A thiophene functionalized column[5] aromatic hydrocarbon and its preparation method and application

Abstract

The present invention discloses a thiophene-functionalized pillar[5]arene and a preparation method and application thereof, belonging to the technical field of organic synthesis. The present invention is based on the property of thiophene ring ligands selectively complexing cadmium ions, fully utilizes the coordination functional groups at the upper and lower edges of the pillar[5]arene, and realizes a click reaction between a pillar[5]arene precursor with an azide group and a thiophene derivative containing an alkynyl group under the action of a copper catalyst, thereby quickly and efficiently obtaining the thiophene-functionalized pillar[5]arene. The thiophene-functionalized pillar[5]arene prepared by the present invention is a simple, rapid and sensitive cadmium ion detection reagent. The cadmium ion concentration can be quantitatively analyzed by measuring the change in the ultraviolet absorption intensity of the thiophene-functionalized pillar[5]arene solution before and after the addition of cadmium ions. The present invention has broad application prospects in water sample environments and life systems.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and in particular relates to a thiophene-functionalized column[5] aromatic hydrocarbon and a preparation method and application thereof. Background Art

[0002] Cadmium ions are easily absorbed and accumulated by living organisms, causing irreversible damage to the environment and organisms. Therefore, measuring cadmium ion levels in environmental and living systems is of great significance. Currently, widely used methods for metal ion detection include atomic absorption spectroscopy, inductively coupled plasma mass spectrometry, and electrochemical analysis. However, these methods require expensive and complex instrumentation and skilled personnel to operate them. The analysis process is cumbersome, time-consuming, and expensive, all of which are drawbacks. Fluorescent probe detection, on the other hand, offers high selectivity, high sensitivity, visual recognition, ease of use, and low intracellular toxicity, making it widely used not only for substance detection but also as an important tool for sensor analysis in environmental and life sciences. In recent years, numerous materials for cadmium ion recognition have been reported, but the complex synthesis steps and low selectivity and sensitivity of these materials have limited their applicability. Therefore, the development of novel cadmium ion recognition materials is of great research value for fluorescent imaging diagnostic analysis of cadmium ions in the environment and living systems.

[0003] In the field of organic chemistry and materials science, macrocyclic compounds have been widely studied due to their unique molecular structure and properties. Among them, pillar[n]arene, as a type of cyclic macromolecule formed by benzene rings bridged by methylene, has become a research hotspot in the fields of supramolecular chemistry, host-guest recognition, controlled drug release, artificial transmembrane channels, catalysis and nanomaterials due to its high symmetry, rigidity and unique electron-rich cavity structure. Thiophene, as a sulfur-containing heterocyclic compound, has excellent electron transport properties and unique chemical properties and is widely used in the fields of organic electronic materials, drug molecules and functional polymer materials. However, the traditional preparation method of thiophene-functionalized pillar[5]arene often has the disadvantages of complicated steps, harsh reaction conditions and low yield, which makes it difficult to meet the needs of practical applications. Therefore, it is particularly important to develop an efficient, simple and high-yield preparation method for thiophene-functionalized pillar[5]arene. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a thiophene functionalized pillar [5] aromatic hydrocarbon and its preparation method and application, so as to solve the technical problems that the synthesis steps of the existing thiophene functionalized pillar [5] aromatic hydrocarbon are complicated and the yield is not high enough.

[0005] In order to achieve the above-mentioned purpose, the technical solution adopted by the present invention is to provide a thiophene functionalized pillar [5] aromatic hydrocarbon, whose structural formula is:

[0006]

[0007] The present invention also discloses a method for preparing thiophene-functionalized pillar[5]arene, comprising the following steps: using a para-substituted phenol compound and a halogenated hydrocarbon as initial raw materials, using an iodine salt as a catalyst in an alkaline environment, and generating a pillar[5]arene monomer through a dinucleophilic substitution reaction between the halogenated hydrocarbon and the para-substituted phenol compound; subsequently, generating a pillar[5]arene intermediate through Lewis acid catalysis, and then reflux-reacting the pillar[5]arene intermediate with an azide salt, and reacting the obtained product with an alkynyl thiophene compound and an azide group through a click reaction to generate a triazole bridge structure unit, thereby linking thiophene with the pillar[5]arene skeleton, and finally obtaining the thiophene-functionalized pillar[5]arene.

[0008] On the basis of the above technical solution, the present invention can also be improved as follows:

[0009] Further, the following steps are included:

[0010] S1. Dissolve a para-substituted phenol compound and a halogenated hydrocarbon in an organic solvent, then add an inorganic base and an iodized salt to the reaction system under a protective atmosphere, and react at 80-90°C for 2-24 hours to obtain a column [5] aromatic hydrocarbon monomer; the molar ratio of the para-substituted phenol compound, the halogenated hydrocarbon, the inorganic base and the iodized salt is 0.5-1.5:3.5-4.5:1.5-3.5:0.04-0.06;

[0011] S2. Dissolve the column [5] aromatic hydrocarbon monomer and raw material 1 in an organic solvent, then add a Lewis acid catalyst and stir to react for 1-3 hours, and finally add an inorganic base to quench the reaction to obtain a column [5] aromatic hydrocarbon intermediate; the raw material 1 is paraformaldehyde or triformaldehyde; the ratio of the column [5] aromatic hydrocarbon monomer, raw material 1, Lewis acid catalyst and inorganic base is 0.5-1.5 mol: 2.8-3.2 mol: 3.5-5.5 mol: 100-300 mL;

[0012] S3, dissolving the pillar[5]arene intermediate and the azide salt in an organic solvent at a molar ratio of 0.5-1.5:12-17, and then reacting at 70-90° C. for 4-7 hours in a protective atmosphere to obtain the azidated pillar[5]arene;

[0013] S4. Dissolve the azidated pillar[5]arene, alkynyl thiophene compound, copper salt and sodium L-ascorbate in water at a molar ratio of 0.5-1.5:12-17:0.5-1.5:1.5-2.5, and then react in a protective atmosphere for 46-50 hours to obtain thiophene-functionalized pillar[5]arene.

[0014] Furthermore, the para-substituted phenol compound is hydroquinone, the halogenated hydrocarbon is 1,4-dibromobutane or 1,4-diiodobutane, the inorganic base is K2CO3, KOH, Na2CO3, NaHCO3 or NaOH, the iodine salt is KI or NaI, and the Lewis acid catalyst is boron trifluoride etherate or ferric chloride.

[0015] Furthermore, the azide salt is potassium azide or sodium azide, the alkynyl thiophene compound is 2-ethynyl thiophene, 2-ethynyl-3-methylthiophene, 3-ethynyl thiophene, 2-bromo-5-ethynyl thiophene, 2-ethyl-5-ethynyl thiophene, 5-ethynyl thiophene-2-carboxaldehyde, 2-ethynyl-5-methylthiophene or 5-ethynyl-2,3-dimethylthiophene, the alkynyl group serves as the reactive group of the click reaction and the coordination site of the thiophene metal ion, and the copper salt is copper sulfate.

[0016] Furthermore, the reaction temperature in S1 is 85° C. and the reaction time is 13 h; the reaction temperature in S3 is 80° C. and the reaction time is 5 h.

[0017] Furthermore, the heating rate during the reaction in S1 and S3 is 2-5°C / min.

[0018] Furthermore, the organic solvent is acetonitrile, dichloromethane or dimethylformamide (DMF).

[0019] Furthermore, the protective atmosphere gas is argon.

[0020] The present invention also discloses the application of thiophene functionalized column [5] aromatic hydrocarbon in the preparation of cadmium pollution detection materials.

[0021] The beneficial effects of the present invention are:

[0022] 1. Significantly improved efficiency: The present invention utilizes copper-catalyzed azide-alkyne click reaction (CuAAC) to achieve the rapid introduction of thiophene groups into pillar[5]arene. The process is simple, the reaction conditions are mild, and the reaction rate is fast, which greatly shortens the synthesis cycle, improves production efficiency, and reduces production costs.

[0023] 2. High product purity and stable yield: The present invention can stably obtain high-yield thiophene-functionalized column[5] aromatics. At the same time, the post-treatment process using column chromatography can effectively remove impurities, improve the purity of the product, and ensure the quality and application effect of the product.

[0024] 3. Environmental protection and sustainability: The raw materials used in the present invention are all common organic chemicals, and the reaction conditions are mild, which reduces the generation of harmful by-products and reduces pollution to the environment.

[0025] 4. The thiophene-functionalized column [5] aromatic hydrocarbon prepared by the present invention is a simple, rapid and sensitive cadmium ion detection reagent. The cadmium ion concentration can be quantitatively analyzed by the change in the ultraviolet absorption intensity of the thiophene-functionalized column [5] aromatic hydrocarbon solution before and after the addition of cadmium ions. It has broad application prospects in the fields of water sample environments and life systems. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Fourier transform infrared spectra of thiophene-functionalized pillar[5]arene;

[0027] Figure 2 The UV-visible absorption spectrum of thiophene-functionalized pillar[5]arene;

[0028] Figure 3 This is the H NMR spectrum of thiophene-functionalized pillar[5]arene;

[0029] Figure 4 UV-visible absorption spectra of thiophene-functionalized pillar[5]arene before and after recognition of cadmium ions. DETAILED DESCRIPTION

[0030] The specific embodiments of the present invention are described below to facilitate understanding of the present invention by those skilled in the art. In the examples, where specific conditions are not specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. Reagents or instruments used where the manufacturer is not specified are conventional products that can be purchased commercially. However, it should be understood that the present invention is not limited to the scope of the specific embodiments. It is obvious to those skilled in the art that various modifications are within the spirit and scope of the present invention as defined and determined by the appended claims, and all inventions and creations utilizing the present invention are protected.

[0031] Example 1

[0032] A method for preparing thiophene-functionalized pillar[5]arene comprises the following steps:

[0033] S1. Dissolve hydroquinone (15.00 g, 136.22 mmol) and 1,4-dibromobutane (65.91 mL, 544.90 mmol) in 300 mL of acetonitrile. After the solid is completely dissolved, introduce argon protection into the reaction system. Then, add anhydrous K2CO3 (41.42 g, 299.69 mmol) and KI (1.13 g, 6.81 mmol) under stirring, and then heat to 85°C and reflux for 13 h. After the reaction, wash the solid impurities with dichloromethane several times, filter, and finally concentrate under reduced pressure at 25°C to remove acetonitrile and dichloromethane. Purify and separate by column chromatography (eluent: petroleum ether: dichloromethane = 2:1, V / V) to obtain a white powder, i.e., column [5] aromatic monomer.

[0034] S2, dissolve the column [5] aromatic monomer (1.5 g, 3.95 mmol) and paraformaldehyde (0.355 g, 11.84 mmol) in 300 mL of dichloromethane. After the solid is completely dissolved, add boron trifluoride ether (C4H) to the reaction system. 10 BF3O (2.48 mL, 19.73 mmol) was stirred and reacted for 2 h until the color of the reaction solution turned dark green. Finally, 200 mL of 10 wt% NaHCO3 was added to quench the reaction. At this time, the color of the reaction solution turned light yellow. The reaction solution was poured into a 1000 mL pear-shaped separatory funnel, and after standing and stratification, the upper aqueous phase was discarded, and the lower organic phase was collected and concentrated under reduced pressure at 25 ° C. The product was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 2:1, V / V) to obtain a white solid powder, i.e., decabromobutoxy-pilmane[5]arene. The structural formula of decabromobutoxy-pilmane[5]arene is:

[0035]

[0036] S3. Decabromobutoxy-pilo[5]arene (1.00 g, 502.33 μmol) was dissolved in 50 mL of DMF, followed by the addition of potassium azide (0.61 g, 7.53 mmol). Argon was introduced into the reaction system, and the temperature was raised to 80°C for 5 h. The light yellow reaction solution was poured into a beaker containing 400 mL of distilled water and stirred for 30 min. The solution was filtered and washed with distilled water (20 mL x 3). The organic phase was dried over anhydrous sodium sulfate and the solvent was removed by rotary evaporation at 25°C to obtain a white solid, i.e., azido-pilo[5]arene, with a yield of 87%.

[0037] S4. Dissolve the azidated column [5] aromatic hydrocarbon (0.1 g, 62.04 μmol), 2-alkynylthiophene (0.1 g, 0.93 mmol), copper sulfate pentahydrate (15.49 mg, 62.04 μmol) and sodium L-ascorbate (24.58 mg, 124.08 μmol) in 1 mL of water, and then react for 48 h in an argon atmosphere. After the reaction is complete, pour the reaction solution into 100 mL of ice water, add 100 mL of dichloromethane, and The organic phase was collected and washed three times with 100 mL of saturated sodium carbonate solution, and then washed three times with 100 mL of saturated saline, 0.1 M EDTA-2Na solution and deionized water. The organic phase was dried over anhydrous sodium sulfate and filtered to obtain a brown solution. After the solvent was removed by concentration under reduced pressure, the solution was purified by column chromatography (DCM: MeOH = 30:1, V / V) to obtain a light brown foamy solid, namely thiophene functionalized column [5] aromatic hydrocarbon, with a yield of 89%.

[0038] Figure 1This is the Fourier transform infrared spectrum of thiophene functionalized column[5]arene. It can be seen from the figure that its characteristic infrared absorption peak is 700cm -1 (CS),796cm -1 (CH),846cm -1 (CH),932cm -1 (CH),1045cm -1 (COC),1204cm -1 (COC),1290cm -1 (N=N),1401cm -1 (C=C),1465cm -1 (C=C),1499cm -1 (C=C),1590cm -1 (CN),1631cm -1 (N=N),1655cm -1 (C=C),2862cm -1 (-CH2-),2929cm -1 (-CH2-),3113cm -1 (CH), comprehensive analysis shows that the infrared spectrum is completely consistent with the theoretical structure of the synthetic product thiophene-functionalized pillar[5]arene, and it can be concluded that the target compound is a pillararene derivative.

[0039] Figure 2 This is the UV-visible absorption spectrum of thiophene-functionalized pillar[5]arene. It can be seen from the figure that its characteristic absorption peak is in the range of 200-240 nm, and the conclusion is that the maximum absorption peak of the compound is 205 nm. It may be that the π-π transition of the thiophene ring leads to strong absorption at lower wavelengths. At the same time, there are interactions such as conjugation effect and steric hindrance effect between the thiophene ring and pillar[5]arene.

[0040] Figure 3 Thiophene functionalized pillar[5]arene 1 H NMR spectrum. As can be seen from the figure, the characteristic proton shift of pillar[5]arene is: 1H NMR (400 MHz, DMSO-d6) δ8.46 (s, 1H), 7.49 (dd, J = 5.1, 1.2 Hz, 1H), 7.38 (dd, J = 3.6, 1.2 Hz, 1H), 7.09 (dd, J = 5.1, 3.6 Hz, 1H), 6.66 (s, 1H), 4.40 (s, 2H), 3.86 (s, 1H), 3.57 (s, 2H), 2.01 (t, J = 7.3 Hz, 2H), 1.65 (s, 2H), among which the peak shift of the bridging methylene proton signal was δ = 3.86 ppm, which indicated that the target compound was a pillar aromatic hydrocarbon derivative. Based on the chemical shift of the ortho-proton of thiophene δ = 8.46 ppm, the characteristic proton signal peak integral ratio is 1:1:1:1:2:2:2:2:2:1:1. The experimental value is consistent with the ratio of the number of protons in the molecule, and it can be concluded that this molecule is the target molecule.

[0041] Example 2

[0042] A method for preparing thiophene-functionalized pillar[5]arene comprises the following steps:

[0043] S1. Dissolve hydroquinone (15.00 g, 136.22 mmol) and 1,4-diiodobutane (65.91 mL, 544.90 mmol) in 300 mL of acetonitrile. After the solid is completely dissolved, introduce argon protection into the reaction system. Then, add anhydrous Na2CO3 (41.42 g, 299.69 mmol) and NaI (1.13 g, 6.81 mmol) under stirring, and then heat to 80°C and reflux for 24 h. After the reaction, wash the solid impurities with dichloromethane several times, filter, and finally concentrate under reduced pressure at 25°C to remove acetonitrile and dichloromethane. Purify and separate by column chromatography (eluent: petroleum ether: dichloromethane = 2:1, V / V) to obtain a white powder, i.e., column [5] aromatic monomer.

[0044] S2, dissolve the column [5] aromatic monomer (1.5 g, 3.95 mmol) and paraformaldehyde (0.355 g, 11.84 mmol) in 300 mL of dichloromethane. After the solid is completely dissolved, add boron trifluoride ether (C4H) to the reaction system. 10 BF3O (2.48 mL, 19.73 mmol) was stirred and reacted for 3 h until the color of the reaction solution turned dark green. Finally, 10 mL of NaHCO3 was added to quench the reaction, and the color of the reaction solution turned light yellow. The reaction solution was poured into a 1000 mL pear-shaped separatory funnel, and after standing and stratification, the upper aqueous phase was discarded, and the lower organic phase was collected and concentrated under reduced pressure at 25 ° C. It was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 2:1, V / V) to obtain a white solid powder, i.e., the column [5] aromatic hydrocarbon intermediate.

[0045] S3. Dissolve the column[5]arene intermediate (1.00 g, 502.33 μmol) in 50 mL of DMF, then add potassium azide (0.61 g, 7.53 mmol), introduce argon into the reaction system, and heat to 90°C for 4 h. Finally, pour the light yellow reaction solution into a beaker containing 400 mL of distilled water and stir for 30 min. Filter with suction, wash the filtrate with distilled water (20 mL×3), dry the organic phase with anhydrous sodium sulfate, and remove the solvent by vacuum rotary evaporation at 25°C to obtain a white solid, i.e., azidated column[5]arene.

[0046] S4. Dissolve the azidated column [5]arene (0.1 g, 62.04 μmol), 2-alkynylthiophene (0.1 g, 0.93 mmol), copper sulfate pentahydrate (15.49 mg, 62.04 μmol) and sodium L-ascorbate (24.58 mg, 124.08 μmol) in 1 mL of water, and then react in an argon atmosphere for 46-50 h. After the reaction is complete, pour the reaction solution into 100 mL of ice water and add 100 mL of The product was extracted and separated with dichloromethane, and the organic phase was collected and washed three times with 100 mL of saturated sodium carbonate solution, and then washed three times with 100 mL of saturated saline, 0.1 M EDTA-2Na solution and deionized water respectively. The organic phase was dried over anhydrous sodium sulfate and filtered to obtain a brown solution. After the solvent was removed by vacuum concentration, the solution was purified by column chromatography (DCM: MeOH = 30:1, V / V) to obtain a light brown foamy solid, namely thiophene functionalized column [5] aromatic hydrocarbon.

[0047] Example 3

[0048] A method for preparing thiophene-functionalized pillar[5]arene comprises the following steps:

[0049] S1. Dissolve hydroquinone (15.00 g, 136.22 mmol) and 1,4-dibromobutane (65.91 mL, 544.90 mmol) in 200 mL of acetonitrile. After the solid is completely dissolved, introduce argon protection into the reaction system. Then, add anhydrous K2CO3 (41.42 g, 299.69 mmol) and KI (1.13 g, 6.81 mmol) under stirring, and then heat to 90°C and reflux for 2 h. After the reaction, wash the solid impurities with dichloromethane several times, filter, and finally concentrate under reduced pressure at 25°C to remove acetonitrile and dichloromethane. Purify and separate by column chromatography (eluent: petroleum ether: dichloromethane = 2:1, V / V) to obtain a white powder, i.e., column [5] aromatic monomer.

[0050] S2. Dissolve column [5] aromatic hydrocarbon monomer (1.5 g, 3.95 mmol) and trioxymethylene (0.355 g, 11.84 mmol) in 300 mL of dichloromethane. After the solid is completely dissolved, add ferric chloride (2.48 mL, 19.73 mmol) to the reaction system and stir to react for 1 hour until the color of the reaction solution turns dark green. Finally, add 10 mL of NaHCO3 to quench the reaction. At this time, the color of the reaction solution turns light yellow. Pour the reaction solution into a 1000 mL pear-shaped separatory funnel, let it stand and separate the layers, discard the upper aqueous phase, collect the lower organic phase, concentrate under reduced pressure at 25°C, and separate and purify by column chromatography (eluent is petroleum ether: dichloromethane = 2:1, V / V) to obtain a white solid powder, i.e., decabromobutoxy column [5] aromatic hydrocarbon.

[0051] S3. Decabromobutoxy-pilo[5]arene (1.00 g, 502.33 μmol) was dissolved in 50 mL of DMF, followed by the addition of potassium azide (0.61 g, 7.53 mmol). Argon was introduced into the reaction system, and the temperature was raised to 70°C for 7 h. The light yellow reaction solution was poured into a beaker containing 400 mL of distilled water and stirred for 30 min. The solution was filtered and washed with distilled water (20 mL x 3). The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation at 25°C to obtain a white solid, i.e., azido-pilo[5]arene.

[0052] S4. Dissolve the azidated column [5]arene (0.1 g, 62.04 μmol), 2-alkynylthiophene (0.1 g, 0.93 mmol), copper sulfate pentahydrate (15.49 mg, 62.04 μmol) and sodium L-ascorbate (24.58 mg, 124.08 μmol) in 1 mL of water, and then react in an argon atmosphere for 46-50 h. After the reaction is complete, pour the reaction solution into 100 mL of ice water and add 100 mL of The product was extracted and separated with dichloromethane, and the organic phase was collected and washed three times with 100 mL of saturated sodium carbonate solution, and then washed three times with 100 mL of saturated saline, 0.1 M EDTA-2Na solution and deionized water respectively. The organic phase was dried over anhydrous sodium sulfate and filtered to obtain a brown solution. After the solvent was removed by vacuum concentration, the solution was purified by column chromatography (DCM: MeOH = 30:1, V / V) to obtain a light brown foamy solid, namely thiophene functionalized column [5] aromatic hydrocarbon.

[0053] Experimental example: Cadmium ion recognition ability

[0054] Taking the thiophene functionalized column [5] aromatic hydrocarbon prepared in Example 1 as an example, 100 mL of 5×10 -5M thiophene functionalized column [5] aromatic hydrocarbon-methanol solution and cadmium chloride-methanol solution were set aside, and then 1 mL thiophene functionalized column [5] aromatic hydrocarbon-methanol solution and 1 mL cadmium chloride-methanol solution were mixed evenly and fixed to 5 mL as the test solution, and 1 mL thiophene functionalized column [5] aromatic hydrocarbon-methanol solution was diluted to 5 mL as the reference solution. The metal ion Cd was detected by ultraviolet spectroscopy. 2+ The recognition ability of the test solution is measured by comparing the UV absorption curve of the test solution with the UV absorption curve of the test solution. If the wavelength of the maximum absorption peak in the UV absorption curve is shifted or the intensity is significantly changed, it indicates that complexation occurs.

[0055] The results are as follows Figure 4 As shown, when 1:1 equivalent of Cd is added to the aromatic solution of thiophene functionalized column [5] 2+ After that, the UV absorption of the solution to be tested was significantly reduced, indicating that the thiophene functionalized column [5] aromatic hydrocarbon prepared by the present invention has a strong affinity for Cd 2+ It has remarkable UV recognition capability.

Claims

1. A thiophene-functionalized pillar[5]arene, characterized in that The structural formula of the thiophene functionalized pillar [5] arene is: 。 2. The method for preparing thiophene-functionalized pillar [5] aromatic hydrocarbons according to claim 1, characterized in that: The method comprises the following steps: using hydroquinone and 1,4-dibromobutane or 1,4-diiodobutane as initial raw materials, using iodine salt as catalyst, generating a pillar[5]arene monomer through a dinucleophilic substitution reaction in an alkaline environment; dissolving the pillar[5]arene monomer and the first raw material in an organic solvent, then adding a Lewis acid catalyst and stirring the reaction for 1-3 hours, and finally adding an inorganic base to quench the reaction to obtain a pillar[5]arene intermediate, wherein the first raw material is polyformaldehyde or triformaldehyde; then refluxing the pillar[5]arene intermediate with an azide salt, and generating a triazole bridge structure unit through a click reaction of the obtained azidated pillar[5]arene with 2-ethynylthiophene, and finally obtaining a thiophene-functionalized pillar[5]arene.

3. The method for preparing thiophene functionalized pillar [5] aromatic hydrocarbons according to claim 2, characterized in that: The following steps are involved: S1. Dissolve hydroquinone and 1,4-dibromobutane or 1,4-diiodobutane in an organic solvent, then add an inorganic base and an iodine salt to the reaction system under a protective atmosphere, and react at 80-90°C for 2-24 hours to obtain a column [5] aromatic hydrocarbon monomer; the molar ratio of the hydroquinone, 1,4-dibromobutane or 1,4-diiodobutane, inorganic base and iodine salt is 0.5-1.5:3.5-4.5:1.5-3.5:0.04-0.06; S2, the column [5] aromatic hydrocarbon monomer, raw material 1, Lewis acid catalyst and inorganic base in a ratio of 0.5-1.5 mol: 2.8-3.2 mol: 3.5-5.5 mol: 100-300 mL; S3, dissolving the pillar[5]arene intermediate and the azide salt in an organic solvent at a molar ratio of 0.5-1.5:12-17, and then reacting at 70-90° C. for 4-7 hours in a protective atmosphere to obtain the azidated pillar[5]arene; S4. Dissolve the azidated pillar[5]arene, 2-ethynylthiophene, copper salt and sodium L-ascorbate in water at a molar ratio of 0.5-1.5:12-17:0.5-1.5:1.5-2.5, and then react in a protective atmosphere for 46-50 hours to obtain thiophene-functionalized pillar[5]arene.

4. The method for preparing thiophene-functionalized pillar [5] aromatic hydrocarbons according to claim 3, characterized in that: The inorganic base is K2CO3, KOH, Na2CO3, NaHCO3 or NaOH, the iodine salt is KI or NaI, and the Lewis acid catalyst is boron trifluoride etherate or ferric chloride.

5. The method for preparing thiophene-functionalized pillar [5] aromatic hydrocarbons according to claim 3, characterized in that: The azide salt is potassium azide or sodium azide, and the copper salt is copper sulfate.

6. The method for preparing thiophene functionalized pillar [5] aromatic hydrocarbons according to claim 3, characterized in that: The reaction temperature in S1 is 85° C. and the reaction time is 13 h; the reaction temperature in S3 is 80° C. and the reaction time is 5 h.

7. The method for preparing thiophene functionalized pillar [5] aromatic hydrocarbons according to claim 3, characterized in that: The heating rate during the reaction in S1 and S3 is 2-5°C / min.

8. The method for preparing thiophene-functionalized pillar[5]arene according to claim 3, characterized in that: The organic solvent is acetonitrile, dichloromethane or dimethylformamide.

9. The method for preparing thiophene-functionalized pillar[5]arene according to claim 3, characterized in that: The protective atmosphere is argon.

10. Use of the thiophene functionalized column [5] aromatic hydrocarbon according to claim 1 in the preparation of cadmium pollution detection materials.

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