KR102099924B1 - Compound, and composition and structure including the same, and detection method of phosgene - Google Patents

Abstract

상기 화학식 1에서, R₁ 내지 R₁₆은 명세서에 기재된 바와 같다.A compound represented by Formula 1, a composition and a structure comprising the compound, and a method for detecting phosgene are provided:
<Formula 1>

In Formula 1, R ₁ to R ₁₆ are as described in the specification.

Description

Compound, composition and structure comprising the compound, and phosgene detection method {Compound, and composition and structure including the same, and detection method of phosgene}

It relates to a compound, a composition and a structure comprising the compound, and a method for detecting phosgene.

Phosgene is a highly toxic gas that is widely used in the chemical industry for the production of isocyanate-based polymers or pharmaceutical compounds. This gas has also attracted much attention because of its potential use as a bioterrorism agent.

Until recently, several attempts have been made to detect this toxic gas, phosgene gas. However, the phosgene-detecting compound or the like found from the above attempts has a problem of poor sensitivity to phosgene gas due to side reactions.

Therefore, there is still a need for novel compounds, compositions and structures comprising them to meet the requirements of high sensitivity to phosgene gas detection and further rapid reaction time to phosgene gas. Furthermore, there is still a need for an easy method for detecting phosgene.

One aspect is to provide a compound capable of detecting phosgene at a low concentration in a short time through color change and fluorescence response.

Another aspect is to provide a composition comprising the compound.

Another aspect is to provide a structure comprising the compound.

Another aspect is to provide a phosgene detection method capable of detecting low concentrations of phosgene in a short time through color change and fluorescence response.

According to one aspect,

A compound represented by Formula 1 is provided:

<Formula 1>

In Chemical Formula 1,

R ₁ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ are independently of each other hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy group , Amino group, carboxy group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C2 to C20 alkenyl group, substituted or unsubstituted C2 to C20 alkynyl group, substituted or unsubstituted C6 to C20 aryl group, substituted or unsubstituted C6 to C20 heteroaryl group, or a combination thereof Can;

R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ are independently of each other -F, -Cl, -Br, -I, amino group, hydroxy group, carboxy group, C1 to C20 alkyl group, C1 to C20 halogenation Alkyl group, C1 to C20 alkylamino group, C1 to C20 dialkylamino group, C6 to C20 arylamino group, C7 to C20 alkylarylamino group, C12 to C20 diarylamino group, C1 to C20 acylamino group, C1 to C20 Aralkylamino group, C1 to C20 aminoalkyl group, C6 to C20 aminoaryl group, C1 to C20 hydroxyalkyl group, C1 to C20 alkoxy group, C1 to C20 alkoxyalkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C7 to C20 aralkyl group, C6 to C20 aryl group, C7 to C20 alkary group, C2 to C20 heterocyclic group, C5 to C20 cycloalkyl group, C5 to C20 cyclo Alkenyl group, C5 to C20 cycloalkynyl group, C6 to C20 aryloxy Group may be a C7 to an arylalkyl group, a C7 to C20 acyloxy group in the C20, or a combination thereof.

According to another aspect,

The aforementioned compounds; And

A composition comprising one or more selected from solvents, acids, bases, and buffer solutions is provided.

According to another aspect,

Polymer matrix; And

A structure comprising the above-described compound embedded in the polymer matrix is provided.

According to another aspect,

Preparing a structure by electrospinning a mixture of a polymer matrix and the aforementioned compound; And

A method for detecting phosgene is provided, including; exposing the structure to phosgene to cause color change and fluorescence to detect phosgene.

The compound according to one aspect, the composition and the structure comprising the compound are compounds represented by Chemical Formula 1, and it is possible to detect low concentrations of phosgene in a short time through color change and fluorescence sensitization.

1A and 1B each show a reaction mechanism in which a compound (Compound 2) according to an embodiment reacts with triphosgene; A compound according to one comparative embodiment (Compound 4) shows a reaction mechanism for reacting with triphosgene.
2 and 3 are chemical compound (compound 2) for chemical sensors according to Preparation Example 1, and compound 3 (compound 2) for chemical sensors according to Preparation Example 1, respectively, produced by reaction with triphosgene 3 (FIG. 1) reference) is a result of the analysis of ¹ H -NMR and C ¹³ -NMR on.
4 is prepared by diluting the stock solution with 3 mL of chloroform after adding 0 μmol / L to 12 μmol / L of triphosgene to the chemical sensor compound (Compound 2) stock solution prepared in Preparation Example 1, respectively. Fluorescence emission spectrum (λ _ex = 530 nm, λ _em = 578 nm, slit: 3 nm ｘ 1.5 nm) according to the concentration of triphosgene for the probe solution.
Figure 5 is a chemical sensor compound (Compound 2) stock solution prepared by Preparation Example 1 and a chemical sensor compound (Compound 4) storage solution prepared by Comparative Preparation Example 1 to each of the solution was added 0.5 eq triphosgene solution Then, the fluorescence emission spectrum (λ _ex = 530 nm, λ _em = 578 nm, slit: 3 nm ｘ 1.5 nm) according to the reaction time for the probe solution prepared by diluting the stock solution with 3 mL of chloroform is an analysis result.
6 is added to each of the phosgene 0 eq to 1.0 eq solution to the chemical sensor compound (Compound 2) stock solution prepared by Preparation Example 1, and then dilute the stock solution with 3 mL of chloroform to the probe solution prepared It is an analysis result of colorimetric response according to the concentration of triphosgene.
7A and 7B are results of FE-SEM analysis of fibers embedded with chemical sensor compounds prepared in Example 1 before and after exposure to phosgene gas, respectively.
8A and 8B are results of analysis of a confocal microscope for fibers in which the chemical sensor compound prepared by Example 1 was embedded before and after exposure to phosgene gas, respectively.
9A and 9B respectively before and after exposure to phosgene gas, the chemical sensor compound prepared in Example 1 was irradiated with UV lamps of 365 nm wavelength for several seconds, respectively, for color for several seconds. / It is an analysis result of fluorescence sensitivity.

Hereinafter, a compound according to an embodiment of the present invention, a composition and a structure comprising the compound, and a method for detecting phosgene will be described in detail with reference to the accompanying drawings. The following is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of claims to be described later.

The term "comprising" is used herein to indicate that other components may be added and / or interposed, rather than excluding other components, unless specifically stated to the contrary.

As the compound for detecting phosgene, for example, a compound containing a reactive group of an o-phenylenediamine moiety is known. However, these compounds have a problem in that by-products such as hydrogen chloride (HCl) are formed when reacted with phosgene. More specifically, when a compound for phosgene detection is reacted with phosgene, when an fused ring is opened, an error that a by-product such as hydrogen chloride (HCl) occurs may degrade the sensitivity of phosgene detection.

The inventors of the present invention provide novel compounds, compositions and structures comprising the same to solve these problems.

The compound according to one embodiment may be represented by Formula 1 below:

<Formula 1>

In Chemical Formula 1,

R ₁ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ are independently of each other hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy group, amino group, Carboxyl group, cyano group, nitro group, amidino group, hydrazino group, hydrazono group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C2 to An alkenyl group of C20, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C6 to C20 heteroaryl group, or a combination thereof;

R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ are independently of each other -F, -Cl, -Br, -I, amino group, hydroxy group, carboxy group, C1 to C20 alkyl group, C1 to C20 halogenation Alkyl group, C1 to C20 alkylamino group, C1 to C20 dialkylamino group, C6 to C20 arylamino group, C7 to C20 alkylarylamino group, C12 to C20 diarylamino group, C1 to C20 acylamino group, C1 to C20 Aralkylamino group, C1 to C20 aminoalkyl group, C6 to C20 aminoaryl group, C1 to C20 hydroxyalkyl group, C1 to C20 alkoxy group, C1 to C20 alkoxyalkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C7 to C20 aralkyl group, C6 to C20 aryl group, C7 to C20 alkary group, C2 to C20 heterocyclic group, C5 to C20 cycloalkyl group, C5 to C20 cyclo Alkenyl group, C5 to C20 cycloalkynyl group, C6 to C20 aryloxy Group may be a C7 to an arylalkyl group, a C7 to C20 acyloxy group in the C20, or a combination thereof.

For example, the compound may be represented by Formula 2 below:

<Formula 2>

In Chemical Formula 2,

R ' ₁ , R' ₈ are independently of each other hydrogen, deuterium, -F, -Cl, -Br, -I, hydroxy group, carboxy group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C1 to C20 An alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, or a combination thereof;

R ' ₂ , R' ₃ , R ' ₄ , R' ₅ , R ' ₆ , R' ₇ are each independently -F, -Cl, -Br, -I, amino group, hydroxy group, carboxy group, C1 to C20 alkyl group , C1 to C20 halogenated alkyl group, C1 to C20 alkylamino group, C1 to C20 dialkylamino group, C6 to C20 arylamino group, C7 to C20 alkylarylamino group, C12 to C20 diarylamino group, C1 to C20 Acylamino group, C1 to C20 aralkylamino group, C1 to C20 aminoalkyl group, C6 to C20 aminoaryl group, C1 to C20 hydroxyalkyl group, C2 to C20 alkenyl group, C5 to C20 cycloalkyl group, C5 To C20 cycloalkenyl group, or a combination thereof.

For example, the compound may be represented by Formula 3 below:

<Formula 3>

In Chemical Formula 3,

R _a , R _b , R _c and R _d are independently of each other -F, -Cl, -Br, -I, amino group, hydroxy group, carboxy group, C1 to C20 alkylamino group, C1 to C20 dialkylamino group, C6 to C20 arylamino group, C7 to C20 alkylarylamino group, C12 to C20 diarylamino group, C1 to C20 acylamino group, C1 to C20 aralkylamino group, C2 to C20 alkenyl group, or a combination thereof. .

For example, the compound may be represented by the following Chemical Formulas 4 to 9.

<Formula 4>

<Formula 5>

<Formula 6>

<Formula 7>

<Formula 8>

<Formula 9>

1A and 1B each show a reaction mechanism in which a compound (Compound 2) according to an embodiment reacts with triphosgene; A compound according to one comparative embodiment (Compound 4) shows a reaction mechanism for reacting with triphosgene.

Referring to Figure 1a, the compound (Compound 2) according to one embodiment includes a rhodamine-based moiety that is fused with benzimidazole spirone, thereby reacting with phosgene to facilitate the ring opening process to react with color or / and Color or / and fluorescence response can easily occur. The compound may be a colorimetric fluorescent chemical sensor for phosgene detection.

1A and 1B, the compound (Compound 2) according to one embodiment does not generate HCl by-products when compared to the compound (Compound 4) according to one comparative embodiment during the ring opening process. Therefore, the compound (Compound 2) according to one embodiment is capable of detecting phosgene at a low concentration in a short time through color change and fluorescence response upon reaction with phosgene.

For example, the compound may have a phosgene detection limit of 3.2 ppb or more. The compound may react with phosgene within 2 minutes to cause color change and fluorescence change.

The composition according to another embodiment includes the above-mentioned compound; And a solvent, acid, base, and buffer solution. The composition may be prepared by adding the above-described compound to a solvent, a buffer solution or a mixture thereof, and adding an acid and / or a base thereto. In addition, the composition may further include other additives that can be used in the art. The content of the solvent, acid, base, and buffer solution included in the composition may be appropriately adjusted according to required performance. Alternatively, the composition may be mixed with a sample.

Structure according to another embodiment of the polymer matrix; And the aforementioned compound embedded in the polymer matrix.

The structure means a one-dimensional, two-dimensional and three-dimensional structure. The structure may be a structure of the scale I. The structure may be at least one selected from fibers, tubes, ribbons, wires, and rods. The structure may be a fiber composed of a plurality of beads.

The polymer matrix may be a polymer matrix that can be used in the art. Examples of the polymer matrix may include poly (ethylene oxide), poly (propylene oxide), poly (ethylene glycol), poly (propylene glycol), or copolymers thereof.

The weight average molecular weight (Mw) of the polymer matrix may be about 10,000 to 1,000,000, for example about 50,000 to 1,000,000, for example about 100,000 to 1,000,000, for example about 200,000 to 1,000,000 May be, for example, about 300,000 to 1,000,000, for example about 400,000 to 1,000,000, for example about 500,000 to 1,000,000, for example about 600,000 to 1,000,000. In this specification, the weight average molecular weight can be measured according to methods well known to those skilled in the art. For example, the weight average molecular weight can be measured according to a gel permeation chromatography (GPC) method.

The above-described compound may be embedded in the surface or / and the interior of the polymer matrix.

Phosgene detection method according to another embodiment comprises the steps of preparing a structure by electrospinning a mixture of a polymer matrix and a compound described above; And exposing the structure to phosgene to cause color change and fluorescence change to detect phosgene. By exposing the structure to phosgene at a low concentration within a short period of time, color change and fluorescence change can be caused to easily detect phosgene. Therefore, it can be used as a phosgene detection method in various places.

In this specification, a substituent is derived by exchanging other atoms or functional groups for one or more hydrogens in the unsubstituted mother group. Unless otherwise stated, when any functional group is considered to be "substituted", it is said that the functional group is an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, a cyclo group having 3 to 40 carbon atoms. It means that it is substituted with one or more substituents selected from alkyl groups, cycloalkenyl groups having 3 to 40 carbon atoms, and aryl groups having 7 to 40 carbon atoms. When the functional group is described as "optionally substituted", it means that the functional group can be substituted with the above-described substituent.

In this specification, a and b of "carbon numbers a to b" mean the number of carbon atoms in a specific group. That is, the functional group may include carbon atoms from a to b. For example, "an alkyl group having 1 to 4 carbon atoms" means an alkyl group having 1 to 4 carbons, that is, CH _3- , CH ₃ CH _2- , CH ₃ CH ₂ CH _2- , (CH ₃ ) ₂ CH-, CH ₃ CH ₂ CH ₂ CH _2- , CH ₃ CH _{2 means} CH (CH ₃ )-and (CH ₃ ) ₃ C-.

In the present specification, the term "alkyl group" means a branched or unbranched aliphatic hydrocarbon group. In one embodiment, the alkyl group may or may not be substituted. Alkyl groups include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, tert-butyl groups, pentyl groups, hexyl groups, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, etc. It is not necessarily limited to these, and each of these may be optionally substituted or not. In one embodiment, the alkyl group may have 1 to 6 carbon atoms. For example, the alkyl group having 1 to 6 carbon atoms may be methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, 3-pentyl, hexyl, and the like, but is not limited thereto.

As used herein, "halogenated alkyl group" means an aliphatic hydrocarbon group in which one to all of hydrogen is substituted with halogen. Halogen may be fluorine. In one embodiment, the halogenated alkyl group may be a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a tetrafluoromethyl group, etc., but is not limited thereto.

In the present specification, the term "alkenyl group" is a hydrocarbon group containing 2 to 20 carbon atoms containing at least one carbon-carbon double bond, an ethenyl group, 1-propenyl group, 2-propenyl group, 2-methyl- 1-propenyl group, 1-butenyl group, 2-butenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, and the like. In one embodiment, an alkenyl group may or may not be substituted. In one embodiment, the alkenyl group may have 2 to 10 carbon atoms.

In the present specification, the term "alkynyl group" is a hydrocarbon group containing 2 to 20 carbon atoms containing at least one carbon-carbon triple bond, an ethynyl group, 1-propynyl group, 1-butynyl group, 2-butynyl group And the like, but are not limited to these. In one embodiment, an alkynyl group may or may not be substituted. In one embodiment, an alkynyl group can have 2 to 10 carbon atoms.

In the present specification, the term "aralkyl" (aralkyl) means an aryl group connected as a substituent via an alkylene group, such as an aralkyl group having 7 to 20 carbon atoms, a benzyl group, 2-phenylethyl group, 3-phenylpropyl group , Naphthylalkyl groups. In one embodiment, the alkylene group is a lower alkylene group (ie, an alkylene group having 1 to 4 carbon atoms).

As used herein, the term “aryl group” refers to an aromatic ring whose ring backbone contains only carbon, a ring system (ie, two or more fused rings sharing two adjacent carbon atoms), or multiple aromatics The ring is a single bond, -O-, -S-, -C (= O)-, -S (= O) _2- , -Si (R _a ) (R _b )-(R _a and R _b are independent of each other As an alkyl group having 1 to 10 carbon atoms), an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with halogen, or a ring connected to each other by -C (= O) -NH-. If the aryl group is a ring system, each ring in the system is aromatic. For example, aryl groups include, but are not limited to, phenyl groups, biphenyl groups, naphthyl groups, phenanthrenyl groups, naphthacenyl groups, and the like. The aryl group may or may not be substituted.

In the present specification, the term "heteroaryl group" includes one or more heteroatoms selected from N, O, P, or S, and the remaining cyclic atoms are carbon monocyclic or bicyclic organic compounds. it means. The heteroaryl group may include, for example, 1-5 heteroatoms, and may include 5-10 ring members. The S or N may be oxidized and have various oxidation states.

In this specification, the term "alkylamino group" or "dialkylamino group" means an amino group in which one or all of hydrogen is substituted with an alkyl group. For example, it is a methylamino group or a dimethylamino group.

In this specification, the term "arylamino group" means an amino group in which one or more of hydrogen is substituted with an aryl group. For example, it is a phenylamino group.

In the present specification, the term "alkylarylamino group" means an amino group substituted with all hydrogen alkyl groups and aryl groups, respectively. For example, it is a methylphenylamino group.

In this specification, the term "diarylamino group" means an amino group in which all hydrogens are substituted with an aryl group. For example, it is a diphenylamino group.

In this specification, the term "acylamino group" means an amino group in which one hydrogen is substituted with an acyl group. For example, it is an acetylamino group.

In this specification, the term "aralkyl amino group" means an amino group in which all hydrogens are substituted with an aralkyl group. For example, it is a 2-phenylethylamino group.

In this specification, the term "aminoalkyl group" means an alkyl group in which one of hydrogen is substituted with an amino group. For example, it is an aminomethyl group.

In this specification, the term "aminoaryl group" means an aryl group in which one of hydrogen is substituted with an amino group. For example, it is an aminophenyl group.

In this specification, the term "hydroxyalkyl group" is an alkyl group having a hydroxy group. For example, it is a hydroxymethyl group.

In this specification, the term "alkoxyalkyl group" is an alkyl group having an alkoxy group. For example, it is a methoxymethyl group.

In the present specification, the term "alkaryl group (alkaryl)" means an aryl group connected as a substituent via an arylene group, such as an alkylaryl group having 7 to 20 carbon atoms, and includes, but is not limited to, methylphenyl group.

As used herein, "heterocyclic group" is a non-aromatic ring or ring system that includes one or more heteroatoms in the ring backbone.

As used herein, the term "cycloalkyl group" means a fully saturated carbocycle ring or ring system. For example, it means cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

As used herein, "cycloalkenyl group" is a carbocytle ring or ring system having one or more double bonds, and is a ring system without an aromatic ring. For example, it is a cyclohexenyl group.

As used herein, "cycloalkynyl group" is a carbocytyl ring or ring system having one or more triple bonds, and is an aromatic ring-free ring system. For example, it is a cyclohexynyl group.

In the present specification, the term "aryloxy" (aryloxy) means an aryl group connected as a substituent via oxygen, including but not limited to a phenoxy group.

In the present specification, the term "arylalkoxy group (arylalkoxy)" means an alkoxy group in which one hydrogen is substituted with an aryl group, and includes, but is not limited to, a phenylmethoxy group.

In the present specification, the term "aryloxy" (aryloxy) means an aryl group connected as a substituent via oxygen, including but not limited to a phenoxy group.

In the present specification, "hydroxy group" is -OH.

In this specification, "amino group" is -NH ₂ .

In the present specification, "carboxy group" is -COOH.

In this specification, "cyano group" is -CN.

In the present specification, "nitro group" is -NO ₂ .

In the present specification, "amidino group" is -CH ₂ -C (= NH) -NH ₂ .

In this specification, "hydrazino group" is -NHNH ₂

In the present specification, "hydrazono group" is -CH ₂ -C (= N-NH ₂ ) -CH ₃

Hereinafter, examples and comparative examples of the present invention will be described. However, the following examples are only examples of the present invention, and the present invention is not limited to the following examples.

[Example]

All reagents used in Preparation Example 1 and Comparative Preparation Example 1 were purchased and used without further purification from Sigma-Aldrich. ^{The 1} H NMR spectrum was recorded using a Bruker 300 MHz spectrometer with deuterium solvent, and the ¹³ C NMR spectrum using a Varian 125 Hz spectrometer, respectively. The unit of chemical shifts is ppm, and the unit of coupling constant (J) is Hz.

Manufacturing example  1: Compound synthesis for chemical sensors

A mixture was prepared by adding lithium aluminum hydride (4.5 mmol) in an ice bath to a solution of Compound 1 (0.9 mmol) in Reaction Scheme 1 in dry THF (10 mL). The mixture was stirred at room temperature under N ₂ atmosphere for 24 hours. To the stirred mixture, 1-butanol was added, quenched, and concentrated in vacuo. The concentrated residue was diluted with water and extracted with ethyl acetate to obtain an extract. The extract was dried over anhydrous MgSO ₄ and concentrated in vacuo to obtain the residue of Compound 2 of Reaction Scheme 1 below, which was purified by column chromatography to prepare a compound for a chemical sensor (light pink, yield: 80%). .

<Reaction Scheme 1>

¹ H NMR (CDCl ₃ , 300 MHz) δ (ppm): 8.13 (d, J = 7.2 Hz, 1H); 7.83 (d, J = 8.4 Hz, 1H); 7.51 (t, J = 7.2 Hz, 1H); 7.40 (t, J = 7.5 Hz, 1H); 7.26 (d, J = 7.5 Hz, 1H); 7.18 (t, J = 8.4 Hz, 1H); 7.04 (t, J = 7.2 Hz, 1H); 6.97 (d, J = 7.2 Hz, 1H); 6.51 (s, 2H); 6.33 (d, J = 9.0 Hz, 2H); 6.18 (d, J = 6.3 Hz, 2H); 3.34 (q, J = 7.2 Hz, 8H); 1.16 (t, J = 7.2 Hz, 12H). ¹³ C NMR (CDCl ₃ , 75MHz) δ (ppm): 156.87, 156.53, 153.30, 149.18, 149.06, 131.15, 130.66, 128.84, 128.52, 128.19, 125.08, 122.75, 122.14, 121.59, 120.35, 110.44, 108.37, 106.53 98.11, 44.57, 12.84. HRMS (ESI) m / z = 515.2823 [M + H] ⁺ , calcd for C ₃₄ H ₃₆ N ₄ O ₂ = 515.2733.

compare Manufacturing example  1: Compound synthesis for chemical sensors

1.1 g (6.9 mmol) of phosphorus oxychloride was added to 1.0 g (2.3 mmol, Compound 1 'of Reaction Scheme 2) in rhodamine B base solution dissolved in dry 1, 2-dichloroethane (8.0 mL) at room temperature. The mixture was prepared by dropping over 5 minutes. After the mixture was refluxed for 4 hours, the mixture was cooled and concentrated in vacuo to obtain rhodamine B acid chloride (Compound 2 'of Reaction Scheme 2 below). The obtained rhodamine B acid chloride was dissolved in dry acetonitrile (10 mL) and a 1.5 g (14 mmol) solution of o-diaminobenzene was added dropwise in dry acetonitrile (6.0 mL) containing triethylamine (8.0 mL). . The mixture in which the o-diaminobenzene solution was dropped was stirred at room temperature for 4 hours, concentrated in vacuo and purified by column chromatography to prepare a compound for chemical sensor of compound 4 of reaction scheme 2 below (white Solid, yield: 70%).

¹ H NMR (CDCl 3, 400 MHz) δ (ppm): 1.14 (t, J = 7.2 Hz, 12H); 3.18 (q, J = 7.2 Hz, 8H); 3.41 (s, 2 H); 6.09 (dd, J1 = 1.2 Hz, J2 = 5.1 Hz, 1H); 6.26 (bs, 2H); 6.30 (d, J = 12 Hz, 2H); 6.39-6.44 (m, 1 H); 6.55 (dd, J1 = 1.2 Hz, J2 = 5.1 Hz, 1H); 6.64 (d, J = 12 Hz, 2H); 6.92-6.98 (m, 1H); 7.23-7.25 (m, 1 H); 7.53-7.57 (m, 2H); 8.01-8.04 (m, 1H).

¹³ C NMR (CDCl 3, 75 MHz) δ (ppm): 12.5; 44.3; 68.0; 98.0; 106.9; 107.9; 117.0; 118.2; 122.1; 123.4; 124.2; 128.3; 128.6; 128.7; 128.8; 131.9; 132.6; 144.5; 148.9; 152.4; 153.9; 166.4.

ESI mass spectrometry (m / z): 533.5 ([M + H] ⁺ ), calculated 532.7

Example  1: Fiber with chemical sensor compound embedded

 A precursor solution for synthesizing fibers for electrospinning was prepared as follows. The chemical sensor compound (Compound 2 of Reaction Scheme 1) synthesized by Preparation Example 1 was completely dissolved in 2.5 mL acetonitrile. 100.0 mg of poly (ethylene oxide) (PEO, Mw: 600,000) as a matrix polymer was added to the compound solution for the chemical sensor and stirred for 1 hour to obtain a precursor mixture for electrospinning.

The obtained electrospinning precursor mixture was injected into a stainless steel syringe connected to a 23 gauge needle, and an electrospinning process was performed under conditions of an applied voltage of 5.0 kV, a flow rate of 0.5 mL / h, and a collecting distance of 15 cm. A fiber having a diameter of about 1 μM in which a compound for a chemical sensor (compound 2 of Reaction Scheme 1) was synthesized in the (ethylene oxide) matrix was prepared by Preparation Example 1 was prepared. The prepared fibers were dried under vacuum at 40 ° C. for one day to prevent agglomeration.

Analysis example One: ^One H  -NMR and ¹³ C-NMR analysis

Compound H for the chemical sensor according to Preparation Example 1 (Compound 2), and Compound 3 for the chemical sensor according to Preparation Example 1 (Compound 2) was reacted with triphosgene 3 for Compound 3 (see FIG. 1) ¹ H − NMR and ¹³ C-NMR analysis experiments were performed. Some of the analysis results are shown in FIGS. 2 and 3, respectively.

Referring to Figure 2, ¹ H -NMR analysis results, it can be confirmed that the peaks corresponding to H8 ', H9', H10 ', and H11' of Compound 3 are shifted downward when compared to the corresponding peaks of Compound 2 have. This is believed to be due to the presence of formyl chloride groups, electron withdrawing groups.

Referring to Figure 3, ¹³ C -NMR analysis results, Compound 3 can be confirmed that the peak is clearly visible at 143. 36 ppm. It can be seen that the peak corresponds to ¹³ C labeled chloroformyl carbonyl carbon. In addition, it can be seen that the byproduct HCl produced when the compound 4 of FIG. 1B is reacted with triphosgene is not produced.

Analysis example  2: Fluorescence emission spectrum analysis

A 1 mM stock solution of the compound (compound 2) for chemical sensors prepared in Preparation Example 1 dissolved in chloroform was prepared. A triphosgene stock solution 10 mM dissolved in chloroform was prepared. 30 uL of the chemical sensor compound (Compound 2) stock solution prepared in Preparation Example 1 was placed in a test tube, and 0 μmol / L to 12 μmol / L of triphosgene was added, respectively, and the stock solution was diluted with 3 mL of chloroform. To prepare a probe solution. Fluorescence emission spectra (λ _ex = 530 nm, λ _em = 578 nm, slit: 3 nm ｘ 1.5 nm) according to the concentration of triphosgene were analyzed for the probe solution. The results are shown in FIG. 4.

The above analysis experiment calculated the detection limit according to the concentration of triphosgene according to the IUPAC method.

Referring to FIG. 4, the chemical sensor compound (Compound 2) prepared by Preparation Example 1 has a phosgene detection limit of 3.2 ppb when the detection limit according to the calculated triphosgene concentration is converted back to the concentration of phosgene. You can confirm that

In addition, 1 mM of the chemical sensor compound (Compound 2) stock solution prepared by Preparation Example 1 dissolved in chloroform and 1 mM of the chemical sensor compound (Compound 4) stock solution prepared by Comparative Preparation Example 1 were prepared, respectively. 10 mM triphosgene stock solution dissolved in chloroform was prepared. 30 uL of the chemical sensor compound (Compound 2) stock solution prepared in Preparation Example 1 and 30 uL of the chemical sensor compound (Compound 4) stock solution prepared in Comparative Preparation Example 1 were respectively placed in a test tube and triphosgene 0.5 After adding the eq solution, the stock solution was diluted with 3 mL of chloroform to prepare a probe solution. Fluorescence emission spectrum according to the reaction time (λ _ex = 530 nm, λ _em = 578 nm, slit: 3 nm 분석 1.5 nm) was analyzed for the probe solution. The results are shown in FIG. 5.

Referring to FIG. 5, the reaction time for the addition of triphosgene of the chemical sensor compound (Compound 2) prepared in Preparation Example 1 was about 2 minutes. The chemical sensor compound (Compound 2) prepared in Preparation Example 1 had a very fast reaction time according to the addition of triphosgene compared to the chemical sensor compound (Compound 4) prepared in Comparative Preparation Example 1.

Analysis example  3: Color change  Colorimetric response analysis

A chemical sensor compound (compound 2) stock solution prepared in Preparation Example 1 dissolved in chloroform was prepared in 1 mM. 10 mM triphosgene stock solution dissolved in chloroform was prepared. The color according to the concentration of triphosgene for the probe solution prepared by adding 30 uL of a storage solution for compound (compound 2) for chemical sensors prepared in Preparation Example 1 into a test tube and adding triphosgene 0 eq to 1.0 eq respectively Change-sensitization assays were performed. The results are shown in FIG. 6.

Referring to FIG. 6, it is possible to observe that the color change gradually occurs from colorless to deep pink as the triphosgene 0 eq to 1.0 eq solution is added to the probe solution.

Analysis example  4: FE-SEM analysis

Before and after exposure to phosgene gas, FE-SEM assays were performed on the fibers embedded with the chemical sensor compound prepared in Example 1, respectively. As the FE-SEM analyzer, JSM-6700F (10.0kV, x10,000) from JEOL was used. The results are shown in FIGS. 7A and 7B.

Referring to Figures 7a and 7b, it can be seen that the chemical sensor compound prepared by Example 1 before and after exposure to phosgene gas is a fiber composed of a plurality of beads.

Before exposure to phosgene gas, the diameter of the fiber in which the compound for chemical sensor prepared by Example 1 was embedded was about 1.0 µm, and it can be seen that it has a minimum number of beads and is evenly distributed. By comparison, it can be seen that the surface of the fiber embedded with the chemical sensor compound prepared in Example 1 after exposure to phosgene gas is uneven and irregular in diameter. It is believed that this is due to the partial deformation of the poly (ethylene oxide) (PEO) matrix due to the reaction of the surface of the fiber with a phosgene gas.

Analysis example  5: Confocal  Confocal microscope analysis

Before and after exposure to phosgene gas, the confocal microscope was used for the chemical sensor-embedded compound prepared in Example 1, respectively. Analytical experiments were conducted. Confocal microscope Fluoview 1200 (x40) of Olympus was used as the analysis device. The results are shown in FIGS. 8A and 8B.

8A and 8B, the compound for the chemical sensor prepared in Example 1 before exposure to phosgene gas is compared with the embedded fiber, and exposed to phosgene gas, followed by Example 1 It can be confirmed that the fibers in which the chemical sensor compound was manufactured exhibited a bright red fluorescence image.

Analysis example  6: Color / fluorescent response analysis

Before and after exposure to the phosgene gas, UV lamps having a wavelength of 365 nm were irradiated for several seconds to the fibers embedded with the chemical sensor compound prepared in Example 1 for several seconds to perform color / fluorescence sensitivity analysis. . The results are shown in FIGS. 9A and 9B.

In FIGS. 9A and 9B, the upper sample shows fibers in which the chemical sensor compound prepared by Example 1 was embedded before each exposure to phosgene gas, and the lower sample was conducted after exposure to phosgene gas, respectively. The chemical sensor compound produced by Example 1 represents the embedded fiber.

Referring to FIG. 9A, it can be confirmed that the fibers embedded with the chemical sensor compound prepared in Example 1 after being exposed to phosgene gas were changed to a dark pink or purple color.

Referring to FIG. 9B, it can be confirmed that the fiber for which the chemical sensor compound prepared by Example 1 was embedded after exposure to phosgene gas exhibits fluorescence close to pink or red.

Claims (12)

Compound represented by the following formula (2):
<Formula 2>

In Chemical Formula 2,
R ' ₁ and R' ₈ are each independently hydrogen, deuterium, or a C1 to C20 alkyl group;
R ' ₂ , R' ₄ , R ' ₅ , R' ₇ are independently of each other hydrogen, -F, -Cl, -Br, -I, amino group, hydroxy group, carboxy group, C1 to C20 alkyl group, or a combination thereof ;
R ' ₃ and R' ₆ are each independently an amino group, a hydroxy group, a carboxy group, a C1 to C20 alkyl group, a C1 to C20 halogenated alkyl group, a C1 to C20 alkylamino group, a C1 to C20 dialkylamino group, and a C6 to C20 aryl. Amino group, C7 to C20 alkylarylamino group, C12 to C20 diarylamino group, C1 to C20 acylamino group, C1 to C20 aralkylamino group, C1 to C20 aminoalkyl group, C6 to C20 aminoaryl group, carbon number 1 To hydroxyalkyl groups of 20 to C2 to C20 alkenyl groups, C5 to C20 cycloalkyl groups, C5 to C20 cycloalkenyl groups, or combinations thereof. According to claim 1,
The compound represented by the following formula (3):
<Formula 3>

In Chemical Formula 3,
R _a , R _d are independently of each other hydrogen, -F, -Cl, -Br, -I, amino group, hydroxy group, carboxy group, C1 to C20 alkyl group, or a combination thereof;
R _b and R _c are independently of each other an amino group, a hydroxy group, a carboxy group, a C2 to C20 alkyl group, or a combination thereof. According to claim 1,
The compound represented by the following formulas 5 to 9:
<Formula 5>

<Formula 6>

<Formula 7>

<Formula 8>

<Formula 9>

According to claim 1,
The compound is a colorimetric fluorescent chemical sensor for phosgene detection. According to claim 1,
The compound is a compound having a phosgene detection limit of 3.2 ppb or more. According to claim 1,
The compound reacts with phosgene within 2 minutes to cause color change and fluorescence change. A compound according to claim 1; And
A composition comprising one or more selected from solvents, acids, bases, and buffer solutions. Polymer matrix; And
A structure comprising the compound according to any one of claims 1 to 6 embedded in the polymer matrix. The method of claim 8,
The structure is one or more structures selected from fibers, tubes, ribbons, wires, and rods. The method of claim 8,
The structure is a structure composed of a plurality of beads. Preparing a structure by electrospinning a mixture of a polymer matrix and a compound according to any one of claims 1 to 6; And
A method of detecting phosgene, comprising exposing the structure to phosgene to detect phosgene by causing color and fluorescence changes.
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