Aluminum ion detection reagent as well as preparation method and application thereof

Abstract

The invention provides an aluminum ion detection reagent as well as a preparation method and application thereof, and aims to solve the technical problems that in the prior art, Al < 3 + > ion detection is high in cost, complex in technology, time-consuming and not allowed to be subjected to high-throughput analysis. The aluminum ion detection reagent provided by the invention has the following structure: # imgabs0 #, the preparation method comprises the following steps: (1) adding 2-chlorobenzaldehyde and 2-chloroaniline into a first solvent, carrying out heating reflux reaction, and purifying to obtain an intermediate product; and (2) adding alkali, 8-hydroxyquinoline and a second solvent into the intermediate product, reacting at room temperature, and purifying to obtain the compound. The aluminum ion detection reagent can qualitatively and quantitatively detect aluminum ions, and the detection limit reaches 2.24 * 10 <-7 > MM.

Description

Technical Field

[0001] The invention belongs to the field of metal ion detection, and specifically relates to an aluminum ion detection reagent and a preparation method and application thereof. Background Art

[0002] Aluminum (Al) is the most abundant metal element in the earth's crust. Over the past few decades, more than 400 million tons of raw aluminum have been used in human social activities (such as aviation, construction, electricity, industrial production, daily necessities, agriculture, medicine, chemical industry, electronic information, etc.) every year. With the large-scale production and use of aluminum in human production and life, more and more aluminum enters the ecosystem. Generally speaking, intake through diet will damage the nervous system and immune system, leading to brain nerve degeneration, memory loss, intelligence and personality will also be affected, and even Alzheimer's disease may occur. Excessive Al 3+ It not only inhibits the intestinal absorption of phosphorus, but also interferes with the normal calcium and phosphorus metabolism in the body, especially for patients with renal failure, which will seriously threaten the patient's bones, brain and nervous system. Therefore, it is necessary to develop a method to detect Al in biological and environmental analysis. 3+ Although there are some fluorescent probes for detecting Al 3+ ions, but for Al 3+ The design of ions with low toxicity, high affinity and high selectivity toward other metal ions remains a challenging task.

[0003] At present, traditional methods such as voltammetry, potentiometry, atomic absorption spectroscopy (AAS), inductively coupled plasma mass spectrometry (ICP-MS) and atomic emission spectroscopy (AES) have been used to detect metal ions. However, their detection costs are high, the technology is complex and time-consuming, and high-throughput analysis is not allowed. The use of fluorescence sensing methods to detect metal ions has the advantages of being fast, simple and low-cost. Therefore, it is of great practical significance to develop a highly sensitive and highly selective aluminum ion fluorescence detection method that can work under weak acidic conditions.

[0004] Patent 202110560215.9 discloses a fluorescent sensor based on quinoline derivatives, its synthesis and application in detecting aluminum ions, but the aluminum ion detection reagent in the scheme is used for the detection of aluminum ions in solution and cannot be used for the detection of aluminum ions in biological cells. Moreover, according to the synthesis method disclosed in the scheme, the product yield is low. Summary of the invention

[0005] The purpose of the present invention is to provide an aluminum ion detection reagent and a preparation method and application thereof, so as to solve the problem of Al 3+Ion detection has the technical problems of high cost, complex and time-consuming technology, and does not allow high-throughput analysis. To achieve the above purpose, the present invention adopts the following technical solution: designing an aluminum ion detection reagent, the aluminum ion detection reagent contains the following structure: .

[0007] Furthermore, the aluminum ion detection reagent contains one of the following structures: , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , .

[0008] Further, its synthetic route is as follows: .

[0009] The present invention provides a method for preparing the aluminum ion detection reagent, comprising the following steps: (1) adding a raw material aldehyde and a 2-chloroaniline derivative raw material into a first solvent, heating under reflux for reaction, and then purifying to obtain an intermediate product; (2) Add a base, a quinoline derivative and a second solvent to the intermediate product, react at room temperature, and then purify to obtain the product.

[0010] Further, the raw material of the 2-chloroaniline derivative is at least one of 2-bromo-6-chloroaniline, 2-chloro-4,6-dibromoaniline, 4-bromo-2-chloroaniline, 2-chloro-4-thiocyanatoaniline, 2-chloro-5-methylaniline, 2,5-dichloroaniline, 4-chloroaniline, 3-chloroaniline, 2,4-dichloroaniline, 2,6-dichloroaniline, 2-chloro-4-methylaniline, 3,5-dichloroaniline, 2,4,6-trichloroaniline and 2,4-dichloro-6-iodoaniline.

[0011] Further, the quinoline derivative includes at least one of 8-hydroxyquinoline, 4-bromo-8-hydroxyquinoline, 8-hydroxyquinoline-4-carboxylic acid methyl ester, 5-chloro-8-hydroxyquinoline, 5-bromo-8-hydroxyquinoline, 5-nitro-8-hydroxyquinoline, 8-hydroxy-7-quinolinecarboxaldehyde, 6-bromo-3-chloro-8-hydroxyquinoline, 8-hydroxy-2-chloroquinoline, 8-hydroxy-6-nitroquinoline, 5,7-dibromo-8-hydroxyquinoline, 8-hydroxy-7-propylquinoline, 5,7-dimethyl-8-hydroxyquinoline, 5-fluoro-8-hydroxyquinoline, 5-octyloxymethyl-8-hydroxyquinoline, and 8-hydroxyquinoline-5-carboxylic acid ethyl ester.

[0012] Furthermore, the structure of the raw material aldehyde contains .

[0013] Furthermore, the raw material aldehyde contains one of the following structures: , , , , , , , , , , , , , , , , , , , , , , , , , .

[0014] Furthermore, the purification method in step (1) is: filtering the solution after the reaction, washing the precipitate with a hot first solvent, and removing the solvent under vacuum conditions to obtain an intermediate product.

[0015] Furthermore, the purification method in step (2) is as follows: filtering the insoluble matter, distilling off the filtrate under reduced pressure, adding the third solvent to the system, stirring for a certain period of time, then starting to dropwise add the fourth solvent, stirring at room temperature until a precipitate appears, filtering, washing the precipitate with the fourth solvent, and removing the solvent under vacuum to obtain the product. The third solvent is a good solvent and the fourth solvent is a poor solvent.

[0016] Further, the first solvent is at least one of anhydrous methanol, anhydrous ethanol, ethylene glycol, isopropanol, acetone, and butanone; the second solvent is at least one of anhydrous chloroform, acetonitrile, 1,4-dioxane, tetrahydrofuran, and carbon tetrachloride; the base is at least one of anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous sodium bicarbonate, anhydrous cesium carbonate, anhydrous potassium bicarbonate, and anhydrous lithium carbonate; the third solvent is at least one of ether, ethyl methyl carbonate, ethyl acetate, butyl acetate, dimethyl carbonate, and benzene; and the fourth solvent is at least one of 1,2-dichloroethane, n-hexane, cyclohexane, n-heptane, butane, and methyl tert-butyl ether.

[0017] Design an Al 3+ The application of detection reagents can detect aluminum ions qualitatively and quantitatively, with a detection limit of 2.24 × 10 -7 M.

[0018] Furthermore, the aluminum ion detection reagent of the present invention is used for detecting aluminum ions in biological cells. The detection method is as follows: the biological cells are cultured with a PBS buffer solution containing the aluminum ion detection reagent for 30 min, the aluminum ion detection reagent outside the biological cells is washed with a PBS buffer solution, and the biological cells are irradiated with UV light with a wavelength of 365 nm, and the color change is observed with an optical microscope. The present invention has the following beneficial effects: 1. The present invention adopts fluorescence sensing technology, which has the advantages of simplicity, fast response speed, good selectivity, high sensitivity, convenient operation, and real-time detection. The fluorophore containing 8-hydroxyquinoline derivatives is introduced for Al in organic solutions and water systems. 3+ The synthesized fluorescent probe almost meets the key characteristics of intracellular fluorescent probes, with an excitation wavelength of 340 nm to prevent ultraviolet-induced cell damage and an emission wavelength close to 500 nm to avoid the natural fluorescence of the cells themselves, so as to facilitate cell imaging experiments using a fluorescence microscope.

[0019] 2. The aluminum (III) ion reagent provided by the present invention has the performance of qualitatively and quantitatively detecting aluminum (III) ions in aqueous solution, and has the application prospect of qualitatively and quantitatively detecting aluminum (III) ions, and the detection limit reaches 2.24 × 10 - 7 M; and the preparation process of the aluminum ion detection reagent of the present invention is simple, and the yield is 93.1%.

[0020] 3. The aluminum ion detection reagent of the present invention can be used for the detection of aluminum ions in biological cells. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 For the present invention A1 3+ Fluorescence comparison of ions and other metal ion test reagents.

[0022] Figure 2 For the present invention A1 3+ Schematic diagram of fluorescence data of each group of solutions measured by adding ion detection reagents to solutions containing different metal ions.

[0023] Figure 3 The aluminum ion detection reagent of the present invention detects Al in HeLa cells 3+ Schematic diagram of .

[0024] Figure 4 The aluminum ion detection reagent and Al 3+ Fluorescence images of incubated HeLa cells. In the figure, cells were incubated with 20 μM L for 30 min (a and b) and then further incubated with 20 μM Al 3+ Incubate for 30 min (c and d); the left images (a and c) were observed using an optical microscope, and the right images (b and d) were taken using a fluorescence microscope.

[0025] Figure 5 The present invention is under natural light and the present invention Al 3+ The color of the ions changes under UV light (365 nm). DETAILED DESCRIPTION

[0026] In order to better illustrate the purpose, technical scheme and beneficial effects of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be noted that the following implementation method is a further explanation of the present invention and should not be used as a limitation of the present invention.

[0027] Example 1 The synthetic route of the aluminum ion detection reagent is as follows:

[0028] The specific synthesis process of the intermediate product is as follows: 2-chloroaniline (1.1 mmol) and 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) solution and reacted under reflux conditions for 2 h. The yellow precipitate was then filtered, washed three times with hot CH3OH (8 mL), and the solvent was removed under vacuum to obtain the intermediate product with a yield of 98%.

[0029] The specific synthesis process of the target product is as follows: The intermediate product (1 mmol), anhydrous K2CO3 (1.5 mmol) and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL). The solution mixture was reacted under reflux conditions for 12 h. The insoluble matter was filtered out, and the filtrate was evaporated to remove the solvent under reduced pressure. 25 mL of ether was added to the residue and stirred to dissolve. 1,2-dichloroethane was added dropwise until precipitation occurred. The mixture was filtered, the filter cake was washed with 1,2-dichloroethane, and the solvent was removed under vacuum to obtain the target product with a yield of 95%.

[0030] Characterization results of the target product: 1) Infrared spectroscopy: Use potassium bromide tableting method at 400~4000cm -1 The main infrared absorption peaks of the obtained compound are: 3074, 1609, 1493, 1442, 1306, 1191, 839, 790, 699 cm -1 .

[0031] 2) Nuclear magnetic resonance hydrogen spectrum determination: Deuterated chloroform was used as solvent, tetramethylsilane was used as internal standard, and the hydrogen spectrum was measured using a Bruker 400 nuclear magnetic resonance spectrometer. The hydrogen nuclear magnetic resonance spectrum of the obtained compound is: 1 H NMR (CDCl3) δ 9.20(s, 1H),8.92(d, J = 8.0 Hz,2H),8.53 (d, J = 8.4 Hz, 2H),7.96(d, J = 8.0 Hz, 2H), 7.68(s, 1H) 7.67 (s,1H), 7.54 (d, J = 7.5 Hz, 2H),7.25(t, J = 8.0 Hz, 2H) 7.20 (d, J = 8.0 Hz,2H),7.23 (s, 1H), 7.03 (d, J = 6.9 Hz, 2H), 6.99 (d, J = 8.0 Hz, 2H), 6.95(s,H), 3) Nuclear magnetic resonance carbon spectrum determination: Deuterated dimethyl sulfoxide was used as solvent and tetramethylsilane was used as internal standard. The carbon spectrum was measured by Bruker 400 NMR spectrometer. The carbon NMR spectrum of the obtained compound is, 160.16, 159.40, 154.48, 153.02, 152.42, 149.37, 148.90, 141.35, 138.51, 138.03, 137.17, 135.20, 135.01, 134.06, 132.54,, 131.55, 130.18, 129.23, 128.03, 127.51, 126.87, 125.55, 125.14, 123.86, 122.74, 121.43, 120.35, 119.82, 117.11, 115.40, 113.12, 112.82.

[0032] 4) Elemental analysis: Elemental analysis was performed using a PE2400-11 elemental analyzer from PE Company, USA: the elemental analysis values ​​of the obtained compound were: Found C 79.88, H 4.56, N 8.77, O:6.79.

[0033] 5) Mass spectrometry: The mass spectrum was measured by Bruker DataAnalysis mass spectrometer: The mass spectrum of the obtained compound was: [M+Na] + :490.15; (theoretical value), found:490.23.

[0034] Application of target product in detection of aluminum ions: The aluminum ion detection reagent obtained in Example 1 was prepared into 3.0×10 -5 mmol / L DMSO solution. + , K + , Ag + , Zn 2+ ,Mg 2+ , Ba 2+ , Ca 2+ , Mn 2+ , Pb 2+ , Hg 2+ , Ni 2+ , Cd 2+ ,Co 2+ , Cu 2+ , Fe 2+ ,Cr 3+ , Fe 3+ , Al 3+ and Eu 3+ The DMSO solution of 100 μg / ml was not tested. The results showed that: Before joining Al 3+ ions, the fluorescence of the test reagent increases, while the fluorescence of the test reagent remains almost unchanged when other metal ions are added, such as Figure 1 In the experiment, 3 mL of Al 3+ The ion detection reagent is added to the cuvette, and then added to the solution containing different types and concentrations of metal ions and mixed evenly, and the fluorescence data of each group of solutions is measured, such as Figure 2 As shown. After fluorescence titration and fitting calculation, it was determined that the detection limit can reach 2.24 × 10 -7 M( Figure 3 ), the aluminum ion detection reagent of the present invention can detect aluminum ions qualitatively and quantitatively.

[0035] Based on the above spectral experimental studies, it can be seen that the aluminum ion detection reagent can specifically and sensitively identify Al 3+ Therefore, in order to further expand the application scope of aluminum ion detection reagents, the Al ion content in HeLa cells of human cervical cancer cell line was measured by laser confocal microscopy. 3+ Conduct testing.

[0036] This example studies the effect of (20 μM) on Al 3+ HeLa cells were incubated with PBS buffer containing aluminum ion detection reagent (10 μM) for 30 min, and the aluminum ion detection reagent outside the cells was washed with PBS buffer of the same concentration, and then the aluminum ion detection reagent was washed with Al 3+ ions (20 μM) in PBS buffer and incubate the cells for another 30 min. Figure 4 As shown, when Al 3+ Before the addition of Al ions, no blue fluorescence was observed under the optical microscope, indicating that the aluminum ion detection reagent can penetrate the cell wall and enter the cell. 3+ After the ions were detected, the fluorescence was significantly enhanced under the optical microscope. The above fluorescence images obtained by optical microscope show that the probe aluminum ion detection reagent has great potential for basic biological research.

[0037] Figure 5 It is shown that the excitation wavelength of the aluminum ion detection reagent of the present invention is around 365 nm, which can prevent ultraviolet-induced cell damage.

[0038] In some other embodiments, 2-bromo-6-chloroaniline, 2-chloro-4,6-dibromoaniline, 4-bromo-2-chloroaniline, 2-chloro-4-thiocyanatoaniline, 2-chloro-5-methylaniline, 2,5-dichloroaniline, 4-chloroaniline, 3-chloroaniline, 2,4-dichloroaniline, 2,6-dichloroaniline, 2-chloro-4-methylaniline, 3,5-dichloroaniline, 2,4,6-trichloroaniline, 2,4-dichloro-6-iodoaniline are used to replace the 2-chloroaniline in Example 1; Substituting 8-hydroxyquinoline in Example 1 with 4-bromo-8-hydroxyquinoline, 8-hydroxyquinoline-4-carboxylic acid methyl ester, 5-chloro-8-hydroxyquinoline, 5-bromo-8-hydroxyquinoline, 5-nitro-8-hydroxyquinoline, 8-hydroxy-7-quinolinecarboxaldehyde, 6-bromo-3-chloro-8-hydroxyquinoline, 8-hydroxy-2-chloroquinoline, 8-hydroxy-6-nitroquinoline, 5,7-dibromo-8-hydroxyquinoline, 8-hydroxy-7-propylquinoline, 5,7-dimethyl-8-hydroxyquinoline, 5-fluoro-8-hydroxyquinoline, 5-octyloxymethyl-8-hydroxyquinoline, or 8-hydroxyquinoline-5-carboxylic acid ethyl ester; The 2-chlorobenzaldehyde in Example 1 was replaced with a raw material aldehyde having the following structure: , , , , , , , , , , , , , , , , , , , , , , , , , .

[0039] An aluminum ion detection reagent having a corresponding chemical formula structure was obtained, and the results were determined according to the characterization method of Example 1 and applied in an experiment, and were close to those of Example 1.

[0040] In some other embodiments, anhydrous ethanol, ethylene glycol, isopropanol, acetone, butanone are used to replace the anhydrous methanol in Example 1; anhydrous chloroform, 1,4-dioxane, tetrahydrofuran, carbon tetrachloride are used to replace the acetonitrile in Example 1; anhydrous sodium carbonate, anhydrous sodium bicarbonate, anhydrous cesium carbonate, anhydrous potassium bicarbonate, anhydrous lithium carbonate are used to replace the anhydrous potassium carbonate in Example 1; ethyl methyl carbonate, ethyl acetate, butyl acetate, dimethyl carbonate, benzene are used to replace the ether in Example 1; n-hexane, cyclohexane, n-heptane, butane, methyl tert-butyl ether are used to replace 1,2-dichloroethane in Example 1; the aluminum ion detection reagent in Example 1 is also obtained, and the yield is close to that in Example 1.

[0041] In one test example, the steps for synthesizing the intermediate product are consistent with those in Example 1. The intermediate product (1 mmol), anhydrous K2CO3 (1.5 mmol) and 8-hydroxyquinoline (2.0 mmol) are added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL). The solution mixture is reacted under reflux conditions for 12 h, the solvent is evaporated under reduced pressure, 25 mL of 5% saline solution is added to the residue, and the mixture is extracted three times with CHCl3 (25 mL) to obtain an organic layer, which is dried with anhydrous Na2SO4, and the solvent is removed in vacuo. The crude product is separated and purified by a silica gel chromatography column (ethyl acetate / petroleum ether = 1:9) to obtain the target product. The yield of the target product in this test example is only 85.5%, while the yield of the target product in Example 1 reaches 93.1%. By comparison, the yield can be improved by using the method of Example 1.

[0042] The following examples use different raw materials to synthesize the corresponding aluminum ion detection reagents, and perform infrared spectroscopy on the synthesized products to prove that the corresponding target products are synthesized: Embodiment 2: 2-Bromo-6-chloroaniline (1.1 mmol) and 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) solution and reacted under reflux for 2 h. The yellow precipitate was then filtered and washed three times with hot CH3OH (8 mL). The solvent was removed under vacuum to obtain the intermediate product with a yield of 97.8%.

[0043] The intermediate product (1 mmol), anhydrous K2CO3 (1.5 mmol) and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL). The solution mixture was reacted under reflux conditions for 12 h. The insoluble matter was filtered out, and the filtrate was evaporated to remove the solvent under reduced pressure. 25 mL of ether was added to the residue and stirred to dissolve. 1,2-dichloroethane was added dropwise until precipitation occurred. The mixture was filtered, the filter cake was washed with 1,2-dichloroethane, and the solvent was removed under vacuum to obtain the target product with a yield of 95.2%.

[0044] m . p.: 205-206℃. Infrared spectrum (cm -1 ): 3074, 2957, 1609, 1617, 1493,1442, 790, 699.

[0045] Embodiment 3: 4-Bromo-2-chloroaniline (1.1 mmol) and 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) solution and reacted under reflux conditions for 2 h. The yellow precipitate was then filtered, washed three times with hot CH3OH (8 mL), and the solvent was removed under vacuum to obtain the intermediate product with a yield of 98.02%.

[0046] The intermediate product (1 mmol), anhydrous K2CO3 (1.5 mmol) and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL). The solution mixture was reacted under reflux conditions for 12 h. The insoluble matter was filtered out, and the filtrate was evaporated to remove the solvent under reduced pressure. 25 mL of ether was added to the residue and stirred to dissolve. 1,2-dichloroethane was added dropwise until precipitation occurred. The mixture was filtered, the filter cake was washed with 1,2-dichloroethane, and the solvent was removed under vacuum to obtain the target product with a yield of 95.04%.

[0047] m . p.: 205-206℃. Infrared spectrum (cm -1 ): 3074, 2957, 1609, 1617, 1493,1442, 790, 699.

[0048] Example 4: 2-Chloro-5-methylaniline (1.1 mmol) and 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) solution and reacted under reflux for 2 h. The yellow precipitate was then filtered, washed three times with hot CH3OH (8 mL), and the solvent was removed under vacuum to obtain the intermediate product with a yield of 97.5%.

[0049] The intermediate product (1 mmol), anhydrous K2CO3 (1.5 mmol) and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL). The solution mixture was reacted under reflux conditions for 12 h. The insoluble matter was filtered out, and the filtrate was evaporated under reduced pressure to remove the solvent. 25 mL of ether was added to the residue and stirred to dissolve. 1,2-dichloroethane was added dropwise until precipitation occurred. The mixture was filtered, and the filter cake was washed with 1,2-dichloroethane. The solvent was removed under vacuum to obtain the target product with a yield of 95.3%.

[0050] m . p.: 205-206℃. Infrared spectrum (cm -1 ): 3074, 2957, 1609, 1617, 1493,1442, 790, 699.

[0051] Example 5: 2-Chloro-4-methylaniline (1.1 mmol) and 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) solution and reacted under reflux for 2 h. The yellow precipitate was then filtered, washed three times with hot CH3OH (8 mL), and the solvent was removed under vacuum to obtain the intermediate product with a yield of 97.8%.

[0052] The intermediate product (1 mmol), anhydrous K2CO3 (1.5 mmol) and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL). The solution mixture was reacted under reflux conditions for 12 h. The insoluble matter was filtered out, and the filtrate was evaporated to remove the solvent under reduced pressure. 25 mL of ether was added to the residue and stirred to dissolve. 1,2-dichloroethane was added dropwise until precipitation occurred. The mixture was filtered, the filter cake was washed with 1,2-dichloroethane, and the solvent was removed under vacuum to obtain the target product with a yield of 94.6%.

[0053] m . p.: 204-205℃. Infrared spectrum (cm -1 ): 3074, 2957, 1609, 1617, 1493,1442, 790, 699.

[0054] Example 6: 3-Chloroaniline (1.1 mmol) and 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) solution and reacted under reflux for 2 h. The yellow precipitate was then filtered, washed three times with hot CH3OH (8 mL), and the solvent was removed under vacuum to obtain the intermediate product with a yield of 98.3%.

[0055] The intermediate product (1 mmol), anhydrous K2CO3 (1.5 mmol) and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL). The solution mixture was reacted under reflux conditions for 12 h. The insoluble matter was filtered out, and the filtrate was evaporated under reduced pressure to remove the solvent. 25 mL of ether was added to the residue and stirred to dissolve. 1,2-dichloroethane was added dropwise until precipitation occurred. The mixture was filtered, the filter cake was washed with 1,2-dichloroethane, and the solvent was removed under vacuum to obtain the target product with a yield of 95.4%.

[0056] m . p.: 204-205℃. Infrared spectrum (cm-1 ): 3074, 2957, 1609, 1617, 1493,1442, 790, 699.

[0057] Example 7: 3-Chloroaniline (1.1 mmol) and 2-chlorobenzaldehyde (1 mmol) were added to anhydrous CH3OH (15 mL) solution and reacted under reflux for 2 h. The yellow precipitate was then filtered, washed three times with hot CH3OH (8 mL), and the solvent was removed under vacuum to obtain the intermediate product with a yield of 98.0%.

[0058] The intermediate product (1 mmol), anhydrous K2CO3 (1.5 mmol) and 8-hydroxyquinoline (2.0 mmol) were added to anhydrous CH3CN (25 mL) and anhydrous DMF (3 mL). The solution mixture was reacted under reflux conditions for 12 h. The insoluble matter was filtered out, and the filtrate was evaporated under reduced pressure to remove the solvent. 25 mL of ether was added to the residue and stirred to dissolve. 1,2-dichloroethane was added dropwise until precipitation occurred. The mixture was filtered, and the filter cake was washed with 1,2-dichloroethane. The solvent was removed under vacuum to obtain the target product with a yield of 94.7%.

[0059] m . p.: 204-205℃. Infrared spectrum (cm -1 ): 3074, 2957, 1609, 1617, 1493,1442, 790, 699.

Claims

1. An aluminum ion detection reagent, characterized in that The aluminum ion detection reagent contains the following structure: 。 2. The aluminum ion detection reagent according to claim 1, characterized in that Its synthetic route is as follows: 。 3. A method for preparing the aluminum ion detection reagent according to claim 1, characterized in that: The following steps are involved: (1) adding a raw material aldehyde and a 2-chloroaniline derivative raw material into a first solvent, heating under reflux for reaction, and then purifying to obtain an intermediate product; (2) Add a base, a quinoline derivative and a second solvent to the intermediate product, react at room temperature, and then purify to obtain the product.

4. The preparation method according to claim 3, characterized in that: The raw material of the 2-chloroaniline derivative is at least one of 2-bromo-6-chloroaniline, 2-chloro-4,6-dibromoaniline, 4-bromo-2-chloroaniline, 2-chloro-4-thiocyanatoaniline, 2-chloro-5-methylaniline, 2,5-dichloroaniline, 4-chloroaniline, 3-chloroaniline, 2,4-dichloroaniline, 2,6-dichloroaniline, 2-chloro-4-methylaniline, 3,5-dichloroaniline, 2,4,6-trichloroaniline and 2,4-dichloro-6-iodoaniline.

5. The preparation method according to claim 3, characterized in that: The quinoline derivative includes at least one of 8-hydroxyquinoline, 4-bromo-8-hydroxyquinoline, 8-hydroxyquinoline-4-carboxylic acid methyl ester, 5-chloro-8-hydroxyquinoline, 5-bromo-8-hydroxyquinoline, 5-nitro-8-hydroxyquinoline, 8-hydroxy-7-quinolinecarboxaldehyde, 6-bromo-3-chloro-8-hydroxyquinoline, 8-hydroxy-2-chloroquinoline, 8-hydroxy-6-nitroquinoline, 5,7-dibromo-8-hydroxyquinoline, 8-hydroxy-7-propylquinoline, 5,7-dimethyl-8-hydroxyquinoline, 5-fluoro-8-hydroxyquinoline, 5-octyloxymethyl-8-hydroxyquinoline, and 8-hydroxyquinoline-5-carboxylic acid ethyl ester.

6. The preparation method according to claim 3, characterized in that: The structure of the raw material aldehyde contains .

7. The preparation method according to claim 6, characterized in that: The raw material aldehyde contains one of the following structures: , , , , , , , , , , , , , , , , , , , , , , , , , .

8. The preparation method according to claim 3, characterized in that: The purification method in step (1) is as follows: filtering the solution after the reaction, washing the precipitate with a hot first solvent, and removing the solvent under vacuum conditions to obtain an intermediate product.

9. The preparation method according to claim 8, characterized in that: The purification method in step (2) is as follows: filter the insoluble matter, evaporate the filtrate under reduced pressure, add the third solvent to the system, stir for a certain period of time, then start to dropwise add the fourth solvent, stir at room temperature until a precipitate appears, filter, wash the precipitate with the fourth solvent, and remove the solvent under vacuum to obtain the target product.

10. The preparation method according to claim 9, characterized in that: The first solvent is at least one of anhydrous methanol, anhydrous ethanol, ethylene glycol, isopropanol, acetone, and butanone; the second solvent is at least one of anhydrous chloroform, CH3CN, 1,4-dioxane, tetrahydrofuran, and carbon tetrachloride; the base is at least one of anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous sodium bicarbonate, anhydrous cesium carbonate, anhydrous potassium bicarbonate, and anhydrous lithium carbonate; the third solvent is at least one of ether, ethyl methyl carbonate, ethyl acetate, butyl acetate, dimethyl carbonate, and benzene; and the fourth solvent is at least one of 1,2-dichloroethane, n-hexane, cyclohexane, n-heptane, butane, and methyl tert-butyl ether.

11. An application of the aluminum ion detection reagent according to claim 1, characterized in that: Used for qualitative and quantitative detection of aluminum ions.

12. The use of the aluminum ion detection reagent according to claim 11, characterized in that: Used for the detection of aluminum ions in biological cells. The detection method is to culture the biological cells with PBS buffer containing aluminum ion detection reagent, then wash the aluminum ion detection reagent outside the biological cells with PBS buffer, irradiate with UV light with a wavelength of 365nm, and observe the color change with an optical microscope.

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