KR102119011B1 - A novel porphyrin derivatives having various substituents, composition for detecting cyanide ion conmprising the same and method for detecting cyanide ion using the same - Google Patents

Abstract

The present invention provides a novel dicyanovinylporphyrin compound having various substituents, a composition for detecting cyan ions comprising the same, and a method for detecting cyan ions using the same.
The dicyanovinylporphyrin compound having various substituents of the present invention, a composition for detecting cyan ions comprising the same, and a method for detecting cyan ions using the same may be useful as a cyan ion specific detection technique in the field of cyan ion detection.

Description

A novel porphyrin derivatives having various substituents, composition for detecting cyanide ion conmprising the same and method for detecting cyanide ion using the same }

The present invention relates to a porphyrin derivative having various substituents used for detecting cyan ions, and more specifically, a novel dicyanovinylporphyrin compound having various substituents, a composition for detecting cyan ions comprising the same, and cyan ion detection using the same It's about how.

In many fields, such as the chemical, biological, medical, and environmental fields, it is necessary to quickly and accurately analyze the concentrations of various ions contained in a test solution, and chemical sensor materials having selectivity for specific ions are used for such analysis. These materials are applied to the analysis of specific ions by measuring changes in electrical properties such as electricity and resistance to specific ions or optical properties such as color and fluorescence. Among the various types of chemical sensors, the chemical sensors of anions and cations based on colorimetric methods have many advantages such as relatively simple, low reversibility, and rapid detection of substances to be analyzed. Therefore, the colorimetric sensor has received a lot of attention recently because it can detect color changes visually without additional expensive equipment.

Cyanide ion (CN ^-) is fast, the reactivity, it is known as a fatal poison. The toxicity is due to the tendency of cyan ions to bind strongly to the iron ions of cytochrome c oxidase in animal cells, and it interferes with electron transport and inhibits cellular respiration, resulting in hypoxia. However, despite these toxicity, cyan ions are widely used in industries such as electroplating, plastic manufacturing, gold and silver refining, dyeing, photo printing, and the like. Therefore, there is a need to develop a method for selectively and sensitively detecting cyan ions.

Porphyrin (porphyrin) is a macrocyclic compound containing four pyrrole rings as a kind of a compound constituting a pigment component that plays an important role in an oxidation-reduction reaction in vivo. The porphyrin absorbs light of a long wavelength, and thus is used for photodynamic treatment using a laser. In particular, it has been used as a semiconductor material in the application research of organic devices such as organic transistors and organic solar cells with recent developments in organic electronics.

Among various sensor systems that recognize negative ions, the fluorescence sensor system has recently been spotlighted in that it has various advantages such as excellent selectivity, low cost, easy detection, and biological applicability. Therefore, efforts to develop a novel chemical sensor using a fluorescent reaction are required.

Republic of Korea Patent Publication No. 1990-0007853 (June 02, 1990)

Ravi Kumar, et al., Dalton Trans. 2015 May 21;44(19):9149-57 (21st May 2015) Mandeep K. Chahal, et al., Phys Chem Chem Phys. 2017 Feb 8;19(6):4530-4540 (February 8, 2017)

The present inventors studied cyanide-specific high-sensitivity sensing technology capable of detecting cyanide ions, and dicyanovinylporphyrin derivatives having various substituents reacted specifically with cyanide ions according to the change of the substituent, thereby absorbing visible light. It was confirmed that the reaction specificity for cyan ions was changed by exhibiting a change in the degree of increase and decrease in fluorescence.

Accordingly, an object of the present invention is to provide a dicyanovinylporphyrin compound having various substituents, a composition for detecting cyan ions comprising the same, and a method for detecting cyan ions using the same.

According to an aspect of the present invention, there is provided a compound represented by the following formula (4).

[Formula 4]

또는 CF₃일 수 있다.Where R is

Or CF ₃ .

In one embodiment, the compound represented by Formula 4 may be a compound represented by Formula 1 or a compound represented by Formula 3 below.

[Formula 1]

[Formula 3]

및 디피로메탄올을 반응시키는 단계를 포함하는 제1항의 화합물의 제조방법(여기서 R은

또는

이다.)이 제공된다.According to another aspect of the invention, the dicyanovinyl benzaldehyde and

And reacting dipyromethanol to produce the compound of claim 1 (where R is

or

Is provided.)

및 디피로메탄올을 반응시키는 단계를 포함하는 하기 화학식 1로 표시되는 화합물의 제조방법이 제공된다.In one embodiment, dicyanovinylbenzaldehyde and

And it provides a method for producing a compound represented by the following formula (1) comprising the step of reacting dipyromethanol.

[Formula 1]

및 디피로메탄올을 반응시키는 단계를 포함하는 하기 화학식 3으로 표시되는 화합물의 제조방법이 제공된다.In one embodiment, dicyanovinylbenzaldehyde and

And it provides a method for producing a compound represented by the following formula (3) comprising the step of reacting dipyromethanol.

[Formula 3]

According to another aspect of the present invention, a composition for detecting cyan ions comprising the compound is provided.

In one embodiment, the composition for detecting cyanide may include tetrahydrofuran, chloroform and dichloromethane as solvents.

According to another aspect of the present invention, there is provided a method for detecting cyanide ions comprising reacting the compound with a sample.

In one embodiment, in the cyan ion detection method, tetrahydrofuran, chloroform, and dichloromethane may be used as a solvent, absorbance is measured in a visible light wavelength range 400-410 nm, and fluorescence in a fluorescence wavelength range 630-640 nm. The measuring step may further include.

According to another aspect of the present invention, a cyan ion detection device using the compound is provided.

In one embodiment, the cyan ion detection device may use tetrahydrofuran, chloroform and dichloromethane as a solvent, measure absorbance in the visible light wavelength range 400-410 nm, and fluorescence in the fluorescence wavelength range 630-640 nm. Can be measured.

According to the present invention, the cyanide ion reacts specifically with the dicyanovinylporphyrin derivative containing various substituents to increase the absorbance and decrease the fluorescence, so that the dicyanovinylporphyrin having various substituents has excellent reaction specificity for cyanide. It turned out. In particular, the dicyanovinylporphyrin derivative containing a substituent having a high electron density due to high electron mobility (affinity) showed excellent specificity in reducing fluorescence for cyan ions more than twice as compared to phenyl dicyanovinylporphyrin.

Accordingly, the dicyanovinylporphyrin compound containing various substituents of the present invention, a composition for detecting cyan ions comprising the same, and a method for detecting cyan ions using the same may be useful as a cyan ion specific detection technique in the field of cyan ion detection.

1 is a schematic diagram showing the synthesis of a dicyanovinylporphyrin compound having various substituents.
2 is a MALDI-TOF spectrum of the compound of Formula 1 in CDCl ₃ .
3 is a MALDI-TOF spectrum of a compound of Formula 2 in CDCl ₃ .
4 is a MALDI-TOF spectrum of the compound of Formula 3 in CDCl ₃ .
5 is an absorbance spectrum and colorimetric change (a) and fluorescence spectrum (b) for compound 1 and various anions in THF solvent.
6 is an absorbance spectrum and colorimetric change (a) and fluorescence spectrum (b) for compound 2 and various anions in THF solvent.
7 is an absorbance spectrum and colorimetric change (a) and fluorescence spectrum (b) for compound 3 and various anions in THF solvent.
8 is a summary diagram showing specificity for cyan ions according to electron mobility (affinity) of a dicyanovinylporphyrin compound having various substituents.

The present invention provides a compound represented by the following formula (4).

[Formula 4]

또는 CF₃일 수 있다.Where R is

Or CF ₃ .

In one embodiment, the compound may be a compound represented by Formula 1 or a compound represented by Formula 3.

[Formula 1]

[Formula 3]

및 디피로메탄올을 반응시키는 단계를 포함하는 화학식 4로 표시되는 화합물의 제조방법(여기서 R은

또는

이다.)을 제공한다.In addition, the present invention is a dicyanovinyl benzaldehyde and

And a method of preparing a compound represented by Chemical Formula 4, comprising reacting dipyromethanol (where R is

or

Is provided.)

및 디피로메탄올을 반응시키는 단계를 포함하는 화학식 1로 표시되는 화합물의 제조방법을 제공한다.In one embodiment, dicyanovinylbenzaldehyde and

And it provides a method for producing a compound represented by the formula (1) comprising the step of reacting dipyromethanol.

[Formula 1]

Reaction Scheme 1 is dipyrromethane, dicyanovinylbenzaldehyde, 4-(diphenylamino)benzaldehyde, dichloromethane, DCM, and acid catalyst in a round bottom flask. After dropping and cyclizing the reactant, block the light and stir for 8 hours or more. After oxidizing the porphyrin intermediate using an oxidizing agent, the mixture is stirred for 2 hours or more. To remove the residual trifluoroacetic acid, triethylamine was added dropwise and stirred for 30 minutes or more. The reaction mixture was dissolved in chloroform (Chlroroform) and separated by column chromatography to obtain the above product.

[Scheme 1]

및 디피로메탄올을 반응시키는 단계를 포함하는 화학식 3으로 표시되는 화합물의 제조방법을 제공한다.In one embodiment, dicyanovinylbenzaldehyde and

And it provides a method for producing a compound represented by the formula (3) comprising the step of reacting dipyromethanol.

[Formula 3]

Scheme 3 below shows dipyromethane, 4-(trifluoromethyl)benzaldehyde, 4-(diphenylamino)benzaldehyde in a round-bottom flask, Dichloromethane (DCM) was added, and an acid catalyst was added dropwise to cyclize the reactant to block light and stir for at least 8 hours. After oxidizing the porphyrin intermediate using an oxidizing agent, the mixture is stirred for 2 hours or more. To remove the residual trifluoroacetic acid, triethylamine was added dropwise and stirred for 30 minutes or more. The reaction mixture was dissolved in chloroform (Chlroroform) and separated by column chromatography to obtain the above product.

[Scheme 3]

In addition, the present invention provides a composition for detecting cyan ions containing the compound.

In one embodiment, the composition for detecting cyanide may include tetrahydrofuran, chloroform and dichloromethane as solvents.

In addition, the present invention provides a method for detecting cyanide ions comprising the step of reacting the compound with a sample.

In one embodiment, in the cyan ion detection method, tetrahydrofuran, chloroform, and dichloromethane may be used as a solvent.

In the cyan ion detection method, the compound of Formula 4 increases the absorbance in the visible light wavelength range 400-410 nm, in particular, 405 nm, when the cyan ion is added, and fluoresces in the fluorescence wavelength range 630-640 nm, especially 634 nm. This decrease appears. The reaction is a strong nucleophilic anion because the carbon α- (α-Carbon) of dicyano vinyl group E is low in the compound of formula (4) ^- can attack the (CN, hydrazine, etc.) α- carbon, as a result It is presumed that a colorimetric or fluorescence-based reaction appears.

Reaction specificity and an anion-selective experiment for cyan ion is tetrahydrofuran (THF) different anions in the solvent ^{(F -, Cl -, Br} +, I -, HSO4 -, ClO 4 - and CN ^-) with the fluorescence emission spectrum And all anions were used as tetrabutyl ammonium salts. Compound 1 (DPTPA) is fluoride (F ^-), iodine cargo (I ^-), cyanide ion (CN ^{-) -} represents an off fluorescence behavior chloride (Cl ^-) weak turn in the presence of, bromine cargo (Br _{^{-), nO 2 -, HSO}} 4 - and ClO ₄ ^- does not appear in the change (see Fig. 5). Compound 2 (DPP) is fluoride (F ^-), cyanide ion (CN ^{-) -} represents an off fluorescence behavior chloride (Cl ^-) turned out in the presence of bromine cargo (Br ^-), iodide (I ^-) , nO ₂ ^-, HSO ₄ ^- and ClO ₄ ^- does not appear in the variation (see FIG. 6). Compound 3 (DPTFM) is a cyan ion (CN ^{-) -} represents an off fluorescence behavior of fluoride (F ^-) specific to turn on, chloride (Cl ^-), bromine cargo (Br ^-), iodide (I ^{- _{), nO 2 -, HSO 4}} - and ClO ₄ ^- does not appear in the change (see Fig. 7).

In addition, the present invention provides a cyan ion detection device using the compound.

In one embodiment, the cyan ion detection device may use tetrahydrofuran, chloroform and dichloromethane as a solvent, measure absorbance in the visible light wavelength range 400-410 nm, and fluorescence in the fluorescence wavelength range 630-640 nm. Can be measured.

As a result of measuring the absorbance and fluorescence of Compound 1, Compound 2 and Compound 3, respectively, using tetrahydrofuran as a solvent as the cyan ion detection device, Compound 1 (DPTPA) decreased in absorbance by addition of cyan ions, and Compound 1 When cyanide was added to (DPTPA), a color change was observed in which the color of the solution changed from dark red to dark brown, and fluorescence emission was reduced by 28% by addition of cyanide, and compound 2 (DPP) was cyanide. Absorption increased by addition, and color change in which the color of the solution changed from orange to pink when cyan ions were added to compound 2 (DPP) was observed, and fluorescence emission was found to decrease by 40% by addition of cyan ions. In addition, Compound 3 (DPTFM) significantly increased absorbance compared to Compound 2 (DPP) by adding cyan ions, and a color change in which the color of the solution changed from orange to pink when cyan ion was added to Compound 3 (DPTFM) was observed. The fluorescence emission was reduced by 86% by the addition of cyan ions and more than twice that of Compound 2 (DPP).

Therefore, cyanide ion reacted specifically with dicyanovinylporphyrin derivatives containing various substituents to increase absorbance and decrease fluorescence, and dicyanovinylporphyrin with various substituents was confirmed to have excellent reaction specificity for cyanide. . Particularly, the dicyanovinylporphyrin derivative containing a substituent having a high electron density due to high electron mobility (affinity) showed excellent specificity to reduce fluorescence for cyan ions more than twice as compared to phenyl dicyanovinylporphyrin, The dicyanovinylporphyrin compound containing various substituents of the present invention, the composition for detecting cyan ions comprising the same, and the method for detecting cyan ions using the same can be useful as a cyan ion specific detection technique in the field of cyan ion detection.

Hereinafter, the present invention will be described in more detail through examples and test examples. However, the following examples and test examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Examples 1 to 2. Synthesis of dicyanovinylporphyrin compounds synthesized with various substituents

(1) Synthesis method of dicyanovinylporphyrin compound synthesized dicyanovinylporphyrin (DPP) and substituents

Dicyanovinylporphyrin (DPP) and dicyanovinylporphyrin compounds with substituents (DPTPA and DPTFM) were synthesized as shown in Scheme 1, Scheme 2, and Scheme 3 using Lindsey's condensation reaction.

Scheme 1 (Example 1: DPTPA)

Scheme 2 (DPP)

Scheme 3 (Example 2: DPTFM)

Specifically, the synthesis process is as follows.

Scheme 1 shows dipyromethane (0.5 g, 0.003424 mol, 2 eq), dicyanovinylbenzaldehyde (0.312 g, 0.001712 mol, 1 eq), 4-(diphenylamino)benzaldehyde in a 1L round-bottom flask. After adding 600ml of 4-(Diphenylamino)benzaldehyde, 0.468 g, 0.001712 mol, 1 eq), dichloromethane (DCM) and blowing nitrogen gas at room temperature for 30 minutes to remove the gas in the solution, the acid catalyst is trifluoroacetic acid (Trifluoroacetic) acid, TFA, 0.234 g, 0.00205 mol, 1.2 eq) was added dropwise to cyclize the reaction. After that, block the light and stir for 12 hours. After oxidizing the porphyrin intermediate using p-chloranil (p-Chloranil, 1.05 g, 0.00428 mol, 1.25 eq) as an oxidizing agent, the mixture is stirred for 4 hours. To remove the residual trifluoroacetic acid (TFA), 1 ml of triethylamine is added dropwise and stirred for 1 hour. The reaction mixture was dissolved in chloroform (Chlroroform) and separated by column chromatography (silica, CHCl ₃ 100% (v/v)) to obtain the above product.

Scheme 2 shows dicyanovinylbenzaldehyde (0.31 g, 0.001712 mol, 1 eq), benzaldehyde (Benzaldehyde, 0.18 g, 0.001712 mol, 1 eq), dipyromethane (Dipyrromethane, 0.5 g, 0.003424 mol) in a 1 L round-bottom flask. , 2 eq), dichloromethane (dichloromethane, DCM) 600ml was added and nitrogen gas was blown at room temperature for 30 minutes to remove the gas in the solution and stirred for 12 hours. Trifluoroacetic acid (0.234 g, 0.00205 mol, 1.2 eq) was added dropwise to cyclize the reaction. After that, block the light and stir for 12 hours. After oxidizing the porphyrin intermediate using p-chloranil (p-Chloranil, 1.05 g, 0.00428 mol, 1.25 eq) as an oxidizing agent, the mixture is stirred for 4 hours. To remove the residual trifluoroacetic acid (TFA), 1 ml of triethylamine is added dropwise and stirred for 1 hour. The reaction mixture was dissolved in chloroform (Chlroroform) and separated by column chromatography (silica, CHCl ₃ 100% (v/v)) to obtain the above product.

Scheme 3 shows dipyromethane (0.5 g, 0.003424 mol, 2 eq), 4-(trifluoromethyl)benzaldehyde, 0.312 g, 0.001712 mol, 1 in a 1 L round-bottom flask. eq), 4-(diphenylamino) benzaldehyde ((Diphenylamino)benzaldehyde, 0.4298 g, 0.001712 mol, 1 eq), dichloromethane (dichloromethane, DCM) 600ml and put nitrogen gas at room temperature for 30 minutes while blowing gas in solution After removal, the acid catalyst trifluoroacetic acid (Trifluoroacetic acid, 0.234 g, 0.00205 mol, 1.2 eq) was added dropwise to cyclize the reaction. After that, block the light and stir for 12 hours. After oxidizing the porphyrin intermediate using p-chloranil (Chloranil, 1.05 g, 0.00428 mol, 1.25 eq) as an oxidizing agent, the mixture is stirred for 4 hours. To remove the residual trifluoroacetic acid (TFA), 1 ml of triethylamine is added dropwise and stirred for 1 hour. The reaction mixture was dissolved in chloroform and separated by column chromatography (silica, CHCl ₃ 100% (v/v)) to obtain the above product.

(2) Structure analysis

The compounds of formula 1 of CDCl ₃ (DPTPA), was compound (DPP) and 2, the MALDI-TOF spectrum of a compound of formula 3 (DPTFM) each of the formula (2) shown in FIGS.

Test Example 1. Evaluation of reaction specificity and anion selectivity of cyanovinyl porphyrin compounds synthesized with various substituents on cyan ions

Reaction specificity and an anion-selective experiment for cyan ion is tetrahydrofuran (THF) different anions in the solvent ^{(F -, Cl -, Br} +, I -, HSO4 -, ClO 4 - and CN ^-) with the fluorescence emission spectrum And all anions were used as tetra butyl ammonium salts. Compound 1 (DPTPA) is fluoride (F ^-), iodine oxide (I ^-), cyanide ion (CN ^{-) -} showed the off fluorescence behavior chloride (Cl ^-) weak turn in the presence of, bromine oxides ( _{^{Br -), NO 2 -,}} HSO 4 - and ClO ₄ ^- in did not change. Compound 2 (DPP) is fluoride (F ^-), cyanide ion (CN ^{-) -} showed the off fluorescence behavior chloride (Cl ^-) turned out in the presence of bromine cargo (Br ^-), iodide (I ^{- _{), nO 2 -, HSO 4}} - and ClO ₄ ^- in the did not change. Compound 3 (DPTFM) is a cyan ion (CN ^{-) -} showed the off fluorescence behavior of fluoride (F ^-) specific to turn on, chloride (Cl ^-), bromine cargo (Br ^-), iodide (I _{^{-), nO 2 -, HSO}} 4 - and ClO ₄ ^- in the did not change.

Compound 1 (DPTPA), compound 2 (DPP) and compound 3 (DPTFM) in THF solvent all showed absorbance at 405 nm and fluorescence emission at 640 nm, 632 nm or 635 nm, 630 nm or 635 nm ( 5 to 7). As shown in Figure 5, THF solvent in the compound 1 (DPTPA) decreased the absorption by the cyan ion addition, various ions, including the cyan ion to the compound ^{1 (DPTPA) (F -,} Cl -, Br +, I - , HSO4 ^-, ClO ₄ ^-) a when specific to the color at the time of the cyanide ion is added a solution was observed that the color change is changed to dark brown in deep red, showed that the fluorescence emission is 28% reduced by the cyan ion added is added.

On the other hand, as shown in Fig. 6, THF solvent in the compound 2 (DPP) has increased the absorbance by the cyanide ion is added, various ions, including the cyan ion to compound ^{2 (DPP) (F -,} Cl -, Br + ^{, I -, HSO4 -, ClO} 4 -) a if was observed that the color change is changed to pink in the specific color in orange at the time of the addition of cyanide ion solution is added, the fluorescent emission of 40% reduction by the cyanide ion is added Appeared.

In addition, as shown in FIG. 7, compound 3 (DPTFM) in THF solvent significantly increased absorbance compared to compound 2 (DPP) by adding cyan ions, and compound 3 (DPTFM) contains various ions including cyan ions (F). ^{-, Cl -, Br +,} I -, HSO4 -, ClO 4 -) a if was observed that the color change is changed to pink in the specific color of the cyan ion added and the solution orange color, the fluorescence emission is cyanide ions added was added It was found to be reduced by more than 2 times compared to compound 2 (DPP) by 86%.

The reaction seems to be due to a mechanism in which the dicyanovinyl group chemically reacts with the cyanide ion when cyanide ion is added to the THF solution in which the dicyanovinylpropyrin derivative compound is dissolved. In particular, changes in absorbance and fluorescence intensity upon addition of cyan ions have acceptor substituents with stronger electron mobility (affinity) than substances with donor substituents (Compound 1, DPTPA) and reference substances (Compound 2, DPP). It appeared to react specifically with the substance (Compound 3, DPTFM), and was confirmed to be affected by substituents that affect electron density.

Claims (13)

Compound represented by the following formula (4):
[Formula 4]

Where R is

Or CF ₃ . According to claim 1, wherein the compound represented by Formula 4 is a compound represented by Formula 1 or a compound represented by Formula 3 below.
[Formula 1]

[Formula 3]

Dicyanovinyl benzaldehyde and

And reacting dipyromethanol
Method of preparing a compound of claim 1, wherein R is

or

to be.). According to claim 3, Dicyano vinyl benzaldehyde and

And reacting dipyromethanol
Method for producing a compound represented by the formula (1) comprising a.
[Formula 1]

According to claim 3, Dicyano vinyl benzaldehyde and

And reacting dipyromethanol
Method for producing a compound represented by the formula (3) comprising a.
[Formula 3]

A composition for detecting cyan ions comprising the compound of claim 1. 7. The composition for detecting cyan ions according to claim 6, comprising tetrahydrofuran, chloroform and dichloromethane. A method of detecting cyan ions, comprising reacting the compound of claim 1 with a sample. The method of claim 8, wherein tetrahydrofuran, chloroform and dichloromethane are used as solvents. The method of claim 8, comprising measuring the absorbance in the visible light wavelength range 400-410 nm and measuring the fluorescence in the fluorescence wavelength range 630-640 nm. Cyan ion detection device using the compound of claim 1. The cyan ion detection device according to claim 11, wherein tetrahydrofuran, chloroform and dichloromethane are used as solvents. The cyan ion detection apparatus according to claim 11, wherein the absorbance is measured in the visible light wavelength range 400-410 nm, and the fluorescence is measured in the fluorescence wavelength range 630-640 nm.

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