JPH04224568A - Cyclic polyether diamide compound and calcium ion-selective composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyclic polyether diamide compound having selective coordination ability for calcium ions and a composition thereof.

0002

[Prior Art] Conventionally, a calcium ion-selective electrode using an organic phosphorus compound as a ligand has been mainly used to quantify calcium ion concentration (USPAT
3932233). However, since these ion-selective electrodes are susceptible to interference with hydrogen ions, they cannot be used in measuring liquids where the hydrogen ion concentration can vary from measurement to measurement.

In contrast, research on calcium ion-selective electrodes using macrocyclic polyetheramide as a ligand has led to
It has been carried out by Riva et al. (COLLECTIO
NCZECHOSLOVAK CHEMICAL
COMMUNICATION, Vol45, (1980
), 1567) Although these series of compounds are not affected by hydrogen ions, their selectivity toward other alkali metals and alkaline earth metals is not necessarily satisfactory, and their lifetimes are generally extremely short. It had the following drawback.

[0004] Shono et al. synthesized the following bis-macrocyclic polyether amide based on the research of Rieber et al. (Japanese Patent Laid-Open No. 61-50972). Although this ligand has improved selectivity, it cannot be said to be industrially suitable because it uses preparative liquid chromatography for synthesis, is expensive, and cannot be synthesized in large quantities.

[0005]

[Problem to be solved by the invention] As a result of our repeated research to overcome the inherent disadvantages of these compounds, we have found that
The present invention has been completed by successfully synthesizing a ligand that can be manufactured industrially and forming an electrode that has sufficient selectivity and provides stable measurement results over a long period of time.

[0006]

[Means for Solving the Problems] That is, the present invention provides the following general formula (I)

[C7]

(wherein R1, R2, R3 and R4
are the same or different groups selected from hydrogen atoms and methyl groups, or when R3 and R4 are hydrogen atoms, R1
and R2 may be interconnected to form a cyclohexane ring, and R5 is a hydrogen atom or has the general formula R7 OCH
2 CH2 - [wherein R7 is a group selected from a hydrogen atom, an alkyl group, and an alkylcarbonyl group having 3 to 20 carbon atoms], and R6 is a group represented by the following general formula (II). The group to be

[Chemical formula 8]

[In the formula, X1, X2, X4 and X5
are the same or different groups selected from a hydrogen atom, a halogen atom, a nitro group, and a trifluoromethyl group; A group selected from alkoxy groups] Each of the following groups,

[Chemical formula 9]

[0009]

[Chemical formula 10]

and a group represented by the following general formula,

[Chemical formula 11]

It is a cyclic polyether diamide compound represented by a group selected from the following formula: [wherein n is an integer from 1 to 20].

The present invention also provides (a) a thermoplastic resin 10
0 parts by weight, (b) 0.1 to 40 parts by weight of the cyclic polyether diamide compound represented by the general formula (I), (c) the organic boron compound represented by the following general formula (III), 0.01 to ether diamide
1.0 (molar ratio),

[Chemical formula 12]

(In the formula, Y1, Y2, Y3 and Y4
are the same or different hydrogen atoms, halogen atoms, alkyl groups or haloalkyl groups, h, i, j, k are 1 to 5
and M is an alkali metal or an alkaline earth metal.

When the cyclic polyether diamide compound represented by the general formula (I) is used in a calcium-selective electrode, the selectivity to calcium ions and water resistance depend on the type of each substituent in the general formula (I). somewhat influenced by. Among the compounds represented by the general formula (I), R1
, R2, R3 and R4 are not particularly limited as long as they are hydrogen atoms or methyl groups, but R1, R2
, R3 and R4 is more preferably a methyl group because the calcium ion selectivity is high.

R5 is a hydrogen atom or R7 OCH2 C
It is a group represented by H2-, and R7 is selected from a hydrogen atom, an alkyl group, and an alkylcarbonyl group. When R7 is an alkyl group, from the viewpoint of calcium ion selectivity, an alkyl group having 6 or more carbon atoms is R7.
If is an alkylcarbonyl group, the number of carbon atoms is 8 for the same reason.
The above alkylcarbonyls are preferably used. R6
teeth,

[Chemical formula 13]

[0016]

[Chemical formula 14]

[0017]

[Chemical formula 15]

[0018]

[Chemical formula 16]

A group selected from (the definitions of X1 to X5 and n are as described above). When R6 is a group of general formula (II) and X3 is an alkyl group or an alkoxy group,
From the viewpoint of calcium ion selectivity, those having 6 or more carbon atoms are preferred. Similarly, when the group is a group of general formula (II), at least one, preferably two, more preferably three or more of X1, X2, X3, X4 and X5 are other than hydrogen atoms. It is preferable that it is based on

The cyclic polyether diamide compound represented by the general formula (I) of the present invention is a new compound, and its identity is usually confirmed by the following measurements.

(1) Infrared absorption spectrum 1640cm-
A strong peak originating from the carbonyl of the amide bond is observed near 1, a strong peak originating from the ether bond near 1120 cm-1, and a strong peak originating from the ester bond near 1740 cm-1.

(2) Proton nuclear magnetic resonance spectrum a.
1.1-1.3 ppm of methyl group b. 3.0-3.9
methylene group of ethylene oxide and methine in ppm, c. A peak of the methylene group next to the carbonyl appears at 4.3 to 4.5 ppm, and the relative intensity ratio of these peaks agrees with the ratio of the number of hydrogens calculated from each compound of the general formula (I).

(3) Elemental Analysis The amounts of carbon, hydrogen, nitrogen, and halogen calculated from each compound of the general formula (I) almost match the amounts of each element as determined by the analysis.

(4) Mass spectrometry spectrum As one method of mass spectrometry, the molecular ion peak (
M+) is observed. (However, M+ may not be observed for molecules with molecular weights around 1000 or over 1000.)

Typical properties of the cyclic polyether diamide compound of the present invention are as follows.

[0026] In general, distillation is not possible and it is difficult to obtain a clear boiling point.

■ It is generally a highly viscous liquid, but if the substituent R6 in the general formula (I) is a group containing three or more aromatic rings, it is a white or yellowish-white solid or a yellowish brown to reddish brown solid. May be solid. Moreover, when an azo compound is contained, an orange liquid or solid is obtained.

The solubility of the cyclic polyether diamide compound depends somewhat on the substituents R5 and R6 in the general formula (I), but it can be dissolved in methylene chloride, chloroform, benzene, toluene, acetone, tetrahydrofuran, dioxane, dimethylformamide, Most of them dissolve in methanol, ethanol, etc. at room temperature, but they hardly dissolve in water.

The method for producing the cyclic polyether diamide compound represented by the general formula (I) is not particularly limited, but industrially suitable synthesis methods are shown below (i) to (iv).
Shown below.

(i) Synthesis of dichloride compound represented by the following general formula (IV)

[Chemical formula 17]

(The definitions of R1 to R4 are as described above.) The method of synthesizing the dichloride compound is not particularly limited, and Helvetica chimica acta (Helvetica chimica acta)
a Chimica Acta). Volume 58, No. 6 (1
975) on page 1535 or the collection
Czechoslovak Chemical Communication (C
Collection Czecholsovak
Chemical Communication)4
8, (1983), p. 1944, etc., can be suitably employed.

(ii) The following structural formulas (V-1) to (V-3
) Synthesis of diamino compound represented by H2NCH2CH2OCH2CH2OCH2CH2
NHCH2CH2OH
(V-1) HOCH2CH2
NHCH2CH2OCH2CH2OCH2CH2NHC
H2CH2OH
(V-2) R7OCH2CH2NHCH2CH2O
CH2CH2OCH2CH2NHCH2CH2OH
(V-3) The diamino compound can be obtained by reacting known 1,2-bis(aminoethoxy)ethane and 2-chloroethanol. At this time, if the equimolar amount of 2-chloroethanol is added to the diamine, a large excess of 2-chloroethanol can be added to the primary raw material (V-1) of the cyclic polyether diamide compound in which R5 is a hydrogen atom. ba, R5
A primary raw material (V-2) in which is other than a hydrogen atom is given, respectively. In addition, when R7 is an alkyl group, the above primary raw material (V-3) can be prepared by adding the corresponding alkyl halide in an equal amount to 2-chloroethanol.
can be synthesized.

In this reaction, it is generally possible to proceed without using a solvent. The reaction temperature of this reaction is generally 100°C or higher and 200°C or lower, preferably between 120°C and 150°C. The reaction time of this reaction is not particularly limited, but is generally 10 hours to 1 hour.
A period of 50 hours is sufficient. The above structural formula (V-2
) and the compound of general formula (V-3) can also be obtained by a similar reaction using 1,2-bis(chloroethoxy)ethane and aminoethanol, which is also an industrially suitable synthesis method.

(iii) The dichloride compound represented by the above general formula (IV) and the above (V-1) to (V-2)
By reacting the diamino compound represented by the following general formula (
Secondary raw materials represented by VI), (VII), and (VIII) are obtained.

[0035]

[Chemical formula 18]

[0036]

[Chemical formula 19]

[0037] In this reaction, the reaction can proceed smoothly by adding an acid acceptor. The acid acceptor used in the reaction is not particularly limited as long as it is a tertiary amine, but examples include aromatics such as pyridine and N,N-dimethylaniline, and trialkylamines such as trimethylamine and triethylamine. . The solvent used in this reaction may be used without any restriction as long as it does not react with the raw materials represented by the above general formulas (IV) and (V-3) or the above structural formulas (V-1) and (V-2). I can do it. Examples include aromatic hydrocarbons such as benzene and toluene, chlorinated aliphatic hydrocarbons such as methylene chloride and chloroform, ethers such as tetrahydrofuran and dioxane, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. By adding the above-mentioned raw materials and acid acceptor little by little into a reactor using a large amount of these solvents, the target compound can be efficiently synthesized. The reaction temperature of this reaction is not particularly limited, but since at high temperatures side reactions between molecules and side reactions with hydroxyl groups occur, it is preferably carried out at 30°C or lower, preferably 10°C or lower. The reaction time of this reaction is not particularly limited, but generally, 1 hour to 100 hours is sufficient.

(iv) The above general formulas (VI) and (VII)
, by reacting the secondary raw material represented by (VIII) with an acid halide compound represented by the following formula, preferably an acid chloride compound, and further with an alkyl carboxylic acid halide having 3 to 20 carbon atoms as necessary. General formula of the present invention (
A cyclic polyether diamide compound represented by I) can be obtained.

[0039]

[C20]

[0040]

[C21]

(The definitions of X1 to X5 and n are as described above,
(Y is a halogen atom) The solvent used in this reaction is the acid chloride and the secondary raw materials (VI), (VII) and (VI
If it is inactive against II), it can be used without any particular problem. Examples include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, chlorinated aliphatic hydrocarbons such as methylene chloride and chloroform, ethers such as tetrahydrofuran and dioxane, acetone, methyl ethyl ketone, and methyl Ketones such as isobutyl ketone. In this reaction, reaction (iii)
By adding acid acceptors similar to those listed in
The reaction can proceed smoothly. Although the reaction temperature of this reaction is not particularly limited, it is generally sufficient to carry out the reaction between 0°C and 100°C. The reaction time of this reaction is not particularly limited, but is generally 1 hour to 1 hour.
Preferably, this is carried out between 00 and 00 hours.

Since the obtained cyclic polyether diamide compound generally has a high boiling point, it is often difficult to distill it. Therefore, it is usually preferable to purify by extraction, recrystallization, column chromatography, or other means. In particular, the general formulas (VI), (VII) and (VI
Column chromatography is most preferably used for efficient separation from the secondary raw material compound represented by II). When employing this method, the optimum conditions for the column packing material and developing solvent can be determined in advance by techniques such as thin layer chromatography.

The cyclic polyether diamide compound represented by the general formula (I) of the present invention has a high selective coordination ability for calcium ions, so it can be used as a selective absorbent for calcium ions or as a calcium selective electrode. It can be used as a component of The mode of use as an absorbent differs depending on the state of presence of calcium ions, but typical examples are as follows. That is, when selectively extracting and removing calcium salts coexisting with magnesium salts in an aqueous solution, a cyclic polyether diamide compound is dissolved in an organic solvent that is immiscible with water, and the organic solvent is brought into contact with a water bath to remove calcium ions. is extracted into an organic solvent selectively from the aqueous phase.

One of the necessary components of the calcium ion selective composition containing the cyclic polyether diamide compound of the present invention is a thermoplastic resin. As the thermoplastic resin used in the present invention, any known thermoplastic resin can be used without any restriction. When the cyclic polyether composition of the present invention is formed into a membrane and used for a calcium electrode, it is usually used in an aqueous solution, so it is desirable that the thermoplastic resin is insoluble in water. Furthermore, a wide range of molecular weights can be used. Generally, in the present invention, the ease of molding the obtained composition onto a membrane and the mechanical strength of the obtained membrane are determined from cotton to 1,000 to 1,000,000.
Thermoplastic resins having a molecular weight in the range of 0.00 are preferably used.

Specific examples of the thermoplastic compound include:
Examples include polyurethane, polysiloxane, polyvinyl chloride, polystyrene, and the like.

Another component constituting the calcium ion selective composition of the present invention is an organic boron compound represented by the general formula (III). In general formula (III), Y1,
As the halogen atoms represented by Y2, Y3, and Y4, fluorine, chlorine, bromine, and iodine atoms are used. Among these, compounds having fluorine atoms and chlorine atoms are preferably used in the present invention because they are easily available. Further, the haloalkyl groups represented by Y1, Y2, Y3 and Y4 are not limited to the number of carbon atoms, but those having one carbon number are generally easily available and are preferably used in the present invention. As the alkali or alkaline earth metal represented by M, potassium, rubidium, cesium, and calcium are preferable because they have low solubility in water.

The calcium ion selective composition of the present invention is a composition containing a cyclic polyether diamide compound represented by the general formula (I), a thermoplastic resin, and an organic boron compound represented by the general formula (III). It is. The blending ratio of the cyclic polyether diamide compound is not particularly limited as long as it exhibits the desired properties, but it is generally 0.1 to 40 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of the thermoplastic resin. It is preferable to use it in a range of 10 parts by weight. When the amount of the cyclic polyether diamide compound is less than the above range, the selectivity for calcium ions tends to decrease, which may not be preferable as a calcium electrode. Moreover, if it is larger than the above range, layer separation may occur between the compound and the thermoplastic resin, and the film may become non-uniform, which is generally not preferred.

[0048] It is also possible to construct a calcium electrode which can be used in practical use with a composition composed of the above-mentioned cyclic polyether diamide compound and thermoplastic resin.
Furthermore, by using the organic boron compound represented by the general formula (III) in a molar ratio of 0.01 to 1.0, preferably 0.02 to 0.8 with respect to the cyclic polyether diamide compound, The measurement sensitivity of the calcium electrode can be improved. If the amount of the organic boron compound exceeds the above range, the selectivity and sensitivity of calcium ions may be significantly reduced when the cyclic polyether diamide composition used in the present invention is used as a calcium electrode, which is not preferable.

Since the calcium ion selective composition of the present invention contains a thermoplastic resin, it can be molded into any shape, such as a membrane, granules, or fibers, depending on the intended use. When formed into a membrane, it can be used as a calcium electrode.
When formed into granules or fibers, it can be applied to ion exchange resins or chromatography materials.

[0050] Below, a case in which the cyclic polyether diamide composition of the present invention is molded into a film-like product will be explained.

[0051] When the film-like material obtained by molding the composition of the present invention is used as a component of a calcium electrode, the thickness of the film-like material is not particularly limited, but as long as it is selected within the range of 1 to 2000 μm. It is enough. In addition, it is better for the above-mentioned film-like material to have flexibility, and generally the tensile modulus (2
5℃) is preferably 5000 kg/cm2 or less,
In particular, those having a weight of 5 to 2000 kg/cm2 are preferably used. Therefore, when polyurethanes and polysiloxanes, which generally give flexible film-like materials, are used as thermoplastic resins, these resins can be used as they are, but thermoplastic resins that give film-like materials that are relatively inflexible When using materials such as polyvinyl chloride and polystyrene, it is preferable to use a plasticizer. The plasticizer is not particularly limited and any known plasticizer can be used, but generally the following may be used. For example, dimethyl phthalate,
Examples include phthalic acid esters such as diethyl phthalate, dibutyl phthalate, and dioctyl phthalate; fatty acid esters such as dioctyl adipate and dioctyl sebacate; and orthonitrophenyl alkyl ethers such as orthonitrophenyl octyl ether. The amount of these plasticizers to be added may be appropriately selected depending on the purpose of use of the film-like material, but it is generally preferable to select the amount of plasticizer in the range of 30 to 300 parts by weight per 100 parts by weight of the thermoplastic resin. be.

[0052] The method for producing the above film-like material is not particularly limited. Typical manufacturing methods that are generally suitably employed are as follows.

(a) A cyclic polyether diamide compound is dissolved in an organic solvent together with a thermoplastic resin or with the addition of a plasticizer, and the solution is applied or poured onto the board surface, and then the organic solvent is removed. A method of evaporating to form a film. As the organic solvent, any known organic solvent can be used without any restriction as long as it dissolves the thermoplastic resin and the cyclic polyether diamide compound. Furthermore, when adding an organic boron compound represented by the general formula (III), even if the organic boron compound alone is poorly soluble in an organic solvent, if a cyclic polyether diamide compound is present, the molar ratio to the compound is 1. If it is less than .0, it will often become solubilized, so it is desirable to select a solvent after carrying out a dissolution test in advance.

(b) There is a method in which a mixture of a cyclic polyether diamide compound, a thermoplastic resin, a plasticizer, and, if necessary, an organic boron compound is heated and formed into a film. The heat forming method is not particularly limited, and any known method can be employed. For example, a method may be employed in which the above-mentioned mixture is melt-extruded at a temperature higher than the softening temperature or melting temperature of the thermoplastic resin and formed into a film-like material, or a method in which the mixture is formed into a film-like material by hot pressing.

The film-like material obtained by the method described above is particularly suitable for use as a calcium electrode.

[0056] There are no particular limitations on the mode of constructing the calcium-selective electrode using the cyclic polyether diamide compound of the present invention. Rose in Analytical Chemistry (Plenum Press 1978) [Ion Selective
e Electrodes in Analyts
ical Chemistry, (Phenum
Press)] Chapters 3 and 4, Analytical Chemistry
ry] Vol. 47, p. 2238 (1975) and the like can be used. A specific example is as follows. A cyclic polyether diamide compound is dissolved in a water-insoluble organic solvent such as nitrobenzene, bromobenzene, diphenyl ether, etc., and a glass capillary is used.
A method of retaining it in a porous ceramic membrane or a porous polymer 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. A calcium-selective electrode can be constructed by attaching an object to the electrode or by forming a thin film directly on a silver wire, platinum wire, or gate portion of a silicon semiconductor. FIGS. 1 and 2 show schematic diagrams of an apparatus and an electrode in which a membrane-like material containing a cyclic polyether diamide compound is used as a calcium-selective electrode.

[0057]

[Examples] The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 0.88 mol of ethyl diazoacetate and 0.4 mol of 2,3-butanediol were dissolved in 1 liter of methylene chloride, and 6 ml of boron trifluoride ethyl ether was dissolved in 50 ml of methylene chloride. things at 0℃
It dripped quietly. After completion of the dropwise addition, the mixture was stirred for 1 hour, further reacted at 45°C for 1 hour, and the solvent was distilled off.
Distilled with Hg. 4,5-dimethyl 3,6 at boiling point 90℃
-Dioxaoctanedicarboxylic acid diethyl ester was obtained in a yield of 71%. This compound and 200 ml of hydrochloric acid were dissolved in 1 liter of water and heated under reflux for 8 hours. The reaction solution was distilled off and recrystallized from a benzene acetone mixed solvent to obtain 4,5-dimethyl 3,6-dioxaoctanedicarboxylic acid in a yield of 61%. 0.1 mol of the carboxylic acid,
12 ml of dehydrated N,N-dimethylformamide, 0.4 mol of thionyl chloride and 150 ml of dehydrated benzene
1 was placed in a 500 ml Erlenmeyer flask and stirred at room temperature for 8 hours. The mixture was further heated at 80°C for 1 hour to distill off benzene and N,N-dimethylformamide, and then distilled at 0.1 mmHg. was obtained in a yield of 30%.

In a 500 ml eggplant-shaped flask equipped with a cooling tube, 0.2 mol of 1,2-bis(chloroethoxy)ethane and 3.3 mol of monoethanolamine were heated and stirred at 130° C. for 24 hours. After cooling, 16.3 grams of sodium hydroxide was added and stirred at 100° C. for 30 minutes. After cooling, add 50 ml of tetrahydrofuran and filter the precipitated salt, 0.5 mmHg, 50°C.
Excess monoethanolamine was removed. Further, cooled tetrahydrofuran was added to recrystallize to obtain a diamine compound having the following structure in a yield of 92%.

HOCH2CH2NHCH2CH2OCH
2CH2OCH2CH2NHCH2CH2OH 2.5 g of 4,5-dimethyl 3,6-dioxaoctanedicarboxylic acid chloride was dissolved in 100 ml of dehydrated benzene and charged into a dropping funnel. After 2.4 g of the above diamino compound and 3 g of triethylamine were dissolved in 20 ml of dehydrated chloroform, 80 ml of dehydrated benzene was added and charged into the other dropping funnel. 1.5 liters of dehydrated benzene was added to a 3-liter three-necked flask, and the above two solutions were added dropwise evenly over 4 hours at 10°C. After dropping, react at room temperature for 4 hours, filter the reaction solution to remove triethylamine hydrochloride, concentrate the filtrate, and use a silica gel column (Wakogel C-200).
Column separation was performed using a mixed solution of chloroform:methanol=95:5, and a secondary raw material compound having the following structure was obtained in a yield of 63%.

[0061]

[C22]

30 ml of dehydrated methylene chloride, 5 mmol of the above secondary raw material compound, 5 mmol of 3,5-dinitrobenzoyl chloride, and 5 mmol of triethylamine were added to a 100 ml Erlenmeyer flask equipped with a cooling tube, and the mixture was heated for 6 hours. The mixture was heated to reflux. After the reaction,
Neutralize by adding 10ml of water, separate the organic layer,
Concentration and separation using an alumina column with a 70, 20 and 4 mixture of ethyl acetate, acetone and water gave 0.9 grams of product (30% yield).

The following analysis was performed on the obtained product. Infrared absorption spectrum (cm-1) Amide 1640 ester
1740 ether
1120 nitro group 1530 proton nuclear magnetic resonance spectrum (ppm) measurement solvent: deuterated chloroform standard material: tetramethylsilane (in the following examples,
Measurement solvent and standard substance are the same as in this example) Aromatic ring 9.2; s Methylene and methine 3.4 to 3.9; m Carbonyl side
4.3; bs methyl
1.1 to 1.3; ddAlso, the ratio of hydrogen amounts obtained by integration matched that of the target product. elemental analysis
C H
N Actual value (%)
49.85 5.93
9.44 Calculated value as C25H36O13N4 50.00 6.00 9.33 Mass spectrometry spectrum (FD) m/e 600 (M+) From the above measurement results, it was confirmed that the product was the target product with the following structure. did.

[0064]

[C23]

Examples 2 to 23 A compound represented by the general formula (VII) was synthesized in the same manner as in Example 1, and then the compound and the group represented by the substituent R6 in the general formula (I) were combined. Reacting with a compound to which a chlor atom is bonded, that is, the above-mentioned acid chloride compound,
The structural compounds shown in Table 1 were synthesized. The obtained compounds and their yields are shown in Table 1. The compounds synthesized in Examples 2 to 23 were confirmed to be target compounds in the same manner as in Example 1. Identification data are shown in Table 2.

Example 24 0.2 mol of 1,12-diamino-3,6,9 trioxaundecane (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.2 mol of 2-chloroethanol were added to a 200 ml eggplant equipped with a cooling tube. The mixture was placed in a molded flask and refluxed for 48 hours. After cooling, add 16.3 grams of sodium hydroxide to 100
The mixture was stirred at ℃ for 30 minutes. After cooling, 50 ml of tetrahydrofuran was added and the precipitated salt was filtered to a size of 0.1 mm.
The diamino compound with the following structure was distilled with Hg in a yield of 35.
Obtained in %.

H2NCH2CH2OCH2CH2OCH
2CH2NHCH2CH2OH 2.5 g of 4,5-dimethyl 3,6-dioxaoctanedicarboxylic acid chloride obtained in the same manner as in Example 1 was dissolved in 100 ml of dehydrated benzene and charged into a dropping funnel. The above diamino compound 2
．． After dissolving 4 grams and 3 grams of triethylamine in 20 ml of dehydrated chloroform, 80 ml of dehydrated benzene was added and charged into the other dropping funnel. 1. Dehydrated benzene in a 3-liter three-necked flask.
5 liters were added thereto, and the above two solutions were evenly added dropwise over 4 hours at 10°C. After the dropwise addition, the reaction was carried out at room temperature for 4 hours, the reaction solution was filtered to remove triethylamine hydrochloride, and the filtrate was concentrated and treated with a mixed solution of chloroform:methanol = 95:5 using a silica gel column (Wakogel C-200). Column separation was performed to obtain a secondary raw material having the following structural formula in a yield of 68%.

[0068]

[C24]

40 ml of dehydrated methylene chloride was placed in a 100 ml Erlenmeyer flask equipped with a cooling tube.
5 mmol of the above secondary raw material compound, 5 mmol of 3,5-dinitrobenzoyl chloride, and 5 mmol of triethylamine were added, and the mixture was heated under reflux for 6 hours. After the reaction, 10 ml of water was added to neutralize, the organic layer was separated and concentrated, and 70 ml of ethyl acetate, acetone and water were separated using an alumina column.
, 20 and 4 to give the product 1.8
gram (yield 65%).

The following analysis was performed on the obtained product. Infrared absorption spectrum (cm-1) Amide 1640 ester
1740 ether
1120 Nitro group 1540 Proton nuclear magnetic resonance spectrum (ppm) Aromatic ring
9.2;s methylene and methine
3.4-3.9; m carbonyl horizontal 4.
3; bs methyl 1.1~
1.3; dd amide 5.
8 to 6.0; t Also, the ratio of hydrogen amounts obtained by integration matched that of the target product. elemental analysis
C H
N Actual value (%)
49.88 5.
81 10.04 Calculated value as C23H32O12N4 49.64 5.76 10.
07 Mass spectrometry spectrum (FD) m/e 556 (M
+) From the above measurement results, it was confirmed that the product was the desired product having the following structure.

[0071]

[C25]

Examples 25 to 34 A compound represented by the general formula (VI) was synthesized in the same manner as in Example 24, and then chloride was added to the compound and the group represented by R6 in the general formula (I). A compound having bonded atoms, that is, the above-mentioned acid chloride compound is reacted with
A compound with the structure shown in the table was synthesized. The obtained compounds and their yields are shown in Table 1.

The compounds synthesized in Examples 25 to 34 were confirmed to be the target compounds in the same manner as in Example 1. Identification data are shown in Table 2.

Example 35 37 g (0.2 mol) of triethylene glycol dichloride was placed in a 500 ml eggplant-shaped flask equipped with a cooling tube.
, 61 g (1 mol) of monoethanolamine and 75 g (1 mol) of methoxyethanolamine were added. An exotherm occurred immediately after the addition. This was heated at 130°C for 48 hours.

After cooling, add 16 g (0.4 m
ol) was added thereto, and the mixture was heated and stirred at 100°C for 1 hour. After removing excess raw materials such as ethanolamine, the mixture was fractionated. At 0.05 mmHg, methoxyethanolamine bound to both ends flows out at 130°C to 140°C.
At ~180°C, 13 g of a diamino compound having the following structure was obtained (yield 27%).

CH3OCH2CH2NHCH2CH2O
CH6CH2OCH2CH2NHCH2CH2OH 24 g of the compound and 3 g of triethylamine were dissolved in 20 ml of dehydrated chloroform, and then 80 ml of dehydrated benzene was added and charged into one dropping funnel.

4,5-dimethyl 3,6-dioxaoctanedicarboxylic acid chloride 2 obtained in the same manner as in Example 1
．． 5 g was dissolved in 100 ml of dehydrated benzene and charged into the other dropping funnel. Add 1.5 liters of dehydrated benzene to a 3-liter three-necked flask and heat the above 2 at 10°C.
The solution was added dropwise evenly over 4 hours. After the dropwise addition, the reaction was carried out at room temperature for 4 hours, the reaction solution was filtered to remove triethylamine hydrochloride, the filtrate was concentrated, and a silica gel column (Wako gel
C-200), chloroform:methanol=9
Column separation was performed using a 5:5 mixed solution to obtain a secondary raw material compound having the following structure in a yield of 65%.

[0078]

[C26]

40 ml of dehydrated methylene chloride was placed in a 100 ml Erlenmeyer flask equipped with a cooling tube.
5 mmol of the above secondary raw material compound, 5 mmol of 3,5-dinitrobenzoyl chloride, and 5 mmol of triethylamine were added, and the mixture was heated under reflux for 6 hours. After the reaction, the same operation as in Example 1 was performed to obtain 1.3 grams of product (yield: 42
%) was obtained.

The following analysis was performed on the obtained product. Infrared absorption spectrum (cm-1) Amide 1645 ester
1735 ether
1120 Nitro group 1530 Proton nuclear magnetic resonance spectrum (ppm) Aromatic ring
9.2;s methylene and methine
3.4-3.9; m carbonyl horizontal 4.
3; bs methyl 1.1~
1.3; dd Also, the ratio of hydrogen amounts obtained by integration matched that of the target product. elemental analysis
C H
N Actual value (%)
49.99 6.15
9.06 Calculated value as C25H36O13N4 50.81 6.19 9.12 Mass spectrometry spectrum (FD) m/e 614 (M+) From the above measurement results, it was confirmed that the product was the target product having the following structure. did.

[0081]

[C27]

Examples 36 to 42 A compound represented by the general formula (VIII) was synthesized in the same manner as in Example 35, and then the compound and the general formula (I) were synthesized.
The structural compounds shown in Table 1 were synthesized from acid chloride compounds containing the substituent R6 in the formula. The obtained compounds and their yields are shown in Table 1.

The compounds synthesized in Examples 36 to 42 were confirmed to be the target compounds in the same manner as in Example 35. Identification data are shown in Table 2.

Example 43 30 ml of dehydrated toluene, 5 mmol of the cyclic polyether diacid compound obtained in Example 1, 5 mmol of triethylamine, and n-octanoyl chloride were placed in a 100 ml Erlenmeyer flask equipped with a cooling tube. adding 5 mmol and 5 mmol of triethylamine;
The mixture was heated under reflux for 24 hours. After the reaction, 10 ml of water was added to neutralize, the organic layer was separated and concentrated, and ethyl acetate, acetone and water were mixed with 70, 20 and 4
1.8 grams of product (yield: 5
0%) was obtained.

The following analysis was performed on the obtained product. Infrared absorption spectrum (cm-1) Amide 1640 ester
1735 ether
1110 nitro group
1530 proton nuclear magnetic resonance spectrum (
ppm) aromatic ring
9.1; sO lateral methylene and methine 3.4-3.9
;m carbonyl horizontal 4.3;b
s Methyl and methylene 1.1-2.7; m Also,
The ratio of hydrogen amounts obtained by integration agreed with that of the target product. elemental analysis
C H
N Actual value (%)
54.40 6.85
7.86 Calculated value as C33H50O14N4 54.54 6.89 7.71 Mass spectrometry spectrum (FD) m/e 726 (M+) From the above measurement results, it was confirmed that the product was the target product with the following structure. It was done.

[0085]

[C28]

Examples 44 to 61 The structures shown in Table 1 were prepared by using the compounds obtained in Examples 2 to 23 in the same manner as in Example 43 and an alkylcarboxylic acid chloride compound having 3 to 20 carbon atoms. A compound with the following was synthesized. The obtained compounds and their reaction yields are shown in Table 1.

The synthesized compound was confirmed to be the target compound in the same manner as in Example 43. The same data are shown in Table 2.

[0088]

[Table 1]

[0089]

[Table 2]

[0090]

[Table 3]

[0091]

[Table 4]

[0092]

[Table 5]

[0093]

[Table 6]

[0094]

[Table 7]

[0095]

[Table 8]

[0096]

[Table 9]

[0097]

[Table 10]

[0098]

[Table 11]

0099

[Table 12]

[0100]

[Table 13]

[0101]

[Table 14]

[0102]

[Table 15]

[0103]

[Table 16]

[0104]

[Table 17]

[0105]

[Table 18]

[0106]

[Table 19]

[0107]

[Table 20]

Examples 62 to 68 Examples of application of the compounds of the present invention to calcium-selective electrodes are shown.

Examples 1, 13, 22, 27, 35, 43
and 5 milligrams of the cyclic polyether diamide compound of the present invention obtained from No. 56, 50 milligrams of polyvinyl chloride (average degree of polymerization 1100), and 80 milligrams of O-nitrophenyl octyl ether were dissolved in 2.5 milliliters of tetrahydrofuran. After this solution was cast on a smooth glass plate, the tetrahydrofuran was evaporated to obtain a film approximately 150 μm thick. This membrane was mounted as shown in FIG. 2, and the electrode performance was evaluated using the apparatus shown in FIG. All measurements were performed at 25°C. The selectivity of calcium ions with respect to interfering ions was determined by the mixed solution method described in "Ion Selective Electrode" (Kyoritsu Shuppan, Chapter 2, Section 3). Specifically, when the interfering ion is sodium ion, the concentration of calcium chloride is constant in an aqueous solution containing sodium chloride and calcium chloride,
(1×10 −5 M) and the electromotive force was measured by changing the concentration of sodium chloride. Next, the relationship between the electromotive force and the concentration of sodium chloride was plotted, and the value obtained by dividing the concentration of sodium chloride at the inflection point by the concentration of calcium chloride was taken as the selection ratio for sodium ions. The higher this value is, the better the electrode is as a calcium selective electrode. The selection ratio for magnesium ions was determined using the same method. In addition, only calcium chloride
The electromotive force of an aqueous solution containing a concentration range of -1 to 10-4 M was measured, and the amount of change in the electromotive force when the electromotive force and calcium chloride concentration changed tenfold was determined in units of mV/decade. The results are shown in Table 3. As a comparative example, Comparative Example 1 was a membrane prepared in accordance with the method described in Example 2 of US Pat. No. 3,932,233 for a compound represented by the following structural formula, which is a conventional calcium-selective substance.

[0110]

[C29]

[0111] Regarding the compound represented by the following structural formula, which is a conventional calcium-selective substance, COLLECTI
ON CZECHOSLOVAK CHEMICA
L COMMUNICATION, Vol. 45, (
Comparative Example 2 was a membrane prepared by the method described in 1980), 1567.

[0112]

[C30]

[0113]

[Table 21]

[0114]

[Effect of the invention] The cyclic polyether diamide of the present invention is
As mentioned above, the selectivity for calcium ions is extremely good, and a film-like product formed from a composition containing this is ideal as a film-like product constituting a calcium electrode. In particular, compositions containing organic boron compounds have excellent selectivity and sensitivity for calcium ions,
It also has excellent durability when used as a calcium electrode. In addition, the calcium ion-selective composition of the present invention has a selective transport ability or a selective absorption ability for calcium salts, and can be applied to removal and even concentration of calcium salts.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of an apparatus for measuring electromotive force.

2 is an explanatory diagram showing various constituent elements built into the electrode 1 of FIG. 1. FIG.

[Explanation of symbols]

1 Electrode 2 Measurement solution 3 Magnetic rotor 4 Magnetic stirrer 5 1M lithium acetate salt bridge 6 Saturated aqueous potassium chloride solution 7 Saturated electrode 8 Electrometer (Hokuto HE-103 type) 11
Acrylic membrane holder 12 Diagonal lines 13 Covered glass tube 14 Silver monochloride internal standard electrode 15 10-3M sodium chloride internal standard solution 16
Membrane-like material 17 containing a cyclic polyether diamide compound
O-ring.

Claims (1)

[Claims] Claim 1: The following general formula (I) [Formula 1] (wherein R1, R2, R3 and R4 are the same or different groups selected from a hydrogen atom and a methyl group, or R
When 3 and R4 are hydrogen atoms, R1 and R2 may be connected to each other to form a cyclohexane ring, and R5
is a hydrogen atom or the general formula R7 OCH2 CH2
-[In the formula, R7 is a hydrogen atom, an alkyl group, and a carbon number of 3]
A group selected from ~20 alkylcarbonyl groups]
R6 is a group represented by the following general formula (II), [In the formula, X1, X2, X4 and X5 are hydrogen atoms, halogen atoms, nitro groups and trifluoromethyl [X3 is a group selected from a hydrogen atom, a halogen atom, a nitro group, an alkyl group, a trifluoromethyl group, and an alkoxy group having 1 to 20 carbon atoms] Each of the following groups , [Chemical 3] [Chemical 4] and a group represented by the following general formula, [Chemical 5] (where n is an integer of 1 to 20)) Polyether diamide compound [Claim 2] (a) 100 parts by weight of thermoplastic resin, (b)
Cyclic polyether diamide compound 0 according to claim 1
．． 1 to 40 parts by weight, (c) 0.01 to 40 parts by weight of an organic boron compound represented by the following general formula (III) to the cyclic polyether diamide.
1.0 (molar ratio), [Formula 6] (wherein, Y1, Y2, Y3 and Y4 are the same or different hydrogen atoms, halogen atoms, alkyl groups or haloalkyl groups, and h, i, j, k are an integer from 1 to 5, and M is an alkali metal or an alkaline earth metal.