Fluorine-containing monocyclic aromatic compounds and methods for producing the same, and adsorbents for metal ions

Abstract

To provide a fluorine-containing monocyclic aromatic compound that has high chemical resistance, and also has fluorine affinity and metal ion adsorption characteristics.SOLUTION: A fluorine-containing monocyclic aromatic compound, represented by a formula (3), comprises a fluorous structure and a functional group in a part of a benzene ring structure.SELECTED DRAWING: Figure 6

Description

[Technical Field]

[0001] This invention relates to the chemical structure of fluorine-containing monocyclic aromatic compounds and methods for producing the same, and more particularly to techniques that are effective when applied to adsorbents for metal ions. [Background technology]

[0002] Fluorous compounds, whose main structure consists of CF bonds, are chemically stable and possess excellent resistance to chemicals and radiation. Therefore, they are used in a wide range of fields, including general industry and nuclear facilities. Furthermore, their immiscibility with water and aliphatic organic solvents makes them promising for use in purification processes such as solvent extraction.

[0003] As background technology for this field, for example, there is technology such as that described in Patent Document 1. Patent Document 1 discloses "fluorine-containing polycyclic aromatic compounds in which at least one of the aromatic groups located at both ends of a conjugated polycyclic aromatic group with three or more rings is substituted with a perfluoroalkyl group."

[0004] Furthermore, Non-Patent Document 1 discloses a method for synthesizing polycyclic aromatic compounds and their physical properties.

[0005] Furthermore, Non-Patent Documents 2 and 3 disclose examples of fluorescein extractants, such as iminodiacetic acid-type fluorescein extractants and phosphate-type fluorescein extractants. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Patent No. 7061804 [Non-patent literature]

[0007] [Non-Patent Document 1] Synthesis and properties of perfluoroalkylated TIPS - pentacenes, T. Agou et al., Tetrahedron 2019, 75, 130678. [Non - Patent Document 2] E. Kiyokawa et al., J. Chromatogr. B 2018, 1074, 86. [Non - Patent Document 3] Ueda, Y. et al., Solvent Extraction and Ion Exchange, 37, 5, (2019) [Summary of the Invention] [Problems to be Solved by the Invention]

[0008] In the use of fluorine - containing compounds, in consideration of the liquid property of the liquid to be treated, the valence of the target element, and complex formation, it is necessary to design the entire fluorine - containing compound including functional groups. However, in addition to controlling the parent fluorophilicity of the fluorine - containing compound, a method for introducing arbitrary functional groups is an issue.

[0009] It is difficult to arbitrarily change the structural part of the perfluoroalkyl group, and it is not easy to control the parent fluorophilicity. Also, due to the reactivity of the perfluoroalkyl group, there is a problem that the functional groups that can be introduced are limited.

[0010] As in Non - Patent Documents 2 and 3 above, there are many reported examples of fluorine - containing extractants, but there are only experimental examples of solvent extraction, and there are no reports on introduction into various media.

[0011] The present invention has been made in view of the above - described conventional problems. The object of the present invention is to provide a fluorine - containing monocyclic aromatic compound having high chemical resistance, as well as properties of adsorbing parent fluorophilicity and metal ions, a method for producing the same, and an adsorbent for metal ions using the same. [Means for Solving the Problems]

[0012] In order to solve the above problems, the present invention is characterized by having a fluorine-containing structure and a functional group in a part of the benzene ring structure and being represented by the following formula (3).

[0013]

Chemical formula

[0014] Further, the present invention is characterized by having a fluorine-containing structure and a functional group in a part of the benzene ring structure and being represented by the following formula (7).

[0015]

Chemical formula

[0016] Further, the present invention is characterized by having a fluorine-containing structure and a functional group in a part of the benzene ring structure and being represented by the following formula (12).

[0017]

Chemical formula

[0018] Further, the present invention has a fluorine-containing structure and a functional group in a part of the benzene ring structure, and is characterized by being represented by the following formula (17).

[0019]

Chemical formula

[0020] Further, the present invention is characterized by synthesizing a compound represented by the following formula (3) using a compound represented by the following formula (2).

[0021] <000014​​​​​​​​​​​

[0023] Furthermore, the present invention is characterized by comprising the steps of (a) synthesizing a compound represented by formula (5) using a compound represented by formula (4) below, (b) synthesizing a compound represented by formula (6) below using a compound represented by formula (5) below, and (c) synthesizing a compound represented by formula (7) below using a compound represented by formula (6) below.

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[0028] Furthermore, the present invention is characterized by comprising the steps of (a) synthesizing a compound represented by formula (9) using a compound represented by formula (18) and a compound represented by formula (8); (b) synthesizing a compound represented by formula (10) using a compound represented by formula (9); (c) synthesizing a compound represented by formula (11) using a compound represented by formula (10); and (d) synthesizing a compound represented by formula (12) using a compound represented by formula (11).

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] [ka]

[0033] [ka]

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[0035] Furthermore, the present invention is characterized by comprising the steps of (a) synthesizing a compound represented by formula (14) using a compound represented by formula (18) and a compound represented by formula (13); (b) synthesizing a compound represented by formula (15) using a compound represented by formula (14); (c) synthesizing a compound represented by formula (16) using a compound represented by formula (15); and (d) synthesizing a compound represented by formula (17) using a compound represented by formula (16).

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[0039] [ka]

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[0041] [ka] [Effects of the Invention]

[0042] According to the present invention, it is possible to realize a fluorine-containing monocyclic aromatic compound having high chemical resistance as well as fluorophilicity and the property of adsorbing metal ions, a method for producing the same, and a metal ion adsorbent using the same.

[0043] Specifically, by changing the type of fluorescein compound, it is possible to control the fluorophilicity, making it possible to impart ligand functionality to various media. Furthermore, because functional groups can be arbitrarily selected, it can be used as an adsorbent for a wide range of metals, including useful metals such as rare earths and precious metals, as well as heavy metals such as cadmium and chromium, and radioactive materials such as uranium and plutonium. It is expected to be used in a wide range of fields, such as recycling, wastewater treatment in general industry, and the recovery of radioactive materials in medical and nuclear facilities.

[0044] Other issues, configurations, and effects not mentioned above will be clarified by the following description of the embodiments. [Brief explanation of the drawing]

[0045] [Figure 1] This figure shows the effect of the fluorine-containing monocyclic aromatic compound of the present invention as an adsorbent for metal ions. [Figure 2] This figure shows the effect of the fluorine-containing monocyclic aromatic compound of the present invention as an adsorbent for metal ions. [Figure 3] This figure shows a first example of its use as an adsorbent for metal ions. [Figure 4] This figure shows a second example of its use as an adsorbent for metal ions. [Figure 5] This figure shows a second example of its use as an adsorbent for metal ions. [Figure 6] This figure shows a second example of its use as an adsorbent for metal ions. [Figure 7] This figure shows a third example of its use as an adsorbent for metal ions. [Figure 8] This figure shows a fourth example of its use as an adsorbent for metal ions. [Figure 9] This figure shows a fifth example of its use as an adsorbent for metal ions. [Modes for carrying out the invention]

[0046] The fluorine-containing monocyclic aromatic compounds of the present invention will be described in detail below, with reference to the drawings. In each drawing, identical components are denoted by the same reference numerals, and some redundant explanations are omitted for parts that overlap.

[0047] The fluorine-containing monocyclic aromatic compound of the present invention is specifically a fluorine-containing monocyclic aromatic compound represented by any of the following formulas (3), (7), (12), and (17).

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[0052] Note that perfluorohexyl group (C6F 13 Base) is C3F7~C8F 17 It can be replaced with any perfluorocarbon group.

[0053] The adsorption performance of the fluorine-containing monocyclic aromatic compound of the present invention when used as an adsorbent for metal ions will be explained with reference to Figures 1 and 2. Figures 1 and 2 show the results of investigating the adsorption performance as a solid adsorbent by impregnating porous silica coated with a polymer with the fluorine-containing monocyclic aromatic compound of the present invention (fluorus extractant; a compound with iminodiacetic acid as a functional group). Figure 1 shows an example of the pH dependence of the iminodiacetic acid type adsorbent, and Figure 2 shows an example of evaluating the adsorption performance for zircomium (Zr) loaded into a simulated PUERX waste solvent. The simulated PUERX waste solvent is a solvent diluted with dodecane so that the tributyl phosphate concentration is 1.0 mol / L and the dibutyl phosphate concentration is 150 mmol / L, and Zr is loaded at a concentration of 10 mmol / L.

[0054] As shown in Figure 1, the fluorine-containing monocyclic aromatic compound of the present invention exhibited high adsorption reactions to both zircoum (Zr) and nickel (Ni) in the neutral range, showing the typical adsorption behavior of iminodiacetic acid. This confirms that the fluorine-containing monocyclic aromatic compound of the present invention functions as an adsorbent.

[0055] Furthermore, as shown in Figure 2, the fluorine-containing monocyclic aromatic compound of the present invention exhibited higher adsorption performance than commercially available adsorbents.

[0056] In the following, the methods for producing each of the fluorine-containing monocyclic aromatic compounds of formulas (3), (7), (12), and (17) will be described in Examples 1 to 4, and examples of applications of the fluorine-containing monocyclic aromatic compounds of the present invention will be described in Examples 5 to 9. [Examples]

[0057] ≪(3) Method for producing fluorine-containing monocyclic aromatic compounds≫ The method for producing the fluorine-containing monocyclic aromatic compound of formula (3) will be described below. 1 1H NMR and 19 For measuring the 1F NMR spectrum, an AVANCE III NMR spectrometer from Bruker BioSpin, Inc. was used.

[0058] First, the compound of formula (1), which is used to synthesize the compound of formula (2) that will be the raw material for the fluorine-containing monocyclic aromatic compound of formula (3), was synthesized with reference to Non-Patent Document 1 mentioned above.

[0059] Next, compound (2) was obtained by the following reaction using compound (1) as a starting material. Note that compound (2) is known from the above-mentioned Patent Document 1.

[0060] [ka]

[0061] Compound (1) (2.0 g, 2.7 mmol), N-bromosuccinimide (NBS) (0.96 g, 5.4 mmol), benzoyl peroxide (BPO) (0.066 g, 0.27 mmol), and carbon tetrachloride (20 mL) were added to a 50 mL three-necked flask and stirred at 80 °C for 24 hours. The reaction solution was cooled to 0 °C, succinimide was filtered off, and the mixture was concentrated using a rotary evaporator to obtain 2.4 g (2.7 mmol) of the yellow liquid compound (2). The yield was 100%.

[0062] The NMR results of the product are shown below.

[0063] 1 H NMR (400 MHz, CDCl3): δ 7.76 (s, 2H), 4.66 (s, 4H). 19F NMR (376 MHz, CDCl3): δ -80.77 (t, 6F), -103.53 (s, 4F), -118.00 (s, 4F), -121.89 (s, 4F), -122.70 (s, 4F), -126.06 (s, 4F). Furthermore, using the compound of formula (2) as a starting material, the fluorine-containing monocyclic aromatic compound of formula (3) according to Example 1 of the present invention was obtained by the following reaction. In the following reaction, two bromomethyl groups (CH2Br) are each replaced with iminomethyl dicarbon groups (CH2N(CH2COOH)2).

[0064] [ka]

[0065] Compound (2) (1.8 g, 2.0 mmol), iminodiacetic acid (0.8 g, 6 mmol), potassium hydroxide (1.1 g, 20 mmol), and anhydrous methanol (20 mL) were added to a 100 mL three-necked flask and stirred at 65 °C for 15 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and filtered with methanol using filter paper. The filtrate was concentrated using a rotary evaporator to obtain a crude product, which was purified by column chromatography (silica gel, hexane:dichloromethane = 8:2) to obtain 1.7 g (1.7 mmol) of compound (3) as a yellow liquid. The yield was 85%.

[0066] The NMR results of the product are shown below.

[0067] 1 H NMR (400 MHz, CDCl3): δ 7.83 (s, 2H), 4.57 (s, 4H), 3.48 (s, 8H). 19 F NMR (376 MHz, CDCl3): δ -81.02 (t, 6F), -103.93 (s, 4F), -118.11 (s, 4F), -122.03 (s, 4F), -122.87 (s, 4F), -126.28 (s, 4F). In the above reaction, when potassium hydroxide (KOH) was changed to triethylamine (NEt3) and anhydrous methanol (MeOH) was changed to chloroform (CH2Cl2), and the mixture was stirred at room temperature (rt) for 12 hours under a nitrogen atmosphere, the fluorine-containing monocyclic aromatic compound of formula (3) was obtained from the compound of formula (2).

[0068] As described above, the fluorine-containing monocyclic aromatic compound of formula (3) of the present invention can be synthesized in one step using the compound of formula (2) known from Patent Document 1 as a raw material.

Example

[0069] ≪Production method of fluorine-containing monocyclic aromatic compound of formula (7)≫ The production method of the fluorine-containing monocyclic aromatic compound of formula (7) will be described. The fluorine-containing monocyclic aromatic compound of formula (7) can be obtained through the following three steps.

[0070] First, using the compound of formula (4) as a raw material, the compound of formula (5) was obtained by the following reaction. In the following reaction, the bromo group (Br) was replaced with a perfluorohexyl group (C6F 13 group).

[0071]

Chemical formula

[0072] Copper (27 g, 0.40 mol) dried at 150 °C and 0.1 mmHg for 1 hour was placed in a 300 mL three-necked flask. 4-bromo-benzyl alcohol (compound (4)) (7.6 g, 40 mmol), C6F13I (26 mL, 0.12 mol), and anhydrous dimethyl sulfoxide (DMSO) (200 mL) were added, and the mixture was stirred at 110 °C for 22 hours under a nitrogen atmosphere. After adding water to the reaction mixture, it was filtered using Celite filtration with chloroform as the solvent. The aqueous layer of the filtrate was extracted three times with chloroform, and the organic layer was washed five times with water to remove DMSO. The organic layer was dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the mixture was concentrated using a rotary evaporator to obtain 19 g (45 mmol) of compound (5) as a yellow liquid. The crude yield was 112%.

[0073] The NMR results of the product are shown below.

[0074] 1 H NMR (400 MHz, CDCl3): δ 7.61 (d, J = 8.2 Hz, 2H), 7.52 (d, J = 8.2 Hz, 2H), 4.79 (s, 2H), 3.34 (s, 1H). 19 F NMR (376 MHz, CDCl3): δ -80.75 (t, 3F), -110.78 (s, 2F), -121.47 (s, 2F), -121.81 (s, 2F), -122.81 (s, 2F), -126.13 (s, 2F) Next, using the compound of formula (5) as a starting material, the compound of formula (6) was obtained by the following reaction. In the following reaction, the hydroxymethyl group (CH2OH) is replaced with a bromomethyl group (CH2Br).

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[0076] Compound (5) (1.5 g, 3.0 mmol), phosphorus tribromide (3.0 g, 30 mmol), and chloroform (60 mL) were added to a 100 mL three-necked flask and stirred at room temperature (0 °C) for 3 hours. A sodium bicarbonate aqueous solution cooled to 0 °C was added to the reaction mixture, followed by three extractions with chloroform. The organic layer was washed five times with water. The organic layer was dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the crude product was concentrated using a rotary evaporator and purified by column chromatography (silica gel, hexane:dichloromethane = 8:2) to obtain 0.82 g (1.7 mmol) of compound (6) as a brown liquid. The yield was 56%.

[0077] The NMR results of the product are shown below.

[0078] 1 H NMR (400 MHz, CDCl3): δ 7.58 (d, J = 8.5 Hz, 2H), 7.54 (d, J = 8.5 Hz, 2H), 4.51 (s, 2H). 19 F NMR (376 MHz, CDCl3): δ -80.75 (t, 3F), -110.78 (s, 2F), -121.47 (s, 2F), -121.81 (s, 2F), -122.81 (s, 2F), -126.13 (s, 2F) Furthermore, using the compound of formula (6) as a starting material, the fluorine-containing monocyclic aromatic compound of formula (7) according to Example 2 of the present invention was obtained by the following reaction. In the following reaction, the bromomethyl group (CH2Br) is replaced with an iminomethyl dicarbon group (CH2N(CH2COOH)2).

[0079] [ka]

[0080] Compound (6) (0.82 g, 1.7 mmol), iminodiacetic acid (0.48 g, 3.4 mmol), potassium hydroxide (2.8 g, 34 mmol), and anhydrous methanol (50 mL) were added to a 100 mL three-necked flask, and the mixture was stirred at 65 °C for 15 hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature, dilute hydrochloric acid was added, and the mixture was filtered through filter paper using methanol as the solvent. The filtrate was concentrated using a rotary evaporator to obtain 0.33 g (0.61 mmol) of compound (7) as a white solid. The yield was 36%.

[0081] The NMR results of the product are shown below.

[0082] 1 H NMR (400 MHz, CDCl3): δ 7.59 (d, J = 8.2 Hz, 2H), 7.48 (d, J = 8.2 Hz, 2H), 4.53 (s, 2H), 3.43 (s, 4H). 19 F NMR (376 MHz, CDCl3): δ -80.75 (t, 3F), -110.78 (s, 2F), -121.47 (s, 2F), -121.81 (s, 2F), -122.81 (s, 2F), -126.13 (s, 2F). [Examples]

[0083] ≪(12) Method for producing fluorine-containing monocyclic aromatic compounds≫ A method for producing the fluorine-containing monocyclic aromatic compound of formula (12) will be described. The fluorine-containing monocyclic aromatic compound of formula (12) can be obtained through the following four steps.

[0084] First, using the compounds of formula (18) and (8) as raw materials, the compound of formula (9) was obtained by the following reaction.

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[0086] Compound (18) (C6F) in a 50 mL Schlenk flask. 13 CH2O3SCF3(C6F 13 5.0 g (10 mmol) of CH2OTf)), 0.50 g (2.9 mmol) of methyl gallate (compound (8)), 1.6 g (11 mmol) of potassium carbonate, and 25 mL of dimethylacetamide (DMAc) were added, and the mixture was stirred at 90 °C for 2 hours under an argon atmosphere. After adding aqueous ammonium chloride to the reaction mixture, the mixture was filtered by suction to obtain 2.5 g (2.1 mmol) of compound (9) as a colorless solid. The crude yield was 74%.

[0087] The results of the NMR measurement of the product are shown below.

[0088] 1 H NMR (400 MHz, CDCl3): δ 7.42 (s, 2H), 4.55 (q, J = 13Hz, 4H), 3.94 (s, 3H). 19 F NMR (376 MHz, CDCl3): δ -80.84 (t, 9F), -119.43 (s, 6F), -121.12 (s, 6F), -121.14 (s, 6F), -122.97 (s, 6F), -126.13 (s, 6F). Next, using the compound of formula (9) as a starting material, the compound of formula (10) was obtained by the following reaction.

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[0090] In a 50 mL three-necked flask, 1.1 g (1.0 mmol) of compound (9) and 3.0 mL of tetrahydrofuran were added and cooled on ice. Then, 0.10 g (23 mmol) of lithium aluminum hydride was added and the mixture was stirred at room temperature for 24 hours. Ethyl acetate, methanol, and hydrochloric acid were added sequentially to the reaction mixture, and the mixture was filtered using Celite filtration with chloroform as the solvent. The aqueous layer of the filtrate was extracted three times with chloroform, and the organic layer was dried over anhydrous sodium sulfate. After filtering off the sodium sulfate, the mixture was concentrated using a rotary evaporator to obtain 0.76 g (0.66 mmol) of compound (10) as a colorless solid. The crude yield was 66%.

[0091] The results of the NMR measurement of the product are shown below.

[0092] 1 H NMR (400 MHz, CDCl3): δ 6.75 (s, 2H), 4.67 (s, 2H), 4.55-4.41 (m, 6H). 19 F NMR (376 MHz, CDCl3): δ -80.84 (t, 9F), -119.60 (s, 4F), -21.13 (s, 6F), -122.19 (s, 6F), -123.09 (s, 6F), -126.17 (s, 6F). Next, using the compound of formula (10) as a starting material, the compound of formula (11) was obtained by the following reaction.

[0093] [ka]

[0094] In a 50 mL three-necked flask, 0.66 g (0.57 mmol) of compound (10) and 20 mL of chloroform were added and cooled with ice. Then, 1.0 mL of phosphorus tribromide was added and the mixture was stirred for 3 hours. Sodium bicarbonate aqueous solution was added to the reaction mixture, and the aqueous layer was extracted five times with chloroform. The organic layer was washed once with sodium bicarbonate aqueous solution and four times with distilled water. After drying the organic layer over anhydrous sodium sulfate, the sodium sulfate was filtered off, and compound (11) was concentrated using a rotary evaporator to obtain 0.73 g (0.60 mmol) of compound (11) as a brown solid. The crude yield was 91%.

[0095] The results of the NMR measurement of the product are shown below.

[0096] 1 H NMR (400 MHz, CDCl3): δ 6.76 (s, 2H), 4.55-4.46 (m, 6H), 4.41 (s, 2H). 19 F NMR (376 MHz, CDCl3): δ -80.85 (t, 9F), -19.58 (s, 6F), -21.17 (s, 6F), -122.21 (s, 6F), -123.05 (s, 6F), -126.20 (s, 6F). Furthermore, using the compound of formula (11) as a raw material, the fluorine-containing monocyclic aromatic compound of formula (12) according to Example 3 of the present invention was obtained by the following reaction.

[0097] [ka]

[0098] In a 100 mL three-necked flask, 0.73 g (0.60 mmol) of compound (11), 0.16 g (1.2 mmol) of iminodiacetic acid, 0.96 g (12 mmol) of potassium hydroxide, and 20 mL of methanol were added and refluxed at 65 °C for 12 hours. Hydrochloric acid was added to the reaction mixture, and the aqueous layer was extracted three times with chloroform and dried over anhydrous sodium sulfate. After filtering off the sodium sulfate, the mixture was concentrated using a rotary evaporator to obtain 0.62 g (0.49 mmol) of compound (12) as a colorless solid. The crude yield was 82%.

[0099] The results of the NMR measurement of the product are shown below.

[0100] 1 H NMR (400 MHz, CDCl3): δ 6.71 (s, 2H), 4.50-4.44 (m, 6H), 4.39 (s, 2H), 3.41(s, 2H). 19 F NMR (376 MHz, CDCl3): δ -80.84 (t, 9F), -119.60 (s, 6F), -121.13 (s, 6F), -122.20 (s, 6F), -123.90 (s, 6F), -126.17 (s, 6F). [Examples]

[0101] ≪(17) Method for producing fluorine-containing monocyclic aromatic compounds≫ A method for producing the fluorine-containing monocyclic aromatic compound of formula (17) will be described. The fluorine-containing monocyclic aromatic compound of formula (17) can be obtained through the following four steps.

[0102] First, using the compounds of formula (18) and (13) as raw materials, the compound of formula (14) was obtained by the following reaction.

[0103] [ka]

[0104] Compound (18) (C6F) in a 50 mL three-necked flask. 13 6.6 g (14 mmol) of CH2OTf, 1.1 g (6.0 mmol) of compound (13) (methyl 3,5-dihydroxybenzoate), 2.9 g (15 mmol) of potassium carbonate, and 50 mL of DMAc were added, and the mixture was stirred at 90 °C for 2 hours. After adding aqueous ammonium chloride to the reaction mixture, compound (14) was obtained as a colorless solid of 3.7 g (4.4 mmol) by suction filtration. The crude yield was 74%.

[0105] The results of the NMR measurement of the product are shown below.

[0106] 1 H NMR (400 MHz, CDCl3): δ 7.31 (s, 2H), 6.77(s, 1H), 4.55 (t, J = 12 Hz, 6H), 3.94 (s, 3H). 19 F NMR (376 MHz, CDCl3): δ -80.75 (t, 6F), -119.33 (s, 4F), -122.10 (s, 4F), -122.75 (s, 4F), -123.03 (s, 4F), -126.07 (s, 4F). Next, using the compound of formula (14) as a starting material, the compound of formula (15) was obtained by the following reaction.

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[0108] In a 50 mL three-necked flask, 1.2 g (1.5 mmol) of compound (14) and 5.0 mL of tetrahydrofuran were added and cooled on ice. 0.15 g (3.8 mmol) of lithium aluminum hydride was added and the mixture was stirred for 24 hours. Ethyl acetate, methanol, and hydrochloric acid were added sequentially to the reaction mixture, and the mixture was filtered using Celite filtration with chloroform as the solvent. The aqueous layer of the filtrate was extracted three times with chloroform, and the organic layer was dried over anhydrous sodium sulfate. After filtering off the sodium sulfate, the mixture was concentrated using a rotary evaporator to obtain 1.1 g (1.3 mmol) of compound (15) as a yellow liquid. The crude yield was 89%.

[0109] The results of the NMR measurement of the product are shown below.

[0110] 1 H NMR (400 MHz, CDCl3): δ 6.65 (s, 2H), 6.47(s, 1H), 4.68(s, 2H), 4.46 (t, J = 13 Hz, 6H). 19 F NMR (376 MHz, CDCl3): δ -80.81 (t, 6F), -119.43 (s, 4F), -122.13 (s, 4F), -122.78 (s, 4F), -123.11 (s, 4F), -126.12 (s, 4F). Next, using the compound of formula (15) as a starting material, the compound of formula (16) was obtained by the following reaction.

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[0112] In a 50 mL three-necked flask, 1.1 g (1.3 mmol) of compound (15) and 44 mL of chloroform were added and cooled with ice. Then, 2.2 mL of phosphorus tribromide was added and the mixture was stirred for 3 hours. Sodium bicarbonate aqueous solution was added to the reaction mixture, and the aqueous layer was extracted five times with chloroform. The organic layer was washed once with sodium bicarbonate aqueous solution and four times with distilled water, and the organic layer was dried over anhydrous sodium sulfate. After filtering off the sodium sulfate, the mixture was concentrated using a rotary evaporator to obtain 0.99 g (1.2 mmol) of compound (16) as a brown solid. The crude yield was 91%.

[0113] The results of the NMR measurement of the product are shown below.

[0114] 1 H NMR (400 MHz, CDCl3): δ 6.67 (s, 2H), 6.49(s, 1H), 4.46 (t, J = 12 Hz, 6H), 4.41 (s, 2H). 19 F NMR (376 MHz, CDCl3): δ -80.76 (t, 6F), -119.35 (s, 4F), -122.09 (s, 4F), -122.75 (s, 4F), -123.05 (s, 4F), -126.08 (s, 4F). Furthermore, using the compound of formula (16) as a raw material, the following reaction yielded the fluorine-containing monocyclic aromatic compound of formula (17) according to Example 4 of the present invention.

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[0116] In a 100 mL three-necked flask, 0.99 g (1.2 mmol) of compound (16), 0.32 g (2.4 mmol) of iminodiacetic acid, 1.9 g (24 mmol) of potassium hydroxide, and 40 mL of methanol were added and refluxed at 65 °C for 12 hours. Concentrated hydrochloric acid was added to the reaction mixture, and the aqueous layer was extracted three times with chloroform and dried over anhydrous sodium sulfate. After filtering off the sodium sulfate, the mixture was concentrated using a rotary evaporator to obtain 0.80 g (0.87 mmol) of compound (17) as a brown liquid. The crude yield was 72%.

[0117] The results of the NMR measurement of the product are shown below.

[0118] 1 H NMR (400 MHz, CDCl3): δ 6.61 (d, J=2.5Hz, 2H), 6.47(t, J = 2.3Hz, 1H), 4.46 (t, J = 14 Hz, 6H), 4.42 (s, 2H), 3.41(s, 2H). 19 F NMR (376 MHz, CDCl3): δ -80.77 (t, 6F), -119.45 (s, 4F), -122.17 (s, 4F), -122.81 (s, 4F), -123.12 (s, 4F), -126.15 (s, 4F). [Examples]

[0119] ≪Examples of Uses of Fluorine-Containing Monocyclic Aromatic Compounds 1≫ Referring to Figure 3, examples of the applications of fluorine-containing monocyclic aromatic compounds according to Examples 1 to 4 of the present invention as adsorbents for metal ions will be described.

[0120] Figure 3 schematically illustrates the use of fluorescein solvent extraction as an extractant.

[0121] For example, in contaminated water containing metal ions M such as uranium (U), a fluorine-containing monocyclic aromatic compound of the present invention is used as a fluorine solvent (C6F 14By adding (etc.), the metal ion adsorption site adsorbs metal ions M, allowing for efficient separation of metal ions M from contaminated water. [Examples]

[0122] <<Examples of applications of fluorine-containing monocyclic aromatic compounds, Part 2>> Referring to Figures 4 to 6, examples of the applications of fluorine-containing monocyclic aromatic compounds according to Examples 1 to 4 of the present invention as adsorbents for metal ions will be described.

[0123] Figures 4 to 6 schematically illustrate the use of column chromatography separation as a stationary phase.

[0124] As shown in Figure 4, the fluorine-containing monocyclic aromatic compound of the present invention can be used as an adsorbent to adsorb metal ions M, such as uranium (U), by impregnating it with nonwoven fabrics, silica beads, etc.

[0125] As shown in Figure 5, by filling a nonwoven fabric or silica beads impregnated with the fluorine-containing monocyclic aromatic compound of the present invention into a fluorine-based adsorbent-packed column 1, uranium dioxide ions (UO2) can be absorbed. 2+ It can selectively adsorb radioactive materials such as ions and fission products (FP) and separate reusable metal ions M.

[0126] Furthermore, as shown in Figure 6, the type of metal ions that can be adsorbed can be selected by changing the functional group of the fluorine-containing monocyclic aromatic compound of the present invention. For example, using a fluorine-based adsorbent-packed column 1 supported with a fluorine-containing monocyclic aromatic compound having an amide ligand or the like introduced into its functional group, U and Pu can be selectively separated from spent fuel dissolution containing uranium (U), plutonium (Pu), minor actinides (MA), and fission products (FP). Moreover, using a fluorine-based adsorbent-packed column 1 supported with a fluorine-containing monocyclic aromatic compound having a phosphorus ligand or the like introduced into its functional group, MA and FP can be selectively separated from spent fuel dissolution containing MA and FP after U and Pu have been removed. [Examples]

[0127] ≪Examples of Uses of Fluorine-Containing Monocyclic Aromatic Compounds (3)≫ Referring to Figure 7, examples of the applications of fluorine-containing monocyclic aromatic compounds according to Examples 1 to 4 of the present invention as adsorbents for metal ions will be described.

[0128] Figure 7 is a schematic diagram illustrating an example of selectively separating each radioactive substance from contaminated water containing radioactive materials. It is a modified example of Example 6 (Figure 6).

[0129] As shown in Figure 7, for example, using a fluorine-based adsorbent packed column 1 supporting a fluorine-containing monocyclic aromatic compound with an amide ligand introduced into its functional group, U and Pu can be selectively separated from contaminated water containing U, Pu, α-nuclides (MA), and FP. Furthermore, using a fluorine-based adsorbent packed column 1 supporting a fluorine-containing monocyclic aromatic compound with a phosphorus ligand introduced into its functional group, α-nuclides (MA) can be selectively separated from contaminated water containing α-nuclides (MA) and FP after U and Pu have been removed. In addition, using a fluorine-based adsorbent packed column 1 supporting a fluorine-containing monocyclic aromatic compound with an iminodiacetic acid ligand introduced into its functional group, tritium can be selectively separated from contaminated water containing FP after U, Pu, and α-nuclides (MA) have been removed. 3 It can selectively separate H, strontium (Sr), cesium (Cs), cobalt (Co), and nickel (Ni).

[0130] The fluorine-containing monocyclic aromatic compounds of the present invention can freely coordinate functional groups, and as described above, it is possible to design adsorbents corresponding to radionuclides. [Examples]

[0131] ≪Examples of Uses of Fluorine-Containing Monocyclic Aromatic Compounds (Part 4)≫ Referring to Figure 8, examples of the applications of fluorine-containing monocyclic aromatic compounds according to Examples 1 to 4 of the present invention as adsorbents for metal ions will be described.

[0132] Figure 8 schematically illustrates the use of so-called urban mines, represented by electronic substrates 2, for extracting useful metals and rare metals 5.

[0133] As shown in Figure 8, in the recycling of useful metals from urban mines, for example, an electronic circuit board 2 is immersed in aqua regia or nitric acid 4 in a container 3 to dissolve useful metals such as gold, platinum group metals, lithium, and iridium. Therefore, a method for efficiently recovering the metal resources dissolved in aqua regia or nitric acid 4 has been a long-standing challenge. Because aqua regia and nitric acid, which have extremely strong oxidizing power, are used, an adsorbent that can withstand strong acids is required, and the number of adsorbents that can handle extraction is limited.

[0134] Therefore, in this embodiment, the fluorine-containing monocyclic aromatic compound of the present invention is added to aqua regia or nitric acid 4 in which useful metals and rare metals 5 are dissolved and used as an adsorbent. Fluorine compounds are known to exhibit chemical stability and extraction reactions even in aqua regia and nitric acid 4.

[0135] The fluorine-containing monocyclic aromatic compound of the present invention enables the efficient recovery of useful and rare metals by selecting the appropriate functional group. Furthermore, since the adsorbent itself is resistant to aqua regia and nitric acid, repeated adsorption and elution processes are possible. [Examples]

[0136] ≪5 Examples of Uses of Fluorine-Containing Monocyclic Aromatic Compounds≫ Referring to Figure 9, the recycling of fluorine-containing monocyclic aromatic compounds according to Examples 1 to 4 of the present invention as adsorbents for used metal ions will be explained.

[0137] Figure 9 is a schematic diagram illustrating the recycling process of used adsorbent materials.

[0138] It has been found that mineralization of fluorine-based ligands with added functional groups is possible by utilizing hydrothermal reactions such as those using subcritical water. Therefore, the spent metal ion adsorbent using the fluorine-containing monocyclic aromatic compound of the present invention can be decomposed by hydrothermal reactions such as those using subcritical water, and the mineralized fluorine can be recovered as fluorite (CaF2) for recycling. Recycling of the adsorbent can contribute to reducing the amount of waste generated and lowering the cost of the adsorbent.

[0139] In addition to the examples 5 to 9 described above, it can also be used as a mercury adsorbent, for example. The burning of coal in coal-fired power plants has brought to light the environmental problem of trace amounts of mercury being released into the atmosphere. Besides ionization and alloying (amalgamation), organic mercury is also known as a chemical species of mercury. A mercury adsorption reaction via the chelation reaction of dithiocarbamic acid is known, and by combining it with a fluorine-based ligand, it is expected to be applicable to the development of more efficient extractants.

[0140] Furthermore, the present invention is not limited to the embodiments described above, and various modifications are included. For example, the embodiments described above are described in detail to make the present invention easier to understand, and are not necessarily limited to those having all the configurations described. Also, it is possible to replace parts of the configuration of one embodiment with the configuration of another embodiment, and it is also possible to add configurations from other embodiments to the configuration of one embodiment. In addition, it is possible to add, delete, or replace parts of the configuration of each embodiment with other configurations. [Explanation of Symbols]

[0141] 1...Fluorine-based adsorbent packed column, 2...Electronic circuit board (urban mining), 3...Container, 4...Aqua regia / nitric acid, 5...Useful metals / rare metals.

Claims

1. The benzene ring has a fluorescein structure and a functional group in part of its structure. A fluorine-containing monocyclic aromatic compound represented by the following formula (3). 【Chemistry 1】

2. The benzene ring has a fluorescein structure and a functional group in part of its structure. A fluorine-containing monocyclic aromatic compound represented by the following formula (7). 【Chemistry 2】

3. The benzene ring has a fluorescein structure and a functional group in part of its structure. A fluorine-containing monocyclic aromatic compound represented by the following formula (12). 【Transformation 3】

4. The benzene ring has a fluorescein structure and a functional group in part of its structure. A fluorine-containing monocyclic aromatic compound represented by the following formula (17). 【Chemistry 4】

5. A method for producing a fluorine-containing monocyclic aromatic compound, characterized by synthesizing a compound represented by formula (3) below using a compound represented by formula (2) below. 【Transformation 5】 【Transformation 6】

6. (a) A step of synthesizing a compound represented by formula (5) below using a compound represented by formula (4) below, (b) A step of synthesizing a compound represented by formula (6) below using a compound represented by formula (5) below, (c) A step of synthesizing a compound represented by formula (7) below using a compound represented by formula (6) below, A method for producing a fluorine-containing monocyclic aromatic compound, characterized by having the following characteristics. 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】

7. (a) A step of synthesizing a compound represented by formula (9) using a compound represented by formula (18) and a compound represented by formula (8) below, (b) A step of synthesizing a compound represented by formula (10) below using a compound represented by formula (9) below, (c) A step of synthesizing a compound represented by formula (11) below using a compound represented by formula (10) below, (d) A step of synthesizing a compound represented by formula (12) below using a compound represented by formula (11) below, A method for producing a fluorine-containing monocyclic aromatic compound, characterized by having the following characteristics. 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】

8. (a) A step of synthesizing a compound represented by formula (14) using a compound represented by formula (18) and a compound represented by formula (13) below, (b) A step of synthesizing a compound represented by formula (15) below using a compound represented by formula (14) below, (c) A step of synthesizing a compound represented by formula (16) below using a compound represented by formula (15) below, (d) A step of synthesizing a compound represented by formula (17) below using a compound represented by formula (16) below, A method for producing a fluorine-containing monocyclic aromatic compound, characterized by having the following characteristics. 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】

9. A metal ion adsorbent using a fluorine-containing monocyclic aromatic compound according to any one of claims 1 to 4.

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