KR102251167B1 - Novel betaine compounds, dye compositions comprising the same and uses thereof - Google Patents

Abstract

The present invention relates to a novel betaine-based compound, a dye composition comprising the same, and a use thereof, wherein the compound has water discoloration, ionic discoloration, thermal discoloration, and solvent discoloration properties, and when used as the dye composition, has water discoloration, ionic discoloration, thermal discoloration, and solvent discoloration properties, thereby being very useful as a sensor. In addition, a polymer film containing the novel betaine-based compound has water discoloration, ionic discoloration, thermal discoloration, and solvent discoloration properties.

Description

Novel betaine compounds, dye compositions comprising the same and uses thereof {Novel betaine compounds, dye compositions comprising the same and uses thereof}

The present invention relates to a novel betaine-based compound, a dye composition comprising the same, and a use thereof, and more specifically, a novel compound that can be used as a sensor by color change of a novel betaine-based compound, a dye composition containing the same, and uses thereof It is about.

Chromism is a reversible process associated with the change in the color of chemical compounds that can generally be detected using a human eye or spectrophotometer.

Due to a number of applications, discoloration is caused by photo-, thermal-, hydro-, electro-, piezo-, solvent-, Mechano-, and gas. It is divided into several categories such as (Gaso-), Iono- and Chrono- discoloration.

Hydrochromism, which represents a unique colorimetric reaction to water, can be applied to a humidity sensor for a bio-solvent and a device for measuring the moisture content of an organic solvent, and thus can be applied to various fields.

The ionochromism indicates a color change in the presence of ionophores useful for detecting corrosion of metals, and the color change can be activated by the flow of charged particles, so it is necessary to detect specific ions. It is highly likely to be used for purposes.

Thermochromism is a temperature-responsive color change and is useful in the ink, plastics, paints and textile industries.

Finally, Solvatochromism describes the color change of a chemical solution with solvent polarity, which applies to sensors, molecular switches and molecular electronics.

Conventionally, it has been confirmed that various compounds exist in the water-chromic compound or the thermochromic compound, and among them, various dyes such as fluorane-based compounds, conjugated polymers, spiropyran-based compounds, crystal violets, and inorganic compounds have been suggested.

However, the dye material relates to a compound capable of exhibiting a color change in one property such as water discoloration or thermal discoloration, and a compound having a plurality of discoloration properties in one compound has not been identified.

If a specific compound can exhibit multiple discoloration properties, it means that it can be used in combination with dyes for various purposes, and it will be said that it can be used as a sensor that can be applied in complex situations.

In addition, even if the dye composition is not used for purposes such as ink, paint, and indicator, but is used as a component in a polymer film, it is necessary to develop a compound capable of maintaining discoloration properties without losing its properties in the polymer.

KR 10-1649480 B1

It is an object of the present invention to provide a novel betaine-based compound, a dye composition comprising the same, and a use thereof.

Another object of the present invention is to provide a novel betaine-based compound having all of the features of water discoloration, ionic discoloration, thermal discoloration, and solvent discoloration, a dye composition comprising the same, and a use thereof.

Another object of the present invention is to provide a novel betaine-based compound capable of producing a polymer film having the characteristics of water discoloration, ionic discoloration, thermal discoloration, and solvent discoloration, a dye composition comprising the same, and a use thereof.

In order to achieve the above object, the compound according to an embodiment of the present invention is a betaine compound represented by the following formula (1), wherein the compound is hydrochromic, ionic, and thermochromic. ) And solvent discoloration (Solvatochromism):

[Formula 1]

here,

n, m and p are the same as or different from each other, and each independently an integer of 0 to 5,

q is an integer from 0 to 4,

X ^- is -O of the anionic substituent ^-, -COO ^-, -R ₅ COO ^- is selected from the group consisting ^of-O and -R ₆

R ₁ to R ₆ are the same as or different from each other, and each independently hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted A C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 alkynyl group, substituted or unsubstituted A substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms , A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C6-C30 arylamino group, a substituted or unsubstituted C6-C30 alkoxy group Aralkylamino group, substituted or unsubstituted C2-C24 hetero arylamino group, substituted or unsubstituted C1-C30 alkylsilyl group, substituted or unsubstituted C6-C30 arylsilyl group, and substituted or unsubstituted It is selected from the group consisting of an aryloxy group having 6 to 30 carbon atoms,

When the R ₁ to R ₆ are substituted, hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, carboxyl group, alkoxy group having 1 to 10 carbon atoms, alkylthio group having 1 to 4 carbon atoms, carbon number 1 to 30 alkyl group, C 1 to C 20 cycloalkyl group, C 2 to C 30 alkenyl group, C 2 to C 24 alkynyl group, C 7 to C 30 aralkyl group, C 6 to C 30 aryl group, C 2 to C 60 Heteroaryl group, C6-C30 heteroarylalkyl group, C1-C30 alkoxy group, C1-C30 alkylamino group, C6-C30 arylamino group, C6-C30 aralkylamino group, C2-C30 alkoxy group, It is substituted with a substituent selected from the group consisting of a heteroarylamino group of 24, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, these They are the same or different from each other.

Chromism dye composition according to another embodiment of the present invention may include the compound.

The chromatic polymer film according to another embodiment of the present invention may include the compound.

In the present invention, "hydrogen" is hydrogen, light hydrogen, deuterium or tritium.

In the present invention, the "halogen group" is fluorine, chlorine, bromine or iodine.

In the present invention, "alkyl" refers to a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.

In the present invention, “alkenyl” refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond. Examples thereof include vinyl (vinyl), allyl (allyl), isopropenyl (isopropenyl), 2-butenyl (2-butenyl), and the like, but is not limited thereto.

In the present invention, “alkynyl” refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.

In the present invention, “aryl” refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined. In addition, a form in which two or more rings are simply attached to each other or condensed may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, and dimethylfluorenyl.

In the present invention, "heteroaryl" refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms. At this time, at least one carbon, preferably 1 to 3 carbons in the ring is substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are simply attached to each other or condensed may be included, and further, a form condensed with an aryl group may be included. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl, phenoxathienyl, indolizinyl, indolyl ( indolyl), purinyl, quinolyl, benzothiazole, polycyclic rings such as carbazolyl and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.

In the present invention, "aralkyl" refers to an aryl-alkyl group in which aryl and alkyl are as described above. Preferred aralkyls include lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl and naphthalenylmethyl. Binding to the parent moiety is made through alkyl.

In the present invention, “heteroarylalkyl group” refers to an aryl-alkyl group substituted with a heterocyclic group.

In the present invention, "condensed ring" means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

In the present invention, "adjacent 　 groups are bonded to each other to form a ring" means 　adjacent 　 groups are bonded to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring; A substituted or unsubstituted aromatic hydrocarbon ring; Substituted or unsubstituted aliphatic heterocycle; Substituted or unsubstituted aromatic heterocycle; Or it means to form a condensed ring of these.

In the present invention, "substitution" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent can be substituted. , Two or more substituents may be the same or different from each other.

In the present invention, "chromism" refers to a change in the absorption or emission spectrum of the entire molecule in response to internal or external stimuli, and refers to an embolic phenomenon in which the color changes reversibly.

According to the novel betaine compound of the present invention, the dye composition comprising the same, and the use thereof, it is possible to provide a novel betaine compound having all of the features of water discoloration, ionic discoloration, thermal discoloration, and solvent discoloration.

The dye composition containing the novel betaine-based compound has all of the characteristics of water discoloration, ionic discoloration, thermal discoloration, and solvent discoloration, and thus has excellent utilization as a sensor.

In addition, the polymer film including the novel betaine-based compound may exhibit water discoloration, ionic discoloration, thermal discoloration, and solvent discoloration.

1 is a UV-vis absorption spectrum result before and after water addition of a dye composition according to an embodiment of the present invention.
FIG. 2 relates to a color change result before and after water addition of a dye composition according to an embodiment of the present invention.
3 is an SEM photograph of a polymer film according to an embodiment of the present invention.
4 is a method for manufacturing a polymer film according to an embodiment of the present invention, a color change result by water vapor treatment, and a UV-vis absorption spectrum result.
5 is a UV-vis absorption spectrum result before and after addition of a metal salt of a dye composition according to an embodiment of the present invention.
6 is a view of a color change result before and after addition of a metal salt of a dye composition according to an embodiment of the present invention.
7 is a UV-vis absorption spectrum result according to a temperature change of a dye composition according to an embodiment of the present invention.
8 is a result of a color change according to a temperature change of a dye composition according to an embodiment of the present invention.
9 is a UV-vis absorption spectrum result according to a solvent change of a dye composition according to an embodiment of the present invention.
10 is a result of color change according to a solvent change of a dye composition according to an embodiment of the present invention.
11 is a measurement result of the structure and UV-vis maximum absorption value of the betaine compound according to an embodiment of the present invention.
12 is a result of distribution of electron densities in HOMO and LUMO of a betaine compound according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

A novel betaine compound according to an embodiment of the present invention may be a compound represented by the following Formula 1:

[Formula 1]

here,

n, m and p are the same as or different from each other, and each independently an integer of 0 to 5,

q is an integer from 0 to 4,

X ^- is -O of the anionic substituent ^-, -COO ^-, -R ₅ COO ^- is selected from the group consisting ^of-O and -R ₆

R ₁ to R ₆ are the same as or different from each other, and each independently hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted A C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 alkynyl group, substituted or unsubstituted A substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms , A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C6-C30 arylamino group, a substituted or unsubstituted C6-C30 alkoxy group Aralkylamino group, substituted or unsubstituted C2-C24 hetero arylamino group, substituted or unsubstituted C1-C30 alkylsilyl group, substituted or unsubstituted C6-C30 arylsilyl group, and substituted or unsubstituted It is selected from the group consisting of an aryloxy group having 6 to 30 carbon atoms,

When the R ₁ to R ₆ are substituted, hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, carboxyl group, alkoxy group having 1 to 10 carbon atoms, alkylthio group having 1 to 4 carbon atoms, carbon number 1 to 30 alkyl group, C 1 to C 20 cycloalkyl group, C 2 to C 30 alkenyl group, C 2 to C 24 alkynyl group, C 7 to C 30 aralkyl group, C 6 to C 30 aryl group, C 2 to C 60 Heteroaryl group, C6-C30 heteroarylalkyl group, C1-C30 alkoxy group, C1-C30 alkylamino group, C6-C30 arylamino group, C6-C30 aralkylamino group, C2-C30 alkoxy group, It is substituted with a substituent selected from the group consisting of a heteroarylamino group of 24, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, these They are the same or different from each other.

The compound is characterized by having hydrochromism, ionic discoloration (Ionochromism), thermochromism and solvent discoloration (Solvatochromism).When water is added to the solution, the color changes, and specific ions The color changes even when overreacted, the color changes according to the temperature change, and the color changes according to the change of the solvent.

Compounds having a specific discoloration property are characterized by having one kind of discoloration property such as water discoloration, ionic discoloration, thermal discoloration, or solvent discoloration, but the novel betaine compound of the present invention is water discoloration, ionic discoloration. It is characterized by having a discoloration property, a thermal discoloration property, and a solvent discoloration property at the same time.

The compound represented by Formula 1 may be a compound represented by the following Formula 2:

[Formula 2]

Here, X ^-, q, R ₁ and R ₄ are as defined in formula (I).

[화학식 4]

[화학식 5]

여기서,
R_1, R₄ 및 X^-는 상기 화학식 1에서 정의한 바와 같다.The compound represented by Formula 1 may be a compound selected from the group consisting of compounds represented by the following Formulas 3 to 5:
[Formula 3]

[Formula 4]

[Formula 5]

here,
R _1, R ₄ and X ^- are as defined in Formula 1 above.

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X ^{- is -O-} as an anionic substituent, R ₁ and R ₄ are the same as or different from each other, and each independently may be a halogen group.

More preferably, R ₁ is -Br or -Cl, and R ₄ is -Cl, but is not limited to the above example, and all substituents capable of exhibiting discoloration properties may be used without limitation.

The compound represented by Formula 1 may be selected from the group consisting of compounds represented by the following formula:

Chromism dye composition according to another embodiment of the present invention may include the compound.

The discoloration properties are hydrochromism, ionic discoloration (Ionochromism), thermochromism (Thermochromism) and solvent discoloration (Solvatochromism).

The dye composition is a mixture of the compound in a solvent, and the color may be changed according to the addition of water.

More specifically, the absorption change caused by the addition of water to the dye composition is explained based on the synergistic effect due to the intermolecular solvent-solvent interactions, which creates a new solvent system separate from the two solvents. It was formed and the polarity of the medium increased, mainly because water made strong hydrogen bonds with the oxygen of the phenolate group.

At this time, the solvent of the dye composition is not limited to the type and may be used without limitation. Preferably, the solvent may be selected from the group consisting of chloroform, DMF, acetonitrile, acetone, dichloromethane, and mixtures thereof, but is not limited to the solvent.

As the polarity of the solvent used in the preparation of the dye composition increases, the water discoloration property also increases.

By using the characteristics of the dye composition as described above, it can be used so that a warning phrase appears or a specific image appears when contacted with water. Accordingly, after dissolving the compound in a solvent, it can be used in a manner such as dyeing or coating, so that it can be used for applications such as ink, paint, and indicator.

This use can serve as a water detection sensor.

The dye composition may have ionic discoloration properties in addition to water discoloration.

The ion discoloration property is that the color changes when a metal salt in the solution is added, and the metal salt _{may be selected from the group consisting of LiI, NaI, KI, RbI, CaI 2} and mixtures thereof, but is limited to the above examples. It doesn't work.

The color change of the dye composition is that even if a metal salt is added in the dye composition, the compound in the dye composition maintains the chemical structure, while the internal microstructure of the solvent component is changed. In this way, the solvent polarity and ionic strength of the dye can affect the UV-visible spectrum in the region due to intramolecular charge transfer, resulting in a color change.

The dye composition may exhibit a color change according to the change of heat. The thermochromic properties are a result of the combination of the change in the structural form of the compound in the dye composition and the relative dielectric constant of the solvent.

In other words, the color change may result in a change in a fine structural shape of a compound molecule in a molecular environment, and a color change may occur due to such a small change, thereby exhibiting thermal discoloration characteristics.

Finally, the dye composition may have a solvent discoloration property. The solvent discoloration property is a change in color due to pulverization of dyes having different solvent polarities and non-uniform and differential solvation of excited states. The cause of this anomalous change can be a small energy difference between as many conformers as possible in a solution state, and sometimes a small change in the molecular structure in the betaine dye can be a color change as a difference in the electron spectrum. have.

Chromism dye composition according to an embodiment of the present invention is characterized in that it contains the compound, the color change is hydrochromism (Hydrochromism), ion discoloration (Ionochromism), thermochromism (Thermochromism) And solvent discoloration (Solvatochromism).

The dye composition may include a novel betaine compound and a solvent of the present invention, and the solvent is acetone, acetonitrile, ether, and en-methyl-2-pyrrolidone (NMP), dimethylfomamide, dimethylacetamide, xylene, benzene, chloroform, toluene, tetrahydrofuran (THF), glycerin ), ethylene glycol, dimethylpyrrolydone, cyclohexane, dimethyl sulfoxide, and mixtures thereof, but is not limited to the above examples.

The dye composition can be used for dyeing or printing, and can be used as products such as inks, paints, and indicators.

The chromatic polymer film according to another embodiment of the present invention may include the novel betain compound.

The color-changing polymer film is characterized in that it comprises a novel betaine compound and a polymer resin according to an embodiment of the present invention.

The polymer resin is polyvinyl alcohol (PVA), polyvinyl pyrollidone (PVP), polyethylene oxide (PEO), polyacrylamide (PAAM), polyacrylic acid ( Polye acrylic acid), polystyrenesulfonic acid (PSSA), polysilicic acid (PSiA), polyphosphoric acid (PPA), polyethylene sulfonic acid (PESA), polyethylene It may be selected from the group consisting of imine (Polyethyleneimine, PEI), polyamideamine (PAMAM), polyamine, and a mixture thereof, and is preferably PEO, but is not limited to the above example.

The color-changing polymer film of the present invention is prepared by mixing a new betaine compound with a polymer resin and processing it in a film form. It is characterized.

More specifically, the discoloration properties are hydrochromism, ion discoloration (Ionochromism), thermal discoloration (Thermochromism), and solvent discoloration (Solvatochromism). The discoloration characteristic due to the compound is maintained as it is.

When water vapor comes into contact with the color-changing polymer film of the present invention, the color of the polymer film may be changed due to the color change of the betaine compound contained in the polymer film.

The color-changing polymer film can be used as a flexible polymer film, and can be used as a sensor by detecting a very fine amount of moisture, so it can be used for mapping a sweat hole of a person.

In addition to the above uses, it is a flexible polymer film, and any application capable of utilizing color change properties may be used without limitation.

Preparation of novel betaine compounds

Halogen-substituted 2,4,6-triphenylpyrylium hydrogen sulfate (2 mmol), chloro-substituted aminophenol (2 mmol) and anhydrous sodium acetate A mixture of (anhydrous sodium acetate, 6 mmol) was dissolved in 10 mL of ethanol.

The mixture was refluxed for 3 hours and cooled. Thereafter, the reaction mixture was basified using 10 mL of 5% aqueous sodium hydroxide solution, and stirred for 15 minutes. Thereafter, the reaction mixture was poured into 100 mL of water and extracted with DCM (2100 mL). The synthesized organic layer was dried over sodium sulfate.

Thereafter, the solvent was removed using a rotary evaporator and a red solid was obtained. The solid was recrystallized using water/ethanol. The mixture was dried over _{P 2} O ₅ under a high vacuum overnight.

To synthesize the betaine dye, it was prepared with a bisulfate salt of 2,4,6-triphenylpyrylium. JBK1 to 3 were prepared from a bromo derivative of triphenylpyrylium salt, and JBK4 to 6 were prepared from a chloro derivative of triphenylpyrylium salt.

NMR, ESI-MS and UV-visible spectrum measurement results of the synthesized JBK 1 to 6 are as follows.

4-(2-(4-bromophenyl)-4,6-diphenylpyridin-1-ium-1-yl)-2-chlorophenolate (JBK1)

Yield: 0.909 g, 89%, mp 207 to 209 °C.

¹ H NMR (600 MHz, DMSO-d6): d 8.48 (s, 2H), 8.28-8.19 (m, 2H), 7.70-7.32 (m, 12H), 6.70 (d, J ¼ 8.3 Hz, 1H), 6.02-5.94 (m, 1H), 5.76 (d, J ¼ 8.3 Hz, 1H) ppm;

¹³ C NMR (150 MHz, DMSO-d6): d 157.5, 156.4, 154.2, 134.6, 133.5, 132.8, 131.9, 130.5, 129.7, 129.4, 129.2, 128.8, 128.5, 127.6, 125.7, 125.3, 125.1, 123.5, 119.7 .

HRMS (ESI-MS) m/z calcd for C ₂₉ H ₂₀ BrClNO [M+H] ⁺ : 512.0417, found 512.0432.

2-(2-(4-bromophenyl)-4,6-diphenylpyridin-1-ium-1-yl)-5-chlorophenolate (JBK2)

Yield: 0.889 g, 87%, mp 200-202°C.

¹ H NMR (600 MHz, DMSO-d6): d 8.51 (s, 2H), 8.33-8.23 (m, 2H), 7.69-7.34 (m, 12H), 6.68 (d, J ¼ 8.1 Hz, 1H), 6.12-6.05 (m, 1H), 5.90-5.81 (m, 1H) ppm;

¹³ C NMR (150 MHz, DMSO-d6): d 155.9, 154.7, 154.5, 137.9, 133.4, 133.0, 132.6, 132.7, 132.2, 131.4, 130.7, 129.5, 129.3, 128.6, 128.2, 127.8,125.8,125.2,125.1 ,124.0,123.5,118.5 ppm;

HRMS (ESI-MS) m/z calcd for C ₂₉ H ₂₀ BrClNO [M+H] ⁺ : 512.0417, found 512.0425.

5-(2-(4-bromophenyl)-4,6-diphenylpyridin-1-ium-1-yl)-2-chlorophenolate (JBK3)

Yield: 0.858 g, 84%, mp 207-209°C.

¹ H NMR (600 MHz, DMSO-d6): d 8.63 (s, 2H), 8.42-8.31 (m, 2H), 7.80-7.20 (m, 12H), 7.16 (d, J ¼ 8.3 Hz, 1H), 6.86-6.77 (m, 1H), 6.18 (d, J ¼ 8.3, 1H) ppm;

¹³ C NMR (150 MHz, DMSO-d6): d 157.1, 155.7, 154.6, 141.3, 136.5, 133.4, 133.0, 132.7, 131.6, 131.0, 129.6, 129.4, 128.2, 127.7, 125.8, 124.9, 125.0, 123.4, 120.5 , 116.7 ppm;

HRMS (ESI-MS) m/z calcd for C ₂₉ H ₂₀ BrClNO [M+H] ⁺ : 512.0417, found 512.0435.

2-Chloro-4-(2-(4-chlorophenyl)-4,6-diphenylpyridin-1-ium-1-yl)phenolate (JBK4)

Yield: 0.779 g, 83.5%, mp 202-204°C.

¹ H NMR (600 MHz, DMSO-d6): d 8.53-8.49 (m, 2H), 8.30-8.27 (m, 2H), 7.69-7.60 (m, 3H), 7.52-7.39 (m, 9H), 6.85 (d, J ¼ 3.0 Hz, 1H), 6.53-6.49 (m, 1H), 5.75 (d, J ¼ 9.0, 1H) ppm;

¹³ C NMR (150 MHz, DMSO-d6): d 155.9, 154.7,154.4,137.9,134.6,133.4,132.3,132.1,131.2,129.7,129.5,129.3, 128.8, 128.6, 128.3, 128.1, 127.7, 127.2, 125.7 , 125.2, 125.0, 118.5 ppm;

HRMS (ESI-MS) m/z calcd for C ₂₉ H ₂₀ Cl ₂ NO [M+H] ⁺ : 468.0922, found 468.0933.

5-Chloro-2-(2-(4-chlorophenyl)-4,6-diphenylpyridin-1-ium-1-yl)phenolate (JBK5)

Yield: 0.794 g, 85%, mp 205-207°C.

¹ H NMR (600 MHz, DMSO-d6): d 8.53-8.50 (m, 2H), 8.32-8.29 (m, 2H), 7.69-7.45 (m, 12H), 6.90 (d, J ¼ 8.2 Hz, 1H ), 6.19-6.14 (m, 1H), 5.93 (d, J ¼ 6.9 Hz, 1H) ppm;

¹³ C NMR (150 MHz, DMSO-d6): d 157.0, 155.7, 154.3, 134.4, 133.6, 133.4, 132.5, 132.1, 131.3, 129.5, 129.4, 128.5, 128.3, 128.0, 127.9,127.5,125.0,124.9,120.8 , 117.0 ppm.

HRMS (ESI-MS) m/z calcd for C ₂₉ H ₂₀ Cl ₂ NO [M+H] ⁺ : 468.0922, found 468.0932.

2-Chloro-5-(2-(4-chlorophenyl)-4,6-diphenylpyridin-1-ium-1-yl)phenolate (JBK6)

Yield: 0.808 g, 86.5%, mp 203-205°C.

¹ H NMR (600 MHz, DMSO-d6): d 8.53-8.49 (m, 2H), 8.30-8.27 (m, 2H), 7.72-7.38 (m, 12H), 6.66 (d, J ¼ 8.1 Hz, 1H ), 6.05 (d, J ¼ 2.6 Hz, 1H), 5.84-5.81 (m, 1H), ppm;

¹³ C NMR (150 MHz, DMSO-d6): d 155.9,154.7,154.4,137.9, 134.6,133.4,132.3,132.1,131.2,129.7,129.5,129.3,128.6,127.8,127.7, 125.2, 125.1, 124.0, 118.5 ppm;

HRMS (ESI-MS) m/z calcd for C ₂₉ H ₂₀ Cl ₂ NO [M+H] ⁺ : 468.0922, found 468.0932.

Experimental conditions

All organic solvents used and all reagents with analytical and spectroscopic grades were purchased commercially and used as received unless otherwise specified.

An AVANCE III 600 spectrometer (Akishima, Japan) was operated at 600 and 150 MHz ^{for 1} H and ^{13 C NMR spectroscopy, respectively.} DMSO-d6 was used as a solvent, and Alice 4.0 software was used for spectral analysis.

Chemical shifts (d values) of all compounds were set in parts per million (ppm) downfield from the internal standard (Me4Si).

HRMS spectra were obtained using a 1290 Infinity II/Triple TOF 5600 Plus Mass Spectrometer. The UV-vis absorption spectrum was used with an Agilent 8453 spectrophotometer. Solid UV-vis spectra were measured using a Shimadzu SolidSpec-3700 instrument. The melting point was determined using a TA instrument DSC 2010.

Experimental method and results

Checking the water discoloration characteristics of dyes in solution

0.2 mL of water was added to a 6 mL dye solution dissolved in acetone (1 x 10 ^{4 M).} After adding water to the acetone dye solution, a blue shift was observed in the UV-visible absorption spectrum.

JBK1 dissolved in acetone changed color from red to yellow after water was added, and the maximum absorption value shifted from 525 to 475 nm.

JBK2 dissolved in acetone changed from light brown to yellow and the absorption maximum value shifted from 540 to 480 nm.

JBK3 was observed to change from dark brown to dark yellow as the absorption maximum shifted from 545 to 475 nm.

JBK4 showed maximum absorption at 595 nm in blue color, changed red after adding water, and blue-shifted to 508 nm.

As JBK5 changed color from dark brown to yellow, the maximum absorption value shifted from 540 to 465 nm.

JBK6 is a dark brown solution having a maximum absorption value of 550 nm, and after adding water, the maximum absorption value shifted to 465 nm and changed to yellow (FIG. 1).

In order to further confirm the water discoloration property of the dye composition of the present invention, an additional experiment was conducted using a general polar solvent. The dye composition of the present invention exhibits a change in color in different solvents, which means that it exhibits water discoloration in all solvents.

As shown in Figure 2, as the polarity of the solvent from acetone to DMSO increased, the water discoloration property also increased. FIG. 2 relates to a wide range of water discoloration properties that can be observed using the dye composition of the present invention.

The above experimental results will be said to mean that the dye composition containing the novel betaine compound of the present invention is effectively solvated by water.

In addition, based on the above experimental results, it will be said that the water discoloration betaine dye composition of the present invention is reversible and can be usefully applied to applications related to water-triggered imaging.

Evaluation of water discoloration properties in polymer films

JBK 4 (20 mg) and polyethylene oxide (100 mg) (polyethylene oxide, PEO, MW ¼ 200 K) were dissolved in 3 mL of chloroform, and stirred at room temperature for 2 hours to prepare a uniform solution.

The prepared homogeneous solution was transferred to a 200 mm diameter glass Petri dish, and then dried under vacuum at room temperature for 8 hours. Betaine contained in the polymer was confirmed by SEM analysis (Fig. 3).

The PEO film containing JBK4 exhibited a blue color, and upon contact with water vapor (water vapor generated by the humidifier), an immediate color change appeared in a reversible manner.

This will mean that it exhibits excellent water discoloration detection properties even when it is manufactured as a polymer film using the novel betaine compound of the present invention.

After spraying water vapor, the blue flexible polymer film shifted from 652 nm to 590 nm, and the color changed from blue to red, showing water discoloration (FIG. 4).

From the above results, it was confirmed that even in the solid state containing the betaine dye, the water discoloration property was exhibited as in the liquid state.

The polymer film prepared as described above has flexible properties and can be used for various purposes, and in particular, can be usefully used as a sensor for mapping a sweat hole of a person.

Evaluation of ion discoloration properties

The ionic discoloration properties of LiI, NaI, KI, RbI and CaI ₂ and betaine dyes were investigated.

In the experiment, acetonitrile was used as a solvent in order to avoid high relative dielectric constant of the solvent, strong solvation property with salt, and intermolecular hydrogen bonding.

A salt solution (110M) was added to the acetonitrile solution (110M) in which the dye composition of the present invention was dissolved, and a short wavelength (hypsochromic) shift of the charge transfer band was observed (FIG. 5).

According to FIG. 5, color change according to the addition of the metal salt can be confirmed. The ion discoloration effect increased as the effective cationic charge (ionic charge/radius), that is, increased from rubidium to calcium salt (Rb ⁺ <K ⁺ <Na ⁺ <Li ⁺ <Ca ₂ ⁺ ).

According to Figure 6, from JBK1 to JBK6, all dyes changed from red or reddish brown to yellow when salt was added.

Betaine dyes can exhibit ionic discoloration properties when encountered with metal salts. This ionic discoloration was confirmed that the compound in the dye itself maintained a chemical structure when a salt was added, while the internal microstructure of the solvent component was changed.

In this way, due to the change in solvent polarity and ionic strength in the dye composition, intramolecular charge transfer occurs, and in the region due to such intramolecular charge transfer, the UV-visible spectrum is affected. Using these properties, betaine dyes including metal salts and poly(ethylene oxide) oligomers can be usefully utilized in the design of high-performance ion conductive matrices.

Evaluation of heat discoloration properties

Using UV-visible spectroscopy and visual color change ^{, the betaine dye was observed according to the temperature change in chloroform (1×10 4} M) to confirm thermal discoloration (FIGS. 7 and 8).

From JBK1 to JBK6, as the temperature decreased from 50° C. to 10° C., all compounds showed a blue shift with a reversible color change. This phenomenon is due to the molecular substituent of the betaine compound of the present invention, and the molecular substituent plays an important role in terms of thermal discoloration properties.

In the case of JBK1, when cooling from 50° C. to 10° C., the maximum absorption value shifted from 570 to 550 nm, and a color change occurred from purple to red.

In the case of JBK2, when cooling from 50° C. to 10° C., the maximum absorption value shifted from 590 to 555 nm, and a color change occurred from green to pink.

In the case of JBK3, when cooled from 50° C. to 10° C., an 80 nm blue shift (hypsochromic shift) occurred in the UV-visible light absorption spectrum, and a color change from blue to red was observed.

Under the same temperature change condition, the maximum absorption value of JBK4 shifted from 630 to 600 nm, and a color change occurred from indigo blue to blue.

When the JBK5 solution was cooled under the same conditions, the wavelength shifted from 590 to 550 nm and the color changed from green to reddish purple.

Finally, in the case of JBK6, the maximum absorption value shifted from 590 to 560 nm, and the color changed from green to purple.

By decreasing the temperature, this hypsochromic shift coincided with negative thermal discoloration. The thermochromic property of the dye is a result of the combination of the change in the structural form of the dye and the relative dielectric constant of the solvent. This color change means that a small change in the molecular environment of the dye molecule can cause a large change in the thermal discoloration detection property.

Evaluation of solvent discoloration properties

The solvent discoloration property of the novel betaine dye composition of the present invention was investigated by color change under UV-vis absorption (FIG. 9) and solvent (chloroform, DMF, acetone, EtOH, acetonitrile and dichloromethane) (FIG. 10). .

According to the above experimental results, in the novel betaine dye composition of the present invention, due to the difference in the solvent, a small substitution change in the molecular structure occurs, and due to this phenomenon, a distinct color change and a large change in maximum absorption were obtained. .

As the polarity of the solvent in the dye composition increased, the absorption maximum shifted to a lower wavelength. This phenomenon is called negative solvent discoloration, and for a clear understanding of this phenomenon, the ET-30 value in the excited state was calculated.

The results are shown in Table 1 below.

The betaine dye and phenolate oxygen of the present invention undergo a specific hydrogen bond with the hydrogen bond donating solvent, whereas the interaction with the electron pair donating solvent is weakened or negligible due to the delocalization of the positive charge in the pyridinium ring.

From JBK1 to JBK6, all dyes showed a noticeable color change when the solvent was changed.

By increasing the polarity from DCM to DMF, the maximum value of UV-visible absorption shifted to a short wavelength (hypsochromically) by almost 50 to 100 nm.

The change in color and UV-visible absorption spectrum is due to the pulverization of dyes with different solvent polarities and the heterogeneous and differential solvation of the excited state. Except for the branched para-halogen atom of the phenyl group, the molecular structure of the synthesized JBK2 is the same as that of the JBK4 dye, but the red shift was observed as the longest wavelength due to the very high absorbance for JBK4 compared to JBK2. The cause of this anomalous change can be a small energy difference between as many conformers as possible in solution, and sometimes a small change in the molecular structure in a betaine dye can make a big difference in the electron spectrum.

For all dyes, color and UV-vis absorption in both HBD solvents (hydrogen bond donor solvents, e.g. EtOH) and non-HBD solvents (e.g. chloroform, DMF, acetonitrile, acetone and dichloromethane) Significant changes in the spectrum appeared. The solvent interaction and CT absorption with the betaine dye molecule depend on the electrophilic solvent power of the solvent.

The p-system conjugated in the synthesized betain dye exhibits intramolecular charge transfer in the excited state seen by charge resonance. While betaine dyes are not hydrogen bond donors or exhibit the properties of Lewis acids, dyes can interact with solvents by accepting dipole-induced dipoles, dipole-dipoles and strong hydrogen bonds, and also have high polarization and dispersive interactions. Can indicate the capacity.

Solvent discoloration phenomena in HBD solvents depend on specific intermolecular hydrogen bonding interactions with phenolate oxygen atoms, but in non-HBD solvents, London dispersion forces and induction forces (nonspecific intermolecular dye-solvent interactions) are affected. Is the result of.

It will be said that the betaine dye synthesized in the examples of the present invention exhibits a distinct color change that can be seen with the naked eye in various solvents, and can be used as oil analysis, polymer properties, and biological probes.

Properties of the synthesized vetiin compound

In order to confirm the structure, optical properties, and electronic configuration of the betaine compound synthesized in the present invention, the properties of the compound were evaluated.

DFT and TDDFT calculations were performed using the b3lyp/6-31g (d, p) criteria set with the Gaussian 09 program.

The shape of the betaine compound was optimized using DFT, as shown in FIG. 11A.

The molecular orbital energy level, the band gap, and the total dipole moment of the betaine dye between the ground state and the excited state of the betaine compound are shown in Table 2 below.

E _HOMO (eV) E _LUMO (eV) E _0-0 (eV) Dipole moment
(μ, D) JBK1 -4.47 -2.77 1.70 13.88 JBK2 -4.48 -2.74 1.74 12.10 JBK3 -3.99 -2.99 1.00 16.47 JBK4 -4.48 -2.75 1.73 12.19 JBK5 -4.47 -2.77 1.70 13.98 JBK6 -3.99 -2.99 1.00 16.58

Among the six betaine dyes according to an embodiment of the present invention, ortho and para-O substituted dyes are lower compared to ground state energy (HOMO).

The band gaps for the meta-substituted compound JBK1-6 were found to be 1.70, 1.74, 1.00, 1.73, 1.70 and 1.00 eV, respectively.

Theoretical data confirmed that the donating group increased the bandgap at the ortho and para positions.

The donor O ^- is in the meta position of JBK3 and JBK6, which is less effective at electron donating compared to the ortho and para positions.

In addition, the dipole moment of the dye was calculated theoretically and found to be 13.88, 12.10, 16.47, 12.19, 13.98 and 16.58D respectively for JBK1-6.

The dipole moment of the dye means that the abnormal behavior observed by electron absorption and the apparent dipole moment of these dyes can be due to the hydrogen bonding between the solvent and the dye molecule.

Twenty single vertical excitation energies for betaine dyes were calculated using TDDFT, and five one central energies are shown in Table 3. In addition, UV-Vis spectrum data and vibrator intensity are shown in Table 3 below.

11B, the calculated maximum absorption of JBK1-6 is located at 609, 593, 567, 670, 609 and 566 nm. The absorption result was consistent with the experimental result.

The transitions corresponding to these absorption maxima are H→L+1, H→L+1, H-1→ L+1, H-1→ L, H→ L+1 and H-1→ L+ for JBK1e6, respectively. It is 1. For JBK4, the transitions S0 → S3 and S0 → S2 dominate.

The distribution of the electron cloud is shown in FIG. 12. As shown in FIG. 12, the electron density distribution pattern of the betaine dye is similar. HOMO is mainly located in the N-substituted phenolate ring, and LUMO is distributed in the triphenylpyryllium moiety.

Excitation results in a form of LUMO corresponding to the intramolecular charge transfer from the phenolate donor group to the pyryllium acceptor.

The electron density of the dye was displaced through the oxygen and nitrogen axes or onto the central diphenyl-pyridine fragment, depending on the absorbed photon energy.

In conclusion, the theoretical and empirical values vary because all experiments were performed in a solvent medium and no solvent was used in the theoretical calculations. Thus, the deviation in the results may be due to the presence of an interaction between the solvent and the solute.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention defined in the following claims are also present It belongs to the scope of rights of

Claims (11)

A betaine compound represented by the following formula (1),
The compound has hydrochromism, ionic discoloration (Ionochromism), thermal discoloration (Thermochromism), and solvent discoloration (Solvatochromism).
compound:
[Formula 1]

here,
n, m and p are the same as or different from each other, and each independently an integer of 0 to 5,
q is an integer from 0 to 4,
X ^- is -O of the anionic substituent ^-, -COO ^-, -R ₅ COO ^- is selected from the group consisting ^of-O and -R ₆
R ₁ to R ₆ are the same as or different from each other, and each independently hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted A C 1 to C 30 alkyl group, a substituted or unsubstituted C 1 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 alkynyl group, substituted or unsubstituted A substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms , A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C6-C30 arylamino group, a substituted or unsubstituted C6-C30 alkoxy group Aralkylamino group, substituted or unsubstituted C2-C24 hetero arylamino group, substituted or unsubstituted C1-C30 alkylsilyl group, substituted or unsubstituted C6-C30 arylsilyl group, and substituted or unsubstituted It is selected from the group consisting of an aryloxy group having 6 to 30 carbon atoms,
When the R ₁ to R ₆ are substituted, hydrogen, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, carboxyl group, alkoxy group having 1 to 10 carbon atoms, alkylthio group having 1 to 4 carbon atoms, carbon number 1 to 30 alkyl group, C 1 to C 20 cycloalkyl group, C 2 to C 30 alkenyl group, C 2 to C 24 alkynyl group, C 7 to C 30 aralkyl group, C 6 to C 30 aryl group, C 2 to C 60 Heteroaryl group, C6-C30 heteroarylalkyl group, C1-C30 alkoxy group, C1-C30 alkylamino group, C6-C30 arylamino group, C6-C30 aralkylamino group, C2-C30 alkoxy group, It is substituted with a substituent selected from the group consisting of a heteroarylamino group of 24, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, these They are the same or different from each other. The method of claim 1,
The compound represented by Formula 1 is represented by the following Formula 2
compound:
[Formula 2]

Here, X ^-, q, R ₁ and R ₄ are as defined in claim 1. The method of claim 1,
The compound represented by Formula 1 is selected from the group consisting of compounds represented by the following Formulas 3 to 5
compound:
[Formula 3]

[Formula 4]

[Formula 5]

here,
R _1, R ₄ and X ^- are as defined in claim 1. The method of claim 1,
Wherein X ^- is -O of the anionic ^substituents of
compound. The method of claim 1,
R ₁ and R ₄ are the same as or different from each other, and each independently a halogen group
compound. The method of claim 1,
The compound represented by Formula 1 is selected from the group consisting of compounds represented by the following formula
compound:

Comprising the compound according to any one of claims 1 to 6
Chromism dye composition. The method of claim 7,
The discoloration is water discoloration (Hydrochromism), ion discoloration (Ionochromism), thermal discoloration (Thermochromism) and solvent discoloration (Solvatochromism).
Chromism dye composition. Comprising the compound according to any one of claims 1 to 6
Chromism polymer film. The method of claim 9,
The polymer is polyvinyl alcohol (PVA), polyvinyl pyrollidone (PVP), polyethylene oxide (PEO), polyacrylamide (PAAM), polyacrylic acid (Polye acrylic acid), polystyrenesulfonic acid (PSSA), polysilicic acid (PSiA), polyphosphoric acid (PPA), polyethylene sulfonic acid (PESA), polyethyleneimine (Polyethyleneimine, PEI), polyamideamine (PAMAM), polyamine, and a mixture thereof
Chromism polymer film. The method of claim 9,
The discoloration is water discoloration (Hydrochromism), ion discoloration (Ionochromism), thermal discoloration (Thermochromism) and solvent discoloration (Solvatochromism).
Chromism polymer film.

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