KR19990030873A - Calix [4] arene dibenzo crown ether compound capable of selectively removing cesium ions and preparation method thereof - Google Patents

Abstract

The present invention relates to a carlix [4] arene dibenzo crown ether compound represented by the following formula (1), a method for preparing the same, and a use as a cesium selective ion exchanger.

(In Formula 1, R ₁ , R ₂ and n are as defined in the specification.)

Since the Kalix [4] arene dibenzo crown ether compound of Formula 1 has a function of selectively separating cesium ions (Cs ⁺ ), when treating radioactive wastes, a cesium selective ion exchanger (selective ion exchanger) It can be usefully used.

Description

Calix [4] arene dibenzo crown ether compound capable of selectively removing cesium ions and preparation method thereof

FIELD OF THE INVENTION The present invention relates to the Kalix [4] arene dibenzo crown ether compounds, their preparation methods and their use as ion exchangers capable of selectively separating cesium ions (Cs ⁺ ).

More specifically, the present invention relates to a calix [4] arene dibenzo crown ether compound capable of selectively adsorbing and separating cesium ions in radioactive waste generated from a nuclear power plant and the like, and a method for preparing the cesium ion selective ion exchanger. As related, the compounds of the present invention may be usefully used as ionophores to selectively remove cesium ions in radioactive waste.

As the industry develops, the seriousness of environmental pollution is increasing day by day. In particular, as a source of energy required for various industries, nuclear power has been widely used in various economic aspects such as facility investment costs, and thus, the radioactive waste generated from nuclear power plants and related research institutes has been improved. The development of treatment technology to reduce the volume while reducing the volume is urgent.

The evaporation and concentration method that has been used so far to treat radioactive waste liquid has an excellent decontamination effect, but has a disadvantage of high energy consumption. Recently, most nuclear power plants use radioactive waste liquid treatment using ion exchange. However, since the efficiency of waste treatment depends on the decontamination effect of the ion exchanger, there is an urgent need to develop a selective ion exchanger capable of selectively exchanging radionuclides. Research is actively underway.

Among radioactive materials, cesium (Cs) is an element with a half-life of about 30 years, and has a much longer half-life than other elements such as cobalt (Co) with a half-life of 5.72 years or iodine (I ₂ ) with 8 days. Special control is required in the solidification process after radioactive waste treatment. Therefore, the selective separation and solidification of cesium ions contained in the radioactive waste can be expected to have a great effect in terms of stability and energy efficiency for radioactivity.

In the field of host-guest chemistry, calixarene chemistry focuses on the synthesis and structural specificity of the calixarenes and their derivatives with interesting structures in recent 20 years. Are gathering. Furthermore, in the solidification treatment by volume reduction of low and medium-level radioactive waste liquids that can cause serious problems in terms of environmental pollution, metals such as cesium with long half-lives, such as calix [4] arene-based calix-arene crown ethers A study of selective extraction with compounds has recently been published.

On the other hand, Kalixaren is known to be a macrocyclic compound, including the benzene ring, a compound of Greek Calix and Arene (Vogtle & Weber, Host Guest Complex). Chemistry Macrocycles, 378, Springer-Verlag, 1985 ).

As shown in the following Scheme 1, pt-butylphenol and formaldehyde were reacted in the presence of sodium hydroxide to synthesize the pt-butylcalix [4] arene compound (Cornforth et al., J. Pharmacol. , 73, 10, 1955 ).

Also, as shown in Scheme 2, the molar and the like are pt-butylcalix [4] arene compounds of the structural formula 2 as a starting material and pt-butylcalix [4] as an aluminum chloride (AlCl ₃ ) catalyst. Removal of the pt-butyl group from the arene compound facilitated synthesis of the Kalix [4] arene compound of Structural Formula 3 (Gutsche et al., 1988 ).

On the other hand, by reacting the carlix [4] arene crown compound of the structural formula 3 with the crown ether compound and the crown ether ring is connected to the lower two hydroxyl groups of the carlix arene to synthesize a cyclized calyx [4] areen crown ether compound Research is actively underway (Reinhoudt, J. Am. Chem. Soc., 117 , p.2767, 1995 ).

The present inventors synthesized an organic ligand Kalix [4] arene dibenzo crown ether, which is an ion exchanger capable of selectively separating cesium ions in a radioactive waste solution, and the compound was formed on other ions. The present invention was completed by finding that cesium ions can be selectively separated.

It is an object of the present invention to provide a calix [4] arene dibenzo crown ether compound of formula (1) capable of selectively removing cesium ions, a preparation method thereof and a use thereof.

In order to achieve the above object, in the present invention, the Kalix [4] arene dibenzo crown ether compound of the formula (1) in which the callix [4] arene that can form a complex and complex to the dibenzo crown ether ligand, The preparation method thereof and the use thereof as cesium selective ion exchanger are provided.

Formula 1

Where

R ₁ is a C ₁ -C ₁₀ alkyl group, phenyl, methoxyphenyl, R ₂ is hydrogen , a C ₁ -C ₁₀ alkyl group, n can be selected from 1-2.

Representative compounds of the present invention are 1,3-dipropyloxy calli [4] aren dibenzo crownether and 1,3-dioctyloxy calli [4] aren dibenzo crownether.

In the present invention, the Kalix [4] arene dibenzocrown compound having a 1,3-alternate structure showed selectivity for cesium ions. This is because the size coincides well with the size, and when the crown ether is adsorbed with cesium ion, the cesium ion is adsorbed by oxygen, the electron-donor of the crown ether ring, and by two benzene rings in 1,3-cross position. This is because adsorption between Cs ⁺ -π electrons is easily performed.

The alkyl group substituted by the hydroxy group of the Calix [4] arene compound is preferably hydrophobic, which is adsorbed by the dibenzo crown ether compound of Formula 1 and cesium ion at the interface between the receiving phase and the organic layer. This is because the dibenzo crown ether compound of Formula 1, which is substituted with an alkyl group having high hydrophobicity, has a high solubility in an organic phase, thereby reducing cesium desorption to the external water phase.

The method for preparing the calix [4] arene dibenzo crown ether compound represented by Chemical Formula 1 of the present invention is as shown in Scheme 3 below.

Wherein R ₁ and R ₂ are as defined above.

In the preparation method of the present invention, an alkyloxy callix [4] areene compound of the formula 4 is prepared by reacting the calix [4] arene compound represented by the formula 3 with an alkylhalogen compound, and the compound of the formula 4 is dibenzo crown ether. And a cyclization reaction with a dimesylate compound having a skeletal structure of to obtain a calix [4] arene dibenzo crown ether compound of formula (1).

The pt-butylcalix [4] arene compound of formula 2 used as a starting material in the preparation method of the present invention can be easily synthesized by a known method ( see Scheme 1 ; Cornforth et al., J. Pharmacol. , 73, 10, 1955 ).

The Kalix [4] arene compound of formula 3 used as a starting material in the preparation method of the present invention can be easily synthesized by a known method ( see Scheme 2 ; Gutsche, 1988 ).

Hereinafter, the manufacturing method of the present invention will be described in detail.

1-iodine alkanes (0.5 to 10 equivalents), acetonitrile (1 to 1 × 10 ⁷ equivalents) and potassium carbonate (0.1 to 2.0 equivalents) are added to the starting material Kalix [4] arene dialkyloxy compound (1 equivalent). It puts, and it carries out alkylation reaction for 5 to 30 days in nitrogen or argon (Ar) gas atmosphere which is 0-200 degreeC and inert gas.

The introduction of a propyl or octyl group, which is a three-dimensionally bulky alkyl group, into the two hydroxy groups of the starting substance Kalix [4] Arene compound is carried out by dimesylate of dibenzo crown ether. To introduce in a three-crossed form. This is because when the structure of the Calix [4] arene dibenzocrown compound of the present invention has a 1,3-cross structure (1,3-alternate), the selectivity to cesium ion is exhibited as described above.

To the above obtained calix [4] arene dialkyloxy compound (1 equivalent) of the structural formula 4, dimethylate compound (0.5 to 10 equivalents) of dibenzocrown ether of structural formula 12, cesium carbonate (1 to 100 equivalents) and aceto Nitrile (1-1 × 10 ⁷ equivalents) was added thereto, followed by cyclization reaction at 0-200 ° C. for 5 minutes to 30 days in an inert gas nitrogen or argon (Ar) gas atmosphere. A benzo crown ether compound is obtained.

The dimethylate compound of dibenzocrown ether represented by Chemical Formula 2, which is a compound of Formula 12 in Scheme 3, is a cyclic polyether carboxylic acid (Cycholol) using catechol as a starting material, as shown in Scheme 4 below. acyclic polyether carboxylic acid) (Kim, Jong-Seung et al., Microchemical J. 55, 1997,p.115), lithium aluminum hydride (LiAlH₄Using a catalyst and a tetrahydrofuran solvent to reduce to dibenzo polyether alcohol of formula 11, followed by methanesulfonyl chloride and trimethylamine (Et).₃Prepared using N). At this time, dibenzo polyether alcohol is reacted with methanesulfonyl chloride to introduce mesyl groups (OMs) which are easily released. Conventionally, dibenzo polyether alcohols are reacted with p-tolunesulfonyl chloride and a base such as sodium hydroxide or pyridine to introduce tosyl groups (OTs) into diols (Reinhoudt,J. Am. Chem. Soc., 117, p.2767,1995), p-toluenesulfonyl chloride and pyridine have difficulties in handling such as toxicity and odor, and have a disadvantage in that the yield when the tosyl group is introduced and the cyclization reaction is lower than the yield when the mesyl group is used.

Since the Kalix [4] arene dibenzo crown ether compound represented by the general formula (1) of the present invention can selectively adsorb cesium ions, an adsorbent composition containing these as an active ingredient can be usefully used for cesium selective ion exchangers.

Hereinafter, the present invention will be described in detail by the following examples.

The following examples are illustrative of the invention and are not intended to limit the scope of the invention. In the examples, some characteristic compounds have been described. However, other compounds may be easily prepared according to the method of the present invention. Prior to the Examples, the preparation method of the materials used to prepare the compounds of the present invention will be described.

Preparation Example 1 Preparation of 1,5-bis [2- (2-methanesulfonyloxy) ethyloxy] -3-ozapentane.

(Step 1) Preparation of 1,5-bis [2- (2-hydroxy) ethyleneoxy] -3-ozapentane.

Lithium aluminum hydride (LiAlH ₄ ; 2.8 g, 73.9 mmol) was added to tetrahydrofuran (150 mL) and stirred in a nitrogen atmosphere at 0 ° C., followed by dibenzo polyether alcohol (6.67 g, 16.4 mmol) in 50 mL of tetrahydrofuran. ) Was slowly added dropwise in an ice bath for 30 minutes. After the dropwise addition of the dibenzo polyether alcohol solution was completed, the reaction solution was stirred for 30 minutes in an ice bath and then stirred for 10 hours while refluxing. The reaction was confirmed by thin layer chromatography, and ethyl acetate (5 mL) and sodium hydroxide solution (10%) were added to the reaction solution under ice bath to form a white solid phase. The reaction solution was stirred for 30 minutes at room temperature, filtered under reduced pressure, and washed twice with tetrahydrofuran. The filtrate was distilled under reduced pressure, methylene chloride (100 ml) and hydrochloric acid solution (10%, 100 ml) were added to separate the organic layer. The organic layer was washed twice with distilled water (50 ml), dried over anhydrous sodium sulfate, and distilled under reduced pressure. To remove the organic solvent. The oily residue thus obtained was recrystallized from diethyl ether to obtain the title compound.

mp: 89-90 ° C .; IR spectrum (KBr, cm ⁻¹ ): 3400 (OH), 1115 (CO).

¹ H NMR (CDCl ₃ ): δ 6.91 (s, 8H, ArH), 4.762 (br s, 2H, —CH ₂ CH ₂ O H ), 4.19-4.25 (m, 4H, —CH ₂ CH ₂ O—) , 4.05-4.09 (m, 4H, -CH ₂ CH ₂ O-), 3.84-3.99 (m, 8H, -CH ₂ CH ₂ OH, -CH ₂ CH ₂ O-).

Fast atom bombardment mass spectrometry m / z (M ⁺ ): 378.21 (calculated), 378.20 (experimental).

Elemental Analysis (C ₂₀ H ₂₆ O ₇ ): C; 63.49, H; 6.87 (calculated), C; 63.21, H; 6.90 (experimental).

(Step 2) Preparation of 1,5-bis [2- (2-methanesulfonyloxy) ethyloxy] -3-ozapentane.

1,5-bis [2- (2-hydroxy) ethyleneoxy] -3-ozapentane (5 g, 13.2 mmol) and triethylamine (2.94 g, 29.0 mmol) obtained in (Step 1) were methylene chloride ( 100ml), ice-cold, cooled to 0 ° C, and methanesulfonyl chloride (3.33g, 2.14ml, 29.0mmol) was added dropwise for 30 minutes in a nitrogen atmosphere. After the dropwise addition of methanesulfonyl chloride was completed, the temperature of the reaction vessel was allowed to warm to room temperature and stirred for 10 hours. The reaction solution was separated with an aqueous sodium hydrogen carbonate solution (5%, 50 mL), washed twice with saturated sodium chloride solution (50 mL), dried over anhydrous sodium sulfate, and the organic solvent was removed by distillation under reduced pressure to obtain an oily residue. Got. This residue was recrystallized from diethyl ether to give the title compound.

mp: 98-99 ° C .; IR spectrum (KBr, cm ⁻¹ ): 1579, 1516, 1350 (SO ₂ ), 1181 (SO ₂ ).

¹ H NMR (CDCl ₃ ): δ 6.88-7.00 (m, 8H, ArH), 4.45-4.57 (m, 2H, -CH ₂ CH ₂ O-), 4.05-4.26 (m, 8H, -CH ₂ CH ₂ 0-), 3.75-3.85 (m, 4H), 3.23 (s, 6H, CH ₃ SO ₂ OCH ₂ CH _2- ).

Fast atom bombardment mass spectrometry m / z (M ⁺ ): 534.12 (calculated), 534.20 (experimental).

Elemental Analysis (C ₂₂ H ₃₀ O ₁₁ S ₂ ): C; 49.43, H; 5.61 (calculated), C; 49.21, H; 5.78 (experimental).

<Example 1> Preparation of 1,3-dipropyloxy callix [4] arene dibenzo crown ether compound

(Step 1) Preparation of a 1,3-dipropyloxy callix [4] arene compound

In acetonitrile (150ml), calix [4] arene (5.0g, 11.8mmol), 1-iodine propane (4.20g, 24.7mmol) and potassium carbonate (1.63g, 11.8mmol) were added and nitrogen atmosphere was added for 24 hours. Reflux for a while. The reaction was confirmed by thin layer chromatography (TLC), the acetonitrile was distilled off under reduced pressure, and then the organic layer was separated using hydrochloric acid solution (10%, 50 mL) and methylene chloride (50 mL). The separated organic layer was washed twice with distilled water (50 mL), dried over anhydrous sodium sulfate (Na ₂ SO ₄ ), and distilled under reduced pressure to remove the organic solvent, and recrystallized with a mixed solvent of diethyl ether and hexane (7: 3). The title compound (yield 90%) was obtained.

mp: 268-270 ° C .; IR spectrum (KBr, cm ⁻¹ ): 3400 (ArO-H), 1254,1196.

¹ H NMR (CDCl ₃ ): δ 8.30 (s, ArO H , 2H), 7.04 (d, J = 7.48 Hz, 4H, Ar H ), 6.87 (d, J = 7.48 Hz, 4H, Ar H ), 6.61 -6.69 (m, 4H, Ar H ), 4.30 (d, J = 13.0 Hz, 4H, ArC H ₂ Ar), 3.99 (t, J = 6.2 Hz, 4H, OC H ₂ CH ₂ CH ₃ ), 3.35 ( d, J = 13.0 Hz, 4H, ArC H ₂ Ar), 1.99-2.06 (m, J = 6.2 Hz, 4H, OCH ₂ C H ₂ CH ₃ ), 1.08 [t, J = 6.2 Hz, 6H, O ( CH ₂ ) ₂ C H ₃ ].

¹³ C NMR (CDCl ₃ ): ppm 153.3, 151.8, 133.4, 128.95, 128.91, 128.85, 128.84, 128.40, 128.35, 128.12, 125.31, 125.27, 118.97, 118.9, 78.4, 78.2, 78.1, 31.48, 31.4, 31.39, 31.34 , 23.4, 10.9.

(Step 2) Preparation of a 1,3-dipropyloxy callix [4] arene compound

In acetonitrile (50 mL), 1,3-dipropyloxy callix [4] arene (1.0 g, 2.0 mmol) obtained in (Step 1), 1,5-bis [2- (2) obtained in the preparation example Methanesulfonyloxy) ethyloxy] -3-ozapentane (1.05 g, 2.0 mmol) and cesium carbonate (Cs ₂ CO ₃ ; 3.2 g, 9.8 mmol) were added thereto, followed by stirring for 24 hours while refluxing. After the reaction was cooled to room temperature, the precipitated cesium carbonate was filtered off, and the solvent was distilled off under reduced pressure. Then, an organic layer was added by adding hydrochloric acid solution (10%, 50ml) and methylene chloride (50ml). The separated organic layer was washed twice with hydrochloric acid solution (10%, 50ml) and distilled water (50ml), dried over anhydrous sodium sulfate, and the organic solvent was distilled off under reduced pressure to obtain a white solid material. This white solid was recrystallized from diethyl ether to obtain the title compound (yield 88%).

mp: 178-181 ° C .; IR spectrum (KBr, cm- ¹ ): 3068 (Ar-H), 1501, 1451, 1254, 1196.

¹ H NMR (CDCl ₃ ): δ 6.87-7.02 (m, 16H), 6.70-6.78 (m, 4H), 4.22 (t, J = 5.1 Hz, 4H), 4.08 (t, J = 5.1 Hz, 4H) , 3.89 (t, J = 5.1 Hz, 4H), 3.76 (t, J = 5.1 Hz, 4H), 3.70 (s, 8H, ArC H ₂ Ar), 3.41 (t, J = 7.4 Hz, 4H, -OC H ₂ CH ₂ CH ₃ ), 1.38-1.47 (m, J = 7.4 Hz, 4H, -OCH ₂ C H ₂ CH ₃ ), 0.77 (m, J = 7.4 Hz, 6H, -OCH ₂ CH ₂ C H ₃ ).

¹³ C NMR (CDCl ₃ ): ppm 157.4, 156.8, 150.7, 149.8, 128.91, 1134.4, 134.3, 130.6, 130.5, 123.1, 122.8, 122.6, 122.3, 118.3, 116.1, 73.4, 71.1, 70.6, 69.8, 38.1, 23.7 , 10.8.

Fast atom bombardment mass spectrometry m / z (M ⁺ ): 850.31 (calculated), 850.30 (experimental).

Elemental Analysis (C ₅₄ H ₅₈ O ₉ ): C; 76.20, H; 6.82 (calculated), C; 76.18, H; 6.87 (experimental).

<Example 2> Preparation of a 1,3-dioctyloxy calix [4] arene dibenzo crown ether compound

(Step 1) Preparation of 1,3-dioctyloxy calix [4] arene compound

Using the method of (Step 1) of Example 1, using Kalix [4] arene (5.0 g, 11.8 mmol), 1-iodine octane (5.93 g, 24.7 mmol) and potassium carbonate (1.63 g, 11.8 mmol) The crude product obtained in the same manner was recrystallized with a hexane solvent to obtain the title compound (yield 92%).

mp: 115-117 ° C .; IR spectrum (KBr, cm ⁻¹ ): 3400 (ArO-H), 1254,1196.

¹ H NMR (CDCl ₃ ): δ 8.30 (s, ArO H , 2H), 7.05 (d, J = 7.48 Hz, 4H, Ar H ), 6.88 (d, J = 7.48 Hz, 4H, Ar H ), 6.72 (t, 2H, Ar H ), 6.63 (t, 2H, Ar H ), 4.30 (d, J = 13.0 Hz, 4H, ArC H ₂ Ar), 3.99 [t, J = 6.2 Hz, 4H, OC H ₂ (CH ₂ ) ₆ CH ₃ ), 3.36 (d, J = 13.0Hz, 4H, ArC H ₂ Ar), 2.08 (m, J = 6.2Hz, 4H, OCH ₂ C H ₂ (CH ₂ ) ₅ CH ₃ ) , 1.31-1.72 (m, 22H), 0.89 [t, J = 6.2 Hz, 6H, O (CH ₂ ) ₇ C H ₃ ].

¹³ C NMR (CDCl ₃ ): ppm 154.0, 152.7, 134.1, 129.5, 129.1, 128.9, 125.9, 119.6, 78.0, 32.6, 32.1, 30.7, 30.2, 26.7, 23.4, 14.8.

(Step 2) Preparation of a 1,3-dipropyloxy callix [4] arene compound

1,3-dipropyloxy calix [4] arene (1.0 g, 1.5 mmol) obtained in (Step 1) above, 1,5-bis [2- (2-methanesulfonyloxy) ethyl obtained in Preparation Example A white solid compound obtained by using the same method as in (Step 2) of Example 1 using Oxy] -3-ozapentane (0.82 g, 1.5 mmol) and cesium carbonate (3.2 g, 9.8 mmol) Recrystallization with hexane gave the title compound (yield 92%).

mp: 124-127 ° C .; IR spectrum (KBr, cm ⁻¹ ): 1593, 1501, 1455, 1254, 1208.

¹ H NMR (CDCl ₃ ): δ 6.91-7.08 (m, 16H), 6.70-6.78 (m, 4H), 4.23 (t, J = 5.1 Hz, 4H, -OC H ₂ CH ₂ O-), 4.08 ( t, J = 5.1 Hz, 4H, -OC H ₂ CH ₂ O-), 3.73 (t, J = 5.1 Hz, 4H, -OC H ₂ CH ₂ O-), 3.71 (s, 8H, ArC H ₂ Ar ), 3.44 [s, J = 7.4 Hz, 4H, -OC H ₂ (CH ₂ ) ₆ CH ₃ ], 1.40-1.80 (m, J = 7.4 Hz, 4H, -OCH ₂ (C H ₂ ) ₆ CH ₃ ], 0.91 (t, J = 7.4 Hz, 6H, -OCH ₂ (CH ₂ ) ₆ C H ₃ ].

¹³ C NMR (CDCl ₃ ): ppm 157.5, 156.8, 150.7, 149.8, 134.5, 134.0, 130.6, 130.5, 122.9, 122.7, 122.3, 122.3, 118.3, 116.1, 73.4, 71.9, 71.1, 69.97, 69.90, 38.2 (Ar C H ₂ Ar), 32.6, 30.43, 30.41, 30.13, 26.6, 23.4 [OCH ₂ ( C H ₂ ) ₆ CH ₃ ], 14.8 [OCH ₂ (CH ₂ ) ₆ C H ₃ ].

Fast atom bombardment mass spectrometry m / z (M ⁺ ): 990.20 (calculated), 990.10 (experimental).

Elemental Analysis (C ₆₄ H ₇₈ O ₉ ): C; 77.57, H; 7.87 (calculated), C; 77.60, H; 7.77 (experimental).

In order to confirm that the compound of formula 1 of the present invention exhibited an excellent effect as the cesium ion selective ion exchanger, the cesium ion selective resolution of the Kalix [4] arene dibenzo crown ether using the bulk liquid membrane method was investigated.

<Experimental example> Screening resolution of cesium ion selective resolution of Kalix [4] arene dibenzo crown ether using bulk liquid film method

Bulk liquid membrane method (Cho, Moon-Hwan et al., Bull. Korean Chem. Soc., In order to confirm that Calix [4] arene dibenzo crown ether of the present invention shows excellent effects as a cesium ion selective ion exchanger) . 16 , p. 33, 1995 ), the selective resolution of cesium ions was tested.

The liquid membrane separation method has been widely used to separate metals present in wastewater, and in particular, the bulk liquid membrane method has been widely used in recent years. This method puts an organic solvent between the source phase and the receiving phase, and the ligand dissolved in the organic solvent transfers the metal ions in the water phase to the aqueous phase of the water phase. To remove the metal ions in water.

The bulk liquid film method used in the present invention is as follows. That is, 3 ml of each of the compounds of Examples 1 and 2 were dissolved in chloroform at the lower end of the cylindrical body, and a solution having a concentration of 0.001 M was filled. Lithium nitrate (LiNO) at a concentration of 0.1 M was placed on the outer side of the upper layer of the organic layer. ₃ ), an aqueous solution of sodium nitrate (NaNO ₃ ), potassium nitrate (KNO ₃ ), rubidium nitrate (RbNO ₃ ), and cesium nitrate (CsNO ₃ ) were each filled with 0.8 ml. In addition, deionized distilled water (5 ml) from which the ions were removed was filled in the upper part of the upper layer of the organic layer, which was an external water phase, and stirred with a magnetic bar coated with a Teflon having a size of 13 mm. This experiment was repeated three times or more. In order to compare the mobility of ions at this time, the experiment was performed using an organic layer to which the compound of Formula 1 was not added. The amount of the transferred metal was used in the following molar flux.

In this equation, mole flux is defined as the number of moles moved per unit time, per unit area, and the mobility used in this experiment is converted to units of 10 ^-8 mol · s ^-1 · m ^-2 . It became. Table 1 shows the mobility of ions using the bulk liquid membrane method.

Molar flux ^{(10 -8 mol · s -1 ·} m -2) Example Li Na K Rb Cs One 0.00 1.92 1.28 2.35 11.87 2 0.00 1.51 1.77 1.03 2.90

As can be seen from the above, when the 1,3-dipropyloxy callix [4] arene dibenzo crown ether prepared in Example 1 as the organic ligand, the mobility of cesium ions appears to be greater than other ions In the case of the compound of Example 2 in which R _{1 in} Formula 1 is substituted with an octyl group having a higher hydrophobicity than the propyl group, it can be seen that the selectivity to cesium ion is greatly reduced.

As described above, the Calix [4] arene dibenzo crown ether compound of the present invention has a 1,3-cross structure, and thus has excellent selective adsorption to cesium ions. Dimethylate, which is a skeleton of the crown ether, is reacted in the presence of cesium carbonate, and thus it is an excellent production method capable of synthesizing calix [4] arene dibenzo crown ether with high yield. Therefore, the calix [4] arene dibenzo crown ether compound prepared by the production method of the present invention can be usefully used as a cesium selective ion exchanger capable of selectively separating cesium.

Claims (9)

Calix [4] arene dibenzo crown ether compound capable of selectively removing cesium ions represented by the formula (1): Formula 1 In Formula 1, R ₁ is a C ₁ -C ₁₀ alkyl group, phenyl, methoxyphenyl, R ₂ is hydrogen , a C ₁ -C ₁₀ alkyl group, n can be selected from 1 to 2. [Claim ₂ ] The cesium ion of claim 1, wherein the compound of formula 1 is a 1,3-dipropyloxy calix [4] arene compound wherein R ₁ is a propyl group and R ₂ is hydrogen. Carlix [4] arene dibenzo crown ether compound. [Claim ₂ ] The cesium ion of claim 1, wherein the compound of formula 1 is a 1,3-dioctyloxy calix [4] arene compound wherein R ₁ is an octyl group and R ₂ is hydrogen. Carlix [4] arene dibenzo crown ether compound. A dialkyloxy callix [4] arene compound of formula 4 is prepared by reacting a calyx [4] arene compound represented by formula 3 with an alkyl halide compound, and the compound of formula 4 is converted to a dimesylate compound and a ring. A process for producing a calix [4] arene dibenzo crown ether compound, wherein the reaction is carried out to obtain a calix [4] arene dibenzo crown ether compound represented by formula (1). Scheme 3 The method of claim 4, wherein the dimesylate compound is a compound represented by the following Chemical Formula 2 serving as a skeleton of the dibenzo crown ether. Formula 2 The process for producing a calix [4] arene dibenzo crown ether compound according to claim 4, wherein the reaction temperature is 0 to 200 占 폚. The process for producing a calix [4] arene dibenzo crown ether compound according to claim 4, wherein the reaction time for each step is within 5 minutes to 30 days. The method of claim 4, wherein the reaction of each step is carried out in an inert gas (nitrogen or argon) atmosphere. Use of the calix [4] arene dibenzo crown ether compound of claim 1 as a selective ion exchanger to selectively remove cesium ions.