after the reaction is completed, rotary evaporate to remove acetonitrile, then add ethyl acetate for extraction, and wash the organic phase three times with water; After drying with anhydrous sodium sulfate, collect the organic phase and concentrate it on a rotary evaporator to obtain the crude product; separate and purify it with a silica gel chromatography column using ethyl acetate / n - hexane as the eluent to obtain the pure target product.

5. The method for catalytic hydration carbonylation of arylacetylene by using the photothermal effect of gold nanoparticles according to claim 2, wherein: The molar ratio of arylacetylene, TBAB, and Selectfluor is: 1:5:3, and the molar number of Au nanoparticles relative to arylacetylene is one - millionth.

6. The method for catalytic hydrocarboxylation of arylacetylene by using the photothermal effect of gold nanoparticles according to claim 2, characterized in that: The volume ratio of acetonitrile to water is 1:

1.

7. The method for the hydrocarboxylation of arylacetylene using the photothermal effect of gold nanoparticles according to claim 2, characterized in that: Under normal temperature and pressure, the reaction can be completed in 5 h for the conversion of the reaction substrate.

8. The method for catalytic hydrocarboxylation of arylacetylene by using the photothermal effect of gold nanoparticles according to claim 2, wherein: Weigh 0.644 g (2 mmol) of tetrabutylammonium bromide in a glove box, add it together with a 1 cm × 1 cm aluminum sheet to a glass bottle, then add 46.4 mg (0.4 mmol) of 4-methylphenylacetylene and 8 mL of acetonitrile and dissolve. Take 0.425 g (1.2 mmol) of Selectfluor and dissolve it in 8 mL of a solution of 60 nm Au particles, then add it to the above mixed solution. Stir the reaction under the irradiation of a xenon lamp and use a TLC plate to detect the reaction progress. After the reaction is completed, rotary evaporate to remove acetonitrile, then add ethyl acetate for extraction, and wash the organic phase three times with water. After drying with anhydrous sodium sulfate, collect the organic phase and concentrate it on a rotary evaporator. Purify the obtained crude product by silica gel column chromatography using ethyl acetate / n-hexane as the eluent to obtain the pure target product. The separation yield is 90.5% and the HPLC yield is 95.5%. The specific route is as follows: 。 9. The method for catalytic hydrocarboxylation of arylacetylene by using the photothermal effect of gold nanoparticles according to claim 2, characterized in that: Weigh 0.644 g (2 mmol) of tetrabutylammonium bromide in a glove box, add it together with a 1 cm × 1 cm aluminum sheet to a glass bottle, then add 52.8 mg (0.4 mmol) of 4-methoxyphenylacetylene and 8 mL of acetonitrile and dissolve. Take 0.425 g (1.2 mmol) of Selectfluor and dissolve it in 8 mL of a solution of 60 nm Au particles, then add it to the above mixed solution. Stir the reaction under the irradiation of a xenon lamp and use a TLC plate to detect the reaction progress. After the reaction is completed, rotary evaporate to remove acetonitrile, then add ethyl acetate for extraction, and wash the organic phase three times with water. After drying with anhydrous sodium sulfate, collect the organic phase and concentrate it on a rotary evaporator. Purify the obtained crude product by silica gel column chromatography using ethyl acetate / n-hexane as the eluent to obtain the pure target product. The separation yield is 81% and the HPLC yield is 96.94%. The specific route is as follows: 。

Images