KR101931033B1 - New methyl salicylate derivatives and method for manufacturing same - Google Patents

Abstract

The present invention relates to an oligomer shape of methyl salicylate derivatives which have a pi-conjugated structure with a fluorescent characteristic and a manufacturing method thereof. The purpose of the present invention is to provide a conjugated structure of new methyl salicylate derivatives which have an electronic characteristic, have high solubility to an organic solvent, and can be applied to various technical fields by processing a new structure of methyl salicylate derivatives from halogen substituted methyl salicylate which is a starting material through a cross coupling reaction. Methyl salicylate derivatives of the present invention have an excellent electronic characteristic, absorb a larger wavelength of light compared to methyl salicylate and have fluorescence in a specific wavelength added, and thus can be utilized for a fluorescence-like agent.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel salicylic acid methyl derivative and a method for producing the same. BACKGROUND ART [0002]

The present invention relates to a novel salicylic acid methyl derivative applicable as a similar chemical agent and a method for preparing the same. More particularly, the present invention relates to a novel salicylic acid derivative having an oligomer form Methyl derivatives. ≪ / RTI >

A chemical agent is a compound used in war for the purpose of killing or neutralizing a person through physiological effects. It is mainly a toxic chemical agent. Unlike general war weapons, chemical agents have colorless and odorless properties and are one of the lethal weapons that can not be seen by mankind because they can be recognized only when nerve shock, dyspnea and blisters are generated.

Methyl salicylate is a plant-derived fragrance, a substance that is originally produced to keep animals and insects eating plants from scenting by the self-defense of plants. Because it has analgesic effect, it is also added to mouth cleaner and so on, so it has a disinfecting effect when rinse mouth. It is toxic, but it is one of the most commonly used chemical agents because it is ingested in large quantities, it is safe to be exposed to a small amount of smell or touch the skin.

A similar chemical agent refers to a substance having similar physical and chemical properties to a chemical agent and having a functional group or structure. Since chemical agents and similar chemical agents are similar in physical properties such as vapor pressure, viscosity, dipole moment or enthalpy of vapor pressure, similar chemical agents can be applied instead of chemical agents. Therefore, methyl salicylate can be applied as a similar chemical agent instead of chemical agents such as o-pinacolyl methylphosphonofluoridate (soman, GD) and bis (2-chloroethyl) sulfide (sulfur mustard, HD)

An organic oligomer having a conjugated system, that is, a pie-conjugated structure, is formed of two or more monomeric bonds. By measuring the physical, chemical, electrical, stereoscopic, and optical properties of the oligomers and related derivatives, Are used for predicting the properties of the materials.

Particularly, conjugated oligomers composed of repeating single bonds and double bonds have been widely used because they exhibit good characteristics in electronic devices such as electrochromic devices, transistors, and sensors.

In general, an oligomer consisting of a donor and an acceptor repeating structure is formed by the hybridization of the high HOMO energy of the donor and the low LUMO energy of the acceptor, The band gap, which is a value indicating a difference, tends to be lowered. Therefore, it can be applied to various fields such as fluorescence-like agents because it has better electric characteristics and optical characteristics.

Korean Registered Patent Publication No. 10-1144169 (2012.05.02.) Korean Patent Publication No. 10-2008-0098657 (November 11, 2008) Korean Patent Publication No. 10-2010-0123795 (Nov. 25, 2010)

It is an object of the present invention to provide a novel methyl salicylate derivative which is excellent in electronic properties, has high solubility in an organic solvent, exhibits fluorescence at a specific wavelength, and can be applied to various technical fields.

Still another object of the present invention is to provide a process for synthesizing a novel salicylic acid methyl derivative in the form of a conjugated oligomer having a new structure having a pi-conjugated structure from a salicylic acid methyl monomer.

The salicylic acid methyl derivative of the present invention for achieving the above object provides a salicylic acid methyl derivative of the conjugated oligomer type represented by the following general formula (1).

≪ Formula 1 >

In the above formula (1), A is a group selected from the group consisting of the following formulas (2) to (4).

(2)

(3)

≪ Formula 4 >

Preferably, the methyl salicylate derivative represented by the formula (1) is methyl 2-hydroxy-4- (thiophen-2-yl ) benzoate, methyl 2-hydroxy-4- (selenophen-2-yl) benzoate represented by the following formula 6, (Methyl 2-hydroxy-4- (pyridin-2-yl) benzoate) represented by the following formula.

≪ Formula 5 >

(6)

≪ Formula 7 >

Furthermore, the methyl salicylate derivative of the present invention, which is a compound represented by the above formula (1), has a form of a pie-conjugated oligomer, and thus can be usefully used as a similar chemical agent.

According to another aspect of the present invention, there is provided a method for preparing a methyl salicylate derivative represented by Formula 1, comprising the steps of:

Specifically, methyl 4-iodo-2-hydroxybenzoate represented by the following formula (8), methyl 4-bromo-2-hydroxybenzoate represented by the following formula (9) Methyl 4-bromo-2-hydroxybenzoate, Methyl 4-chloro-2-hydroxybenzoate represented by Chemical Formula 10, and 2- ( 2- (tributylstannyl) thiophene, 2- (trimethylstannyl) selenophene and 2- (tributylstannyl) pyridine ) Is stirred with a solvent at a constant temperature in the presence of a palladium catalyst to form a mixture; And a step of raising the temperature of the mixture to a predetermined temperature, followed by reflux stirring, or irradiating with microwave to synthesize a methyl salicylate derivative.

(8)

≪ Formula 9 >

≪ Formula 10 >

In the step of forming the mixture, it is preferable to use the second monomer in an amount of 2.0 to 2.6 equivalents based on 1 equivalent of the first monomer.

The palladium catalyst may be selected from the group consisting of bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), or tetrakis A catalyst in which tetrakis (triphenylphosphine) palladium (0)) and tri (o-tolyl) phosphine are mixed can be used.

Wherein the palladium catalyst may be used in an amount of 0.02 to 0.08 equivalents based on 1 equivalent of the first monomer.

The solvent may be any one selected from anhydrous benzene, toluene, xylene, chlorobenzene and N, N-dimethylformamide (DMF). have.

The step of forming the mixture may be stirred at a temperature of 50 ° C to 70 ° C.

The step of synthesizing the methyl salicylate derivative may raise the temperature of the mixture to 100 ° C to 120 ° C.

In the case of the reflux stirring reaction in the step of synthesizing the methyl salicylate derivative, the reaction can be carried out for 10 hours to 12 hours.

In the synthesis of the methyl salicylate derivative, in the case of microwave irradiation, a microwave may be irradiated with a microwave for 10 minutes to 20 hours at a heating source for 1 hour to 2 hours.

After the step of synthesizing the salicylic acid methyl derivative, a step of separating and purifying the synthesized salicylic acid methyl derivative may be additionally performed.

For example, the separation and purification may be carried out by using a column chromatography. The column chromatography may be carried out by using two or more kinds selected from hexane, chloroform, acetone and methanol. Can be used as a mobile phase.

The column chromatography may be carried out once to several times until a single compound is purified.

The salicylmethyl derivative of the present invention having the above characteristics has low steric hindrance and has a low band gap and high conductivity. When compared to methyl salicylate, the conjugated oligomer having a low-band gap and a UV-vis spectrum The oligomer exhibits a wide absorption range of about 200 to 400 nm, exhibits the largest absorption near the wavelength of 310 nm, and has fluorescence that emits light at a specific wavelength, so that it can be applied not only to similar chemical agents for fluorescence but also to various electronic materials industries There are advantages.

Specifically, the conjugated oligomer according to the present invention exhibits a bathochromic shift to the longer wavelength side compared with the precursor methyl salicylate monomer, and emits blue-based light. Thus, the active layer of the LED device (active layer synthesized according to the present invention, and a polymer synthesized according to the present invention, which is a methyl salicylate derivative or a derivative thereof and a synthesized compound, can be applied to the LED industry.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart of a method for preparing a novel methyl salicylate derivative in the form of a conjugated oligomer according to the present invention.
Fig. 2 is a diagrammatic illustration of a methyl 2-hydroxy-4- (thiophen-2-yl) benzoate as a methyl salicylate derivative in the form of a conjugated oligomer according to Example 1 of the present invention -yl) benzoate. < / RTI >
FIG. 3 is a graph showing the results of methyl 2-hydroxy-4- (thiophen-2-yl) benzoate as a methyl salicylate derivative in the form of a conjugated oligomer according to Example 1 of the present invention -yl) benzoate. < / RTI >
4 is a graph showing a hydrogen atom nuclear magnetic resonance spectroscopy ( ¹ H-NMR) characteristic of a methyl salicylate derivative in the form of a conjugated oligomer according to Example 1 of the present invention.
5 is a graph showing a carbon atom nuclear magnetic resonance ( ¹³ C-NMR) characteristic of a novel methyl salicylate derivative in the form of a conjugated oligomer according to Example 1 of the present invention.
6 is a graph showing ultraviolet-visible light (UV-vis) absorption spectroscopic characteristics of a methyl salicylate derivative of the form of conjugated oligomer according to Example 1 of the present invention.
7 is a graph showing the photoluminescence characteristics of a novel methyl salicylate derivative in the form of a conjugated oligomer according to Example 1 of the present invention in a solid form.
8 is a graph showing the photoluminescence characteristics of a novel salicylic acid methyl derivative in the form of a conjugated oligomer according to Example 1 of the present invention under an aprotic solvent (chloroform).
9 is a graph showing infrared (IR) absorption spectroscopic characteristics of a novel methyl salicylate derivative in the form of a conjugated oligomer according to Example 1 of the present invention.
10 is a graph showing the results of the measurement of methyl 2-hydroxy-4- (selenophen-2 (2-hydroxy-4- -yl) benzoate. < / RTI >
Fig. 11 is a graph showing the results of measurement of methyl 2-hydroxy-4- (selenophen-2 (2-hydroxy-4- -yl) benzoate. < / RTI >
12 is a graph showing the hydrogen nuclear magnetic resonance spectroscopy ⁽¹ H-NMR) properties of the new acid-methyl derivative of a conjugated oligomer forms in accordance with the second exemplary embodiment of the present invention.
13 is a graph showing a carbon atom nuclear magnetic resonance spectroscopy ( ¹³ C-NMR) of a methyl salicylate derivative of the form of a conjugated oligomer according to Example 2 of the present invention.
14 is a graph showing ultraviolet-visible (UV-vis) absorption spectroscopic characteristics of a methyl salicylate derivative of the form of a conjugated oligomer according to Example 2 of the present invention.
15 is a graph showing photoluminescence characteristics in the form of a solid of a methyl salicylate derivative of the present invention in the form of a conjugated oligomer according to Example 2 of the present invention.
16 is a graph showing the photoluminescence characteristics of a methyl salicylate derivative in the form of a conjugated oligomer according to Example 2 of the present invention under an aprotic solvent (chloroform).
17 is a graph showing infrared (IR) absorption spectroscopic characteristics of a novel methyl salicylate derivative in the form of a conjugated oligomer according to Example 2 of the present invention.
FIG. 18 is a graph showing the results of measurement of methyl 2-hydroxy-4- (pyridin-2-yl) benzoate as a methyl salicylate derivative in the form of conjugated oligomer according to Example 3 of the present invention. yl) benzoate.
FIG. 19 is a graph showing the results of measurement of methyl 2-hydroxy-4- (pyridin-2-yl) benzoate as a methyl salicylate derivative in the form of a conjugated oligomer according to Example 3 of the present invention. yl) benzoate).
20 is a graph showing a hydrogen atom nuclear magnetic resonance ( ¹ H-NMR) characteristic of a methyl salicylate derivative of the form of a conjugated oligomer according to Example 3 of the present invention.
21 is a graph showing the carbon atom nuclear magnetic resonance spectroscopy ( ¹³ C-NMR) characteristics of the methyl salicylate derivative of the conjugated oligomer type according to Example 3 of the present invention.
22 is a graph showing ultraviolet-visible (UV-vis) absorption spectroscopic characteristics of a novel methyl salicylate derivative in the form of a conjugated oligomer according to Example 3 of the present invention.
23 is a graph showing the photoluminescence characteristics of a novel methyl salicylate derivative in the form of a conjugated oligomer according to Example 3 of the present invention in a solid form.
24 is a graph showing the photoluminescence characteristics of a novel salicylic acid methyl derivative in the form of a conjugated oligomer according to Example 3 of the present invention under an aprotic solvent (chloroform).
25 is a graph showing infrared (IR) absorption spectroscopic characteristics of a novel salicylic acid methyl derivative in the form of a conjugated oligomer according to Example 3 of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart showing a method for producing a novel methyl salicylate derivative in the form of a conjugated oligomer according to the present invention. FIG.

As shown in FIG. 1, the method for preparing a methyl salicylate derivative in the form of a conjugated oligomer according to the present invention comprises a step (S110) of forming a mixture by stirring a first monomer and a second monomer together with a solvent at a constant temperature in the presence of a palladium catalyst, , Synthesizing a salicylic acid methyl derivative through a stille-cross coupling reaction (S120), and separating and purifying the synthesized salicylic acid methyl derivative (S130).

The first monomer is a methyl salicylate monomer as a starting material of the present invention, preferably methyl 4-iodo-2-hydroxybenzoate represented by the following formula (8) Methyl 4-bromo-2-hydroxybenzoate represented by Chemical Formula 10, methyl 4-chloro- 2-hydroxybenzoate represented by Chemical Formula 10, 2-hydroxybenzoate).

(8)

≪ Formula 9 >

≪ Formula 10 >

The second monomer is a monomer that undergoes a stille-cross coupling reaction with the first monomer, and is a 2- (tributylstannyl) thiophene ), 2- (trimethylstannyl) selenophene represented by the formula (12), and 2- (tributylstannyl) pyridine represented by the formula (13) It is one.

≪ Formula 11 >

≪ Formula 12 >

≪ Formula 13 >

The palladium catalyst may be selected from the group consisting of bis (triphenylphosphine) palladium (II) dichloride, Pd ₂ Cl ₂ (PPh ₃ ) ₂ , tetrakis (triphenylphosphine) palladium, palladium (0), Pd (PPh 3) 4) , or tetrakis (triphenylphosphine) palladium (tetrakis (triphenylphosphine) palladium (0)) and tri (ortho-tolyl) phosphine (tri (o-tolyl) phosphine) Or a catalyst mixed in the ratio of 1 to 4 equivalents may be used.

Wherein the palladium catalyst may be used in an amount of 0.02 to 0.08 equivalents based on 1 equivalent of the first monomer.

Specifically, the palladium catalyst may be added in an amount of about 0.04 to about 0.08 equivalent, which is about 2 to 4 times, because it plays a role in assisting the reaction to add 0.02 equivalents. However, since the palladium catalyst is generally expensive, it is wasteful to add 0.08 equivalent each time, and since it is difficult to separate the residual catalyst after the reaction, it is most preferable to add 0.02 to 0.04 equivalents.

The solvent may be any one selected from anhydrous benzene, toluene, xylene, chlorobenzene and N, N-dimethylformamide (DMF). have.

In the step of forming the mixture (S110), the first monomer, the second monomer, and the palladium catalyst are added to the solvent and stirred at a constant temperature until the reactants added to the solvent are completely dissolved in the solvent for a predetermined reaction time.

The step S120 of synthesizing the salicylic acid methyl derivative is a step of synthesizing a methyl salicylate derivative through a stille-cross coupling reaction of the mixture formed in the step S110, The reaction may be carried out by reflux stirring or by irradiation of microwave as a heat source.

It is theoretically preferable to raise the temperature to near the boiling point of the solvent to be used in order to carry out the reaction of the stetocross coupling using the palladium catalyst. Therefore, the reaction can be carried out by raising the temperature of the mixture to 100 to 120 ° C And it is most preferable to conduct the reaction at the temperature and time because the experimental results obtained the best yield when the reaction was conducted at 120 ° C for 12 hours.

Hereinafter, a methyl salicylate derivative according to the present invention and a method for producing the same will be described in detail.

As described above, the methyl salicylate derivative is a conjugated oligomer form represented by the following formula (1).

≪ Formula 1 >

In the above formula (1), A is a group selected from the group consisting of the following formulas (2) to (4).

(2)

(3)

≪ Formula 4 >

The salicylic acid methyl derivative represented by the above formula (1) is obtained by reacting methyl 2-hydroxy-4- (thiophen-2-yl) benzoate Methyl 2-hydroxy-4- (selenophen-2-yl) benzoate represented by the following general formula (6), methyl 2-hydroxy- It is preferably any one of methyl 2-hydroxy-4- (pyridin-2-yl) benzoate.

≪ Formula 5 >

(6)

≪ Formula 7 >

Compound 1 as a compound represented by Chemical Formulas 5 to 7 is methyl 2-hydroxy-4- (thiophen-2-yl) benzoate , Compound 2 is methyl 2-hydroxy-4- (selenophen-2-yl) benzoate and compound 3 is methyl 2-hydroxy- (2-hydroxy-4- (pyridin-2-yl) benzoate), hereinafter referred to as Compound 1, Compound 2 and Compound 3, respectively.

Hereinafter, a method for preparing methyl 2-hydroxy-4- (selenophen-2-yl) benzoate as a methyl salicylate derivative will be described in more detail.

Preparation of Compound (1)

In a round flask, 5 to 10 mL of N, N-dimethylformamide was used as a solvent, and methyl 4-iodo-2-hydroxybenzoate was used as a first monomer. 0.147 g (0.3596-0.4675 mmol) of 2- (tributylstannyl) thiophene as a second monomer, bis (triphenylphosphine) palladium it binds the ^-palladium dichloride (bis (triphenylphosphine) palladium (II ) dichloride) 0.0050 ~ 0.101 g (5 mol 7.1929 × 10 -6 ~ 1.4386 × 10). The mixture is stirred at 60 캜 until the mixture is dissolved transparently, and then the temperature is gradually raised to 120 캜 and stirred while refluxing for 10 to 12 hours to synthesize the compound.

Then, the temperature of the reactant containing the synthesized compound is lowered to room temperature, and the solvent is removed using a rotary evaporator. Then, the obtained organic mixture was separated by column chromatography (eluent: dichloromethane / Hexane = 1/49, vol / vol) to finally obtain Compound 1 as shown in Fig.

The reason for limiting the value of the second monomer, 2- (tributylstannyl) thiophene, is that the starting material, methyl 4-iodo-2-hydroxybenzoate Thiophene should be substituted at the position where iodine (I), which is a halogen element of 2-hydroxybenzoate, is substituted, at least 1.0 equivalent should be added based on 1.0 equivalent of the first monomer, and 1.0 equivalent There is a problem that the reaction does not proceed properly. It is preferable to add 1.1 to 1.2 equivalents based on 1.0 equivalents of the first monomer so as to reduce the waste of the reagent.

Preparation of Compound 2

In a round flask, 5 to 10 mL of N, N-dimethylformamide was used as a solvent, and methyl 4-iodo-2-hydroxybenzoate was used as a first monomer. (Trimethylstannyl) selenophene 0.1057-0.1374 g (0.3596-0.44675 mmol) as a second monomer, bis (triphenylphosphine) palladium it binds the ^{- (5 mol 7.1929 × 10 -6} ~ 1.4386 × 10) dichloride, (bis (triphenylphosphine) palladium (II ) dichloride) 0.0050 to 0.101g. The mixture is stirred at 60 캜 until the mixture is dissolved transparently, and then the temperature is gradually raised to 120 캜 and stirred while refluxing for 10 to 12 hours to synthesize the compound.

Then, the temperature of the reactant containing the synthesized compound is lowered to room temperature, and the solvent is removed using a rotary evaporator. The resulting organic mixture was separated by column chromatography (eluent: dichloromethane / hexane = 1/49, vol / vol) to finally obtain Compound 2 as shown in FIG.

The reason for limiting the value of the second monomer, 2- (trimethylstannyl) selenophene, is that the starting material, methyl 4-iodo-2-hydroxybenzoate, Thiophene should be substituted at the position where iodine (I), which is a halogen element of 2-hydroxybenzoate, is substituted. Therefore, at least 1.0 equivalent should be added based on 1.0 equivalent of the first monomer, There is a problem in that the reaction does not proceed properly. It is preferable to add 1.1 to 1.2 equivalents based on 1.0 equivalents of the first monomer so as to reduce the waste of the reagent.

Preparation of Compound 3

In a microwave tube, 4 to 6 mL of N, N-dimethylformamide as a solvent and methyl 4-iodo (N, N-dimethylformamide) 0.114 g (0.3596-0.4675 mmol) of 2- (tributylstannyl) pyridine as the second monomer and 0.100 g (0.3596 mmol) of tetrakis (triphenylphosphine) palladium it binds the ⁵ mol) ^- phenyl phosphine) palladium (tetrakis (triphenylphosphine) palladium (0 )) 0.0083 ~ 0.1662 g (7.1929 × 10 -6 ~ 1.4386 × 10. A methyl salicylate derivative is synthesized by a microwave irradiation process using a microwave irradiation instrument. Here, the microwave irradiation conditions were set so that the temperature was raised to 110 ° C over 20 minutes by irradiating microwaves of about 20w, and then maintained at 110 ° C for 40 minutes.

Then, the temperature of the reactant containing the synthesized compound is lowered to room temperature, and the solvent is removed using a rotary evaporator. The obtained organic mixture was then separated using column chromatography (eluent: dichloromethane 100%) to finally obtain Compound 3 as shown in Fig.

The reason for limiting the value of the second monomer, 2- (tributylstannyl) pyridine, is that the starting material, methyl 4-iodo-2-hydroxybenzoate, Thiophene should be substituted at the position where iodine (I), which is a halogen element of 2-hydroxybenzoate, is substituted. Therefore, at least 1.0 equivalent should be added based on 1.0 equivalent of the first monomer, There is a problem in that the reaction does not proceed properly. It is preferable to add 1.1 to 1.2 equivalents based on 1.0 equivalents of the first monomer so as to reduce the waste of the reagent.

Hereinafter, preferred embodiments of the present invention will be described. It is to be understood that the embodiments are not limited to the embodiments described herein because they may be embodied in many different forms without departing from the scope of the present invention.

Example 1

To the round flask was added 7 mL of N, N-dimethylformamide, 0.1000 g (0.3596 mol) of methyl 4-iodo-2-hydroxybenzoate as starting material 0.1476 g (0.3956 mmol) of 2- (tributylstannyl) thiophene, bis (triphenylphosphine) palladium (II) dichloride, Pd _{2 Cl 2 (PPh 3) 2} ) 0.0050 g (7.1929 × 10 - it binds the ⁶ mol). After the reaction mixture was stirred at 60 캜 until it was dissolved in a transparent state, the temperature was slowly raised to 120 캜 and stirred while refluxing for 10 hours.

The temperature of the reaction mixture is then lowered to room temperature and the solvent is removed using a rotary evaporator. Compound 1 was then isolated using column chromatography (eluent: dichloromethane / Hexane = 1/49, vol / vol). The reaction formula of the synthesis process according to the first embodiment of the present invention is as shown in FIG.

The physical properties of the synthesized Compound 1 are shown in FIG. 4 to FIG.

4 is a graph showing the hydrogen atom nuclear magnetic resonance spectroscopy ( ¹ H-NMR) characteristics of Compound 1 synthesized according to Example 1 at 7.43 ppm, 7.25 ppm, 7.17 ppm peak, Three hydrogens could be identified.

5 is a graph showing the carbon atom nuclear magnetic resonance spectroscopic ( ¹³ C-NMR) characteristics of Compound 1 synthesized according to Example 1, and four carbon of thiophenes can be identified through peaks at 142 ppm, 128 ppm, 126 ppm and 124 ppm there was.

FIG. 6 is a graph showing ultraviolet absorption spectral characteristics of Compound 1 synthesized according to Example 1, and it can be confirmed that light is absorbed between 250 nm and 390 nm. The maximum absorption wavelength (λ _MAX ) value is found at 338 nm and the λ _EDGE value is found at 379 nm.

7 and 8 are graphs showing the luminescent characteristics of the compound 1 synthesized according to Example 1 in the solid form and the luminescent properties of the compound 1 synthesized in Example 1 in an aprotic solvent.

Emission wavelength (Spec Ex) in the graph of Figure 7 is a λ 392nm _Em. The emissive wavelength (Em Spec) on the right side indicates the wavelength depending on the energy emitted when the emitter emits to the bottom state when the _Em了_Em is fixed at 368 nm and 300 nm. it means. Therefore, it can be seen that similar energy is emitted through the intensity of the emitted wavelength relative to the absorption wavelength, which confirms that the substance is fluorescent.

FIG. 8 is a graph comparing the theoretical point of view with the graph of FIG. 7, showing that fluorescence at a broader wavelength when measured in the solid form in FIG. 7 than in the non-protonic solvent of Compound 1 of Example 1 Can be confirmed.

9 is a graph showing infrared (IR) absorption spectroscopic characteristics of Compound 1 synthesized according to Example 1. Fig. The visible peaks with strong peak at 694cm ^-1 at 3100cm ^-1, as shown in Figure 9 bar, it can be seen that a substituted thiophene.

Example 2

To the round flask was added 7 mL of N, N-dimethylformamide, 0.1000 g (0.3596 mol) of methyl 4-iodo-2-hydroxybenzoate as starting material 0.1162 g (0.3956 mmol) of 2- (trimethylstannyl) selenophene, bis (triphenylphosphine) palladium (II) dichloride, Pd _{2 Cl 2 (PPh 3) 2)} 0.0050 g (7.1929 × 10 - it binds the ⁶ mol). After the reaction mixture was stirred at 60 캜 until it was dissolved in a transparent state, the temperature was slowly raised to 120 캜 and stirred while refluxing for 10 hours.

The temperature of the reaction mixture is then lowered to room temperature and the solvent is removed using a rotary evaporator. Compound 2 was then separated by column chromatography (eluent: dichloromethane / Hexane = 1/49, vol / vol). The reaction scheme for the synthesis of Compound 2 according to Example 2 is as shown in FIG.

The physical properties of the synthesized Compound 2 are shown in Figs. 12 to 17. Fig.

12 is a graph showing a hydrogen atom nuclear magnetic resonance spectroscopy ( ¹ H-NMR) characteristic of the compound 2 synthesized according to Example 2. Fig. As shown in FIG. 12, three hydrogens substituted for selenophene can be identified through the 7.82 ppm, 7.69 ppm, and 7.19 ppm peaks.

13 is a graph showing the carbon atom nuclear magnetic resonance spectroscopic ( ¹³ C-NMR) characteristics of Compound 2 synthesized according to Example 2, and showing a peak of 143 ppm, 132 ppm, 130 ppm and a peak of 127 ppm, .

14 is a graph showing ultraviolet absorption spectral characteristics of Compound 2 synthesized according to Example 2. It can be seen that Compound 2 absorbs light between 250 nm and 380 nm, and the maximum absorption wavelength ( _max ) is 323 nm And the value of λ _EDGE appears at 377 nm.

FIG. 15 is a graph showing the luminescence characteristics in the solid form of Compound 2 synthesized according to Example 2, and FIG. 16 is a graph showing the luminescence characteristics of Compound 2 in an aprotic solvent.

In the graph of FIG. 15, the emission wavelength (Ex Spec) means the wavelength emitted according to the intensity of the excited state when fixed at 392 nm and 430 nm, and the absorption wavelength (Em Spec, λ _Ex ) And it means the wavelength depending on the energy released to the bottom state. Thus, it can be seen that similar energy is emitted through the intensity of the emitted wavelength relative to the absorption wavelength, which proves that the material is fluorescent.

FIG. 16 shows that the compound 2 is fluorescent at a broader wavelength when measured in the solid form of FIG. 15 than when the compound 2 is measured in an aprotic solvent.

17 is a graph showing infrared (IR) absorption peaking characteristics of Compound 2 synthesized according to Example 2. As shown in FIG. 17, a peak at 3128 cm ^-1 and a strong peak at 714 cm ^-1 are shown in FIG. .

Example 3

In a microwave tube, 4 to 6 mL of N, N-dimethylformamide as a solvent and methyl 4-iodo (N, N-dimethylformamide) 0.1721 g (0.4675 mmol) of 2- (tributylstannyl) pyridine, 0.100 g (0.3596 mmol) of 2- (2-hydroxybenzoate) palladium (0), Pd (PPh ₃ ) ₄ ) (0.008 g, 7.1929 × 10 ^-6 mol). The microwave is irradiated using a microwave irradiation apparatus (Discover system, CEM). At this time, the microwave irradiation condition was such that the microwave of about 20w was irradiated, the temperature was raised to 110 ° C over 20 minutes, and then the reaction was continued at 110 ° C for 40 minutes.

The temperature of the reaction mixture is then lowered to room temperature and the solvent is removed using a rotary evaporator. Compound 3 was then separated using column chromatography (eluent: dichloromethane 100%). The reaction scheme for the synthesis of Compound 3 according to Example 3 is shown in FIG.

The physical properties of the synthesized Compound 3 are shown in FIGS. 20 to 25.

20 is a graph showing the ¹ H-NMR characteristics of Compound 3 synthesized according to Example 3. Fig. As shown, four hydrogens substituted with pyridine can be identified through peaks at 10.80 ppm, 8.74 ppm, 7.94 ppm, and 7.27 ppm.

FIG. 21 is a graph showing ¹³ C-NMR characteristics of Compound 3 synthesized according to Example 3, and five carbons of pyridine can be identified through peaks at 155 ppm, 149 ppm, 137 ppm, 123 ppm, and 121 ppm.

22 is a graph showing ultraviolet absorption spectroscopic characteristics of Compound 3 synthesized according to Example 3. It can be confirmed that Compound 3 absorbs light between 250 nm and 390 nm. The maximum absorption wavelength (λ _MAX ) appears at 315 nm and the λ _EDGE value at 380 nm.

FIG. 23 is a graph showing the luminescence characteristics in the solid form of Compound 3 synthesized according to Example 3, and FIG. 24 is a graph showing the luminescence characteristics of Compound 3 in an aprotic solvent.

Emission wavelength (Spec Ex) in the graph of Fig. 23 is a λ 392nm _Em. The emissive wavelength (Em Spec) means the wavelength depending on the energy emitted when the wavelength λ _Ex is fixed to 368 nm and 300 nm to the bottom state. do. Thus, it can be seen that similar energy is emitted through the intensity of the emitted wavelength relative to the absorption wavelength, demonstrating that compound 3 is fluorescent.

FIG. 24 shows a comparison between the theoretical point of view as shown in the graph of FIG. 23 and the fact that fluorescence is observed at a wider wavelength when measured in a solid form as shown in FIG. 23 than when measured in an aprotic solvent of Compound 2 have.

25 is a graph showing infrared (IR) absorption spectroscopic characteristics of Compound 3 synthesized according to Example 3. Fig. Showing a strong peak at 700cm ^-1 and the peak at the peak, 1200cm ^-1 at the peak, 1410cm ^-1 at the peak, 1575cm ^-1 at 3100cm ^-1, as shown, can be concluded that the substituted pyridine .

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims and their equivalents. Of course, such modifications are within the scope of the claims.

Claims (12)

A salicylic acid methyl derivative of conjugated oligomer type represented by the following formula (1).
≪ Formula 1 >

In the above formula (1), A is a group selected from the group consisting of the following formulas (2) to (4).
(2)

(3)

≪ Formula 4 >

The method according to claim 1,
The salicylic acid methyl derivative represented by the above formula (1) is obtained by reacting methyl 2-hydroxy-4- (thiophen-2-yl) benzoate Methyl 2-hydroxy-4- (selenophen-2-yl) benzoate represented by the following general formula (6), methyl 2-hydroxy- Methyl derivative of salicylic acid is characterized in that it is any one of methyl 2-hydroxy-4- (pyridin-2-yl) benzoate.
≪ Formula 5 >

(6)

≪ Formula 7 >

Methyl 4-iodo-2-hydroxybenzoate represented by the following formula (8), methyl 4-bromo-2-hydroxybenzoate represented by the following formula (9) -bromo-2-hydroxybenzoate, Methyl 4-chloro-2-hydroxybenzoate represented by Chemical Formula 10, and 2- (tributyl 2- (tributylstannyl) thiophene, 2- (trimethylstannyl) selenophene and 2- (tributylstannyl) pyridine. Stirring the selected one second monomer with a solvent at a predetermined temperature in the presence of a palladium catalyst to form a mixture; And
A step of raising the temperature of the mixture to a predetermined temperature and reflux stirring or a microwave irradiation to synthesize a methyl salicylate derivative; and synthesizing the conjugated oligomeric methyl salicylate derivative represented by the following formula (1).
≪ Formula 1 >

In the above formula (1), A is a group selected from the group consisting of the following formulas (2) to (4).
(2)

(3)

≪ Formula 4 >

(8)

≪ Formula 9 >

≪ Formula 10 >

The method of claim 3,
Wherein the forming of the mixture comprises using the second monomer in an amount of 2.0 to 2.6 equivalents based on 1 equivalent of the first monomer. The method of claim 3,
The palladium catalyst may be selected from the group consisting of bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), or tetrakis Wherein the catalyst is any one of a catalyst in which tetrakis (triphenylphosphine) palladium (0) and tri (o-tolyl) phosphine are mixed with each other to produce a salicylic acid methyl derivative Way. The method of claim 3,
Wherein the palladium catalyst is used in an amount of 0.02 to 0.08 equivalents based on 1 equivalent of the first monomer. The method of claim 3,
Wherein the solvent is any one selected from the group consisting of anhydrous benzene, toluene, xylene, chlorobenzene and N, N-dimethylformamide. Methyl < / RTI > The method of claim 3,
Wherein the step of forming the mixture is carried out at a temperature of 50 to 70 占 폚. The method of claim 3,
Wherein the step of synthesizing the salicylic acid methyl derivative comprises raising the temperature of the mixture to 100 ° C to 120 ° C. The method of claim 3,
Wherein the step of synthesizing the salicylic acid methyl derivative is carried out for 10 hours to 12 hours in the case of the reflux stirring reaction. The method of claim 3,
Wherein in the step of synthesizing the salicylic acid methyl derivative, the microwave irradiation is carried out at 10 to 20 watts for 1 hour to 2 hours in the case of microwave irradiation. The method of claim 3,
And separating and purifying the synthesized salicylic acid methyl derivative after the step of synthesizing the salicylic acid methyl derivative.

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