KR20100028273A - Bodipy appended crown ether derivatives, methods for preparing the same, and methods for selective metal ion detection - Google Patents

Abstract

PURPOSE: A method for selectively detecting a metal ion using a crown ion derivative conjugated with BODIPY is provided to strengthen fluorescence by selectively binding the derivative with a mercury ion in order to be used to detect mercury. CONSTITUTION: A crown ether derivative conjugated with BODIPY is denoted by chemical formula 1 or 2. According to reaction formula 1, the derivative of chemical formula 1 is prepared by reacting 2,4-dimethyl pyroll and p-chloranil with a compound of chemical formula 3. The compound of chemical formula 3 is prepared by reacting a compound of chemical formula 5 with a compound of chemical formula 7. A method for detecting a metal ion selectively comprises: a step of dissolving the compound of chemical formula 1 or 2 in an aqueous solution; a step of adding a sampling containing a metal ion to the solution; a step of irradiating light to the solution to excite the compound of chemical formula 1 or 2; and a step of measuring the fluorescence emitted from the solution.

Description

BODIPY appended crown ether derivatives, methods for preparing the same, and methods for selective metal ion detection}

The present invention relates to a crown ether derivative bonded to BODIPY, a method for preparing the same, and a method for selectively detecting metal ions using the same, and more particularly, to a crown bound with BODIPY used in the field of environment, medicine and fine chemistry. An ether derivative, a method of preparing the crown ether derivative in a high yield in a short time by a two-step reaction, and a method for easily detecting mercury ions using the same.

Recently, the study of fluorescent chemosensors with the ability to detect metal ions has become one of the most challenging in the field of organic chemistry and supramolecular chemistry.

When complexed with a metal ion in a fluorophore unit in which a macrocyclic compound is introduced, various wavelength changes and quantum efficiency increase and decrease have been reported. Macrocyclic compounds containing fluorescent emitters have organic synthesis, solvent extraction, membrane permeation process, ion selective electrodes and similar analytical chemical applications. In recent years, it has also been applied to the functionalization of color sources of macrocyclic compounds for optical analysis. Optical response mechanisms generally induce a change in energy from the exited singlet state to the triplet state for most cations such as alkali and alkaline earth metals. As a result, in the presence of a cation, the duration of phosphorescence of the macrocyclic compound increases and the duration of fluorescence decreases. However, it is known that enhanced fluorescence is observed by complex formation when the duration of phosphorescence decreases depending on the type of cation, spacer and fluorophore.

The most effective fluorescence emitting chemical receptors must be able to recognize metal ions by ionopores and convert them into light signals of fluorophores in order to give high sensitivity. In particular, in designing such a chemical sensor, the ion carrier connected to the fluorescent emitter should be considered in advance, because it affects the selectivity and binding efficiency of the entire chemical receptor. In order to develop an ion-selective, ion-sensitive material, there is a growing interest in the synthesis of macromolecular compounds (macromolecule) combined with a fluorescence emitting material capable of catching changes in cations, anions and heavy component complexes. Hard ether oxygen contained in macromolecular cyclic compounds (macrocycles) shows a preferential binding to hard alkali or alkaline earth metals. However, incorporation of soft sulfide or amine linkages changes to have priority over soft heavy metal cations. In addition, ligands of macromolecular cyclic compounds containing nitrogen-sulfur donor atoms are known to act as highly selective complex formers for transition metal cations. It has also been found that macromolecular cyclic compounds containing nitrogen-sulfur donor atoms act as complex formers with transition metal cations and have very high selectivity, and in this respect include sulfur such as sulfur-crown ethers. Macromolecular cyclic compounds have been prepared and the properties of complexes formed with them have been studied with various metal cations.

In recent years, it has become a focus of interest for the fluorescence emission to chemical receptor ^{2 +} Pb, Cd ^{+ 2,} Hg ^{+ 2} ions and. Optionally to quickly detect heavy metal ions, which are toxic as. In particular, Hg ^{2 +} ions are converted into methylmercury by bacteria and can affect human health after being bioaccumulated continuously through the food chain.Methylmercury can cause mercury poisoning, and it can be central to diseases like Minamata disease. It can cause abnormalities in the nervous system.

Therefore, there has been a need for a method of selectively detecting the above-described metal ions with good sensitivity, and for this purpose, a research has been made on a chromogenic chemical receptor capable of selectively binding to a specific metal ion and detecting the same. For example, a method of selectively detecting cesium ions using an N-phenyl calix [4] crown azacrown derivative has been proposed (Korean Patent No. 10-0411495). However, among the various metal ions, the development of a fluorescent emitting chemical receptor which has a selective binding ability to mercury ions which can cause a fatal disease in humans and at the same time provides excellent sensitivity is insufficient.

The first problem to be solved by the present invention is to provide a fluorescence emitting chemical receptor having a selective binding force to the metal ions such as mercury and at the same time excellent sensitivity.

The second problem to be solved by the present invention is to provide a method for producing the fluorescence emission chemical receptor.

A third object of the present invention is to provide a method for selectively detecting metal ions such as mercury using the fluorescence emission chemical receptor.

The present invention provides a crown ether derivative bonded to BODIPY represented by the following formula (1) or formula (2) to solve the first problem.

N is 1 or 2 in the said General formula (2).

In order to solve the second problem, according to the following scheme 1 or 2 2,4-dimethylpyrrole and p-chloranil (p-chloranil) using the BODIPY bonded crown of the formula (1) or (2) Provided are methods for preparing ether derivatives.

      (3) (1)

    (4) (2)

In Scheme (2), n is 1 or 2.

According to one embodiment of the present invention, the compound of formula (3) may be prepared by the reaction of the compound of formula (5) and the compound of formula (7) according to the following scheme 3.

  (7) (3)

According to another embodiment of the present invention, the compound of formula (4) may be prepared by the reaction of a compound of formula (6) with a compound of formula (7) according to Scheme 4.

  (7) (4)

In Scheme (4), n is 1 or 2.

In order to solve the third object of the present invention, (a) dissolving the compound represented by the formula (1) or (2) in an aqueous solution; (b) adding a sample containing metal ions to the solution obtained in (a); (c) applying light to excite the compound of formula (1) or (2) contained in the solution obtained in (b); And (d) measuring the fluorescence emitted from the solution obtained in (c).

According to one embodiment of the present invention, the concentration of the compound of Formula (1) may be 0.1 μM to 1 mM in the aqueous solution.

According to another embodiment of the present invention, the metal ion may be mercury ion.

According to another embodiment of the present invention, the light may be a wavelength of 490nm to 500nm.

According to another embodiment of the present invention, the aqueous solution may be composed of H ₂ O and CH ₃ CN.

According to another embodiment of the present invention, the ratio of the volume of H ₂ O and CH ₃ CN may be 4: 6 to 6: 4.

According to the present invention, a crown ether derivative that selectively binds to metal ions such as mercury can be produced in a high yield by a simple two-step reaction, and the BODIPY-bonded crown ether prepared by the present invention is a heavy metal having high toxicity. It selectively binds with one of the mercury ions to enhance the fluorescence to detect mercury can be useful in the detection of mercury in nature and the human body.

Hereinafter, the present invention will be described in more detail.

The crown ether derivative to which the BODIPY is bound according to the present invention is represented by Formula (1) or Formula (2), wherein n is 1 or 2 in Formula (2).

Crown ether derivatives bonded to BODIPY represented by the formula (1) of the present invention can be prepared by the above scheme 1, the compound of formula (3) may be prepared by the above scheme 2.

Crown ether derivatives bonded to BODIPY represented by Formula (2) may be prepared by Scheme 3, and the compound of Formula (4) may be prepared by Scheme 4.

The compounds of formula (3) or (4) are each treated with 2,4-dimethylpyrrole under trifluoroacetic acid (TFA), sequentially oxidized to p-chloranyl, neutralized by Et ₃ N, and finally Is treated with Et ₃ N / BF ₃ · OEt ₂ to obtain compounds of formula (1) or (2), respectively.

The present invention (a) dissolving the compound represented by the formula (1) or (2) in an aqueous solution; (b) adding a sample containing metal ions to the solution obtained in (a); (c) applying light to excite the compound of formula (1) or (2) contained in the solution obtained in (b); And (d) measuring the fluorescence emitted from the solution obtained in (c).

1 is a schematic view showing a state of forming a composite by combining the Hg ^{+ 2} ions and the chemical formula (1) compound and emit fluorescence. Referring to FIG. 1, when mercury and the compound of formula (1) are combined, fluorescence is emitted by the BODIPY group, and thus fluorescence may be measured to selectively detect mercury ions.

The light may be a wavelength of 490nm to 500nm, because the light of the wavelength is the absorption wavelength band of the compound of formula (1) or (2).

The aqueous solution consists of H ₂ O and CH ₃ CN, preferably the ratio of the volume of the H ₂ O and CH ₃ CN is 4: 6 to 6: 4. The compound of formula (1) is well dissolved in an aqueous solution containing CH ₃ CN, preferably the compound of formula (1) when the volume ratio of H ₂ O to CH ₃ CN is 4: 6 to 6: 4 This is because the fluorescence is strong when mercury ions are bound.

Preferably, the compound of Formula (1) is added to the aqueous solution at a concentration of 0.1 μM to 1 mM. When the concentration of the compound of Formula (1) is less than 0.1 μM, the amount of mercury ions to be bound is also reduced to If the increase is not significant and exceeds 1 mM, it is possible to detect sufficient fluorescence required for analysis by a smaller amount of the compound of formula (1), but to add more compound of formula (1) than necessary. This is because the compound of 1) is consumed unnecessarily.

Hereinafter, the present invention will be described in more detail with reference to preferred examples and experimental examples, but the present invention is not limited thereto. The structure of the compound obtained through the following example was confirmed by NMR and mass spectrometry spectra.

Example  1-1: Compound Synthesis of Formula (5)

Under nitrogen, 0.5 g (5.3 mmol) of 1,2-ethanedithiol and 0.44 g (10.6 mmol) of sodium hydroxide were added to 100 mL of ethanol and stirred at room temperature. 1.38 g (10.6 mmol) of 2- (2-chloroethoxy) ethanol was added thereto under stirring, and the mixture was refluxed under a nitrogen atmosphere for 2 hours. After stirring for a further 24 hours, the solvent was evaporated in vacuo. The resulting brownish oil was used directly in the next reaction, treated with tosyl chloride (1.47 g, 7.4 mmol) and sodium hydroxide (0.3 g, 7.7 mmol) dissolved in THF (100 mL). After stirring at room temperature for 24 hours, the solvent was evaporated in vacuo and the resulting mixture was dissolved in 100 mL of dichloromethane. The organic layer thus obtained was washed with 300 mL of water, dried over anhydrous Na ₂ SO ₄ and filtered. Thereafter, ethyl acetate / hexane (1: 4) was purified by silica gel column chromatography using a mobile phase solution to obtain 1.5 g (50%) of the yellow colored compound of Chemical Formula (5).

¹ H NMR (400 MHz, CDCl ₃ ): δ 7.74 (d, 4H, Ar H ), 7.30 (d, 4H, Ar H ), 4.06 (m, 4H, -OC H ₂ CH ₂ O-), 3.59 ( m, 4H, -OCH ₂ C H ₂ O-), 3.51 (m, 4H, -OC H ₂ CH ₂ O-), 2.66 (s, 4H, -SC H ₂ C H ₂ S-), 2.58 (m , 4H, -SC H ₂ CH ₂ O-), 2.37 (s, 6H, -OC H ₂ CH ₂ O-).

¹³ C NMR (100 MHz, CDCl ₃ ): δ 145.1, 133.0, 130.1, 128.1, 71.3, 69.4, 68.5, 38.7, 37.7, 32.8, 32.1, 31.6, 21.8 ppm. FAB MS m / z (M ⁺ ): calcd, 578.11 Found, 578.0

Example  1-2: Synthesis of Compounds of Formula (3)

3.4-dihydroxybenzaldehyde (1 g, 7.24 mmol) which is a compound of Formula (7), and K ₂ CO ₃ A mixture of (1 g, 7.24 mmol) was added to 50 ml of acetonitrile (CH ₃ CN). Of the formula (5) 1.43 g (7.23 mmol) of the compound were added thereto, and the mixture was refluxed for 18 hours under a nitrogen atmosphere. The solvent was evaporated to dryness in the cooled mixture thus obtained and extracted three or four times with chloroform. The extract was evaporated to dryness until a viscous oil was obtained, purified by silica gel column chromatography using ethyl acetate / hexane (1: 2) as a mobile phase solution, and finally 2.1 g (77%). (3) The compound was obtained.

¹ H NMR (400 MHz, CDCl ₃ ): δ 9.83 (s, 1H, C H O), 7.46 (d, 2H, Ar H ), 6.9 (d, 1H, Ar H ), 4.36 (m, 4H,- OC H ₂ CH ₂ O-), 3.93 (m, 8H, -OCH ₂ C H ₂ O-), 3.86 (m, 4H, -OC H ₂ CH ₂ S-), 2.95 (s, 4H, -SC H ₂ C H ₂ S-), 1.22 (s, 4H, -OC H ₂ CH ₂ O-).

¹³ C NMR (100 MHz, CDCl ₃ ): δ 190.9, 155.1, 150.2, 131.1, 127.4, 447.9, 72.8, 72.2, 71.9, 68.9, 32.9, 32.0, 29.9 ppm.

FAB MS m / z (M ⁺ ): calcd, 372.11 Found, 372.0

Example  1-3: Synthesis of Compound of Formula (1)

Two drops of TFA were added to 0.18 g (1.89 mmol) of 2,4-dimethylpyrrole and 300 mg (1.1 mmol) of the compound of formula (3) in dried dichloromethane. The resulting yellow solution was stirred at room temperature under N _{2 for} 3 hours. It was added chloranil (p -chloranil) (0.47 g ( 1.89 mmol)) solution - here the p dissolved in dichloromethane 100ml. After stirring for 30 minutes, Et ₃ N and BF ₃ · OEt ₂ were added continuously until bright green fluorescence was observed. The solution thus obtained was washed with water, and the organic layer was dried over anhydrous MgSO ₄ . The organic solvent was removed in vacuo to yield a reddish solid. Then, flash silica gel column chromatography was carried out using ethyl acetate as a mobile phase solution, and a pale yellow viscous oil solvent was evaporated in a cold state to obtain 250 mg (53%) of the compound of formula (1).

¹ H NMR (400 MHz, CDCl ₃ ): δ 6.94 (d, 2H, Ar H ), 6.77 (d, 1H, Ar H ), 5.97 (s, 2H, Ar H ), 4.20 (m, 4H, -OC H ₂ CH ₂ O-), 3.92 (m, 4H, -OCH ₂ C H ₂ O-), 3.80 (m, 4H, -OC H ₂ CH ₂ O-), 2.88 (s, 4H, -SC H ₂ C H ₂ S-), 2.80 (q, 4H, -SC H ₂ CH ₂ O-), 2.54 (s, 6H,-Ar H ), 1.46 (s, 6H,-Ar H ).

¹³ C NMR (100 MHz, CDCl ₃ ): δ 146.9, 143.5, 143.2, 138.2, 129.0, 126.1, 125.6, 121.3, 119.4, 119.2, 72.6, 69.7, 46.4, 32.8, 29.9, 14.7, 8.8 ppm.

FAB MS m / z (M ⁺ ): calcd, 590.23 Found, 590.0

Example  2: Synthesis of Compound of Formula (2) when n is 1

300 mg (57%) of the compound of formula (2) was carried out in the same manner as described in Example 1, except that 300 mg (1 mmol) of compound of formula (4), wherein n was 1, was added instead of the compound of formula (3). Got.

¹ H NMR (400 MHz, CDCl ₃ ): δ 6.95 (d, 2H, Ar H ), 6.79 (d, 1H, Ar H ), 5.97 (s, 2H, Ar H ), 4.20 (m, 4H, -OC H ₂ CH ₂ O-), 3.96 (m, 4H, -OCH ₂ C H ₂ O-), 3.79 (m, 4H, -OC H ₂ CH ₂ O-, 4H, -OCH ₂ C H ₂ O-) , 2.54 (s, 6H,-Ar H ), 1.46 (s, 6H,-Ar H ).

¹³ C NMR (100 MHz, CDCl ₃ ): δ 155.7, 143.4, 130.0, 128.2, 121.3, 113.6, 70.9, 70.7, 70.0, 69.5, 68.9, 14.7 ppm.

FAB MS m / z (M ⁺ ): calcd, 514.25 Found, 514.0

Example  3: Synthesis of Compound of Formula (2) (when n is 2)

Instead of the compound of formula (3), 250 mg (0.73 mmol) of compound of formula (4) having n is 2, and then the mobile phase solution was replaced with ethyl acetate, and the mobile phase solution was replaced with EtOAc-hexane (2: 0.29 g (70%) of the compound of formula (2) was obtained in the same manner as described in Example 1, except that silica gel column chromatography (1) was performed.

¹ H NMR (400 MHz, CDCl ₃ ): δ 6.95 (d, 2H, Ar H ), 6.76 (d, 1H, Ar H ), 5.97 (s, 2H, Ar H ), 4.20 (m, 4H, -OC H ₂ CH ₂ O-), 3.98 (m, 4H, -OCH ₂ C H ₂ O-), 3.80 (m, 4H, -OC H ₂ CH ₂ O-), 3.73 (m, 4H, -OCH ₂ C H ₂ O-, 4H, -OC H ₂ C H ₂ O-), 2.54 (s, 6H,-Ar H ), 1.46 (s, 6H,-Ar H ).

¹³ C NMR (100 MHz, CDCl ₃ ): δ 155.6, 143.4, 131.9, 131.8, 121.4, 121.3, 121.0, 70.4, 70.3, 70.2, 14.8, 14.7 ppm.

FAB MS m / z (M ⁺ ): calcd, 558.27 Found, 558.0

Experimental Example  1: of the compound of formula (1) UV Of vis  Change measurement

The property of the metal ion to combine with the compound of formula (1) is Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ , Ag ⁺ , Cd ^{2 +} , Mg ^{2 +} , Ca ^{2 +} , Sr ^{2 +} , Ba ^{2 +, Zn 2 +, Hg 2} +, Pb 2 +, Co 2 +, Cu 2 + , and Al ^{3 +} ions _{H 2 O / CH 3 CN (} 6: 4, v / v) was added to the fluorescence and UV / The change was observed through vis. The reason for using an aqueous solution of H ₂ O / CH ₃ CN (6: 4, v / v) is that an aqueous solution is required when the fluorescent compound is applied to a biological system as a photo-emitting chemical acceptor. 2 shows the UV / vis spectrum of the compound of formula (1) in which several metal ions or mercury ions are bound. FIG kind of metal ions used in the 2, ^{Li +, Na +, K +} , Rb +, Cs +, Ag +, Cd 2 +, Mg 2 +, Ca 2 +, Sr 2 +, Ba 2 +, Zn 2 ^+, Hg ^{+ 2,} Pb ^{2 +,} Co ^{2 +,} Cu ^{2 +,} and Al was ^{3 +} ion, ClO ₄ ^- was added in the form of a salt with. At this time, the aqueous solution used was H ₂ O / CH ₃ CN (6: 4, v / v), the compound of formula (1) was added to 15.0μM, metal ions were added to each 50 equivalents. 2, if, while ropgo compound free the formula (1) are not bonded to the metal is pointed at 498.0 nm, can see what appears a strong absorption band Hg ^{2 +} is combined with the Formula (1) compound It can be seen that the absorption band of the compound of formula (1) shifted to 499.5 nm by slightly shifting red color at 498 nm (Δλ = 1.5 nm). However, when the formula (1) compound in combination with said other metal ion than the Hg ^{+ 2} has been confirmed to be free from any detectable change in the chemical formula (1) compound.

Mode in which ^two sulfur atoms in the compound of formula (1) are bonded to sulfur atoms and Hg ²⁺ in the compound of formula (1) by comparing the compound of formula (2) and (1), which is a crown ether of ordinary oxygen Could be looked at in more detail. The crowns of Crown-5 and Crown-6 of the compound (2) are well known to accept Na ⁺ and K ⁺ ions, but do not cause UV / vis band shift. This is because BODIPY is located perpendicular to the benzocrown unit so that intramolecular charge transfer (ICT) changes no longer affect the binding of metal ions.

Experimental Example  2: Measurement of Fluorescence Change of Compound of Formula (1) (I)

3 shows the results for the fluorescence change. This experiment was carried out by measuring the change in fluorescence emission ( I - I ₀ ) of the compound of formula (1) or (2) excited at 498 nm to H ₂ O / CH ₃ CN (6: 4, v / v) The fluorescence change is measured after adding 0.50 μM of the solution of Formula (1) or (2) with 50 equivalents of various metal ions. I ₀ represents the fluorescence emission intensity of (1) or (2) in the state not bonded with any metal ion and I represents the fluorescence emission intensity of (1) or (2) in the state combined with metal ion, (+ ) Indicates increased fluorescence emission (-) indicates reduced fluorescence emission. Referring to Figure 3, it can be seen that show high selectivity and sensitivity with respect to the formula (2) Hg ^{+ 2} Formula (1), whereas visible a low selectivity with respect to most of the metal cation if the compounds are ensured. Similar fluorescence changes of the fluorescence emission increases in the case the general formula (1) compound and a combination of Ag ⁺ is one to suggest that the binding and silver sulfur, is very low compared to the sensitivity shown in engagement with the Hg ^{+ 2.} Fluorescence reinforcement by bonding with these Hg ^{+ 2} is due to the CHEF (Chelation-induced Enhanced Fluorescence) mechanism. Hg ^{+ 2} is thiazol-when the sulfur atom of the crown portion and the interaction, a PET (photo-induced electron transfer) to BODIPY emitting fluorescence from the sulfur atom is inhibited. However, Cu ^{2 +} ions but rather to indicate a quenching effect noticeable, which d ⁹ - and Cu (II) having an electronic array is coupled with a compound of formula (1), is easily give a significant fluorescence quenching by causing the PET .

Experimental Example  3: Measurement of Fluorescence Change of Compound of Formula (1) (II)

Figure 4 is a spectrum showing a change in the fluorescence emission of the formula (I) compounds according to the Hg ^{+ 2} ion titration. Compound (1) was added to the aqueous solution of H ₂ O / CH ₃ CN (6: 4, v / v) at 0.50 μM (λ _ex) = 498 nm). Compound (1), which is not bound with a metal ion, exhibits a strong green fluorescence of 507 nm in H ₂ O / CH ₃ CN (6: 4, v / v) solution. The formula (1) compound is excited at 498 nm the fluorescence intensity was increased noticeably with Hg ^{2 +} concentration. According to the fluorescent emission changes, binding constants of the formula (I) compound for Hg ^{2 +} is K _a = 1.59x10 ⁵ M ^{- 1} was obtained.

Experimental Example  4: of the compound of formula (1) Job  Plot

5 is a result of obtaining a Job plot while changing the concentration of the compound of formula (1) and Hg ^{2 +} . Referring to FIG. 5, by showing the maximum point at a 0.5 molar ratio, it can be seen that the ligand and the metal form a complex 1: 1.

Experimental Example  5: Measurement of Fluorescence Change of Compound of Formula (1) (III)

An important chemical receptor's properties include high selectivity for the analyte to be analyzed among competing materials. In the case 6 and 7 is present with a variety of metal ions and Hg ^{2 +} ion analysis target, it indicates the fluorescence spectrum showing the Hg ^{2 +} ion selectivity of the formula (I) compound. _{H 2 O / CH 3 CN (} 6: 4, v / v) to were the formula (1) compound in 10 mM, Hg ^{2 +} ions with ^{Li +, Na +, K +} , Rb +, Cs +, Ag a ^{+, Cd 2+, Mg 2 +} , Ca 2 +, Sr 2 +, Ba 2 +, Zn 2 +, Pb 2 +, Co 2 +, Cu 2 + , and each of the 10 times the amount of miscellaneous cation with the Al ^{3 +} that was, here in 498 nm sikyeotgo all spectral data were measured in 10 minutes after the Hg ^{+ 2} is added. Referring to Figure 6 and 7, was any significant change in the fluorescence did not occur in the presence of miscellaneous competing cations, and further in the presence of miscellaneous competing cations FIG Hg ^{2 +} ion is still exhibited a result that the similar fluorescence increase. In addition, Hg ^{2 +} increase of fluorescence intensity by addition of ions was also not affected by adding together the other competing cations.

1 is a schematic view showing a state of forming a composite by combining the Hg ^{+ 2} ions and the chemical formula (1) compound and emit fluorescence.

2 shows the UV / vis spectrum of the compound of formula (1) in which several metal ions or mercury ions are bound.

Figure 3 is the result of measuring the change in fluorescence emission ( I - I ₀ ) of the compound of formula (1) or (2) excited at 498 nm.

Figure 4 is a spectrum showing a change in the fluorescence emission of the formula (I) compounds according to the Hg ^{+ 2} ion titration.

Figure 5 is a result obtained by changing the concentration of the Job plots (1) and Hg ^{+ 2.}

In the case 6 and 7 is present with a variety of metal ions and Hg ^{2 +} ion analysis target, it indicates the fluorescence spectrum showing the Hg ^{2 +} ion selectivity of the formula (I) compound.

Claims (11)

Crown ether derivative to which BODIPY is represented by the following formula (1) or formula (2).

                      (1) (2) N is 1 or 2 in the said General formula (2). According to Scheme 1, 2,4-dimethylpyrrole and p-chloranil are reacted with a compound of formula (3) to prepare a crown ether derivative in which BODIPY is bonded to formula (1). Scheme 1

         (3) (1) [Claim 3] The crown ether derivative of claim 2, wherein the compound of formula (3) is prepared by the reaction of a compound of formula (5) with a compound of formula (7) according to Scheme 2 below. How to prepare. Scheme 2

  (7) (3) A method for preparing a crown ether derivative to which BODIPY of formula (2) is bound from a compound of formula (4) according to Scheme 3 below. Scheme 3

        (4) (2) In Scheme 3, n is 1 or 2. [Claim 5] The crown ether derivative of claim 4, wherein the compound of formula (4) is prepared by reaction of a compound of formula (6) with a compound of formula (7) according to Scheme 4 below. How to prepare. Scheme 4

  (7) (4) In Scheme 4, n is 1 or 2. (a) dissolving a compound represented by formula (1) or formula (2) in an aqueous solution; (b) adding a sample containing metal ions to the solution obtained in (a); (c) applying light to excite the compound of formula (1) or formula (2) contained in the solution obtained in (b); And (d) measuring the fluorescence emitted from the solution obtained in (c).

               (1) (2) N is 1 or 2 in the said General formula (2). The method of claim 6, wherein the compound of Formula (1) or Formula (2) is added to the aqueous solution at a concentration of 0.1 μM to 1 mM. 7. The method of claim 6, wherein the metal ions are mercury ions. 7. The method of claim 6, wherein said light is in the range of 490 nm to 500 nm. 7. The method of claim 6, wherein the aqueous solution consists of H ₂ O and CH ₃ CN. The method of claim 10, wherein the ratio of the volume of H ₂ O and CH ₃ CN is 4: 6 to 6: 4.

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