JPS6233170A - Cyclic polyether compound - Google Patents

Abstract

NEW MATERIAL:The compound of formula I[A is group of formula II-V(X is halogen or halogenoalkyl; n is 1-5; R is H or alkyl), etc.; B is group of formula VI-X(l is 0-7)]. USE:It can be used in the field of separation and analysis of sodium ion, e.g. as a sodium-selective electrode, etc. It has high sodium selectivity and is resistant to water for a long period. PREPARATION:The compound of formula I wherein B is group of formula VI-IX can be produced e.g. by reacting hydroxymethyl-12-crown-4 with the compound of formula XI or XII(X is halogen; k is 0 or 1).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a cyclic polyether compound having good selectivity for sodium ions.

[Prior art and problems to be solved by the invention] Conventionally,
From the standpoint of separation and analysis of sodium ions, there has been a demand for organic compounds that selectively and strongly coordinate with sodium ions. Typical research has focused on antibiotics such as monensin, but these have low selectivity toward other alkali metals, especially potassium, so they have not been of practical use.

As another research example, a cyclic polyether having a 12-crown-4 skeleton as shown below is known.

C112- (abbreviated as :12 or -/) However, these materials have extremely insufficient sodium selectivity and are relatively hydrophilic, so they cannot be used, for example, in applications such as sodium-selective electrodes. It has been impossible to apply this method to fields that require high sodium selectivity and long-term water resistance.

[Means and Effects for Solving the Problems] The present inventors have conducted various studies in order to synthesize a cyclic polyether that has excellent selective coordination ability for sodium ions and is hydrophobic. Ta.

As a result, we succeeded in obtaining a cyclic polyether compound with far superior sodium selective coordination ability compared to the structural formulas (A) and (B), and completed the present invention. Furthermore, the cyclic polyether compound of the present invention has significantly lower solubility in water than structural formulas (A) and (B), so it is suitable for applications that require long-term stability such as sodium electrodes. It has the advantage of being used for

That is, the present invention is based on the following general formula [I]''' and n is an integer of 1 to 5.) represents a group represented by ).

In the general formula (I), each of fluorine, chlorine, oxal, and iodine atoms can be used as the halogen atom represented by X. Further, as the halogenoalkyl group represented by X, the alkyl groups substituted with the above-mentioned halogen atoms can be used without any restriction. In particular, perhalogenated alkyl groups such as trifluoromethyl group, pentachloroethyl group, trichloromethyl group, and pentachloroethyl 6 are preferably used. In the general formula CI), the halogenoalkyl group represented by X and the alkyl group represented by R are not limited in number of carbon atoms, but those having 1 to 4 carbon atoms are preferably used.

When the cyclic polyether compound represented by the general formula (1) is used in a sodium-selective electrode, the selectivity and water resistance for sodium ions are determined by A in the general formula [I].
somewhat influenced by the type of

In order to improve sodium selectivity and water resistance, A in general formula (1) preferably satisfies either (1) or (2) below.

(1) Having two or more aromatic nuclei.

(2) It has one aromatic nucleus, and the aromatic nucleus is substituted with three or more halogen atoms or halogenoalkyl groups.

Furthermore, it is preferable that A in general formula (1) is a compound that satisfies any of the following (3) to (5).

(3) Having three or more aromatic nuclei.

(4) One of the following among those having two aromatic nuclei.

(5) It has one aromatic nucleus, and the cough aromatic nucleus is substituted with four or more halogen atoms or halogenoalkyl groups.

Regarding B in the general formula (1), if the number 1 is large, the difficulty of synthesis and purification increases, and furthermore, the sodium selectivity may decrease slightly, so it is preferably 4 or less, More preferably, it is an integer of 3 or less.

The cyclic polyether compound represented by the general formula CI) of the present invention is a novel compound, and can usually be identified as such by the following measurements.

(1) Infrared absorption spectrum Absorption based on the structure of 12-crown-4 is 1140.10
It appears strongly around 80-102102O'.

(21'H- Nuclear Magnetic Resonance Spectrum When measured in deuterated chloroform solvent using tetramethylsilane as a reference, -
The peak derived from H of CH2-0- is 3.3 ppn+
~4.2 ppm, and when the aromatic ring contains a hydrogen atom, the hydrogen atom absorption peak is around 6.6 ppm ~
It appears at 8.2 ppm, and the relative intensity ratio of these peaks matches the ratio of the number of hydrogens bonded to each group calculated from the above general formula (1).

(3) Mass spectrometry By using field desorption method (hereinafter abbreviated as FI method) as a method of mass spectrometry, the general formula CI) of the present invention
A molecular ion peak of the compound shown by is observed.

(4) Elemental analysis Carbon and hydrogen of the compound calculated from the above general formula (T),
The amounts of nitrogen and halogen almost match the amounts of each element in the analysis results.

Typical properties of the compound represented by the above general formula (1) are as follows.

(1) The cyclic polyether compound of the present invention generally cannot be distilled and it is difficult to obtain a clear boiling point.

(2) The cyclic polyether compound of the present invention is a highly viscous liquid at room temperature, but if OA in the general formula (1) has 3 or more aromatic nuclei or the number of n is 2 or more, White,
It often becomes a yellowish-white solid, and -N=N
- When it contains, it is an orange solid, and when it contains iodine, it tends to be brownish.

The solubility of the cyclic polyether compound represented by the general formula (1) differs slightly depending on the types of A and B, but
Many of them dissolve at room temperature, such as methylene chloride, chloroform, benzene, toluene, acetone, tetrahydrofuran, dioxane, dimethylformamide, methanol, and ethanol. Almost insoluble in water.

Since these properties can be confirmed very easily, they can be confirmed in advance before use.

The method for producing the cyclic polyether compound represented by the general formula (1) of the present invention is not particularly limited, and any method may be employed. Specific examples of industrially suitable methods are as follows.

(1) In the general formula CI), B is 11] or -C-N-CH2(:CH2''+-C-0-CI+
In the case of □, general! The following general formulas (I[T), (I
It can be obtained by reacting any one type of compound of V) or (V).

to 1000-CHz square "beC) I2u-CHz-X
(III) (However, A and l are general formula CI
), X is a halogen atom, and k is 0 or 1. ) (However, A and l are the same as in the general formula (T), X represents a halogen atom, and k is O or 1.) ((V)
II (However, A and ρ are the same as in general formula (1), and k is 0
or 1).

(ii) In addition, in the general formula [■], B is represented by the general formula [■] (however, ! is the same as in general formula (1)). It is the same as (I), and X is a halogen atom.) It can be obtained by reacting with an acid halide represented by

The compound represented by the above general formula (VI) is a compound represented by the above general formula (VI).
II) Hydroxymethyl-12-crown-
4 and ω-aminoalkylcarboxylic acid (HJ-CHzJC
HzlCOOIl) in the presence of an acid catalyst! It can be obtained by reacting with

(iii) Furthermore, in the above general formula [■], when B is, the cyclic polyether compound of the present invention can also be obtained by the following method.

(However, X is a halogen atom.) Halogenomethyl-12-crown-4 represented by the general formula (IX) A40-C)12C1l□→C1l□←Y'
(IX'l! (However, A and β are the same as in general formula (1), and k is O
or 1, and Y is a hydroxyl group or a carboxyl group.

) React with the compound shown in

In the reactions (i), (ii), and (iii) above,
The molar ratio of the raw materials used can be varied over a wide range, but usually the molar ratio of one to the other is 0.5.
It is preferably in the range of 1.5 to 1.5, more preferably around equimolar. Moreover, the solvent used can be used without any restriction as long as it is an inert solvent that does not react with the raw materials. For example, aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene and toluene; chlorinated aliphatic hydrocarbons such as methylene chloride and chloroform; chlorinated aromatic hydrocarbons such as monochlorhenzene and dichlorohenzene; tetrahydrofuran , dioxane, and other ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, and other ketones. The reaction temperature is not particularly limited, but is usually between 0 and
Preferably, the temperature is within the range of 150°C. Further, the reaction time is not particularly limited and can be adopted from a wide range, but it is generally 1 to 100 hours.

In the reactions (i) to (iii) above, it is preferable to use a catalyst depending on the type of raw material used. For example, when using a compound represented by general formula [111] as a raw material in the reaction (i), an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, etc. Further, when a compound represented by general formula (IV) is used as a raw material in the reaction (i), and in the case of the reaction (ii), triethylamine, pyridine, N.

When a tertiary amine such as N-dimethylaniline, N,N-dimethyltoluidine, etc. is further used as a raw material and a compound represented by general formula (V) in the reaction (i),
It is desirable to use an acid catalyst such as hydrogen chloride, hydrogen fluoride, sulfuric acid, phosphoric acid, benzenesulfonic acid, p-toluenesulfonic acid, or boron trifluoride ethyl ether. next,
In the reaction (iii) above, general formula C is used as a raw material.
Among the compounds represented by IX), when Y is a hydroxyl group, it is preferable to use the alkali metal hydroxide described above,
When Y is a carboxyl group, diazabicyclo-[5,
Preferably, a strong base such as 4,O)-undecene-7 is used. The amount of the above catalyst used is 0.01 to 5 % for the compound represented by general formula (n) for acid catalysts.
It is preferable to use it in a range of 0% by weight, and for other catalysts, it is preferable to use it in an equimolar amount with respect to one raw material.

Since the compound represented by the above general formula (1) generally has a high boiling point, many of the compounds are difficult to distill. Therefore, it is usually preferable to purify by means such as extraction, recrystallization, and column chromatography. In particular, the general formula (1) of the present invention
The compound represented by and the raw material hydroxymethyl-1
Column chromatography is most preferably used to effectively separate 2-crown-4. When employing this method, it is desirable to determine the optimal conditions for the column packing material and developing solvent in advance by a technique such as thin layer chromatography.

Since the compound represented by the general formula CI) of the present invention has a high selective coordination ability for sodium ions,
It can be used as a selective absorbent for sodium ions or as a component of a sodium-selective electrode. The mode of use as an absorbent differs depending on the state of existence of sodium ions, but typical examples are as follows.

That is, when selectively extracting and removing sodium salt coexisting with potassium salt in an aqueous solution, the general formula (1
) is dissolved in an organic solvent that is immiscible with water, and the organic solvent is brought into contact with the aqueous phase, whereby the sodium ions are selectively extracted from the aqueous phase into the organic solvent.

There are no particular limitations on the mode of constructing a sodium-selective electrode using the compound represented by the general formula (I) of the present invention as one component.
) Chapter 7, Ion Selective Electrodes in Analytical Chemistry (Blenheim Press, 1978) (Ion 5elective El
electrodes in AnalyticalC
hemisyry (Plenum Press 1
978)) Chapters 3 and 4 Analytical Chemistry 4
Various known methods can be used, such as those described in Vol. 7, p. 2238 (1975). A specific example is as follows.

A method of dissolving the compound represented by the general formula (I) of the present invention in a water-insoluble organic solvent such as nitrohenzene, bromobenzene, diphenyl ether, etc., and retaining the compound in a glass capillary, ceramic porous membrane, or polymer porous membrane. Silicone rubber, polyvinyl chloride containing a plasticizer, polymethyl methacrylate containing a plasticizer, etc. are dissolved together in a common solvent, and then the solvent is evaporated to form a film-like product. The sodium-selective electrode can be constructed by attaching a material to the electrode, or by forming a thin film directly on a silver wire, a platinum wire, or a gate portion of a silicon semiconductor. Here, known plasticizers can be used without particular limitation. Examples include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, and dioctyl phthalate; fatty acid esters such as dioctylazibe-1. and dioctyl sebacate; and 0-nitrophenyl alkyls such as orthonitrophenyl octyl ether. Examples include ethers. FIGS. 24 and 25 show schematic diagrams of an electrode in which a membrane-like material containing the compound represented by the general formula N) is used as a sodium-selective electrode.

Examples are given below to further specifically explain the present invention, but the present invention is not limited to these Examples.

Example 1 In an eggplant-shaped flask with an internal volume of 100 mA equipped with a cooling tube,
5 mmol of p-chloromethylbiphenyl, 4.5 mmol of hydroxymethyl-12-crown, and 5 mmol of potassium hydroxide were charged, and the mixture was heated under reflux in acetone for 96 hours. After the reaction was cooled and neutralized with hydrochloric acid, the resulting salt was filtered off, and the solvent was removed using a rotary evaporator. The obtained product was separated using a column packed with silica gel (Wako Gel C-200) using ethyl acetate as a developing solvent, and 0.78 g (yield: 42%) of a compound represented by the following structural formula was obtained.

The following analysis was performed on the obtained product.

(1) Infrared absorption spectrum (results are attached as Figure 1) Aromatic N 30 Q O~31 (l Ocm-
'Cyclic ether 1020-1160cm-'(2)'
H-Nuclear Magnetic Resonance Vector (Results are attached as Figure 2) Measurement solvent Double chloroform Standard material: Tetramethylsilane (In the following examples, the measurement solvent and standard material are the same as in this example, so they are described. ) (a) (cl
a) 7.0 to 7.5 ppm b) 4.3 to 4.4 ppm c) 3.2 to 4.0 The ratio of hydrogen amounts obtained by integration matched that of the target product.

(3) Mass spectrometry spectrum FD method m/e=372 (M') (4) Elemental analysis From the above measurement results, it was confirmed that the product was the desired product.

Examples 2 to 58 Compounds represented by the general formula [1] were synthesized from a compound having an ω-chloro group and hydroxy-12-crown-4 in the same manner as in Example 1, and are shown in Table 1.

The compounds synthesized according to Examples 2 to 58 are as follows: Example 1
The target compound was confirmed using the same method as above. For reference, the infrared absorption spectrum and IH
- Nuclear magnetic resonance spectra are shown in FIGS. 3 and 4, respectively.

The above measurement results confirmed that the product was the desired product.

Examples 60 to 98 In the same manner as in Example 59, compounds represented by the general formula were synthesized from an acid chloride compound and hydroxy-12-crown-4. The results are summarized in Table 2. These compounds were analyzed in the same manner as in Example 59 and confirmed to be the target compounds. For reference, the infrared absorption spectrum and IH-nuclear magnetic resonance spectrum of Example 62 are shown in FIGS. 7 and 8, respectively.

Example 99 100-shaped eggplant-shaped flask with cooling tube and water metering receiver Nitoluene 50 sd, 2,4-dichlorophenyl ff
[5 mmol of hydroxyl 12-crown-4 = 5 mmol, and 2.5 mmol of p-toluenesulfonic acid monohydrate were charged and heated under reflux for 96 hours, and the produced water was removed by azeotropic dehydration. After the reaction, neutralize with sodium hydroxide,
Water was added to separate the toluene layer, and the toluene was distilled off using a rotary evaporator. The product was separated and purified using a column packed with silica gel (Wako Gel C-200) using ethyl acetate as a solvent to obtain a compound 1.01P (yield 51%) represented by the following structural formula. The following analysis was performed on the obtained compound.

←) Infrared absorption spectrum (results are shown in Figure 9) Aromatic ring 6050-3100 cm-' Cyclic ether
1020-1160 cm-'Ester 1740 a
n-' (2) 'H-Nuclear Magnetic Resonance vector (result 10th
Shown as a diagram. ) (a) 6.6-7.4 ppm (υ 3,6
~4.5 ppm (C) 2.0-2.1 ppm (3) Mass spectrometry spectrum FD method m/e=440,442.444 (M'') These are isotopes according to C25S ct57.

(4) From the measurement results beyond elemental analysis, it was confirmed that the product was the desired product.

Examples 100 to 169 Compounds represented by general formula (1) were synthesized from a carboxylic acid compound and hydroxy 12-crown-4 in the same manner as in Example 99.

Table 3 summarizes the results. These compounds were analyzed in the same manner as in Example 99, and it was confirmed that they were the desired compounds. For reference, the infrared absorption spectrum and 1H-nuclear magnetic resonance spectrum of Example 116 are shown in FIG. 11 and FIG. 12, respectively.

Examples with blank spaces below
0 mmol of ethylene dibromide and 600 mmol of ethylene dibromide were added, and the mixture was heated under reflux in acetone for 96 hours. After the reaction, the reaction solution was neutralized with hydrochloric acid, and the resulting salt was separated, and acetone and excess ethylene dibromide were distilled off using a rotary evaporator. The product was recrystallized from inpropyl alcohol to obtain compound 4.5F (yield: 40%) represented by the following structural formula.

5 mmol of the compound, 45 mmol of hydroxymethyl-12-crown, and 5 mmol of potassium hydroxide were charged into an eggplant-shaped flask with a capacity of 100 gd and equipped with a condenser, and heated under reflux for 96 hours. After the reaction, the resulting salt was neutralized with hydrochloric acid, divided into portions, and the solvent was concentrated using a rotary evaporator.
Separation and purification was carried out using ethyl acetate as a solvent using nine columns packed with 00). The result is compound 01 shown by the following structural formula.
89t (yield 36%) was obtained.

The following analysis was performed on the obtained compound.

(1) Infrared absorption spectrum (results are shown in Figure 13) Cyclic ether k 1020-1160 cM-' (2)
'H-nuclear magnetic resonance spectrum (results are shown in Figure 14) b) 3.5-4.2 ppm (3) Mass spectrometry spectrum m/e = 496,498,500,502°504
(M+) These are isotopes based on C155 and ct57.

(4) Elemental analysis The above results confirmed that the product was the desired product.

Examples 141 to 251 In the same manner as in Example 140, cyclic polyether compounds represented by the general formula (1) were synthesized. The results are summarized in Table 4. Reference 1 shows the infrared absorption spectrum and 1H-nuclear magnetic resonance spectrum of Example 172, respectively.
5 and 16.

Remainder: 3; Table 4" Example 252 Eggplant-shaped flask LC with internal volume of 200 mg equipped with a cooling tube
, 50 mmol of 2,4.5-toIJ chlorophenol,
30 mmol of potassium hydroxide, 30 mmol of ethyl chloroacetate, and 100 mmol of acetone were charged and heated under reflux for 96 hours.

After the reaction, the mixture was neutralized with hydrochloric acid, the resulting salt was divided into portions, and the solvent was distilled off using a rotary evaporator.

The product was heated in a mixed solution of 100ml of acetone, 20ml of water and 10ml of hydrochloric acid at 50°C for 10 hours to hydrolyze the ester. After the reaction, the solvent was distilled off and recrystallization was performed from toluene to obtain compound 8.3F (yield 92%) represented by the following general formula.

t 5 mmol of this compound, hydroxy 12-crown-4
5 mmol of p-toluenesulfonic acid and 2.5 mmol of p-toluenesulfonic acid were placed in a 100-volume eggplant-shaped flask equipped with a condenser and a moisture meter, and heated under reflux in toluene to remove the produced water. After the reaction, it was cooled, neutralized by adding 50% of water, the organic layer was separated and toluene was removed using a rotary evaporator, and the product was separated and purified using ethyl acetate as a solvent in a column packed with silica gel (Wako Gel C200). , a compound t11t (yield 50%) represented by the following structural formula was obtained.

The following analysis was performed on the obtained compound.

(1) Infrared absorption spectrum (results are shown in Figure 17) Aromatic ring 3100 cm-' Cyclic ether 1020-1160 cm-' Ester 1750 cm-' (2) +H- nuclear magnetic resonance spectrum (results shown in Figure 18)
Shown as a diagram. ) (ω 6.8-7.4 ppm (b) 3.4-4.3 ppm (c) 4.
7-4.8 ppm (3) Mass spectrometry spectrum m/e = 442.444,446.448
It is an isotope according to t, ct.

(4) Elemental analysis From the above results, it was confirmed that the product was the desired product.

Examples 253 to 340 In the same manner as in Example 252, the compounds represented by the general formula (1) were synthesized by performing an esterification reaction. 5th result
It is summarized in the table. For these synthesized compounds,
The same analysis as in Example 252 confirmed that it was the desired product. For reference, the infrared absorption spectrum and IH-nuclear magnetic resonance spectrum of Example 269 are shown in FIGS. 19 and 20, respectively.

Table 1 Example 341 In a eggplant-shaped flask with an internal volume of 200 mm and equipped with a condenser, 450 mmol of hydroxymethyl-12-crown, 50 mmol of glycine, and 7 mmol of p-1 sulfonic acid were added.
7 mol of MI was charged and heated under reflux in toluene for 12 hours. After the reaction, the reaction mixture was cooled, 100% of water was added, neutralized with sodium hydroxide, the organic phase was separated, and toluene was distilled off. To the product, 1005 g of chloroform and 50 g of water were added, and while stirring, sodium hydroxide was added until H became weakly basic. The organic phase was separated and the 0roform was distilled off to obtain compound 8.4? shown by the following structural formula. (yield 65%)
I got it.

4 mmol of this compound and 4 mmol of triethylamine were placed in an eggplant-shaped flask with an internal volume of 10 f), and 480 mol of azobenzene to p-carganyl cucolide were added.
The mixture was stirred in MF for 2 hours at room temperature. After the reaction, the resulting salt was separated and dimethylformamide was distilled off using a rotary evaporator. The product was separated and purified using a column filled with silica gel (Wako Gel C-200) using ethyl acetate as a solvent, and 0.5 t of a compound represented by the following structural formula was obtained.
(yield 27%). The following analysis was performed on the compound concerned.

(1) Infrared absorption spectrum (results are shown in Figure 21) Aromatic ring 3100 cm-' Cyclic ether 1040-116o Sen-1 amide bond 1720 cm-' (2) 'H-Nuclear magnetic resonance spectrum (results) The 22nd
Shown as a diagram. ) a) 7.2~B-'5 ppm b) 3. ! 1 to 4.6 ppm (3) Mass spectrometry spectrum m/e = 471 (M+) (4) Elemental analysis Examples 642 to 408 Hydroxy-12-crown-4 and β-alanine were analyzed in the same manner as in Example 341. , and 6-aminobutyric acid. A compound represented by the general formula (1) was synthesized in the same manner as in Example 341 by reacting these compounds with various acid chlorides. The results are shown in Table 6. The synthesized compound was analyzed in the same manner as in Example 341, and it was confirmed that it was the desired compound.

Table 6: Application Examples of the Compounds of the Invention An example of application of the compound of the present invention to an IJ selective electrode is shown.

Compound 20 of the present invention obtained in Examples 1 to 408, polyvinyl chloride (average degree of polymerization 1100) 200"P, o-
400q of nitrophenyl octyl ether was dissolved in 10-tetrahydrofuran. After this solution was cast onto a smooth glass plate, the tetrahydrofuran was evaporated to obtain a film about 100 μm thick. This membrane was mounted as shown in FIG. 24, and the electrode performance was evaluated using the apparatus shown in FIG. All measurements were performed at 25°C. Determination of the selection ratio of sodium IJium ion to potassium ion is as follows:
It was determined by the mixed solution method described in "Ion Selective Electrode" (Imori Publishing, Chapter 2, Section 3). Specifically, in an aqueous solution containing sodium chloride and potassium chloride, sodium chloride is kept at a constant concentration (1X f O-'mol),
The electromotive force was measured by varying the concentration of potassium chloride. Next, the relationship between the electromotive force and the concentration of potassium chloride was plotted, and the selection ratio was determined by dividing the concentration of potassium chloride at the inflection point by the concentration of sodium chloride.

The higher this value, the better the material is as a sodium-selective substance. In addition, only sodium chloride was added to 10-1 to 10-
The electromotive force of the aqueous solution contained in the concentration range of 'mot/l was measured, and the electromotive force and the amount of change in the electromotive force when the sodium chloride concentration changed by ten times were determined in units of mV/decade. The results are shown in Table 7.

As comparative examples, compounds (A) and (B) represented by the following structural formulas, which are conventional sodium-selective substances, were tested in the same manner, and the results are shown in Table 7.

l~lJ20

[Brief explanation of drawings]

1, 5, 5, 7, and 9. 11, 15, 15, and 17. FIG. 19 and FIG. 21 show infrared absorption spectra of the cyclic polyether compound of the present invention. Also, FIGS. 2, 4, 6, and 8. 10, 12, 14, and 16. FIG. 18, FIG. 20, and FIG. 22 show 1H-nuclear magnetic resonance spectra of the cyclic polyether compound of the present invention. Figure 23 is an explanatory diagram of the device for measuring electromotive force;
The figure is an explanatory diagram showing various constituent elements built into the electrode 1 of FIG. 23. FIG. 25 is a schematic diagram of a platinum wire coated with a film containing the cyclic polyether compound of the present invention. In FIG. 23, FIG. 24, and FIG. 25, each number indicates the following content. 1... Electrode, 2... Measurement solution, 3... Magnetic rotor. 4...Magnetic stirrer, 5...1M lithium acetate salt bridge. 6... Potassium chloride saturated aqueous solution, 7... Saturated electrode, 8... - Electrometer (Hokuto HE-10
3W), 11... Acrylic film holder, 12...
Silver wire, 13... Coated glass tube, 14... Silver-silver chloride internal standard electrode, 15... 10-5M sodium chloride internal standard solution, 16... Membrane-like material containing a cyclic polyether compound, 17...-0-IJ song 21...Platinum wire, 2
2...]] A film-like material containing a W-7t polyether compound,
23...Teflon tape.

Claims (2)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X is a halogen atom or a halogenoalkyl group, R is a hydrogen atom or an alkyl group, , m is an integer from 0 to 20, and n is an integer from 1 to 5.), and B is -(CH_2)-_lCH_2-O-CH
＿２−, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -O-(
CH_2)-_l_+_1CH_2-O-CH_2-,
▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, l is an integer from 0 to 7.) Indicates the group shown. ] A cyclic polyether compound represented by: (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, for A, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X is a halogen atom or a halogenoalkyl group, R is a hydrogen atom or an alkyl group, , m is an integer from 0 to 20, and n is an integer from 1 to 5.), and B is -(CH_2)-_lCH_2-O-CH
＿２−, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -O-(
CH_2)-_l_+_1CH_2-O-CH_2-,
Indicates a group represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, l is an integer from 0 to 7.) A sodium absorbent consisting of a cyclic polyether compound represented by ].