JPS61260078A - 14-crown-4 derivative, metallic ion extraction and colorimetric reagent and liquid film transporting agent - Google Patents

Abstract

NEW MATERIAL:A 14-crown-4 derivative expressed by formula I [R<1> is 1-20C alkyl; R<2> and R<3> are H or 1-4C alkyl; R<4> is formula II, III or IV (X is electron attractive group; is 1 or 2; m and n are <=3)]. EXAMPLE:6-Dodecyl-6-(2'-hydroxy-3', 5'-dinitrobenzyl)-1,4,8,11-tetraoxacyclotetra decane. USE:A metallic ion extraction and colorimetric reagent and metallic ion liquid film transporting agent, particularly suitable for lithium ions. PREPARATION:For example, a compound, expressed by the formula R<5>CH2Br [R<5> is a group obtained by converting OH in R<6> (R<4> is a group containing no electron attractive group in R<4>) into alkoxide], and prepared by converting the hydroxyl group in the aromatic ring into the alkoxide, is reacted with a compound expressed by the formula R<1>CH(CO2Et)2 to give a compound expressed by formula V, which is then reduced to afford a compound. A compound expressed by formula VI is then added thereto and the resultant addition product is reduced to give a compound expressed by formula VII. A group X is then introduced thereinto to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel 14-crown-4 derivative and a metal ion extraction colorimetric reagent containing the same as an active ingredient.

and metal ion liquid membrane transport agents.

[Conventional technology]

Traditionally, compounds with crown ether rings form complexes with alkali metal ions, alkaline earth metal ions, and other cations, so solvent extraction reagents, phase transfer catalysts, column packing materials, and cations are used as extractants for these ions. Applications in the fields of liquid membrane transport agents, ion-selective electrodes, etc. are being attempted.

Furthermore, recently, various non-dissociated and dissociated crown compounds having a chromophore have been synthesized as solvent extraction colorimetric reagents. When using a non-dissociated crown compound as a solvent extraction reagent, a counter anion such as picric acid that is easily extracted into the organic phase is required, and if the crown compound complex does not have an absorption band in the visible to ultraviolet region, The method also has the disadvantage that metal ions must be quantified by conventional methods such as flame photometry.

However, dissociated crown compounds having a chromophore have the advantage that metal ions can be easily quantified by measuring visible-ultraviolet absorption spectra only by adjusting the pH of the aqueous layer.

Taking advantage of these advantages, various dissociated crown compounds are known as solvent extraction colorimetric reagents that exhibit excellent extraction selectivity for sodium ions, potassium ions, etc. and have nine chromophores. For example, Anal.

Cheta, Acta, 139.219 (1982
), J, Am, CheIl, Sac.

92, 386 (1970) reported a dissociated crown compound having excellent selectivity for sodium and potassium ions and having a chromophore, and CheyI.

Lett, 1853 (1982), Chell,
In Lett, 1305 (1981).

As a lithium-selective extraction colorimetric reagent, N-(4-methylumbelliferoQ-8-methylene)-monoaza-15-
Crown 5, N-(2-hydroxy-5-nitrobenzyl)-aza-18-crown 6, and the like are described.

[Problem that the invention seeks to solve]

However, although the dissociated crown compounds that have a chromophore that has a known metal ion selective extraction property as mentioned above have selectivity for sodium and potassium ions, they often have low selectivity for lithium ions, and conventional Compounds containing a nitrogen atom in the crown ring that have been reported as lithium extraction colorimetric reagents have problems such as fading in the presence of water and insufficient selectivity for lithium.

[°Means to solve the problem]

The present invention is aimed at solving the above-mentioned problems, and includes a novel and useful 14-crown-4 derivative, a metal ion extraction colorimetric reagent having high selectivity for metal ions, especially lithium ions, and a metal ion liquid membrane transporter. The aim is to provide a drug.

The present invention includes the following three inventions.

(1) A 14-crown-4 derivative represented by the following general formula (1).

(In the formula, R1 represents an alkyl group having 1 to 20 carbon atoms.

R2 and R3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R4 represents an electron-withdrawing group, Q represents 1 or 2, m
, n represents an integer of 3 or less. ) (2) A metal ion extraction colorimetric reagent containing the 14-crown-4 derivative represented by the general formula I.

(3) A metal ion liquid membrane transport agent containing a 14-crown-4 derivative represented by the general formula (1).

The compound of the first invention is a 14-crown-4 derivative represented by the above general formula I, into which a phenol group or naphthol group having an electron-withdrawing group is introduced together with an alkyl group. In general formula I, the alkyl group represented by R1 includes a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group,
Among these alkyl groups, those having 8 to 16 carbon atoms have particularly high metal ion selectivity. This is preferable.

The alkyl group represented by R2 and R3 includes a methyl group,
Examples include ethyl group, propyl group, butyl group, etc. R
4 is a group having a hydroxyl group and an electron-withdrawing group in the aromatic ring, and forms a chromophore. Examples of the electron-withdrawing group represented by X include a nitro group, a cyano group, a trifluoromethyl group, an acetyl group, and a halogen group.

The compound of the present invention has R1. R2, R3,
There are many compounds with combinations of R4. Typical 14-crown-4 derivatives thereof include, for example, 6-octyl-6-(2'-hydroxy-3'-nitrobenzyl)-1,4,8,11-tetraoxacyclotetradecane, 6-tuniru 6-(2'-hydroxy-3'-cyanonaphthylmethyl)-1,4,8,11-tetraoxacyclotetradecane, 6-zosil-6-(2'-hydroxy-5'-nitrobenzyl)-13-methyl -1,
4,8,11-tetraoxacyclotetradecane, 6-
Unzosilu-6- (2',4'-dihydroxy-3'
-trifluoromethylbenzyl)-1,4,8,11-
Tet-laoxacyclotetradecane, 6-dozosilu6
-(2'-hydroxy-3'-nitrobenzyl)-1,
4,8,11-tetraoxacyclotetradecane, 6-
Dozosil-6-(2'-hydroxy-3',5'-dinitrobenzyl)-1,4,8,11-tetraoxacyclotetradecane, 6-dozosil-6-(2'-hydroxy-3'-cyanobenzyl) -1,4,8゜11-tetraoxacyclotetradecane, 6-dozosil-6-(
2'-Hydroxy-3'-acetylnaphthylmethyl)-
13-ethyl-1,4,8,11-tetraoxacyclotetradecane, 6-dozosil-6-(2'-hydroxy-3',4'-dichlorobenzyl)-1,4,8,11
-tetraoxacyclotetradecane, 6-dozosil-6
-(2'-hydroxy-3'-trifluoromethylbenzyl)-1,4,8,11-tetraoxacyclotetradecane, 6-titradecyl-6-(2'-hydroxy-
3'-cyanobenzyl) -13,13'-dimethyl-
1,4,8,11-tetraoxacyclotetradecane,
Examples include 6-hexadicyl-6-(2-hydroxy-3'-nitrobenzyl)-1,4,8°11-tetraoxacyclotetradecane.

There are various methods for producing the above-mentioned 14-crown-4 derivatives.1 For example, R'-CH2Br, in which the hydroxyl group in the aromatic ring is alkoxidized, is added to R'-CH2Br using a base catalyst and reduced. can get. Furthermore, the desired - compound can be synthesized by introducing an electron-withdrawing group X into the aromatic ring by a suitable treatment.

(In the above chemical formula, R1, R2, R3, and R4 are the same as above, R6 is a group that does not contain an electron-withdrawing group in R4, and R5 is a group obtained by converting hydroxylation of R6 to alkoxide.) (Et represents an ethyl group, and Ts represents a toluenesulfonic acid group.) To show a more specific production method, first, 2-alkyl malonic acid dialkyl ester and 2-methoxybenzyl bromide are mixed in an appropriate solvent, 2-Alkyl-2-(2'-
Synthesize methoxybenzyl) malonic acid dialkyl ester, and further synthesize the obtained 2-alkyl-2-(2'-methoxybenzyl) malonic acid dialkyl ester in a suitable non-polar solvent such as lithium aluminum hydride, lithium borohydride, etc. 2-alkyl-2-(2'
-Methoxybenzyl)-1,3-propanediol is synthesized.

When this diol and 3,7-thioxanonan-1,9-diol ditosylate are reacted with a base in an appropriate solvent, 6-alkyl-6-(2'-methoxybenzyl), -1,4,8 , 11-tetraoxacyclotetradecane is obtained. Further reduction of this crown compound yields a 14-crown-4 derivative having an alkyl group and a phenol group. Introduction of an electron-withdrawing group such as a nitro group involves nitration of the obtained 14-crown-4 derivative,
Although cyanation is carried out, depending on the group, 2-methoxybenzyl bromide into which an electron-withdrawing group has been introduced can also be used as a raw material. Other compounds are also produced according to the above method.

The compound of general formula (■) is fat-soluble and has the ability to selectively form a complex with metal ions, especially lithium ions, and can be used as an extractant for metal ions, such as solvent extraction reagents, phase transfer catalysts, column packing materials, and ion-selective electrodes. It can be used as a metal ion extraction colorimetric reagent and a metal ion liquid membrane transport agent.

The second invention of the present invention is 14-crown-4 of the general formula (1).
This is a metal ion extraction colorimetric reagent containing a derivative as an active ingredient. When extracting alkali metal ions, alkaline earth metals, etc. using the compound of the general formula I as a colorimetric reagent for metal ion extraction, the derivative is dissolved in an organic solvent, and then the derivative is dissolved in a water-organic solvent system or an organic solvent. -By simply adding it to an organic solvent system, the compound of general formula (■) and metal ions easily form a complex, and the metal ions in water or organic solvent can be extracted, and the visible-ultraviolet absorption spectrum of this complex is measured. if.

It is possible to detect and quantify metal ions. Particularly in such extraction, since the compound of general formula I has high selectivity for lithium ions, the selectivity of lithium in mixed metal ions is 100 times that of a compound that has normal selective extraction properties for lithium ions. It will be about.

Solvents used for extraction include benzene, toluene, dioxane, diethyl ether, tetrahydrofuran, petroleum ether, ethanol, n-hexane, n-hebutane, carbon tetrachloride, chloroform, dichloromethane, trichlene, etc. singly or in combination. It can be used in a mixture of more than one species.

The amount of the compound of general formula I used is 1×10 m
It is preferable to use it within the range of ol/Q to I x 10-'mol/Q.

The compound of general formula I is a dissociable crown ether, and when performing solvent extraction, the acid dissociation constant pKa of the phenol hydroxyl group is small, and extraction can be performed without the need for a counter anion, and depending on the type, water or Although it is not necessary to adjust the pH of the organic solvent, it is also possible to use a pH adjuster for the purpose of increasing coloration due to metal ion complex formation and sensitivity of visible-ultraviolet absorption spectroscopy. In this case, as the pH adjuster, acids and bases such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, triethylamine, hydrochloric acid, and 3-(N-morpholino)propanesulfonic acid can be used.

The third aspect of the present invention is a metal ion liquid membrane transport agent containing the compound of the general formula I as an active ingredient.

This liquid film transport agent forms a liquid film with the compound of general formula 1, and selectively transports metal ions through this liquid film. In order to form a liquid film using the compound of the general formula I, the compound of the general formula I is used as a porous polymer.

In particular, it can be formed by impregnating a porous polymer disk, film, membrane, etc., and the formed liquid film can be used as an alkali metal ion active transport membrane. The compound of general formula (1) has particularly high selectivity for lithium ions, and is therefore effective for active transport of lithium ions from an alkali metal ion mixture.

The porous polymer used in this case is:

Examples include polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl chloride, polysulfone, etc.
By forming these porous polymers into thin films and hollow fibers, it is possible to further increase the transport efficiency. The liquid membrane transport method involves placing a solution containing metal ions in one or both of two chambers separated by a liquid membrane of the compound of general formula I, and creating a pH gradient between the two chambers to transport the metal from the alkaline side to the acidic side. Ions are selectively transported. At this time, the ion transport membrane is Li">>Na4">K+~Pb+
~C8+, and the Li''/Na+Na sex ratio is at least 20.

〔Effect of the invention〕

The 14-crown-4 derivative of the first aspect of the present invention is novel and useful.

In addition, the metal ion extraction colorimetric reagent of the second invention uses a 14-crown-4 derivative, which is a dissociated crown ether having an alkyl group and a phenol group having an electron-withdrawing group, and therefore has a small pKa and a counter anion. It easily forms complexes with alkali metal and alkaline earth metal ions and exhibits coloration. In particular, it has high selectivity for lithium ions, reaching hundreds of times the extraction equilibrium constant of other metal ions, and has a large acid dissociation constant.
It forms a stable complex with lithium ions and is excellent as a lithium-selective extraction colorimetric reagent.

Furthermore, the metal ion liquid membrane transport agent of the third invention can be impregnated into a porous polymer or the like to form a film and used as an active transport material for metal ions, and can selectively transport metal ions, especially lithium. be.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 Synthesis of 14-crown-4 derivative having nitrophenol group (a) 2-dodecyl-2-(2'-methoxybenzyl)
Synthesis of malonic acid diethyl ester 300 mQ of dry ethanol and 3.92 g of metallic sodium were added and dissolved in an IQ 3-tube flask equipped with a calcium chloride tube, a cooling tube, and a stirrer.

While heating and stirring at 60°C, 46.7 g of diethyl 2-dodecylmalonate was added, and the mixture was heated under reflux for 1 hour.

Thereafter, 34.3 g of 2-methoxybenzyl bromide was added dropwise, and the mixture was heated under reflux for 20 hours. After the reaction is complete, ethanol is removed, 200 mQ of water is added to dissolve the residue, and the mixture is extracted with chloroform. After washing the chloroform layer with water and dehydrating it with magnesium sulfate, the chloroform was distilled off and distilled under reduced pressure.
2-Dodecyl-2-(2'-methoxybenzyl)malonic acid diethyl ester was obtained in a yield of 88.0%.

(b) 2-dodecyl-2-(2'-methoxybenzyl)
Synthesis of -1,3-propanediol 100 Q of heptane and 2.5 g of lithium aluminum hydride were placed in a 500 mm 3-tube flask equipped with a condenser and a stirrer and stirred. A solution of 20 g of dodecyl-2-(2'-methoxybenzyl)malonic acid diethyl ester in 100 mQ of hebutane was dropped into the system. Further at room temperature 12
After stirring for an hour, 30 mfi of methanol was added to decompose excess lithium aluminum hydride, heptane and methanol were removed, and the residue was dissolved in 10% sulfuric acid and extracted with chloroform. The chloroform layer was washed with a 10% aqueous sodium carbonate solution, dehydrated with magnesium sulfate, and the chloroform was distilled off to obtain 2-dodecyl-2-(2'
-methoxybenzyl)-1,3-propanediol was purified by recrystallization from petroleum ether (yield 89.2%)
.

(c) 6-dozosil-6-(2'-methoxybenzyl)
-Synthesis of 1,4,8,11-tetraoxacyclotetradecane Add 500 van of dry dioxane to an IQ 3 flask equipped with a calcium chloride tube and a cooling tube, and add 2-dodecyl-2 obtained in (b). -(2'-methoxybenzyl)-1,3-propanediol 3.64
g and 2 g of sodium hydride were added thereto, and the mixture was heated under reflux for 30 minutes. Thereafter, 2 g of lithium chlorate was added as a template, and then a solution of 5.04 g of 3,7-thioxanonan-1.9-diol ditosylate dissolved in 10 mm of dry dioxane was added dropwise, and the mixture was further heated under reflux for 24 hours. Further water was added to decompose excess sodium hydride, and the aqueous layer was made acidic with hydrochloric acid and then extracted with chloroform.

The chloroform layer was washed with water, the chloroform was distilled off, petroleum ether was added to the residue, unreacted raw materials were filtered off, the petroleum ether in the filtrate was distilled off, impurities were removed using a silica gel column, and the mixture was separated and purified using methanol. 6-dozosil-6-(2'-methoxybenzyl) - with a yield of 32.5%.
1,4,8,11-tetraoxacyclotetradecane was obtained.

(d) Synthesis of 6-dozosil-6-(2'-hydroxybenzyl)-1,4,8,11-tetraoxacyclotetradecane (compound A) 6-6-
Dozosil-6-(2'-methoxybenzyl)-1,4
,8,11-tetraoxacyclotetradecane 100m
g was dissolved in 70 mfi of heptane, further 0.5 g of lithium aluminum hydride was added, and the mixture was heated under reflux for 15 hours. After the reaction was completed, it was extracted with chloroform, and after distilling off the chloroform, it was separated and purified using an ODS column to give 6-dozosilyl-6-(2'-hydroxybenzyl)- in a yield of 32.5%.
1,4゜8.11-tetraoxacyclotetradecane (
Compound A) was obtained. Its structural formula and analytical values are shown below.

Mass spectrum (M" = 478) Elemental analysis CHO Calculated value 72.76 10.53 16.71 Analysis value ?2.46 10.60 -Hl-NMR δ=0.88 (3H= -CCHx)xx-
LiLt) 1.00 to 1.50 (22H, -(C9-)1
□-) 1.56 to 1.80 (2H, -0CH2sj, -
CH, 0-)2.36 (2B, φ-CH
@-)3.20-3.45 (4H,)C-CH,0-)
3.48-3.70 (12H, -505-) 7.88
(IH,0H) (e) 6-dozosil-6-(2'-hydroxy-3'-
nitrobenzyl)-1,4,8,11-tetraoxacyclotetradecane (compound 1), and 6-dothycil-6-(2'-hydroxy-5'-nitrobenzyl) -
1,4,8,11-tetraoxacyclotetradecane (
Synthesis of Compound 2) Compound A was mixed with concentrated nitric acid in a chloroform solution for 1 hour at room temperature.
After the reaction was completed with stirring for 0 minutes, chloroform was distilled off, and the residue was separated into compounds 1 and 2 using an ODS column.
Purified. Compound 1 had a yield of 29.3%, and its structural formula and analytical values are shown below.

Elemental analysis CHN O Calculated value 66.51 9.43 2.67 2
1.39 Analysis value 66.42 9,67 2.7
3 -Hl-NMR δ=0.88 (3H, -(CH*)zz-Ω1
)1.00~1.50(22H,-(Cjil)at-
)1.64 (2H,-0CI(,sujj,CH
,0-)2.64 (2H.

3.28.3.32 (4H,〉C-CH,0-)3.4
5-3.70 (12H, -CH, OCH, -) 11.0
0 (IH,OH) Compound 2 had a yield of 41.0%, and its structural formula and analytical values are shown below.

Elemental analysis CHNO Calculated value 66.51 9.43 2.67 2
1.39 Analysis value 66.46 9,37 2.3
0 -Hl-NMR δ=0.88 (3B--(CH,)ax-5)
1.00-1.50(228,-(Cu,)tt-)1
．． 69 (2B, -OCH, 5CO, 0-)2.
46 (2H, -CH, -φ)3.23.3.4
5(4H,)C-C1,-)3.50-3.75(12
H, -CH,0CH2-)6.87,7.89,8.0
2 (3H,.

9.05 (IH, -0H) (f) 6-dozosyl-6-(2'-hydroxy-3',
Synthesis of 5'-dinitrobenzyl)-1,4,8,11-tetraoxacyclotetradecane (compound 3) 500 mg of compound (2) was added to 0.9α
of chloroform solution and stirred vigorously for 25 minutes.
0! Add IQ fuming nitric acid and stir for 8 minutes.

Further water was added, the chloroform layer was separated, the chloroform was distilled off, and the residue was separated and purified using an ODS column. Yield 7
Compound 3 was obtained at 7.4%. Its structural formula and analytical values are shown below.

Elemental analysis CHNO Calculated value 61.25 8.51 4.95 2
5.32 Analysis value 61.25 8,51 4.8
6 -Hl-NMR δ=0.88 (3H, -(CH,)L □- mark 3) 1.10 to 1.47 (22H, -(5), □-) 1
．． 65 (2H, -OCH, Sj, CI20-
)2.73 (211,-nail L-φ)3.15
~3.70(16H,-CH,OCH,,)C-C1,
0-)11.78 (IH, -0H) Example 2 pKa, which is an indicator of metal ion extraction ability in dissociated crown ether, of the above synthesized compound, and complex formation balance between dissociated crown ether and metal ion The constant KML and the color development against various metal ions were measured.

In this case, the method for determining the acid dissociation constant is 7
A 10% aqueous solution of tetramethylammonium hydroxide was dropped into 50-' of a water-dioxane (1:1) solution containing 10'M of the crown compound, 0.099M of tetramethylammonium chloride, and 0.001M of hydrochloric acid, Each ptt
pKa was calculated from the change in the visible-ultraviolet absorption spectrum according to the formula below.

εHL: Molar extinction coefficient of the crown compound εL: Molar extinction coefficient of the crown compound after dissociation A: Absorbance during measurement All: Absorbance of the crown compound Also, equilibrium constant K for evaluating the ability to capture metal ions
The method for determining ML is to use a pH adjuster and IX 10-
Crown compound 7X10-5~1.75X10"H
After adding 4 mQ of chloroform solution and shaking in a cell with a stopper, KML was calculated from the change in visible-ultraviolet absorption spectrum according to the formula below.

(H”): Proton ion concentration (H+): Metal ion concentration εNL: Molar extinction coefficient of the crown compound formed with metal ion complex Furthermore, the coloring property for various metal ions is 1.46X
Chloroform solution 1 containing 10-' to 3.5 X 10-'M crown compound and equimolar triethylamine
The measurement was performed by adding 0.5 g of perchlorate metal salt such as LiClO4, NaClO4, etc. to 5.5a, shaking it, and then measuring the visible-ultraviolet absorption spectrum.

The results are shown in Table 1 and Figures 1 to 3.

For comparison, a conventional crown compound (compound B) was used.

Parallel to C).

Table 1 From Table 1, compared to Compound A, Compounds 1 to 3, which have a nitro group introduced into the aromatic ring, have a small pKa and a large proton dissociation property of the hydroxyl group, and concomitantly, a small PKML representing Li+ extraction ability. The extraction capacity is also increased. Furthermore, from the ratio of PKML of Li'' and Na+, Comparative Example A
, it can be seen that the selectivity of K 1/K Na is significantly greater than that of B. Moreover, from FIGS. 1 to 3, Compounds 1 to 3 have a significantly higher absorption for Li+ than other alkali metal ions and alkaline earth metal ions, and have a significantly greater coloring property for Li+.
It is understood that the selectivity for

Example 3 Polypropylene (diameter 3.3 cm) Porous II (
The pore size (0.04 x 0.4 μm) was
It was immersed in a nitrophenol ether solution, and then excess solution was removed using filter paper to form a liquid film of compound 3. This liquid film was placed in a device having two phases separated by a cross-sectional area of 1 d, one of which contained 2 phases of LiOH or NaOH at pH 13.
X IP2M 20+*fl aqueous solution, the other one is PH1
with metal hydroxide 2X10-2M and hydrochloric acid 2X10-'H
A 20 mj2 aqueous solution was added, and changes in metal ion concentration were examined at 25°C.

The results are shown in Figure 4. In FIG. 4, CM'')o is the initial metal ion concentration, and (M'')t is the metal ion concentration after time t. It is understood from FIG. 4 that it has excellent selectivity for Li+ and is effective as a highly selective dynamic transport membrane.

[Brief explanation of drawings]

1 to 3 are graphs showing the results of Example 2, and FIG. 4 is a graph showing the results of Example 3. Agent Patent Attorney Yanagihara Figure 1 Mugi length/nm Wavelength 11η Figure 3 Density length/nm B! Procedural amendment dated September 10, 1985 1, Case description 1985 Patent Application No. 102236 2, Title of the invention 14-Crown-4 derivative, metal ion extraction colorimetric reagent and liquid membrane transport agent 3 , Relationship with the case of the person making the amendment Patent Applicant Address 1-10-1 Yurakucho, Chiyoda-ku, Tokyo Name (434) Teruji Ogawa, Representative of Nippon Oil & Fats Co., Ltd. - 4, Agent Address: 105 Telephone: 436-470
0 Address 3-15-8-6 Nishi-Shinbashi, Minato-ku, Tokyo Subject of amendment Claims in the specification and details of the invention 7 Contents of amendment (1) The scope of claims will be corrected as shown in the attached sheet. . (2) Corrections are made to page 8, line 7 and page 13, line 1 of the specification. (3) On page 11, line 19, "2" is corrected by "2'". (4) Correction to page 12, line 5. (5) Correction to page 12, line 6. (6) Correct “ ” on page 12, lines 10 and 12. (7) On page 13, line 5, "hydroxylation" is corrected to "hydroxyl group." (8) On page 18, line 1, rPJ is corrected to rRj. (9) On page 21, line 6, "salt" is corrected to "hypersalt." (10) On page 27, line 7 from the bottom, "complex formation" is corrected to "extraction." (11) Page 29, lines 2-3 r1.46xlO-'~
3.5" to rl6 (12) Correct figures 1 to 3 as shown in the attached drawings. 2. Claims (1) The following general formula! A 14-crown-4 derivative represented by R2 and R2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, H4 represents an electron-withdrawing group, and the 1st base is 1 or 2, m
, n represents an integer of 3 or less.) (2) The 14-crown-4 derivative according to claim 1, wherein R1 is an alkyl group having 8 to 16 carbon atoms. (3) The 14-crown-4 derivative according to claim 1 or 2, wherein X is a nitro group, a cyano group, a trifluoromethyl group, an acetyl group, or a halogen group. (4) A metal ion extraction colorimetric reagent containing a 14-crown-4 derivative represented by the following general formula I. (In the formula, R1 represents an alkyl group having 1 to 20 carbon atoms, and R
2, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R4 represents an electron-withdrawing group, Q represents 1 or 2, m
, n represents an integer of 3 or less. ), (5) The metal ion extraction colorimetric reagent according to claim 4, wherein R1 is an alkyl group having 8 to 16 carbon atoms. (6) Claims 4 and 9 are the metal ion extraction colorimetric reagents according to claim 5, wherein X is a nitro group, a cyano group, a trifluoromethyl group, an acetyl group, or a halogen group. (7) A metal ion liquid membrane transport agent containing a 14-crown-4 derivative represented by the following general formula I. (In the formula, R1 represents an alkyl group having 1 to 20 carbon atoms, and R
2, R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R4 represents or an electron-withdrawing group, a is 1 or 2, m
, n represents an integer of 3 or less.) (8) The metal ion liquid membrane transport agent according to claim 7, wherein R1 is an alkyl group having 8 to 16 carbon atoms. (9) The metal ion liquid membrane transport agent according to claim 7 or 8, wherein X is a nitro group, a cyano group, a trifluoromethyl group, an acetyl group, or a halogen group. Figure 1 JL length/nm JL length/nm

Claims (9)

[Claims] (1) A 14-crown-4 derivative represented by the following general formula I. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, R^1 represents an alkyl group having 1 to 20 carbon atoms,
R^2 and R^3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R^4 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲Mathematical formulas , chemical formulas, tables, etc.▼ where X represents an electron-withdrawing group, l is 1 or 2, m
, n represents an integer of 3 or less. ) (2) The 14-crown-4 derivative according to claim 1, wherein R^1 is an alkyl group having 8 to 16 carbon atoms. (3) The 14-crown-4 derivative according to claim 1 or 2, wherein X is a nitro group, a cyano group, a trifluoromethyl group, an acetyl group, or a halogen group. (4) A metal ion extraction colorimetric reagent containing a 14-crown-4 derivative represented by the following general formula I. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, R^1 represents an alkyl group having 1 to 20 carbon atoms,
R^2 and R^3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R^4 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲Mathematical formulas , chemical formulas, tables, etc.▼ where X represents an electron-withdrawing group, l is 1 or 2, m
, n represents an integer of 3 or less. ) (5) The metal ion extraction colorimetric reagent according to claim 4, wherein R^1 is an alkyl group having 8 to 16 carbon atoms. (6) The metal ion extraction colorimetric reagent according to claim 4 or 5, wherein X is a nitro group, a cyano group, a trifluoromethyl group, an acetyl group, or a halogen group. (7) A metal ion liquid membrane transport agent containing a 14-crown-4 derivative represented by the following general formula I. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] (In the formula, R^1 represents an alkyl group having 1 to 20 carbon atoms,
R^2 and R^3 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R^4 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲Mathematical formulas , chemical formulas, tables, etc.▼ where X represents an electron-withdrawing group, l is 1 or 2, m
, n represents an integer of 3 or less. ) (8) The metal ion liquid membrane transport agent according to claim 7, wherein R^1 is an alkyl group having 8 to 16 carbon atoms. (9) The metal ion liquid membrane transport agent according to claim 7 or 8, wherein X is a nitro group, a cyano group, a trifluoromethyl group, an acetyl group, or a halogen group.