WO2015174663A1 - Dye comprising pyrromethene-boron complex compound - Google Patents

Abstract

The present invention relates to dye comprising a pyrromethene-boron complex compound. Dye comprising a pyrromethene-boron complex compound, according to the present invention, has no fluorescence and can absorb light of a particular wavelength and thus can be utilized for dye for display.

Description

 Specification

 FIELD OF THE INVENTION The present invention relates to a dye comprising a novel pyrromethene boron complex, and more particularly to a pyrromethene boron complex which is non-fluorescent and can absorb light of a specific wavelength. It relates to a dye for display. Background Art As a flat panel display, a liquid crystal display (LCD), in addition to an organic light-emitting diode (OLED) and a plasma display panel (PDP), is widely used.

 An LCD is a light receiving device that displays an image by controlling the amount of light coming from the outside. Therefore, a backlight unit (BLU) in the form of a back light source that can maintain uniform brightness across the screen is required.

 BLU is a device that can express information by supplying lamp light to LCD which does not light itself. It is located on the back of LCD.

 Color filters are commonly used to color LCDs. The color filter has three primary colors, that is, red, green, and blue patterns formed on the glass substrate, and only light having a wavelength band of the required color among the light supplied from the backlight to obtain a desired color. By transmitting the light and blocking the light of unnecessary wavelength bands in the light source, the red, green and blue light are obtained, respectively.

Colored LCD has been developed as a display for displaying visual information such as texts, pictures, and images, and is widely used in devices such as television sets, computer monitors, and mobile phones. In addition, the technology to make the image displayed on the display exhibit a shape and color close to the actual material It becomes important. The higher the color purity of each of the three primary colors, the easier it is to express the color of the actual material on the display. For this purpose, the emission wavelength band of the required color should be selective, and the emission spectrum should be sharp and the emission region should be narrow. Pigments used in the past show relatively high transparency and color clarity, but in recent years, higher transparency and color purity are required.

 0LED refers to a device that emits light by using electroluminescence which emits light when current flows through an organic compound. 0LEDs are attracting attention as next-generation flat panel displays because they can be driven at low voltages, have a thin film thickness, and have a wide viewing angle and fast response speed.

 In order to use 0LED as a light source of a display, a method of realizing white light is required as in LCD, but white light is generated by combining red, green, and blue light sources, or white light is formed by combining yellow light emitting material with blue 0LED. There are ways to implement color with color filters. However, the color conversion method of producing white light by combining yellow light emitting material with blue 0LED has a problem in that the color purity is improved by blocking unnecessary light due to poor quality. Meanwhile, as a method for implementing high color purity on the LCD, it may be considered to use a color filter material for improving color purity. This method suppresses unnecessary emission wavelengths and improves color purity by including a compound having a wavelength band that selectively absorbs unnecessary emission wavelengths in the color filter, in order to eliminate the phenomenon that color purity decreases due to unnecessary emission wavelengths resulting from the backlight. can do.

In the case of a transmissive LCD, red and green light emission color purity is a problem because unnecessary light emission in the 480 to 600 nm wavelength region is not blocked sufficiently. Therefore, if the compound capable of selectively absorbing light in the .wavelength region is used as a color filter material for improving color purity, the color purity of red and green is expected to be increased. Examples of the compound having absorption characteristics in the light region of 550 to 600 nm, preferably 550 to 590 nm wavelength include pyrromethene-based boron complex compounds. Since the pyrromethene-based boron complex compound has a selective absorption region, it does not absorb unnecessary wavelength bands and may contribute to increase color purity. In addition, it is possible to design the material through various structural modifications, thereby having a selective absorption region, it is possible to implement a fluorescence characteristics. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a dye comprising a pyrromethene boron complex that is non-fluorescent and capable of absorbing light of a particular wavelength.

 Another object of the present invention to provide a filter for a display comprising the dye. The present invention to achieve the above object, the present invention provides a dye comprising a pyrromethene boron complex represented by the following formula (1):

 [Formula 1]

 In the above formula,

R ¹ to R ³ , and R ⁶ are each independently hydrogen; d- ₆ alkyl; d- ₆ alkoxy; C ₆ - ₂₀ aryl; D- ₆ alkyl substituted with halogen; Substituted by halogen, C ₆ - ₂₀ aryl; Or d- ₆ alkoxy substituted with halogen, where n is an integer from 0 to 6;

R ⁴ and R ⁵ are each independently d- ₆ alkyl; d- ₆ alkoxy; C ₆ - ₂₀ aryl; 6-20 membered heteroaryl; D- ₆ alkyl substituted with halogen; Halogen, d- ₆ alkyl and ¾ eu a C ₆ substituted with a substituent selected from the group consisting of _12-aryl-20 aryl; Substituted with a substituent selected from the group eojin yitu to ₁₂ aryl- or halogen, d- ₆ alkyl and C ₆

6-20 membered heteroaryl;

A is C ₆ - ₂₀ aryl is.

 The present invention also provides a display filter comprising the dye. According to the present invention, the dye containing the pyrromethene boron complex compound represented by the formula (1) of the present invention is not fluorescent, and can absorb light of a specific wavelength can be usefully used as a dye for display. DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described in more detail.

 The dye of the present invention comprises a pyrromethene boron complex represented by the following formula (1):

 [Formula 1]

 In the above formula,

R ¹ to R ³ , and R ⁶ are each independently hydrogen; d- ₆ alkyl; d- ₆ alkoxy; C ₆ - ₂₀ aryl; D- ₆ alkyl substituted with halogen; Substituted by halogen, C ₆ - ₂₀ aryl; Or d- ₆ alkoxy substituted with halogen, where n is an integer from 0 to 6;

R ⁴ and R ⁵ are each independently d- ₆ alkyl; d-6 alkoxy; C ₆ - ₂₀ aryl; 6-20 membered heteroaryl; D- ₆ alkyl substituted with halogen; Halogen, d- ₆ alkyl and C ₆ - C ₆ substituted with the substituents selected from the group consisting of _12-aryl-20 aryl; or Halogen, d- ₆ alkyl and C ₆ - with a substituent selected from the group consisting of _12, substituted aryl

6-20 membered heteroaryl;

A is C ₆ - ₂₀ aryl is. In one example of the dye according to the present invention,

R ¹ and R ³ are each independently hydrogen or d- ₆ alkyl;

R ² is hydrogen; C- ₆ alkyl; C ₆ - ₂₀ aryl; Or substituted by halogen, C ₆ - ₂₀ aryl;

R ⁴ and R ⁵ are each independently d- ₆ alkyl; C ₆ ᅳ ₂₀ aryl; 6-20 membered heteroaryl; D- ₆ alkyl substituted with halogen; Halogen, d- ₆ alkyl and C ₆ - C ₆ substituted with the substituents selected from the group consisting of _12-aryl-20 aryl; Or halogen, d- ₆ alkyl and C ₆ - substituted by substituents selected from the group consisting of aryl 6 _12: to 20-membered heteroaryl of;

R ⁶ is hydrogen; C - ₆ alkyl, C ₆ - ₂₀ aryl, and, wherein n is an integer from 0 to 4;

A is C ₆ - ₂₀ aryl is. In another example of the dye according to the present invention,

R ¹ and R ³ are each independently hydrogen or d- ₆ alkyl;

R ² is hydrogen; C ₆ - ₁₂ aryl; Or the refinancing by halogen C ₆ - ₁₂ aryl;

R ⁴ and R ⁵ are each independently alkyl; C ₆ - ₁₂ aryl; 6-12 membered heteroaryl; D- ₆ alkyl substituted with halogen; Halogen, d- ₆ alkyl and C ₆ - C ₆ substituted with the substituents selected from the group consisting of _12-aryl-12 aryl; Or halogen, d- ₆ alkyl and C ₆ - ₁₂ aryl heteroaryl group of 6 to 12-membered optionally substituted with substituents selected from the group consisting of a;

R ⁶ is hydrogen or d- ₆ alkyl, where n is an integer of 0 or 1;

A is C ₆ - ₁₂ aryl is. In another example of the dye according to the invention

R ¹ and R ³ are each independently hydrogen;

R ² is hydrogen or phenyl; R ⁴ and R ⁵ are each independently phenyl; Phenyl substituted with halogen or dihalogen; Naphthyl; 6 to 12 membered heteroaryl; d- ₆ alkyl; Or 6-12 membered heteroaryl substituted with C- ₆ alkyl or phenyl;

R ⁶ is hydrogen or d- ₆ alkyl, where n is an integer of 0 or 1;

 A is a phenyl ring or a naphthalene ring. In another example of the dye according to the present invention, the pyrromethene boron complex may be represented by the following formula (2):

 [Formula 2]

In the above formula

R ¹ and R ³ are each independently hydrogen,

R ² is hydrogen or phenyl;

R ⁴ and R ⁵ are each independently phenyl, chlorophenyl, dichlorophenyl ᅳ fluorophenyl, naphthyl, methyltetrazolyl methylimidazolyl, benzooxazolyl, alkyl, phenyltetrazolyl, or benzimidazolyl;

 A is a phenyl ring or a naphthalene ring. As used herein, the term "halogen" means fluorine chlorine, bromine or iodine unless otherwise noted.

 As used herein, the term 'alkyl' refers to a straight or branched hydrocarbon moiety unless stated otherwise.

As used herein, the term "alkoxy" refers to the group -ORa, where Ra is alkyl as defined above. Specific examples are methoxy, Ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, and the like, but are not limited thereto.

 The term 'aryl' as used herein refers to an aromatic group including phenyl, naphthyl and the like unless otherwise indicated.

 As used herein, the term “heteroaryl”, unless stated otherwise, refers to a monocyclic or bicyclic or more aromatic group containing at least one, for example one to four heteroatoms selected from 0, N and S. it means. Examples of monocyclic heteroaryl include thiazolyl, oxazolyl thiophenyl, furanyl, pyrrolyl, imidazolyl, isoxazolyl, pyrazolyl, triazolyl, thiadiazoleyl, tetrazolyl, oxadiazolyl and pyridinyl , Pyridazinyl, pyrimidinyl, pyrazinyl, and the like, but are not limited to these. Examples of bicyclic heteroaryl include indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzthiazolyl, benzthiadiazolyl, benztriazolyl, quinolinyl, Isoquinolinyl, purinyl, puropyridinyl and similar groups, but is not limited to these. Preferred examples of the pyrromethene boron complex compound may be represented by the following formula la to formula lm:

[Formula le]

[Formula If]

[Formula li]

[Formula ij]

The dye containing the pyrromethene boron complex represented by Formula 1 may have a maximum absorption wavelength at 550 nm to 600 nm, preferably 550 nm to 590 nm. In addition, the dye containing the pyrromethene boron complex represented by Formula 1 is excellent in light resistance and does not exhibit fluorescence.

 The dye containing the pyrromethene boron complex compound can be used for the preparation of the display filter, and thus the present invention also provides a display filter comprising the dye.

 The display filter may, for example, prepare a photosensitive coloring composition comprising the dye, apply the photosensitive coloring composition onto a substrate, and heat-dry the applied composition to form a film, thereby forming a dried film having a desired shape. After selective exposure using a mask, development may be performed, and then the developed film may be manufactured by heating and curing the film, but is not limited thereto. The dye containing the pyrromethene boron complex compound represented by the formula (1) may be used alone or in combination of two or more, and may be used in addition to other auxiliary colorants such as pigments or dyes. Therefore, the display filter of the present invention may include auxiliary pigments such as additional pigments or dyes, in addition to the dye containing the pyrromethene boron complex represented by the formula (1).

 The auxiliary colorant may be used without particular limitation as long as it is an organic pigment or dye having high transparency and color clarity heat resistance, and the organic pigment or dye may be used alone or in combination of two or more.

 When the organic pigment is used, if necessary, the dye containing the compound of Formula 1 may be used by miniaturizing the particles by a method such as solvent salt milling, dry milling, acid paste, or the like as necessary.

In addition, when the organic pigment is used, a dispersant commonly used in the manufacture of a display filter for the dispersion of the organic pigment may be used together. 004352 The dispersant may include, for example, an amine group or an ammonium salt group as a pigment affinity group, preferably an acrylic copolymer, polyurethane, polyethyleneimine, or a combination thereof. Compound of formula 1 of the present invention can be prepared as shown below.

 [Reaction 1]

 In the above formulas,

R ¹ to R ⁶ , A and n are the same as mentioned in the general formula (1). The preparation method of the compound of Formula 1 will be described in detail step by step. Step 0)

Compound (2) (1 equivalent) is added together with Compound (1) and / or Compound (1 ') (20-25 equivalents) to an equilateral bottom three-necked flask and stirred at room temperature for 5-30 minutes. After stirring, trifluoroacetic acid (TFAXO. L to 0.3 equiv) was added thereto, and further stirred at room temperature for 10 minutes to 1 hour 30 minutes. Subsequently, the reaction solution was concentrated, and then subjected to column chromatography with a mixture of ethyl acetate and η-nucleic acid to obtain compound (3) as an intermediate. Step 2

Compound (3) (1 equiv) and anhydrous tetrahydrofuran (THF) were added to an equilateral bottom three neck flask and stirred at room temperature to dissolve Compound (3). When all of the compound (3) is dissolved, react the reaction solution at -60 to -90 ^° C. The suspension solution of N-chlorosuccinimide (NCSK2-2.2 equiv) and anhydrous tetrahydrofuran is dripped and stirring, maintaining each temperature. After the dropping, the reaction solution is kept ^at -60 to -90 ^° C and stirred for 1 to 3 hours. After that, the mixture was heated to room temperature and further stirred for 2 to 5 hours. Subsequently, the organic layer was extracted with dichloromethane and water, filtered through silica gel and concentrated. Compound (4) can be obtained. Step 3

Compound (4) (1 equivalent) obtained in step (2) was placed in a constant-neck three-necked flask without further purification, and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (00 (1.2) To 1.5 equivalents) and dichloromethane (DCM), and then reacted at room temperature for 30 minutes to 2 hours. (5) can be obtained.

Compound (5) (1 equivalent) and dichloromethane are added to a round bottom three-necked polar flask and compound (5) is dissolved at room temperature. When all the compounds (5) are dissolved, triethylamine (TEA) (10 to 15 equivalents) is added and stirred for 5 to 30 minutes. Next, borontrifluoride diethyl ether (BF ₃ 0Et ₂ ) (15 to 20 equivalents) is added dropwise and stirred. After the dropping is finished, the reaction solution is further stirred for 10 to 30 minutes at room temperature. Subsequently, the organic layer was extracted with water, filtered through silica gel, concentrated, and then subjected to column chromatography with a mixture of ethyl acetate and n-nucleic acid to obtain compound (6) as an intermediate. Step 5

Compound (6) (1 equivalent) ᅳ Compound (7) (5-7 equivalents), aluminum chloride (A1CI ₃ ) (2-4 equivalents) and dichloromethanol were added to the back-necked three-neck flask and stirred for 10-30 minutes at room temperature. do. Subsequently, the organic layer was extracted with water, filtered through silica gel, concentrated, and subjected to column chromatography with a mixture of ethyl acetate and n-nucleic acid to obtain Intermediate Compound (8). Step 6

 Chemical formula

Compound (8) (1 equivalent) and acetonitrile solvent were dissolved in a round-bottomed three neck flask, and Compound (8) was dissolved, and then Compound (9) and / or Compound (9 ') (1-4 equivalents) and triethylamine ( 2 to 3 equivalents), and then stirred at room temperature for 10 minutes to 1 hour. After completion of the reaction, the organic layer was extracted with water, filtered through silica gel, concentrated, and then purified by column chromatography with a mixture of ethyl acetate and _n -nucleic acid. It can be carried out to obtain a compound of formula (1).

EXAMPLE

 Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto. 1: Preparation of Compound of Formula la

15 g of benzaldehyde and 237 g of pyrrole were put into a 500 mL back-bottom three-necked flask, which was stirred for 10 minutes at room temperature. After stirring, 1.61 g of trifluoroacetic acid was added thereto, and the mixture was further stirred at room temperature for 30 minutes. After the reaction was completed, the reaction solution was concentrated, and then column chromatography was performed with ethyl acetate and n-nucleic acid mixed solvent (1:10 (v / v)) to obtain 17.3 g of intermediate (1).

¾ 賺 (600MHz, CDCls): δ 7.92 (s, 2H), 7.31 (t, 2H), 7.25 (t, 1H), 7.22-7.20 (d, 2H), 6.69-6.68 (d, 2H), 6.16- 6.15 (m, 2H), 5.91 (s, 2H), 5.47 (s, 1H) Step (2): Preparation of Intermediate (2)

17.3 g of Intermediate (1) obtained in Step (1) and 460 mL of anhydrous tetrahydrofuran were added to a 1,000 mL equilateral bottom three-neck full flask, and dissolved at room temperature with stirring. After all of the intermediate (1) was dissolved, the reaction solution was immersed in -78 ^° C. A suspension of 22.9 g of N-chlorosuccinimide and 170 mL of anhydrous tetrahydrofuran was added dropwise while maintaining the temperature. After the dropping, the reaction solution was stirred at -78 ^° C for 2 hours. After that, the mixture was heated to silver and stirred for additional 3 hours. When the reaction was completed, the organic layer was extracted with dichloromethane and water, and concentrated by silica gel filtration to obtain 23 g of intermediate (2). It was used directly for the synthesis of intermediate (3) without further purification. Step (3): Preparation of Intermediate (3)

Into a 1,000 mL back-bottom three-necked flask, add 21.2 g of intermediate (2), 2, 3-dichloro-5,6-dicyano-1,4-benzoquinone, and 700 mL of dichloromethane to the room temperature at room temperature. Reaction for 1 hour. After the reaction was completed, the reaction solution was concentrated, and then column chromatography was performed with ethyl acetate and n-nucleic acid mixed solvent (1: 100 (v / v)) to obtain 6 g of intermediate (3).

¾ NMR (600 MHz, CDC1 ₃ ): δ 7.49-7.46 (m, 1Η), 7.43-7.42 (m ₍ 4H), 6.52-6.51 (d, 2H), 6.24 (d, 2H) ： Preparation of intermediate (4)

6 g of intermediate (3) obtained in step (3) and 170 mL of dichloromethane were added to a 500 mL back-bottom three-necked flask and dissolved at room temperature. When all the intermediate (3) was dissolved, 21 g of triethylamine was added thereto and stirred for 10 minutes. Then, 44.2 g of boron trifluoride diethyl ether was added dropwise and stirred. After the dropwise addition, the reaction solution was further stirred at room temperature for 20 minutes. After the reaction was completed, the organic layer was extracted with water, filtered through silica gel, concentrated, and subjected to column chromatography with ethyl acetate and n-nucleic acid mixed solvent (1:10 (v / v)) to obtain 4.3 g of intermediate (4). Got it.

¾ NMR (600MHz, CDC1 ₃ ): δ 7.58 (t, 1H), 7.51 (t, 2H), 7.48-7.47 (d, 2H), 6.84-6.83 (d, 2H), 6.43-6.42 (d, 2H) Step (5): Preparation of Intermediate (5)

Intermediate (4) obtained in step (4) above in a 500 mL back-bottom three-necked flask

4.3 g, 7 g of catechol, 3.4 g of aluminum chloride, and 300 mL of dichloromethane were added, followed by stirring at room temperature for 20 minutes. After the reaction was completed, the organic layer was extracted with water, filtered through silica gel, concentrated, and then ethyl acetate and n-nucleic acid. Column chromatography was carried out with a mixed solvent (1: 20 (v / v)) to obtain 4 g of intermediate (5).

¾ NMR (600 MHz, CDC1 ₃ ): δ 7.58 (t, 1H) ᅳ 7.53-7.48 (m, 4H), 6.87-6.86 (d, 2H), 6.82-6.81 (m, 4H), 6.40-6.39 (d, 2H) Step (6): Preparation of Compound (la)

Into a 100 mL back-bottom three-necked flask, add intermediate (5) lg (2.46 mmol) and acetonitrile solvent 30 mL obtained in step (5) to dissolve intermediate (5), and then add benzenethiol l.lg (9.83 圓 ol) and 0.5 g (4.91 mmol) of triethylamine was added thereto, followed by stirring at room temperature for 30 minutes. After the reaction was completed, the organic layer was extracted with water, filtered through silica gel, concentrated, and then column chromatography was performed with ethyl acetate and n-nucleic acid mixed solvent (1: 30 (v / v)) to obtain 0.9 g of the compound of Chemical Formula la. Prepared (yield 66.1%). Example 2: Preparation of Compound of Formula lb

Obtained in step (5) of Example 1 above in a 100 mL back bottom three-necked flask Intermediate (5) lg (2.46 mmol) and 30 mL of acetonitrile solvent were added thereto, and the intermediate (5) was dissolved. Then, 1.4 g (9.83 mmol) of trichlorobenzene and 0.5 g (4.91 mmol) of triethylamine were added thereto. Stir for 30 minutes. After completion of the reaction, the organic layer was extracted with water, filtered through silica gel, concentrated, and then column chromatography was performed with ethyl acetate and n-nucleic acid mixed solvent (1: 50 (v / v)) to prepare a compound of Formula _LOg . (Yield 65.3%).

Example 3: Preparation of Compound of Formula (lc)

Into a 100 mL back-bottom three-necked flask, intermediate (5) lg (2.46 mmol) obtained in step (5) of Example 1 and 30 mL of acetonitrile were dissolved, and the intermediate (5) was dissolved. 1.4 g of 4-chlorobenzenethiol (9.83 mmol) and 0.5 g (4.91 mmol) of triethylamine were added thereto, followed by stirring at room temperature for 30 minutes. After completion of the reaction, the organic layer was extracted with water, filtered through silica gel, concentrated, and then subjected to column chromatography with ethyl acetate and n ᅳ nucleic acid mixed solvent (1:50 (v / v)) to obtain a compound of Chemical Formula _{1 (;} Prepared (Yield 71.8%) Preparation of Compound of Id

Into a 100 mL back-bottomed three-necked flask, intermediate (5) lg (2.46 μL) and acetonitrile solvent 30 mL obtained in step (5) of Example 1 were dissolved, and the intermediate (5) was dissolved, followed by 4-fluorobenzenethiol. 1.3g (9.83 Pa ol) and 0.5 g (4.91 mraol) of triethylamine were added thereto, followed by stirring at room temperature for 30 minutes. After the reaction was completed, the organic layer was extracted with water, filtered through silica gel, concentrated, and then column chromatography was performed with ethyl acetate and n-nucleic acid mixed solvent (1:50 (v / v)) to obtain 0.9g of the compound of formula Id. Prepared (yield 62.0%). Preparation of the compound

In a 100 mL back-bottom three-necked flask, intermediate (5) lg (2.46 mmol) obtained in step (5) of Example 1 and 30 mL of acetonitrile were dissolved, and the intermediate (5) was dissolved, followed by 1.6 g of 2—naphthalenethiol ( 9.83 瞧 ol) and 0.5 g (4.91 mmol) of triethylamine were added thereto, followed by stirring at room temperature for 30 minutes. After completion of reaction, the organic layer was extracted with water, ^' silica gel filtered and concentrated, and then subjected to column chromatography with ethyl acetate and n-nucleic acid mixed solvent (1: 50 (v / v)) to obtain compound l of compound le. Og was prepared (yield 62.2%). Preparation of the compound of f

In a 100 mL back bottom three neck flask, intermediate (5) lg (2.46 μl) obtained in step (5) of Example 1 and 30 mL of acetonitrile were dissolved, and the intermediate (5) was dissolved, followed by 1-methyl-L. Tetrazole— 5-thiol l. lg (9.83 mmol) and 0.5 g (4.91 mmol) of triethylamine were added thereto, followed by stirring at room temperature for 30 minutes. After the reaction was completed, the organic layer was extracted with water, concentrated by silica gel filtration, and then column chromatography was performed with ethyl acetate and n-nucleic acid mixed solvent (1:10 (v / v)) to prepare 0.9 g of a compound of Chemical Formula If. Yield 64.7%. Preparation of the compound of g

 In a 100 mL back-bottom three-necked flask, intermediate (5) lg (2.46 mmol) obtained in step (5) of Example 1 and 30 mL of acetonitrile were dissolved, and the intermediate (5) was dissolved. Then, 1-methyl-L imidazole -2-thiol l. lg (9.83 mmol) and 0.5 g (4.91 mmol) of triethylamine were added thereto, followed by stirring at room temperature for 30 minutes. After completion of the reaction, the organic layer was extracted with water, filtered through silica gel, concentrated, and subjected to column chromatography with ethyl acetate and n-nucleic acid mixed solvent (1:10 (v / v)) to prepare compound lg of formula lg. Preparation of compound of yield 72.3¾.h

Into a 100 raL equipotentially-bottomed three-necked flask, intermediate (5) lg (2.46 mmol) obtained in step (5) of Example 1 and 30 mL of acetonitrile were dissolved, and the intermediate (5) was dissolved. Then, 2,4-dichlorobenzenethiol 1.8 g (9.83 mmol) and 0.5 g (4.91 mmol) of triethylamine were added thereto, followed by stirring at room temperature for 30 minutes. After the reaction was completed, the organic layer was extracted with water, filtered through silica gel, concentrated, and then subjected to column chromatography with ethyl acetate and n-nucleic acid mixed solvent (1: 50 (v / v)) to obtain 1.2 g of the compound of formula lh. Prepared (yield 70.6%).

Into a 100 mL back-bottom three-necked flask, intermediate (5) lg (2.46 μl) and acetonitrile 30 mL obtained in step (5) of Example 1 were dissolved, and the intermediate (5) was dissolved, followed by benzo [^ oxazol ᅳ 2 -Thiol 1.5g (9.83mmol) and triethylamine 0.5g (4.91mmol) was added and stirred at room temperature for 30 minutes. After completion of reaction, the organic layer was extracted with water, filtered through silica gel, concentrated, and then subjected to column chromatography with ethyl acetate and n-nucleic acid mixed solvent (1: 30 (v / v)) to prepare a compound of Formula ^. (Yield _{70. 3¾)} .

Example 10 Preparation of a Compound of Formula lj

3 g of intermediate (4) obtained in step (4) of Example 1, 7.1 g of naphthalene-2, 3-diol, 2.4 g of aluminum chloride, and 300 mL of dichloromethane were added to a 500 mL equipotentially bottomed three-necked flask at 20 ° C. Stirred for a minute. After completion of reaction, the organic layer was extracted with water, filtered through silica gel, concentrated, and then column chromatography was performed with ethyl acetate and n-nucleic acid mixed solvent (1: 20 (v / v)) to obtain 2.9 g of an intermediate. Step (2): Preparation of Compound (l i)

Into a 100 mL back-bottom three-necked flask, lg (2.19 mmol) of the intermediate obtained in step (1) and 30 mL of acetonitrile were dissolved, and the intermediate was dissolved. 1.3 g (8.75 mmol) of benzo] oxazole-2-thiol and triethyl were dissolved. 0.4g (4.38mmol) of amine was added thereto, followed by stirring at room temperature for 30 minutes. After the reaction was completed, the organic layer was extracted with water, filtered through silica gel, concentrated, and column chromatography was performed with ethyl acetate and n-hexane mixed solvent (1:30 (v / v)) to obtain 0.9g of the compound of formula lj. Prepared (yield 59.9%). Preparation of the compounds of lk

Into a 100 mL back-bottom three-necked flask, intermediate (5) lg (2.46 mmol) obtained in step (5) of Example 1 and 30 mL of acetonitrile were dissolved, and the intermediate (5) was dissolved, followed by 0.7 g (9.83) of 1-propanethiol. mmol) and triethylamine 0.5g (4.91mmol) were added thereto, followed by stirring at room temperature for 30 minutes. After completion of the reaction, the organic layer was extracted with water, filtered through silica gel, concentrated, and then subjected to column chromatography with ethyl acetate and n-nucleic acid mixed solvent (1:70 (v / v)) to obtain 0.9g of the compound of formula lk. Was prepared (yield 75.3%). Preparation of Compound of Formula 11

In a 100 mL round bottom three neck flask, intermediate (5) lg (2.46 mmol) obtained in step (5) of Example 1 and 30 mL of acetonitrile solvent were added thereto, and the intermediate (5) was dissolved, followed by 1-phenyl tetrazole- 1.8 g (9.83 mmol) of 5-thiol and 0.5 g (4.91 mmol) of triethylamine were added thereto, followed by stirring at room temperature for 30 minutes. After completion of the reaction, the organic layer was extracted with water, filtered through silica gel, concentrated, and subjected to column chromatography with ethyl acetate and n-hexane mixed solvent (1:20 (v / v)) to obtain a compound of Chemical Formula 11 l. lg was prepared (yield 64.8%). : Preparation of Compound of Formula lm

In a 100 mL back-bottom three-necked flask, intermediate (5) lg (2.46 mmol) obtained in step (5) of Example 1 and 30 mL of acetonitrile solvent were dissolved in the intermediate (5), followed by benzo [^ imidazole-2 -T was added 1.5 g (9.83 mmol) and 0.5 g (4.91 mmol) of triethylamine, followed by stirring at room temperature for 30 minutes. After completing the reaction, the organic layer was extracted with water, filtered through silica gel, concentrated, and subjected to column chromatography with ethyl acetate and n-nucleic acid mixed solvent (1:20 (v / v)) to prepare a compound of Chemical Formula ₁₀₁ . (Yield 70.6%).

Comparative Example 1

Example instead of the intermediate (5) obtained in step (5) of Example 1

A target compound was prepared in the same manner as in Step (6) of Example 1, except that 1 g of the intermediate (4) obtained in Step (4) of 1 was used. Comparative Examples 2 to 10 Examples, except that the intermediate (4) obtained in step (4) of Example 1 was used in place of the intermediate (5) obtained in step (5) of Example 1, respectively.

Through the same process as 2 to 9 to prepare the target compound. In this case, the compound of Comparative Example 10 is the same as the structure of the compound of Comparative Example 9. Comparative Examples 11 to 13 Example instead of the intermediate (5) obtained in step (5) of Example 1

Except that the intermediate (4) obtained in step (4) of I was used, respectively

The target compound was prepared in the same manner as in II to 13. Test Example Test Example 1 Determination of Maximum Absorption Wavelength The compounds obtained in Examples 1 to 13 and Comparative Examples 1 to 13, respectively, were prepared. After diluting with methyl ethyl ketone (MEK) to a concentration of 10 ppm, each maximum absorption wavelength was measured using a UV / VIS spectrophotometer (Perkinelmer, Lamda25). Test Example 2 Evaluation of Fluorescence Quantum Yield (PL) Examples 1 to 13 and Comparative Examples 1 to 13 were each dilute with methanol solvent to measure PL (Perkinelmer, LS ᅳ 55), and then to measure fluorescence quantum yield (Φ). ) Was calculated. In Table 1 below, the maximum absorption wavelength and fluorescence quantum yield in MEK together with the structures of the compounds of Examples 1, 5, 6, 8 to 10 and 12, and Comparative Examples 1, 5, 6, 8, 9 and 12 Indicated.

Example 6 553 ND

Example 8 578 ND

Example 9 567 ND

Example 10 573 ND

Example 12 560 ND

As can be seen from Table 1, since the dye containing the pyrromethene boron complex according to the present invention has a maximum absorption wavelength in the range of 550 to 600 nm, (red and green) of the display to which the display filter comprising the same Can improve the color purity.

 In addition, it can be seen from Table 1 that the dye containing the pyrromethene boron complex according to the present invention has no fluorescence.

Claims

Scope of claim

1. A dye comprising a pyrromethene boron complex compound represented by Formula 1 below:

 [Formula 1]

In the additive formula,

R ¹ to R ³ , and R ⁶ are each independently hydrogen; d- ₆ alkyl; d- ₆ alkoxy; C ₆ - ₂₀ aryl; D- ₆ alkyl substituted with halogen; Substituted by halogen, C ₆ - ₂₀ aryl; Or d- ₆ alkoxy substituted with halogen, where n is an integer from 0 to 6;

R ⁴ and R ⁵ are each independently d- ₆ alkyl; d- ₆ alkoxy; C ₆ - ₂₀ aryl; 6-20 membered heteroaryl; D- ₆ alkyl substituted with halogen; Halogen eu (^ alkali and C ₆ - with a substituent selected from the group consisting of _12, aryl substituted C ₆ - ₂₀ aryl, halogen, alkyl, and C ₆ - 6 substituted with a substituent selected from the group consisting of _12-aryl to 20 won Is heteroaryl;

A is C ₆ - ₂₀ aryl is.

2. The method of paragraph 1,

R ¹ and R ³ are each independently hydrogen or d- ₆ alkyl;

R ² is hydrogen; d- ₆ alkyl; C ₆ - ₂₀ aryl; Or C ₆ — ₂₀ aryl substituted with halogen; R ⁴ and R ⁵ are each independently d- ₆ alkyl; C ₆ - ₂₀ aryl; 6-20 membered heteroaryl; D- ₆ alkyl substituted with halogen; Halogen, d- ₆ alkyl and C ₆ - C ₆ substituted with the substituents selected from the group consisting of _12-aryl-20 aryl; Or halogen, d- ₆ alkyl and C ₆ - ₁₂ aryl-heteroaryl of from 6 to 20 won substituted with a substituent selected from the group consisting of a;

R ⁶ is hydrogen; d- ₆ alkyl, C ₆ - ₂₀ aryl, and, wherein n is an integer from 0 to 4; A is C ₆ - ₂₀ aryl, a dye. The method of claim 1,

R ¹ and R ³ are each independently hydrogen or d- ₆ alkyl;

R ² is hydrogen; C ₆ - ₁₂ aryl; Or a halogen-substituted C ₆ - ₁₂ aryl;

R ⁴ and R ⁵ are each independently d- ₆ alkyl; C ₆ — ₁₂ aryl; 6-12 membered heteroaryl; D- ₆ alkyl substituted with halogen; Halogen, d-6 alkyl and

C ₆ - ₁₂ aryl group substituted with a substituent selected from the group consisting of C ₆ - ₁₂ aryl; Or 6-12 membered heteroaryl substituted with a substituent selected from the group consisting of halogen, d- ₆ alkyl and C ₆ — ₁₂ aryl;

R ⁶ is hydrogen or d- ₆ alkyl, where n is an integer of 0 or 1;

A is C ₆ - ₁₂ aryl dyes. The method of claim 1,

The dye represented by the pyrimethene boron complex compound represented by the following formula (2):

[Formula 2]

In the above formula

R ¹ and R ³ are each independently hydrogen; R ² is hydrogen or phenyl;

R ⁴ and R ⁵ are each independently phenyl, chlorophenyl, dichlorophenyl, fluorophenyl, naphthyl, methyltetrazolyl, methylimidazolyl, benzooxazolyl, d- ₆ alkyl, phenyltetrazolyl, or benzoimimi Dozolyl;

 A is a phenyl ring or a naphthalene ring.

5. The crab of claim 1,

 A dye in which the pyrromethene boron complex is any one of compounds selected from the group consisting of the following formulas la to lm:

 la]

 [Formula lb]

 [Formula lc]

Formula Id

[Formula lh]

O 2015/174663

6. The method of clause 1,

 The dye having a maximum absorption wavelength of 550-600 nm.

7. A display filter comprising the dye according to any one of paragraphs 1 to 6. '