KR100678340B1 - A compound having selectively chromogenic character by binding a specific metal-ion - Google Patents

Abstract

The present invention relates to a compound having selective color development for a specific metal ion, and more particularly, it is composed of a site and a chromophore in which a nitrogen atom and an oxygen atom are combined with a metal ion by acting as an electron-pair donor to selectively color only when reacting with a specific ion. To acyclic compounds.

The compound is characterized by having a selective color development for the transition metal, in particular copper and aluminum ions by having a nitrogen atom and an oxygen atom at the same time.

Chromophore, Copper Ion, Selective Chromaticity, Acyclic

Description

A compound having selectively chromogenic character by binding a specific metal-ion}             

1 is a schematic of the color development process by complex formation of a ligand consisting of a chromophore and a recognition unit.

2 is a schematic of the guest ion recognition mechanism of the host with the chromophore introduced.

G: guest; X, Y: heteroatom; -·-: Join site

3 is a UV absorption spectrum measured after titration of Compound I and metal nitrate (5 equivalents).

Figure 4 is a UV absorption spectrum measured after titration of compound II and metal nitrate (5 equivalents).

5 is a UV absorption spectrum measured after titration of compound III and metal nitrate (5 equivalents).

6 is a titration according to the equivalent of compound III and copper nitrate (II).

Fig. 7 is a graph showing the relationship between the mole fraction of copper and the absorbance at 325 nm, which is the absorption peak of compound III and copper ion complex.

8 is a color confirmation test results for the copper ions and lead ions of compound III.

(a) Compound III, (b) Complex of Compound III with Pb ²⁺ , (c) Complex of Compound III with Cu ²⁺

The present invention relates to a compound having a selective color development for a specific metal ion, and more specifically composed of a metal ion binding site and a chromophore in which a nitrogen atom and an oxygen atom act as an electron pair opening reaction, and selectively color only when reacting with a specific ion. It is about a compound of a li form.

The compound is characterized by having a selective color development for the transition metal, in particular copper and aluminum ions by having a nitrogen atom and an oxygen atom at the same time.

While host-guest chemistry is rapidly developing, various applicability studies are drawing attention based on this. In particular, the emergence of new host compounds with high selectivity for specific guest molecules or ions and the synthesis and structural studies of related supramolecular complexes have attracted much attention due to their various applications. This is because the modification of the structure of the host molecule shows very good selectivity for a particular guest molecule. In addition, the expanded host molecule inherently possesses the guest recognition ability of the existing host and separately has a secondary function by covalently binding specific functional groups. One such category of scalability includes cyclic compounds in which dyes are covalently bonded. The use of coordinating dye molecules to spectroscopically detect specific metal ions has been widely used in environmental analysis, biomedical science and metallurgy. Basically, the color detection reagent has a recognition moiety for a specific sample and a signaling moiety for responding to the recognized sample (FIG. 1).

In the case of the chromophore-introduced host, the chromophore is divided into three types by recognition of guest ions (FIG. 2) (M. Hiraoka, in Crown ethers and analogous compounds , Elsevier, Amsterdam, 1992).

The E1 method is a process in which heteroatoms having unpaired electron pairs such as nitrogen are discolored during complex reaction by participating in a macrocycle. At this time, the unshared electron pair acts as a Lewis base, causing discoloration through charge transfer of the chromophore.

The E2 method is a form in which a heteroatom is hydrogen-bonded at the linkage between the macrocycle and the chromophore. In this form, since guest ions enter, hydrogen of heteroatoms is released and hetero atoms form ion pairs with ion ions as anions, causing chromophore discoloration. This form was named "Acerand" by T. Kaneda. This is the acronym for "acetic acid" and "ligand" (T. Kanada, Y. Ishizaki, S. Misumi, Y. Kai, G. Hirao, N. Kasai, J. Am. Chem. Soc. 1988 , 110 . 2970.).

Lastly, the S-type is different from the one we have seen so far, but in the form of a similar macro ring, the electron donor group and the electron acceptor group are attached to both ends of the chain. As the complex forms, the π-electron donor group and the π-electron acceptor group at both ends of the chain come closer to each other, causing discoloration by charge transfer between the two groups.

Studies on chromogenic hosts are the first in F. Vogtle and J.P. Performed by Dix. An azo group and a didoaniline group were attached as chromophores to ionic receptors that could accommodate guests (JP Dix, F. Vogtle, Angew. Chem., Int. Ed. 1978, 17. 11. JP Dix, F. Vogtle, Chem. Ber. 1980, 113, 457 .; JP Dix, F. Vogtle, Chem. Ber. 1981, 114, 638 .; HG Lhr, F. Votle, Acc. Chem. Res. 1985, 18, 65.).

The compound of Formula 1 having an azo group has a wavelength of 480 nm (red color), and shifts to a short wavelength by forming a complex with an alkali metal. This is because the n-π or π-π energy interval is increased by the donor effect of the unshared electron pair of nitrogen. In particular, when combined with K ⁺ ions, it showed a larger hyperchromic band shift than other metals (JSKim, OJShon, JKLee, SHLee, JY Kim, KMPark, SSLee, J. Org.Chem. 2002, 67, 1372). Christoph Arenz, M. Gartner, V. Wascholowski, A. Giannis, Bio. Med. Chem. 2001, 9 2901.).

On the other hand, the compound of the formula (2) is because the formation of the complex with the metal salt in a bathochromic band shift system, the excitation energy is reduced, it shows a better selectivity to the divalent (2+) metal than monovalent (1+) metal, In particular, it has been shown to be selective for Ca ²⁺ (JP Dix, F. Vogtle, Chem. Ber. 1981, 114, 638.).

R. Marti nez-Ma'nez and his co-workers were the first to study chromogenic functional groups in thio-azacrown ethers with oxygen, sulfur and nitrogen (F. Sancenn, AB Descalzo, R. Marti nez-Ma'nez). , MA Miranda, J. Soto, Angew. Chem. Int. Ed. 2001, 40, 2640., F. Sancenn, R. Marti nez-Ma'nez, J. Soto, Angew. Chem. Int. Ed. 2002, 41, 1416., AB Descalzo, R. Marti nez-Ma'nez, R. Radeglia, K. Rurack, J. Soto, J. Am. Chem. Soc. 2003, 125, 3418.).

Where R is

to be.)

In Formula 3, a compound of R is A absorbs a wavelength of 380 nm, and when ATP is added thereto, the maximum absorption wavelength shifts toward 550 nm (F. Sancenn, AB Descalzo, R. Marti nez-Ma'nez, MA Miranda). , J. Soto, Angew. Chem. Int. Ed. 2001, 40, 2640.).

On the other hand, in Formula 3, the compound of R is B absorbs 490 nm (26000M ^-1 cm ^-1 ), but the wavelength shifted to 520 ~ 540nm by adding Cu ²⁺ , Hg ²⁺ , Fe ²⁺ to it. . In addition to these cationic selectivity showed that the very sensitive to specific anion [HgIV _2] When the anion-titrated with ^{2+ F -, Cl -, Br} -, I -, H 2 PO 4 -, HSO 4 - anions, such as In While there was no wavelength shift at all, NO ₃ ⁻ showed a color change and similar results were reported for compounds with R of C (AB Descalzo, R. Marti nez-Ma'nez, R. Radeglia, K.). Rurack, J. Soto, J. Am. Chem. Soc. 2003, 125, 3418.)

Some scholars, on the other hand, have synthesized acyclic hosts to study negative ions, and have published sensors that can selectively identify negative ions (DHLee, HYLee, KHLee, JIHong, J. Chem. Soc). ., Chem. Comm. 2001.1188 .; DHLee, KHLee, JIHong, Org.Lett. 3. 5 .; DH Lee, HYLee, JIH, Tetrahedron Lett. 2002, 43, 7273.).

In addition, Korean Patent No. 372559 relates to a Kalix [4] arena azacrown ether derivative capable of selectively adsorbing potassium ions, and to a chromogenic Kalix [4] arene azacrown ether derivative that selectively adsorbs potassium ions. It describes about the manufacturing method thereof.

Accordingly, it is an object of the present invention to provide acyclic compounds having selective color development for certain ions of transition metals, in particular copper, aluminum and iron ions.                         

Another object of the present invention is to provide a detection reagent for a metal ion having color development using the compound, and the use of the same for separating and detecting a specific metal ion from industrial wastewater.

In order to achieve the above object, the present inventors have synthesized a compound having a selectivity for a specific metal ion for the detection of a specific ion in the transition metal. The compounds synthesized in the present invention introduced oxygen and nitrogen donor atoms as binding sites of metal ions, that is, ligands, and as chromophores, they have an azobenzene group, a nitro group, a carbonyl group, a C = N group, an unsaturated double or triple bond between carbons, etc. The compound was prepared.

The present invention relates to a compound represented by the following formula 4 and having a selective color development for a particular ion.

(Wherein

이고,R ₁ , R ₂ is a hydrogen atom, C ₁ ~ C ₂₀ linear alkyl group or

ego,

Wherein R ₃ is a hydrogen atom or a straight alkyl group of C ₁ to C ₂₀ , R ₄ is a hydrogen atom or a straight alkyl group of C ₁ to C ₄ ,

X is a compound having at least one chromophore selected from azo group, nitro group, carbonyl group, C = N group, unsaturated double or triple bond between carbons.)

The present invention also relates to a compound having selective color development with respect to a specific ion, wherein X is selected from the group consisting of compounds represented by the following Chemical Formulas 5 to 8.

In addition, the present invention is characterized in that the compound selectively colors for copper ions, aluminum ions and iron ions.

The compounds of the present invention have different UV absorption wavelengths for copper ions, aluminum ions, and iron ions, and different colors can be distinguished from each other.

In addition, the present invention relates to a detection reagent for copper ions, aluminum ions or iron ions containing a compound. The detection reagent is prepared by a general detection reagent production method, characterized in that it comprises a compound of the present invention.

Hereinafter, the configuration of the present invention in more detail through examples. However, the scope of the present invention is not limited to the Examples.

Materials and devices

¹ H NMR spectrum was used DRX-300 (Bruker, 300MHz). Infrared spectra were used with an IFS66 (Bruker) spectrophotometer. UV-Vis absorption spectrum was used with LAMBDA-900 (Perkin elmer) and the progress of the reaction was observed by thin layer chromatography (TLC). Silica gel was manufactured by Merck silica gel 60 (No. 9385, 230-400 mesh). All reagents used in the reaction were Aldrich's special reagent without purification.

Example 1 Preparation of Compound I

As shown in Scheme 1, N-phenyldiethanolamine (N-phenyldiethanolamine (10 g, 55.18 mmol)) was dissolved in 50 mL of pyridine, and the solution was lowered to 0 ° C. in an ice bath. TsCl (22.09 g, 115.85 mmol) was added slowly dropwise. After 2 hours, 500 mL of ice water was added to the solution, and the resultant was filtered using a glass filter, and recrystallized from an ethanol / toluene mixed solution to obtain compound 2 (25.2 g, 55.17 mmol, 93%).

Compound 2: ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.72 (d, 4H, J = 6.60 Hz), δ 7.29 ( d , 4H, J = 9.10 Hz), δ 7.14 (t, 2H, J = 9.00 Hz) , δ 6.72 (t, 1H, J = 7.50 Hz), δ 6.45 (d, 2H, J = 7.80 Hz), δ 4.10 (t, 4H, J = 6.00 Hz), δ 3.56 (t, 4H, J = 6.00 Hz), δ 2.43 (s, 6H)

Compound 2 (8.00 g, 16.34 mmol) was added to a 50 mL round bottom flask, and then 15 mL of DMSO was added and refluxed at about 90 ° C. After 3 hours, the organic layer was extracted with anhydrous magnesium sulfate after extraction using chloroform / water (chloroform / H ₂ O), chloroform was removed using a rotary vacuum evaporator, and compound 3 was obtained without other purification methods.

Compound 3: ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.18 (m, 2H), δ 6.71 (m, 2H), δ 6.63 (m, 1H), δ 3.42 (q, 4H, J = 6.60 Hz), δ 1.52 (q, 4H, J = 6.60 Hz)

Activated carbon and palladium (palladium on activated carbon, 0.35g) were added to a 25 mL round bottom flask, and air was removed and charged with nitrogen. Compound 3 (3.5 g, 15.13 mmol) was dissolved in 10 mL of methanol and carefully placed in a flask. Two atmospheres of hydrogen were added to the flask and filtered after two hours. The solution was removed using a rotary evaporator to give compound 4 as a colorless liquid.

Compound 4: ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.23 (m, 2H), δ 6.76 (m, 2H), δ 6.71 (m, 1H), δ 3.44 (t, 4H, J = 6.60 Hz), δ 3.19 (t, 4H, J = 6.60 Hz), δ 1.28 (s, 4H)

After diluting Compound 4 (450mg, 2.51mmol) in 10mL tetrahydrofurane, triethylamine (2.54g, 25.10mmol) was added thereto and boiled at 70 ° C, followed by propionyl chloride (0.58g, 6.28mmol). Dilute to 5 mL of tetrahydrofuran and slowly dropwise add to the solution and filter after 5 hours. The filtrate was removed using a rotary vacuum evaporator and then separated by a column to obtain compound 5.

Compound 5: ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.31 (m, 2H), δ 6.92 (m, 2H), δ 6.82 (m, 1H), δ 3.85 (t, 4H, J = 7.50 Hz), δ 3.51 (t, 4H, J = 7.50 Hz), δ 2.38 (s, 6H)

Compound I was prepared using diazonium salt (JS Kim, OJ Shon, JK Lee, S, H, Lee, J, Y, Kim, KM Park, SS Lee, J. Org. Chem. 2002 , 67, 1372.). Diazonium salt was prepared by dropwise addition of NaNO ₂ (49.48 mg, 0.72 mmol) in a homogeneous solution of 1 mL of acetic acid containing 4-nitroanilne (99.04 mg, 0.72 mmol) and 0.3 mL of sulfuric acid. Compound 8 (300 mg, 0.55 mmol) was dissolved in 50 mL of DMF, placed in an ice bath, and the diazonium salt was slowly added dropwise and stirred for 12 hours. The organic layer was separated using 250 mL of water and 50 mL of chloroform, dried over anhydrous sodium sulfate, and the solvent was evaporated. Column chromatography was performed on a developing solvent of ethyl acetate: hexane = 9: 1 (v / v) to obtain Compound I, a red solid (R _f = 0.4), in 80% yield.

Compound I: ¹ H NMR (300 MHz, DMSO- d ₆ ) δ 8.35 ( d , 2H, J = 8.10 Hz), δ 7.95 (m, 4H), δ 6.93 ( d , 2H, J = 9.30 Hz), δ 6.04 (s, 2H), δ 3.65 (t, 4H, J = 6.00 Hz), δ 3.53 (t, 4H, J = 6.00 Hz), δ 1.55 (s, 6H)

Example 2: Preparation of Compound II

Compound 4 (450 mg, 2.51 mmol) prepared by the method of Example 1 was diluted in 10 mL of tetrahydrofuran and then triethylamine (2.54 g, 25.10 mmol) was added to boil at 70 ° C., followed by lauroyl A solution obtained by diluting (lauroly chloride, 1.37 g, 6.28 mmol) in 5 mL of tetrahydrofuran was slowly added dropwise to the compound 4 solution and filtered after 5 hours. This filtrate was removed using a rotary vacuum evaporator and then separated by column to obtain compound 6.

Compound 6: ¹ H NMR (300 MHz, CDCl ₃ ) δ 7.24 (t, 2H, J = 7.50 Hz), δ 6.84 ( d , 2H, J = 7.80 Hz), δ 6.43 (t, 1H, J = 7.20 Hz) , δ 5.95 (s, 2H), δ 3.47 (m, 8H), δ 2.15 (m, 4H), δ 1.60 (m, 4H), δ 1.28 (m, 32H), δ 0.90 (t, 6H, J = 6.90 Hz)

Compound II was prepared using a diazonium salt (JS Kim, OJ Shon, JK Lee, S, H, Lee, J, Y, Kim, KM Park, SS Lee, J. Org. Chem. 2002 , 67, 1372.). Diazonium salt was prepared by dropwise addition of NaNO ₂ (49.48 mg, 0.72 mmol) in a homogeneous solution of 1 mL of acetic acid containing 4-nitroanilne (99.04 mg, 0.72 mmol) and 0.3 mL of sulfuric acid.

Compound 8 (300 mg, 0.55 mmol) was dissolved in 50 mL of DMF, and then placed in an ice bath. The first diazonium salt was slowly added dropwise and stirred for 12 hours. The organic layer was separated using 250 mL of water and 50 mL of chloroform, dried over anhydrous sodium sulfate, and the solvent was evaporated. Compound II was obtained as a red solid (R _f = 0.4) in 80% yield using column chromatography through a developing solvent of ethyl acetate: hexane = 9: 1 (v / v).

Compound II: ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.36 ( d , 2H, J = 9.06 Hz), δ 7.96 (m, 4H), δ 6.90 ( d , 2H, J = 9.06 Hz), δ 4.34 (t , 4H, J = 6.00 Hz), δ 3.77 ( d , 4H, J = 6.00 Hz), δ 2.32 ( d , 4H, J = 7.50 Hz), δ 1.61 (m, 4H), δ 1.27 (m, 32H) , δ 0.90 (t, 6H, J = 8.10 Hz)

Example 3: Preparation of Compound III

Alanine (compound 7, 1.83 g, 20.57 mmol) and NaHCO ₃ (4.85 g, 45.71 mmol) were dissolved in 20 mL of H ₂ O, and then 20 mL of tetrahydrofuran was added, and the mixture was placed in an ice bath. Lauroyl chloride (5.00 g, 22.86 mmol) was diluted in 5 mL of tetrahydrofuran and slowly added dropwise to the alanine mixture and left at room temperature for 24 hours. The resultant was concentrated using a vacuum rotary evaporator, extracted with 50 mL of ethyl acetate and 200 mL of H ₂ O, and water was removed using anhydrous magnesium sulfate. The organic layer was removed using a rotary vacuum evaporator, and recrystallized using ethyl ether to obtain Compound 8 as a white solid.

Compound 8: ¹ H NMR (300 MHz, CDCl ₃ ) δ 9.37 (s, 1H), δ 4.45 (m, 1H), δ 2.24 (t, 2H, J = 7.68 Hz), δ 1.58 (m, 2H), δ 1.34 (m, 18H), δ 0.89 (t, 3H, J = 2.76 Hz)

Compound 4 (500 mg, 2.79 mmol) and compound 8 (1.89 g, 6.97 mmol) were dissolved in 5 mL of ethyl acetate, placed in an ice bath, and then mixed with DCC (1.87 g, 9.07 mmol) and HOBt (1.22 g, 9.07 mmol). Was added. The solution was filtered after standing at room temperature for 24 hours. The filter solution was extracted using saturated NaHCO ₃ aqueous solution, saturated NaHSO ₄ aqueous solution, and NaHCO ₃ aqueous solution. The organic layer was removed with anhydrous magnesium sulfate. Compound 9 was obtained by performing a column using 9: 1 ethyl acetate: hexane.

Compound 9: ¹ H NMR (300 MHz, DMSO- d ₆ ) δ 7.54 (s, 2H), δ 7.34 (s, 2H), 7.21 (t, 2H, J = 7.50 Hz), δ 6.79 ( d , 2H, J = 7.80 Hz), δ 6.51 (t, 1H, J = 7.20 Hz), δ 4.14 (m, 2H), δ 3.77 (t, 4H, J = 7.68 Hz), δ 3.35 (t, 4H, J = 7.68 Hz ), δ 2.22 (t, 4H, J = 7.14 Hz), δ 1.64 (m, 8H), δ 1.31 (m, 36H), δ 0.90 (t, 6H, J = 2.76 Hz)

Compound III was synthesized using diazonium salt. Compound 8 (580 mg, 0.85 mmol) was dissolved in 50 mL of DMF, and placed in an ice bath. Then, a diazonium salt prepared in the same manner as in Example 1 was slowly added dropwise and stirred for 12 hours. The organic layer was separated using 50 mL of water and 50 mL of chloroform, dried over anhydrous sodium sulfate, and the solvent was evaporated. Ethyl acetate: methanol = 18: 3 (v / v) was used as a developing solvent, and column chromatography gave Compound III as a red solid (R _f = 0.3) in 40% yield.

Compound III: ¹ H NMR (300 MHz, DMSO- d ₆ ) δ 8.33 ( d , 2H, J = 9.06 Hz), δ 7.92 ( d , 2H, J = 9.06 Hz), δ 7.83 ( d , 2H, J = 9.06 Hz), δ 7.61 (s, 2H), δ 7.38 (s, 2H), δ 7.02 ( d , 2H, J = 9.06 Hz), δ 4.28 (m, 2H), δ 3.88 (t, 4H, J = 7.68 Hz), δ 3.38 (t, 4H, J = 7.68 Hz), δ 2.13 (t, 4H, J = 7.14 Hz), δ 1.53 (m, 8H), δ 1.28 (m, 36H), δ 0.89 (t, 6H, J = 2.76 Hz)

Test Example 1: Confirmation of Selectivity to Cation

This test example is for confirming the selectivity to the cations of the compounds I to III prepared in Examples 1 to 3.

Compounds I-III were completely dissolved in 100 mL of 35.20 mg, 36.05 mg, and 36.89 mg acetonitrile, respectively, to prepare compound I-III solutions. Ag ⁺ , Li ⁺ , K ⁺ , NH ₄ ⁺ , Ba ²⁺ , Ni ²⁺ , Co ²⁺ , Cu ²⁺ , Zn ²⁺ , Cd ²⁺ , Pb ²⁺ , Hg ²⁺ , Al ²⁺ , Fe ^For each cation of ³⁺ , 5 equivalents of nitrate were added to 5 mL of acetonitrile and dissolved. UV-Vis absorption spectrum was measured after mixing 1 mL of nitrates for each of the compounds I to III solution and each cation.

The UV-Vis absorption spectrum was measured in FIGS. 3 to 5. As a result of FIGS. 3 to 5, absorption spectra of compounds I to III were observed at about 480 nm (λ _max = about 30,000 M ⁻¹ cm ⁻¹ red color) in which typical azo-dye derivatives appeared. It was confirmed that the chromophore had an azobenzene group.

As can be seen in Figures 3 to 5, the maximum absorption wavelength of Compounds I-III was hardly changed even when most cations were added. It complexes with compounds I-III and Ag ⁺ , Li ⁺ , K ⁺ , NH ₄ ⁺ , Ba ²⁺ , Ni ²⁺ , Co ²⁺ , Zn ²⁺ , Cd ²⁺ , Pb ²⁺ , Hg ²⁺ ions It does not form or forms a very weak complex.

However, when iron (III) was added to the solution of compounds I, II and III, the color changed from red to pale orange. This is a phenomenon opposite to when metal ions were added, showing a long wavelength shift.

In addition, the solution of Compounds I-III changed from red to colorless with respect to copper (II) ions, and also changed from red to purple when aluminum ions were added. That is, the maximum absorption wavelength of Compounds I to III shifted by about 80-120 nm when the copper and aluminum ions were added. Thus, it was confirmed that the compounds I to III selectively bind with copper and aluminum ions.

In addition, when copper (II) was added in FIGS. 3 and 4, the maximum absorption wavelength of compound I and II having different alkyl chain lengths as hydrophobic groups was about 120 nm. It can be seen that the long alkyl chain attached to the compounds I and II as hydrophobic groups does not significantly affect the selective development of copper and aluminum ions.

On the contrary, as shown in FIG. 5, the compound III having a chirality-added alanine group showed a short wavelength shift of 150 nm when the copper ion was added ( pka = 3.3 × 10 ⁴ ). This suggests that -NH or -CO groups in the alanine group participate as effective binding sites when forming complexes with copper ions, and thus have better selectivity than compound compounds I and II.

Test Example 2: Cu ions (Cu ²⁺ Titration Experiment by Equivalence for

In this test example, in order to confirm the binding properties of the compounds I-III and metal ions, 35.20 mg, 36.05 mg, and 36.89 mg of the compounds I-III were dissolved in 100 mL of acetonitrile, respectively, and then 0.3 equivalents and 0.4 equivalents. 5 mL of Cu (NO ₃ ) ₂ solution was prepared, 0.6 equivalent, 0.8 equivalent, 1.0 equivalent, 1.3 equivalent, 1.5 equivalent, 2.0 equivalent, and 5.0 equivalent. After mixing the compound solution and Cu (NO ₃ ) ₂ solution by 1mL each UV-Vis absorption spectrum was measured.

Figure 6 shows the results observed by UV-vis absorption spectrum as the concentration of copper (II) ion in a certain concentration of compound III solution. As the peak of 479 nm, the maximum absorption peak of Compound III, gradually decreased, a new peak appeared at 325 nm, and this gradually increased. At 380 nm, an isosbestic point appeared. In general, when a single isotherm appears during a chemical reaction, it means that only two species exist. Therefore, it was found that compound III and copper ions effectively form a complex in the acetonitrile solution, and that the bonding ratio of compound III and copper ions is 1: 1.

In addition, in the case of compounds I and II, the iso-absorbance point was shown at 432 nm and 425 nm respectively.

Test Example 3: Job's plot titration experiment

This example used the Job method to determine the stoichiometric ratios of the compounds I to III and copper ions.

The compound II solution prepared in Test Example 2 was prepared in 1/10, 2/10, 1/3, 3/10, 4/10, 5/10, 6/10, 2/3, 7/10, 3/4. Dilute to 8/10, 9/10, and make 10 mL of Cu (NO ₃ ) ₂ and again 9/10, 8/10, 3/4, 7/10, 2/3, 6/10, 5 After diluting with / 10, 4/10, 3/10, 1/3, 2/10, 1/10, and mixing the compound III solution and the metal salt-dissolved solution in 1 mL each, the UV-Vis absorption spectrum is measured. It was.

First, a wavelength of 325 nm, which is an absorption peak of the complex with respect to compound III and copper ions, was selected, and the mole fraction and absorbance of copper were shown in a graph (FIG. 7). As a result, the largest absorbance value was found at molar ratio of 0.5. This means that compound III and copper ions form a complex 1: 1.

As described above, the present invention can provide acyclic compounds having selectivity for specific metal ions. In particular, it can be seen that the compound having an alanine group, which is a chiral compound, is highly dependent on the selective color development of copper ions.

Therefore, the compound of the present invention can be utilized as an effective tool for the recovery and detection of industrial wastewater from the semiconductor industry by using the property of selectively coloring the copper, aluminum and iron ions.

It can also be used in environmental analysis, ion sensor, device, biomedical and metallurgy fields.

Claims (4)

A compound represented by the following formula, and having a selective color development for a specific metal ion.

(Wherein R ₁ , R ₂ is a hydrogen atom, C ₁ ~ C ₂₀ linear alkyl group or

ego, R ₃ is a hydrogen atom or a straight alkyl group of C ₁ to C ₂₀ , R ₄ is a hydrogen atom or a straight alkyl group of C ₁ to C ₄ , X is a compound having at least one chromophore selected from azo group, nitro group, carbonyl group, C = N group, unsaturated double or triple bond between carbons.) The method of claim 1, wherein X is

Compound having a selective color development for a particular ion, characterized in that selected from the group consisting of. The compound of claim 1 or 2, wherein the compound has a color development selective to a specific ion, characterized in that the color for the copper ions, aluminum ions and iron ions. delete

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