KR20170103574A

KR20170103574A - pyrimidine derivatives substituted with aryl- or heteroaryl- substituted fluorene group, and organic electroluminescent device including the same

Info

Publication number: KR20170103574A
Application number: KR1020160026672A
Authority: KR
Inventors: 문성식; 석문기; 고병수; 김남호; 곽세영; 한갑종; 오유진
Original assignee: 주식회사 랩토
Priority date: 2016-03-04
Filing date: 2016-03-04
Publication date: 2017-09-13
Also published as: KR101785701B1

Abstract

Provided is a pyrimidine derivative coupled with aryl- or heteroaryl-substituted fluorene represented by chemical formula 1. In the chemical formula 1, Ar_1 and Ar_2 are respectively and independently hydrogen, methyl or phenyl; L is C_6-C_24 aryl or C_3-C_24 heteroaryl; n is an integer of 0 or 1; and Ar_3 is C_6-C_30 aryl or C_3-C_30 heteroaryl. According to the present invention, an organic electronic device using the derivative as a material for an organic layer has excellent efficiency, driving voltage, lifespan, etc.

Description

(Pyrimidine derivatives substituted with aryl- or heteroaryl-substituted fluorene groups, and organic electroluminescent devices including the same), pyrimidine derivatives having an aryl group or a heteroaryl group substituted fluorene,

The present invention relates to a pyrimidine derivative to which a specific aryl group or heteroaryl group substituted fluorene is bonded, and an organic electroluminescent device including the same. More particularly, the present invention relates to an organic electroluminescent device having high luminous efficiency and a specific aryl group or heteroaryl Substituted pyrimidine derivatives.

From the CRT (Cathode Ray Tube), which was the main market of the early display industry, to the LCD (Liquid Crystal Display) which is the most used now, the display industry has developed remarkably over the past few decades.

Nevertheless, the demand for a flat display device having a small space occupancy has been increased due to the recent enlargement of display devices. However, LCD has a disadvantage of requiring a separate light source because its viewing angle is limited and is not a self-luminous type. For this reason, OLEDs (Organic Light Emitting Diodes) have attracted attention as displays using self-emission phenomenon.

In 1963, OLED was first attempted to study the carrier injection type electroluminescence (EL) using a single crystal of anthracene aromatic hydrocarbons by Pope et al. From these studies, it was found that charge injection, recombination, exciton generation, And the basic mechanism of electroluminescence and electroluminescence characteristics.

In addition, after Tang and Van Slyke in 1987 reported the characteristics of high efficiency using a multilayer thin film structure of organic electroluminescent devices [Tang, C. W., Van Slyke, S. A. Appl. Phys. Lett. 51, 913 (1987)], OLEDs have a high potential for use in LCD backlighting and illumination as well as excellent characteristics as a next generation display, and many studies have been conducted under the spotlight [Kido, J., Kimura, M., and Nagai, K., Science 267,1332 (1995)]. Especially, in order to increase the luminous efficiency, various approaches such as structural change and material development have been performed [Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007) / Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364].

The basic structure of an OLED display generally includes an anode, a hole injection layer (HIL), a hole transporting layer (HTL), an emission layer (EML), an electron transporting layer (ETL) ), And a cathode (cathode), and the electron-emitting organic multi-layer film has a sandwich structure formed between both electrodes.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic layer between them. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected into the anode, electrons are injected into the organic layer, electrons are injected into the organic layer, excitons are formed when injected holes and electrons meet, When it falls to a state, it becomes a light. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The luminescent material has blue, green and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color depending on the luminescent color. Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and a higher luminous efficiency than a host mainly constituting the light emitting layer is mixed with the light emitting layer in a small amount, the excitons generated in the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to sufficiently exhibit the excellent characteristics of the organic light emitting device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material is supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic light emitting device has not yet been sufficiently achieved, and therefore, the development of new materials has been continuously required.

Korean Patent Laid-Open Publication No. 10-2014-0070425 (entitled "Novel compound and organic electronic device using the same) Korean Patent Laid-Open Publication No. 10-2012-0031684 (a novel organic light emitting compound and an organic electroluminescent device employing the same)

As a result of intensive studies, the inventors of the present invention have found that when a pyrimidine derivative compound having a specific aryl group or heteroaryl group substituted fluorene is bonded and used as a material for forming an organic material layer of an organic electronic device, , Lowering of the driving voltage and increase of the stability.

It is another object of the present invention to provide a pyrimidine derivative compound to which the above-mentioned aryl group or heteroaryl group substituted fluorene is bonded, and an organic electronic device using the pyrimidine derivative compound.

According to one aspect of the present invention, there is provided a compound represented by the following general formula (1).

[Chemical Formula 1]

[In the formula 1, Ar ₁ And Ar < ₂ _> are each independently hydrogen, methyl or phenyl,

L is C ₆ -C ₂₄ aryl or C ₃ -C ₂₄ heteroaryl,

n is an integer of 0 or 1,

Ar ₃ is C ₆ -C ₃₀ aryl or C ₃ -C ₃₀ heteroaryl]

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising a pyrimidine derivative to which the specific aryl group or heteroaryl group substituted fluorene is bonded.

According to another aspect of the present invention, there is provided a plasma display panel comprising a first electrode, a second electrode, and at least one organic film disposed between the electrodes, wherein the organic film has a specific aryl group or a heteroaryl group- An organic electroluminescent device comprising the pyrimidine derivative as a light emitting material.

According to still another aspect of the present invention, the pyrimidine derivative in which the aryl group or the heteroaryl group substituted fluorene is bonded to the electron blocking layer, the electron transport layer, the electron injection layer, the electron transport function and the electron injection function constituting the organic film Emitting layer is included in any one selected from the group consisting of a functional layer and a light-emitting layer which are simultaneously provided.

The specific aryl group or heteroaryl group substituted fluorene-bonded pyrimidine derivative compound according to the present invention can be prepared by introducing a specific aryl group or heteroaryl group into a pyrrole-bonded pyrimidine, And can be used as an organic material layer material of an electronic device. The organic electronic device including the organic light emitting device using the compound represented by the formula (1) according to the present invention as the material of the organic material layer exhibits excellent characteristics in terms of efficiency, driving voltage and lifetime.

1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

As used herein, the term "aryl " means a polyunsaturated, aromatic, hydrocarbon substituent which may be a single ring or multiple rings (one to three rings) fused or covalently bonded together unless otherwise stated.

The term "heteroaryl" means an aryl group (or a ring) comprising one to four heteroatoms selected from N, O and S (in each case on a separate ring in the case of multiple rings) Optionally oxidized, and the nitrogen atom (s) are quaternized, as the case may be. Heteroaryl groups can be attached to the remainder of the molecule through carbon or heteroatoms.

The aryl includes a single or fused ring system, suitably containing from 4 to 7, preferably 5 or 6, ring atoms in each ring. Also included are structures in which one or more aryls are attached through a chemical bond. Specific examples of the aryl include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, But are not limited thereto.

The heteroaryl includes 5- to 6-membered monocyclic heteroaryl and polycyclic heteroaryl fused with one or more benzene rings, and may be partially saturated. Also included are structures in which one or more heteroaryls are attached via a chemical bond. The heteroaryl groups include divalent aryl groups in which the heteroatoms in the ring are oxidized or trisubstituted to form, for example, an N-oxide or a quaternary salt.

Specific examples of the heteroaryl include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, Monocyclic heteroaryl such as pyridyl, pyridyl, pyrazinyl, pyridazinyl and the like, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl , Benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, (Such as pyridyl N-oxide, quinolyl N-oxide), quaternary salts thereof, and the like, but are not limited thereto. But is not limited thereto.

"Substituted" in the expression " substituted or unsubstituted ", as used herein, means that at least one hydrogen atom in the hydrocarbon is each independently replaced with the same or different substituents. Useful substituents include, but are not limited to:

Such substituents include, but are not limited to, -F; -Cl; -Br; -CN; -NO ₂ ; -OH; A C ₁ -C ₂₀ alkyl group which is unsubstituted or substituted by -F, -Cl, -Br, -CN, -NO ₂ or -OH; A C ₁ -C ₂₀ alkoxy group unsubstituted or substituted by -F, -Cl, -Br, -CN, -NO ₂ or -OH; C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, -F, -Cl, -Br, -CN , -NO _2, or substituted by -OH or unsubstituted C ₆ ~ C ₃₀ aryl group; C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, -F, -Cl, -Br, -CN , -NO 2 or -OH-substituted or unsubstituted C ₆ ~ C ₃₀ heteroaryl group, a; C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, -F, -Cl, -Br, -CN , -NO 2 , or substituted by -OH or unsubstituted C ₅ ~ C ₂₀ cycloalkyl group; C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, -F, -Cl, -Br, -CN , -NO 2 , or substituted or unsubstituted by -OH unsubstituted C ₅ ~ C ₃₀ heterocycloalkyl group; And a group represented by -N (G ₁ ) (G ₂ ). Wherein G ₁ and G ₂ are each independently selected from the group consisting of hydrogen; A C ₁ -C ₁₀ alkyl group; Or a C ₆ -C ₃₀ aryl group substituted or unsubstituted with a C ₁ -C ₁₀ alkyl group.

Hereinafter, the present invention will be described in detail.

According to one embodiment of the present invention, an aryl group or a heteroaryl group substituted fluorene-bonded pyrimidine derivative may be represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1, Ar ₁ And Ar < ₂ _> are each independently hydrogen, methyl or phenyl,

L is C ₆ -C ₂₄ aryl or C ₃ -C ₂₄ heteroaryl,

n is an integer of 0 or 1,

Ar ₃ is C _{6 to} C ₃₀ aryl or C _{3 to} C ₃₀ heteroaryl.

Wherein L in the above formula (1) is any one selected from the group consisting of the following formula (2): wherein R is a substituted or unsubstituted pyrimidine derivative substituted with an aryl group or a heteroaryl group substituted fluorene.

(2)

,

Wherein Ar ₃ in the formula (1) is any one selected from the group consisting of a group represented by the following formula (3): wherein Ar ₃ is a pyrimidine derivative in which an aryl group or a heteroaryl group substituted fluorene is bonded.

(3)

H, CN, CH _3,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

In Formula 3,

Z is O or S

X ₁ to X ₆ are each independently CH or N,

R ₁ to R ₂ are each independently H, CH ₃ or CN.

As specific examples of the compound represented by the formula (1) of the present invention, an aryl group or a heteroaryl group-substituted fluorene is bonded to the pyrimidine derivative selected from the group represented by the following formula (4). However, the compound represented by the formula (1) of the present invention is not limited to the compounds of the following formula (4).

[Chemical Formula 4]

The pyrimidine derivative represented by the above formula (1) can be synthesized using a known organic synthesis method. The pyrimidine The method of synthesizing the derivatives can be easily recognized by those skilled in the art with reference to the following production examples.

Further, according to the present invention, the pyrimidine represented by the above formula (1) There is provided an organic electroluminescent device comprising a derivative thereof.

The pyrimidine derivative of Formula 1 is useful as an electron transport layer material and can be used as a material for other layers of organic electroluminescent devices.

The organic electroluminescent device according to the present invention includes a first electrode, a second electrode, and at least one organic film disposed between the electrodes. The organic film may be formed by combining an aryl group or a heteroaryl group substituted fluorene represented by the general formula (1) And at least one pyrimidine derivative.

The organic layer includes a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, And at least one layer selected from the group consisting of functional layers having at the same time.

For example, the pyrimidine derivative may be included in at least one selected from the group consisting of a light emitting layer, an organic layer disposed between the anode and the light emitting layer, and an organic layer disposed between the light emitting layer and the cathode. Preferably, the pyrimidine derivative may be contained in at least one layer selected from the group consisting of a light emitting layer, a hole injecting layer, a hole transporting layer, and a functional layer having both a hole injecting function and a hole transporting function. The pyrimidine derivative may be contained in the organic film as a single substance or a combination of different substances. Alternatively, the pyrimidine derivative may be used in combination with a conventionally known compound such as a light emitting layer, a hole transporting layer, and a hole injecting layer.

The organic electroluminescent device according to the present invention can be applied to an organic electroluminescent device including a positive electrode / a light emitting layer / a cathode, a positive electrode / a hole injecting layer / a light emitting layer / a negative electrode, an anode / a hole injecting layer / a hole transporting layer / a light emitting layer / an electron transporting layer / / Light emitting layer / electron transporting layer / electron injecting layer / cathode structure. Alternatively, the organic electroluminescent device may include a functional layer / a light emitting layer / an electron transporting layer / a cathode having both an anode / hole injecting function and a hole transporting function, a functional layer / a light emitting layer / an electron transporting layer / Electron injecting layer / cathode structure, but the present invention is not limited thereto.

The organic electroluminescent device may be manufactured using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. For example, an anode is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate, and an organic film including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer is formed thereon And then depositing a material which can be used as a cathode thereon. In addition to such a method, an organic electroluminescent device may be formed by sequentially depositing a cathode material, an organic film, and a cathode material on a substrate.

The organic layer may be prepared by a variety of polymer materials, not by vapor deposition, but by a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer.

The organic electroluminescent device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[Example]

Intermediate Synthetic example 1: Synthesis of intermediate (4)

(Synthesis of Intermediate (1)

To 31.73 g (237.95 mmol) of aluminum chloride (AlCl ₃ ) is added 800 mL of dichloromethane and 17.24 g (219.64 mmol) of acetylchloride are added. 50 g (183.0 mmol) of 2-bromo 9,9-dimethylfluorene was dissolved in 200 mL of dichloromethane and the solution was gradually added dropwise. The temperature was raised to room temperature and stirred for 16 hours. After confirming the termination of the reaction, the temperature was lowered to 10 ° C or less, 2N HCl was slowly added dropwise, and 300 mL of water was further added thereto. The organic layer was washed with brine (300 mL) and dried over anhydrous Na ₂ SO ₄ . The organic solvent was concentrated under reduced pressure to obtain 57.3 g (yield: 99.3%) of a white solid compound (intermediate (1)).

(Synthesis of Intermediate (2)

In a four-liter 2-L flask, 1,000 mL of ethanol was added to 57.3 g (181.79 mmol) of Intermediate (1), and 21.2 g (199.97 mmol) of benzaldehyde was diluted in 300 mL of ethanol. 13.8 g (345.4 mmol) of caustic soda (NaOH) dissolved in 70 mL of water was added, and the mixture was stirred at room temperature for 16 hours. After confirming the termination of the reaction, 350 mL of water was added, and the mixture was stirred for 1 hour, filtered, washed with 200 mL of ethanol and vacuum dried to obtain 69.13 g (yield: 94.3%) of yellow solid compound (intermediate (2)).

(Synthesis of Intermediate (3)

To a four necked 2 L flask was added 69.0 g (171.08 mmol) of Intermediate (2) in 860 mL of ethanol and then 28.1 g (179.64 mmol) of benzamidine hydrochloride and 13.7 g (342.16 mmol) of caustic soda (NaOH) And the mixture was heated to reflux. After confirming that the reaction was complete, the solvent was removed, 900 mL of DCM and 500 mL of water were added, and the mixture was sufficiently stirred at room temperature, followed by layer separation. The organic layer was dried over anhydrous Na ₂ SO ₄ , filtered, and the organic solvent was concentrated under reduced pressure, followed by the addition of 850 mL of ethanol and refluxing for 3 hours. The mixture was cooled to room temperature, stirred for 3 hours, and filtered to obtain 44.2 g (yield: 51.3%) of a white solid compound (intermediate (3)).

(Synthesis of Intermediate (4)

1 1 intermediate (3) 30.0 g (59.59 mmol ) of L flask, bis (pinacolato) diboron (bis (pinacolato) diboron) 18.16 g (71.51 mmol), Pd (dppf) Cl 2 1.46 g (1.79 mmol ), 11.34 g (119.18 mmol) of KOAc and 300 mL of 1,4-dioxane were mixed, the temperature was raised to 80 DEG C and the mixture was stirred for 20 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the mixture was diluted with chloroform (180 mL), filtered through celite, washed with 800 mL of chloroform and the solvent was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography to obtain 27.5 g (yield: 83.8%) of a white solid compound (intermediate (4)).

Intermediate Synthetic example 2: Synthesis of intermediate (5)

(Synthesis of intermediate 5)

85.0 g (168.8 mmol) of Intermediate (3) are placed in 2 L of anhydrous tetrahydrofuran and maintained at -78 < 0 > C. Slowly add 70.9 mL (177.2 mmol) of n -butyl lithium (2.5 M, n-butyllithium) and keep for 1 hour. To the reaction mixture slowly add 14.3 mL (185.6 mmol) of anhydrous dimethylformamide. The reaction mixture is maintained at -78 < 0 > C for 1 hour and then slowly raised to room temperature. To the reaction mixture is added 100 mL of a 1.0 M aqueous hydrochloric acid solution (1.0 M aq. HCl), stirred for 15 minutes, and the organic layer is separated. The resulting aqueous layer is extracted again with EtOAc. After the obtained organic layer were combined, washed with water and dried over MgSO _4. The organic layer was concentrated under reduced pressure to obtain 53.5 g (yield: 70%) of a solid compound (intermediate (5)).

Intermediate Synthetic example 3: Synthesis of intermediate (6)

(Synthesis of Intermediate (6)

36.9 g (0.200 mol) of 4-bromobenzaldehyde was slowly added to 25.0 g (0.200 mol) of 2-aminobenzenethiol at room temperature, and the mixture was refluxed at 125 to 130 ° C. After confirming the reaction, ethanol was slowly added to solidify it, followed by filtration. The solid compound thus obtained was further refined with EA / MeOH to obtain 22.19 g (yield: 38.3%) of a white solid compound (Intermediate (6)).

Intermediate Synthetic example 4: Synthesis of intermediate (9)

(Synthesis of intermediate 7)

15.0 g (0.087 mol) of 2-bromoaniline and 29.8 g (0.131 mol) of dibenzo [b, d] thiophen-4-ylboronic acid ), and _{Pd (PPh 3) 4 5.04 g} (4.36 mmol), 2.5 MK 3 PO 4 refluxing 220 mL (0.218 mol) and put into a dioxane (dioxane) 430 mL. After the reaction is completed, the solvent is distilled off under reduced pressure, and then the residue is extracted with EA to remove moisture. 18.8 g (yield: 78.3%) of a solid compound (intermediate (7)) was obtained by column chromatography (EA: HEX).

(Synthesis of Intermediate (8)

19.0 mL (0.136 mol) of triethylamine was added slowly while stirring 18.8 g (0.068 mol) of Intermediate (7) and 220 mL of dichloromethane, and the mixture was stirred for 30 minutes. Add 15.0 g (0.068 mol) of 4-bromobenzoyl chloride and 50 mL of DCM slowly dropwise at 0 ° C using a dropping funnel. 0 < [deg.] &Gt; C for one day. After the reaction is complete, slowly add an aqueous solution of sodium carbonate at room temperature. Extract with DCM and wash well with aqueous ammonium chloride solution and water. After removing the water and the solvent, the product was solidified with EA and MeOH to obtain 25.9 g (yield: 82.7%) of a white solid compound (Intermediate (8)).

(Synthesis of intermediate 9)

25.9 g (0.056 mol) of intermediate (8), 26.2 mL (0.282 mol) of phosphoryl chloride and 110 mL of nitrobenzene are added and refluxed at 150 ° C for 8 hours. After the reaction is completed, the reaction mixture is cooled to room temperature, and methanol is slowly added to solidify the reaction mixture. Wash the filtered solid sufficiently with water, then wash it again with methanol. The mixture was solidified with EA and then filtered to obtain 22.8 g (yield: 91.7%) of a white solid compound (Intermediate (9)).

Intermediate Synthetic example 5: Synthesis of intermediate (13)

(Synthesis of intermediate 10)

The 1L flask 1 1-iodine-2-nitrobenzene (1-iodo-2-nitrobenzene ) 50.0 g (0.201 mol), 3- aminopyridine (3-aminopyridine) 18.9 g ( 0.201 mol), Pd (OAc) 2 After adding 1.8 g (8.0 mmol) of K ₂ CO _3, 55.6 g (0.402 mol) of K ₂ CO ₃ and 600 mL of toluene, the mixture was heated to 90 ° C., 7.5 g (0.012 mol) of BINAP was added and the mixture was refluxed for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 500 mL of toluene and 1000 mL of water were added, and the organic layer was separated. 500 mL of 1N HCl solution was added to the separated organic layer, and the mixture was stirred at room temperature for 30 minutes. The aqueous layer was separated and adjusted to pH 8-9 with 250 mL of saturated Na ₂ CO ₃ solution. The precipitate thus formed was filtered under reduced pressure, washed with 500 mL of water and dried under reduced pressure to obtain 38.9 g (yield: 90.0%) of a solid compound (intermediate (10)).

(Synthesis of intermediate 11)

A solution of 64.0 g (0.25 mol) of Intermediate (10) in 756 mL of tetrahydrofuran and 227 g (1.31 mol) of Na ₂ S ₂ O ₄ dissolved in 756 mL of water was slowly added to a ₂ L flask for 1 hour, followed by the addition of 38 mL Respectively. The reaction was stirred at room temperature for 6 hours, then 756 mL of EtOAc was added and the pH was adjusted to 7-8 with saturated Na ₂ CO ₃ solution. The separated organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to obtain 32.07 g (yield: 69.0%) of a compound (Intermediate (11)).

(Synthesis of intermediate 12)

Intermediate (11) 32.07 g (0.173 mol ) of NMP (n -methylpyrrolidone) dissolved in 300 mL, then 4-bromo-benzoyl chloride (4-bromobenzoyl chloride) 45.6 g (0.208 mol) of NMP (n -methylpyrrolidone) at room temperature 50 mL of the solution is slowly added dropwise using a dropping funnel and stirred for one day. After the reaction is complete, add 1500 mL of water slowly at room temperature. The resulting precipitate was filtered under reduced pressure and washed with 500 mL of water to obtain 56.68 g (yield: 89.0%) of a solid compound (Intermediate (12)). The filtrate was concentrated under reduced pressure to a pH of 8 to 9 with saturated sodium carbonate solution. %).

(Synthesis of intermediate 13)

56.0 g (0.15 mol) of intermediate (12), 2.89 g (0.015 mol) of p- toluene sulfonic acid hydrate and 560 mL of xylene were placed in a one liter 1 L flask and refluxed with a Dean- The mixture was cooled to room temperature and concentrated under reduced pressure. 500 mL of DCM was added to the concentrate, and the solution was saturated. The saturated solution was washed with 300 mL of sodium carbonate and 500 mL of water. The separated organic layer was dried over anhydrous MgSO ₄ , filtered under reduced pressure, and concentrated under reduced pressure. 900 mL of ethanol was added to the concentrate, followed by heating and dissolution, followed by slow cooling to room temperature to effect crystallization. The formed crystals were filtered under reduced pressure to obtain 38.5 g (yield: 72.0%) of a white solid compound (Intermediate (13)).

Intermediate Synthetic example 6: Synthesis of intermediate (18)

(Synthesis of intermediate 14)

52.3 g (0.555 mol) of 2-aminopyridine and 500 mL of acetonitrile were placed in a 1 L flask and 103.9 g (0.584 mol) of NBS (N-bromosuccinimide) The temperature was then gradually raised to room temperature and stirred for 24 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, 1000 mL of water and 1000 mL of DCM were added, and the mixture was stirred for 2 hours. The separated organic layer was washed with 500 mL of brine, dried over anhydrous Na ₂ SO ₄ and concentrated. The concentrate was recrystallized under DCM / Hexane to obtain 81.5 g (yield: 84.8%) of a compound as a white solid (Intermediate (14)).

(Synthesis of intermediate 15)

A 3L flask 1 1-iodine-2-nitrobenzene (1-iodo-2-nitrobenzene ) 105.8 g (0.405 mol), intermediate (14) 50 g (0.404 mol ), Pd (OAc) 2 3.6 g (16.18 mmol ), 15.2 g (24.28 mol) of BINAP, 167.8 g (1.21 mol) of K ₂ CO ₃ and 1500 mL of toluene were charged and refluxed for 16 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 500 mL of toluene and 1000 mL of water were added, and the organic layer was separated. 500 mL of 1N HCl solution was added to the separated organic layer, and the mixture was stirred at room temperature for 30 minutes. The aqueous layer was separated and adjusted to pH 8-9 with 250 mL of saturated Na ₂ CO ₃ solution. The precipitate thus formed was filtered under reduced pressure, washed with 500 mL of water and dried under reduced pressure to obtain 63.7 g (yield: 53.6%) of a solid compound (Intermediate (15)).

(Synthesis of intermediate 16)

A solution obtained by dissolving 63.0 g (0.214 mol) of Intermediate (15) in 800 mL of tetrahydrofuran and then dissolving 227 g (1.31 mol) of Na ₂ S ₂ O ₄ in 756 mL of water was slowly added to a ₂ L flask with one neck, followed by addition of 40 mL Respectively. The reaction was stirred at room temperature for 6 hours, then 756 mL of EtOAc was added and the pH was adjusted to 7-8 with saturated Na ₂ CO ₃ solution. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 48.68 g (yield: 86.1%) of a compound (Intermediate (16)).

(Synthesis of Intermediate (17)

A solution obtained by dissolving 49.2 g (0.186 mol) of Intermediate 16 in 550 mL of NMP ( n- methylpyrrolidone) and then dissolving 39.2 g (0.279 mol) of benzoyl chloride in 250 mL of NMP ( n -methylpyrrolidone) The mixture is slowly added dropwise using a pouring funnel and stirred for a day. After the reaction is complete, add 1500 mL of water slowly at room temperature. The resulting precipitate was filtered under reduced pressure and washed with 500 mL of water to obtain 45.9 g of a solid compound (Intermediate (17)) (yield: 76.9%) as a pale yellow oil. The precipitate was filtered off under reduced pressure and the filtrate was adjusted to pH 8-9 with a saturated sodium carbonate solution. %).

(Synthesis of intermediate 18)

In a one liter 1 L flask, 40.9 g (0.111 mol) of Intermediate (17), 2.1 g (0.011 mol) of p- toluene sulfonic acid hydrate and 330 mL of xylene were charged and refluxed with a Dean- The mixture was cooled to room temperature and concentrated under reduced pressure. 500 mL of DCM was added to the concentrate, and the solution was saturated. The saturated solution was washed with 300 mL of sodium carbonate and 500 mL of water. The separated organic layer was dried over anhydrous MgSO ₄ , filtered under reduced pressure, and concentrated under reduced pressure. 900 mL of ethanol was added to the concentrate, followed by heating and dissolution, followed by slow cooling to room temperature to effect crystallization. The formed crystals were filtered under reduced pressure to obtain 36.8 g (yield: 94.6%) of a white solid compound (Intermediate (18)).

Intermediate Synthetic example 7: Synthesis of intermediate (23)

(Synthesis of intermediate 19)

40 g (0.42 mol) of 2-aminopyrimidine and 840 mL of acetonitrile / 84 mL of DCM were placed in a 1 L flask and 78.6 g (0.44 mol) of NBS (N-bromosuccinimide) ) Was added four times and slowly added. After the temperature was raised to room temperature, the mixture was stirred for 24 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, 1000 mL of water and 1000 mL of DCM were added, and the mixture was stirred for 2 hours. The separated organic layer was washed with 500 mL of brine, dried over anhydrous Na ₂ SO ₄ and concentrated. The concentrate was recrystallized under DCM / Hexane conditions to give 67.5 g (yield: 92.4%) of a compound as a white solid (Intermediate (19)).

(Synthesis of intermediate 20)

A 3L flask 1 1-iodine-2-nitrobenzene (1-iodo-2-nitrobenzene ) 78.7g (0.316 mol), intermediate (19) 50 g (0.404 mol ), Pd (OAc) 2 3.2 g (14.4 mmol ), 17.9 g (28.74 mol) of BINAP, 119.2 g (0.862 mol) of K ₂ CO ₃ and 1000 mL of toluene were charged and refluxed for 16 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, 500 mL of toluene and 1000 mL of water were added, and the organic layer was separated. 500 mL of 1N HCl solution was added to the separated organic layer, and the mixture was stirred at room temperature for 30 minutes. The aqueous layer was separated and adjusted to pH 8-9 with 250 mL of saturated Na ₂ CO ₃ solution. The formed precipitate was filtered under reduced pressure, washed with 500 mL of water and dried under reduced pressure to obtain 23.8 g (yield: 28.1%) of a solid compound (Intermediate (20)).

(Synthesis of intermediate 21)

A solution of 23.8 g (0.214 mol) of Intermediate (20) in 800 mL of tetrahydrofuran and a solution of 227 g (1.31 mol) of Na ₂ S ₂ O ₄ in 300 mL of water was gradually added to a ₂ L flask with one neck, followed by the addition of 80 mL Respectively. The reaction was stirred at room temperature for 6 hours, then 756 mL of EtOAc was added and the pH was adjusted to 7-8 with saturated Na ₂ CO ₃ solution. The separated organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to obtain 6.4 g (yield: 39.3%) of a compound (Intermediate (21)).

(Synthesis of intermediate 22)

A solution obtained by dissolving 6.4 g (21.14 mmol) of Intermediate 21 in 150 mL of NMP ( n- methylpyrrolidone) and then dissolving 4.45 g (31.7 mmol) of benzoyl chloride in 25 mL of NMP ( n- methylpyrrolidone) The mixture is slowly added dropwise using a pouring funnel and stirred for a day. After the reaction is complete, add 1500 mL of water slowly at room temperature. The resulting precipitate was filtered under reduced pressure and washed with 500 mL of water to obtain 5.93 g (yield: 66.6%) of a solid compound (Intermediate (22)). The filtrate was concentrated under reduced pressure to a pH of 8 to 9 with saturated sodium carbonate solution. %).

(Synthesis of intermediate 23)

In a one-necked 100 mL flask, add 5.9 g (15.9 mmol) of intermediate (22), 0.3 g (1.6 mmol) of p- toluenesulfonic acid hydrate and 40 mL of xylene and reflux After stirring, the mixture was cooled to room temperature and concentrated under reduced pressure. 500 mL of DCM was added to the concentrate, and the solution was saturated. The saturated solution was washed with 300 mL of sodium carbonate and 500 mL of water. The separated organic layer was dried over anhydrous MgSO ₄ , filtered under reduced pressure, and concentrated under reduced pressure. 900 mL of ethanol was added to the concentrate, followed by heating and dissolution, followed by slow cooling to room temperature to effect crystallization. The formed crystals were filtered under reduced pressure to obtain 5.4 g (yield: 95.9%) of a white solid compound (Intermediate (23)).

Intermediate Synthetic example 8: Synthesis of intermediate (25)

(Synthesis of intermediate 24)

30.0 g (0.24 mol) of 2-aminobenzenethiol and 300 mL of methanol were placed in a 500 mL flask and a solution of 6-bromo pyridine-3-carboaldehyde 44.6 g (0.24 mol) was slowly added in portions. After completion of the reaction for 1 hour, the reaction was completed and the filtrate was concentrated under reduced pressure to obtain 70.01 g (yield: 100%) of a viscous liquid compound (Intermediate 24).

(Synthesis of intermediate 25)

70.0 g (0.24 mol) of Intermediate (24) and 1.19 L of DCM were added to a 1 L 2L flask, and 59.6 g (0.26 mol) of DDQ was slowly added at room temperature and stirred for 1 hour. After completion of the reaction was confirmed, the solution was filtered through a silica plug, and the filtrate was concentrated under reduced pressure. The concentrate was purified in EtOA / methanol to obtain 31.4 g (yield: 45.2%) of a white solid compound (Intermediate (25)).

Intermediate Synthetic example 9: Synthesis of Intermediate (27)

(Synthesis of intermediate 26)

26.2 g (0.24 mol) of 2-aminophenol and 300 mL of methanol were placed in a 500 mL flask having a 1-necked flask, and 6-bromo pyridine-3-carboaldehyde 44.6 g (0.24 mol) was slowly added in portions. After completion of the reaction for one hour, the reaction was completed and the filtrate was concentrated under reduced pressure to obtain 66.4 g (yield: 100%) of a viscous liquid compound (Intermediate 26).

(Synthesis of intermediate 27)

66.4 g (0.24 mol) of Intermediate (26) and 1.19 L of DCM were added to a 1 L 2L flask and 59.6 g (0.26 mol) of DDQ was slowly added at room temperature and stirred for 1 hour. After completion of the reaction was confirmed, the solution was filtered through a silica plug, and the filtrate was concentrated under reduced pressure. The concentrate was purified in EtOA / methanol to obtain 29.7 g (yield: 45.2%) of a white solid compound (Intermediate (27)).

Intermediate Synthetic example 10: Synthesis of intermediate (31)

(Synthesis of intermediate 29)

2-bromo-benzaldehyde (2-bromobenzaldehyde) 80.0 g ( 0.432 mol), 2,4- dichloro-phenylboronic acid (2,4-dichlorophenylboronic acid) 82.5 g (0.432 mol), Pd (PPh 3) 4 4.99 g ( 0.00432 mol), 2M K ₂ CO ₃ A mixture of 865 mL (0.628 mol) and 865 mL of tetrahydrofuran was stirred at reflux for 12 hours. After the reaction mixture was cooled to room temperature, the organic layer was separated and concentrated under reduced pressure to obtain a solid compound (intermediate (28).

Intermediate (28) and 56.1 g (0.518 mol) of 1,2-diaminobenzene were dissolved in 1800 mL of ethanol at room temperature. A solution prepared by dissolving 98.5 g (0.518 mol) of Na ₂ S ₂ O _{5 in} 200 mL of water was added, and the mixture was refluxed with stirring for 6 hours. After cooling to room temperature, 2700 mL of water was added, and the mixture was stirred for 1 hour. The resulting precipitate was filtered, washed with water and ethanol, and dried to obtain 120.7 g (yield: 82%) of a solid compound (intermediate (29)).

(Synthesis of intermediate 30)

120.7 g (0.356 mol) of Intermediate 29 and 34.2 g (0.356 mol) of NaOtBu were dissolved in 1800 mL of dimethylacetamide and refluxed for 3 hours. The reaction mixture was cooled to room temperature, and 1800 mL of ethanol was added thereto, followed by stirring for 1 hour. The resulting precipitate was filtered under reduced pressure, washed with ethanol, water and methanol, and dried to obtain 78.8 g (yield: 73%) of a solid compound (Intermediate (30)).

(Synthesis of intermediate 31)

1 1 intermediate (30) 30.0 g (59.59 mmol ) of L flask, bis (pinacolato) diboron (bis (pinacolato) diboron) 18.16 g (71.51 mmol), Pd (dppf) Cl 2 1.46 g (1.79 mmol ), 11.34 g (119.18 mmol) of KOAc and 300 mL of 1,4-dioxane were mixed, the temperature was raised to 80 DEG C and the mixture was stirred for 20 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the mixture was diluted with chloroform (180 mL), filtered through celite, washed with 800 mL of chloroform and the solvent was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography to obtain 27.5 g (yield: 83.8%) of a white solid compound (intermediate (31)).

Intermediate Synthetic example 11: Synthesis of intermediate (33)

(Synthesis of intermediate 32)

26.2 g (0.24 mol) of 2-aminophenol and 300 mL of methanol were placed in a 500 mL flask and 44.6 g (0.24 mol) of 4-bromobenzaldehyde was slowly added thereto at room temperature . After completion of the reaction for 1 hour, the reaction was completed and the filtrate was concentrated under reduced pressure to obtain 66.4 g (yield: 100%) of a viscous liquid compound (Intermediate 32).

(Synthesis of intermediate 33)

66.4 g (0.24 mol) of Intermediate (32) and 1.19 L of DCM were added to a 1 L 2L flask and 59.6 g (0.26 mol) of DDQ was slowly added at room temperature and stirred for 1 hour. After completion of the reaction was confirmed, the solution was filtered through a silica plug, and the filtrate was concentrated under reduced pressure. The concentrate was purified in EtOA / methanol to obtain 29.7 g (yield: 45.2%) of a white solid compound (Intermediate (33)).

Various pyrimidine derivative compounds were synthesized as follows using the synthesized intermediate compounds.

Example 1: Synthesis of Compound 4-1 (WS15-30-317)

2.5 g (4.97 mmol) of Intermediate (3) and 50 mL of THF were added to a three-necked 250 mL flask and cooled to -78 ° C. Then, 2.2 mL (2.5 M in hexanes) of n- BuLi was slowly added thereto, 0.98 mL of chlorodiphenylphosphine was slowly added thereto, and the mixture was stirred at the same temperature for 2 hours. When the intermediate (3) disappeared by TLC, 5 mL of distilled water was added, and the temperature was gradually raised to room temperature. THF was distilled off under reduced pressure and diluted with 50 mL of DCM, then cooled to 0 < 0 > C and 35% aq. 2.28 mL of H ₂ O ₂ was slowly added thereto and stirred for 6 hours. The reaction mixture was extracted, the solvent was removed, and the residue was purified by silica gel column chromatography to obtain 1.40 g (yield: 45.2%) of Compound 4-1 (WS15-30-317) as a white solid.

Example 2: Synthesis of compound 4-2 (WS15-30-303)

In 1 250 mL flask, intermediate (3) 2.6 g (5.165 mmol ), naphthalene-2-Daily acid (naphthalen-2-ylboronic acid) 0.9 g (5.363 mmol), Pd (PPh 3) 4 0.2 g (0.155 mmol) of triethylamine and 80 mL of toluene, and 40 mL of ethanol and 1.1 g (7.747 mmol) of K ₂ CO _{3 in} 40 mL of H ₂ O were added to the solution while stirring, followed by stirring under reflux for 5 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with DCM. The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 1.3 g of a white solid compound 4-2 (WS15-30-303) : 45%).

Example 3: Synthesis of compound 4-3 (WS15-30-326)

Intermediate 1 (3) to obtain 250 mL flask (2.5 g, 4.96 mmol), 1- naphthyl boronic acid (1-naphthylboronic acid) 0.85 g (4.96 mmol), Pd (PPh 3) 4 0.17 g (0.15 mmol), 1.37 g (9.9 mmol) of K ₂ CO ₃ , 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and refluxed for 20 hours. After the reaction was completed, solvent was evaporated under reduced pressure and CHCl ₃ Diluted to 50 mL and was filtered using Celite, CHCl ₃ 100 mL, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain 1.40 g (yield: 51.3%) of 4-3 (WS15-30-326) as a white solid.

Example 4: Synthesis of compound 4-4 (WS15-30-280)

In 1 250 mL flask, intermediate (4) 3.0 g (5.45 mmol ), 5- bromo-quinoline cattle feeders (5-bromoisoquinoline) 1.43 g ( 5.45 mmol), Pd (PPh 3) 4 0.19 g (0.16 mmol), K 2 1.51 g (10.90 mmol) of CO ₃ , 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and then refluxed and stirred for 12 hours. After the reaction was completed, solvent was evaporated under reduced pressure and CHCl ₃ The mixture was filtered through Celite, washed with 100 mL of CHCl ₃ , and then purified by silica gel column chromatography to obtain 1.61 g (yield: 53.7%) of a white solid compound 4-4 (WS15-30-280).

Example 5: Synthesis of compound 4-7 (WS15-30-278)

Intermediate 1 to obtain 250 mL flask (4) 2.28 g (4.14 mmol ), Int.1 1.52 g (4.14 mmol), Pd (PPh 3) 4 0.14 g (0.12 mmol), K 2 CO 3 1.15 g (8.28 mmol) , 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and then refluxed and stirred for 9 hours. After the reaction was completed, solvent was evaporated under reduced pressure and CHCl ₃ The mixture was filtered through Celite, washed with 100 mL of CHCl ₃ , and then purified by silica gel column chromatography to obtain 2.0 g (yield: 75.2%) of 4-7 (WS15-30-278) as a white solid.

Example 6: Synthesis of compound 4-8 (WS15-30-276)

In 1 250 mL flask, intermediate (4) 3.0 g (5.45 mmol ), 9- bromo-phenanthryl seuren (9-bromophenanthrene) 1.40 g ( 5.45 mmol), Pd (PPh 3) 4 0.19 g (0.16 mmol), K 2 1.51 g (10.90 mmol) of CO ₃ , 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and then refluxed and stirred for 14 hours. After the reaction was completed, solvent was evaporated under reduced pressure and CHCl ₃ was diluted to 50 mL and filtered through Celite and, CHCl ₃ was concentrated under reduced pressure and then washed with 100 mL purified by silica gel column chromatography to give compound 4-8 as a white solid (WS15- 30-276) (yield: 66.4%).

Example 7: Synthesis of compound 4-9 (WS15-30-318)

Intermediate 1 (4) 3.87 g (7.03 mmol ), 9- bromo-10-phenyl anthracene (9-bromo-10-phenylanthracene ) 2.34 g (7.03 mmol), Pd (PPh 3) to obtain 250 mL flask, 0.24 g ₄ (0.21 mmol), 1.94 g (14.06 mmol) of K ₂ CO ₃ , 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and stirred for 14 hours while heating to reflux. After the reaction was completed, solvent was evaporated under reduced pressure and CHCl ₃ Diluted to 50 mL and was filtered through Celite, CHCl ₃ 100 mL, and then concentrated. The residue was purified by silica gel column chromatography to obtain 1.81 g (yield: 37.8%) of a pale yellow solid compound 4-9 (WS15-30-318).

Example 8: Synthesis of Compound 4-10 (WS15-30-313)

A 1-necked 100 mL flask was charged with 2.50 g (4.5 mmol) of intermediate (4), 1.20 g (4.5 mmol) of 2-bromodibenzo [b, d] thiophene, Pd ₃ ) ₄ A mixture of 0.16 g (0.14 mmol), 5 mL ( ₂ mmol) of 2M K ₂ CO ₃ , 13 mL of toluene and 5 mL of ethanol was refluxed for 12 hours. The reaction mixture was cooled to room temperature, diluted with 50 mL of dichloromethane, and washed with water. Dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by column chromatography and then recrystallized with chloroform to obtain 0.81 g (yield: 30%) of a solid compound 4-10 (WS15-30-313).

Example 9: Synthesis of compound 4-11 (WS15-30-279)

Intermediate 1 to obtain 250 mL flask (4) 3.0 g (5.45 mmol ), 4- bromo-modify-benzothiophene (4-bromodibenzothiophene) 1.43 g ( 5.45 mmol), Pd (PPh 3) 4 0.19 g (0.16 mmol), K ₂ CO ₃ 1.51 g (10.90 mmol), toluene 50 mL, ethanol 20 mL, and water 10 mL were mixed and stirred for 14 hours while heating to reflux. After the reaction was completed, the solvent was distilled off under reduced pressure, diluted with 50 mL of CHCl ₃ , and filtered through celite. Washed with 100 mL of CHCl ₃ , concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 2.45 g of a white solid compound 4-11 (WS15-30-279) (yield: 74.0%).

Example 10: Synthesis of compound 4-14 (WS15-30-309)

In 1 250 mL flask, intermediate (3) 2.7 g (5.363 mmol ), dibenzofuran-2-Daily acid (dibenzofuran-2-ylboronic acid) 1.1 g (5.363 mmol), Pd (PPh 3) 4 0.2 g (0.161 mmol) and toluene while stirring put as a 80 mL ethanol was added _{40 mL, K 2 CO 3 1.1} g (8.045 mmol) / H 2 O 40 mL , and the mixture was stirred for 8 hours under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with DCM. The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 1.2 g of a white solid compound 4-14 (WS15-30-309) : 39%).

Example 11: Synthesis of Compound 4-15 (WS15-30-307)

Intermediate 1 to obtain 250 mL flask (3) 2.7 g (5.363 mmol ), dibenzofuran-4-Daily acid (dibenzofuran-4-ylboronic acid) 1.1 g (5.363 mmol), Pd (PPh 3) 4 0.2 g (0.161 mmol) and toluene while stirring as a 80 mL ethanol was added _{40 mL, K 2 CO 3 1.1} g (8.045 mmol) / H 2 O 40 mL , and the mixture was stirred for 7 hours under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with DCM. The organic phase was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 1.1 g of a white solid compound 4-15 (WS15-30-307) 34%).

Example 12: Synthesis of compound 4-16 (WS15-30-332)

Intermediate 1 to obtain 250 mL flask (4) 2.5 g (4.54 mmol ), Int.2 1.35 g (4.54 mmol), Pd (PPh 3) 4 0.16 g (0.14 mmol), K 2 CO 3 1.26 g (9.08 mmol) , 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and stirred for 14 hours while heating to reflux. After the reaction was completed, the solvent was distilled off under reduced pressure, diluted with 50 mL of CHCl ₃ , and filtered using celite. After washing with 100 mL of CHCl _{3, the} solution was concentrated and purified by silica gel column chromatography to obtain 1.51 g (yield: 51.5%) of a white solid compound 4-16 (WS15-30-332).

Example 13: Synthesis of Compound 4-17 (WS15-30-338)

Intermediate (3) 2.5 g (5.0 mmol ), intermediate (31) 1.96 g (5.0 mmol ), Pd (PPh 3) 4 0.17 g (0.15 mmol), 2M K 2 CO 3 5 mL (10 mmol), toluene 13 mL And 5 mL of ethanol was refluxed and stirred for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dissolved by heating in 1400 mL of chloroform. The insoluble precipitate was removed by filtration, and the filtrate was concentrated under reduced pressure until about 100 mL of chloroform remained. The resulting precipitate was filtered under reduced pressure and dried to obtain 2.12 g (yield: 61%) of a solid compound 4-17 (WS15-30-338).

Example 14: Synthesis of Compound 4-18 (MK-26-05)

Intermediate 1 (4) 3.0 g (5.45 mmol ), 3- bromo-flow to the 250 mL flask is X (3-bromofluoranthene) 1.43 g ( 5.45 mmol), Pd (PPh 3) 4 0.19 g (0.16 mmol), K ₂ CO ₃ 1.51 g (10.90 mmol), toluene 50 mL, ethanol 20 mL, and water 10 mL were mixed and stirred for 14 hours while heating to reflux. After the reaction was completed, solvent was evaporated under reduced pressure and CHCl ₃ It was diluted to 50 mL and filtered using celite. CHCl ₃ 100 mL, and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain 2.45 g (yield: 74.0%) of Compound 4-18 (MK-26-05) as a white solid.

Example 15: Synthesis of Compound 4-19 (WS15-30-301)

In 1 250 mL flask was charged 2-bromo-triphenylene (2-bromotriphenylene) 1.5 g ( 4.883 mmol), Intermediate (4) 2.7 g (4.883 mmol ), Pd (PPh 3) 4 0.2 g (0.146 mmol), while stirring as the toluene 80 mL of ethanol was added _{40 mL, K 2 CO 3 1.0} g (7.325 mmol) / H 2 O 40 mL , and the mixture was stirred for 7 hours under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with DCM. The organic phase was dried over MgSO ₄ and purified by silica gel column chromatography to obtain 1.1 g of a white solid compound 4-19 (WS15-30-301) 34%).

Example 16: Synthesis of compound 4-20 (WS15-30-311)

Intermediate (4) 2.5 g (4.5 mmol ), intermediate (6) 1.31 g (4.5 mmol ), Pd (PPh 3) 4 0.16 g (0.14 mmol), 2M K 2 CO 3 5 mL (10 mmol), toluene 13 mL And 5 mL of ethanol was refluxed and stirred for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dried under reduced pressure, and recrystallized from dichloromethane and methanol to obtain 1.21 g (yield: 42%) of solid compound 4-20 (WS15-30-311).

Example 17: Synthesis of Compound 4-21 (WS16-30-036)

Intermediate (4) 2.5 g (4.5 mmol ), Int.6 1.31 g (4.5 mmol), Pd (PPh 3) 4 0.16 g (0.14 mmol), 2M K 2 CO 3 5 mL (10 mmol), 13 mL of toluene and And 5 mL of ethanol was refluxed and stirred for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dried under reduced pressure, and recrystallized from dichloromethane and methanol to obtain 1.21 g (yield: 42%) of solid compound 4-21 (WS16-30-036).

Example 18: Synthesis of Compound 4-22 (WS15-30-314)

Intermediate (4) 2.5 g (4.5 mmol ), intermediate (9) 1.98 g (4.5 mmol ), Pd (PPh 3) 4 0.16 g (0.14 mmol), 2M K 2 CO 3 5 mL (10 mmol), toluene 13 mL And 5 mL of ethanol was refluxed and stirred for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dried under reduced pressure, and recrystallized from dichloromethane and methanol to obtain 1.70 g (yield: 48%) of Compound 4-22 (WS15-30-314).

Example 19: Synthesis of Compound 4-23 (WS15-30-334)

1 intermediate necked 250 mL flask, (4) 2.5 g (4.54 mmol ), intermediate (33) 1.24 g (4.54 mmol ), Pd (PPh 3) 4 0.16 g (0.14 mmol), K 2 CO 3 1.26 g (9.08 mmol ), 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and stirred for 14 hours while heating to reflux. After the reaction was completed, the solvent was distilled off under reduced pressure, diluted with 50 mL of CHCl ₃ , and filtered using celite. After washing with 100 mL of CHCl _{3, the} solution was concentrated and purified by silica gel column chromatography to obtain 1.80 g (yield: 64.3%) of Compound 4-23 (WS15-30-334) as a white solid.

Example 20: Synthesis of Compound 4-26 (WS15-30-300)

Intermediate (3) 2.45 g (4.9 mmol ), phenylboronic acid (phenylboronic acid) 0.59 g (4.9 mmol), Pd (PPh 3) 4 0.17 g (0.15 mmol), 2M K 2 CO 3 5 mL (10 mmol), 13 mL of toluene and 5 mL of ethanol was refluxed and stirred for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dried under reduced pressure, and recrystallized from dichloromethane and methanol to obtain a solid compound 4-26 (WS15-30-300) 1.22 g (Yield: 50%) was obtained.

Example 21: Synthesis of compound 4-33 (WS15-30-306)

Intermediate 1 to obtain 250 mL flask (4) 2.5 g (4.54 mmol ), Int.3 1.59 g (4.54 mmol), Pd (PPh 3) 4 0.16 g (0.14 mmol), K 2 CO 3 1.26 g (9.08 mmol) , 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and stirred for 15 hours while heating to reflux. After the reaction was completed, the solvent was distilled off under reduced pressure, diluted with 50 mL of CHCl ₃ , and filtered using celite. Washed with 100 mL of CHCl ₃ , concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 2.10 g (yield: 66.9%) of Compound 4-33 (WS15-30-306) as a white solid.

Example 22: Synthesis of compound 4-36 (WS15-30-281)

1 intermediate necked 250 mL flask, (4) 2.5 g (4.54 mmol ), intermediate (13) 1.59 g (4.54 mmol ), Pd (PPh 3) 4 0.16 g (0.14 mmol), K 2 CO 3 1.26 g (9.08 mmol ), 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and stirred for 15 hours while heating to reflux. After the reaction was completed, the solvent was distilled off under reduced pressure, diluted with 50 mL of CHCl ₃ , and filtered using celite. Washed with 100 mL of CHCl ₃ , concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 2.00 g (yield: 63.5%) of Compound 4-36 (WS15-30-281) as a white solid.

Example 23: Synthesis of Compound 4-39 (WS16-30-035)

Intermediate 1 to obtain 250 mL flask (4) 2.5 g (4.54 mmol ), Int.8 1.59 g (4.54 mmol), Pd (PPh 3) 4 0.16 g (0.14 mmol), K 2 CO 3 1.26 g (9.08 mmol) , 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and stirred for 15 hours while heating to reflux. After the reaction was completed, the solvent was distilled off under reduced pressure, diluted with 50 mL of CHCl ₃ , and filtered using celite. Washed with 100 mL of CHCl ₃ , concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 2.00 g of a white solid compound 4-39 (WS16-30-035) (yield: 63.5%).

Example 24: Synthesis of Compound 4-42 (WS15-30-305)

Intermediate 1 to obtain 250 mL flask (4) 2.5 g (4.54 mmol ), Int.4 1.59 g (4.54 mmol), Pd (PPh 3) 4 0.16 g (0.14 mmol), K 2 CO 3 1.26 g (9.08 mmol) , 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and stirred for 11 hours while heating and refluxing. After the reaction was completed, solvent was evaporated under reduced pressure and CHCl ₃ It was diluted to 50 mL and filtered using celite. CHCl ₃ 100 mL, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 2.0 g (yield: 64.5%) of 4-42 (WS15-30-305) as a white solid.

Example 25: Synthesis of Compound 4-43 (WS16-30-063)

Intermediate 1 to obtain 250 mL flask (4) 2.5 g (4.54 mmol ), Int.7 1.59 g (4.54 mmol), Pd (PPh 3) 4 0.16 g (0.14 mmol), K 2 CO 3 1.26 g (9.08 mmol) , 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and stirred for 11 hours while heating and refluxing. After the reaction was completed, the solvent was distilled off under reduced pressure, diluted with 50 mL of CHCl ₃ , and filtered using celite. Washed with 100 mL of CHCl ₃ , concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 2.0 g (yield: 64.5%) of 4-43 (WS16-30-063) as a white solid.

Example 26: Synthesis of Compound 4-45 (KBS-17-37)

In 1 250 mL flask Int.5 2.0 g (4.451 mmol), Intermediate (4) 2.5 g (4.451 mmol ), Pd (PPh 3) 4 0.2 g (0.134 mmol), while stirring as the toluene 80 mL ethanol 40 mL, K ₂ CO ₃ 0.9 g was added to _{(8.902 mol) / H 2 O} 40 mL , and the mixture was stirred for 8 hours under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with DCM. The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 0.4 g of a white solid compound 4-45 (KBS-17-37) : 12%).

Example 27: Synthesis of Compound 4-50 (WS15-30-304)

In 1 250 mL flask, intermediate (3) 2.8 g (5.562 mmol ), pyridin-4 Daily acid (pyridin-4-ylboronic acid) 0.7 g (5.562 mmol), Pd (PPh 3) 4 0.2 g (0.155 mmol) , while stirring as the toluene 80 mL of ethanol was added _{40 mL, K 2 CO 3 1.2} g (8.343 mmol) / H 2 O 40 mL , and the mixture was stirred for 12 hours under reflux. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with DCM. The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 1.9 g of a white solid compound 4-50 (WS15-30-304) : 68%).

Example 28: Synthesis of compound 4-51 (WS15-30-299)

Intermediate (3) 2.45 g (4.9 mmol ), pyridine-3 Daily acid (pyridin-3-ylboronic acid) 0.66 g (4.9 mmol), Pd (PPh 3) 4 0.17 g (0.15 mmol), 2M K 2 CO 3 5 mL (10 mmol), 13 mL of toluene and 5 mL of ethanol was refluxed with stirring for 12 hours. The reaction mixture was cooled to room temperature, diluted with 100 mL of dichloromethane, and washed with 100 mL of water. Dried over anhydrous magnesium sulfate, concentrated by filtration, and then purified by column chromatography to obtain a solid compound 4-51 (WS15-30-299) 1.56 g (Yield: 64%) was obtained.

Example 29: Synthesis of compound 4-56 (WS15-30-327)

1 intermediate necked 250 mL flask, (4) 2.5 g (4.54 mmol ), intermediate (25) 1.32 g (4.54 mmol ), Pd (PPh 3) 4 0.16 g (0.14 mmol), K 2 CO 3 1.26 g (9.08 mmol ), 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and stirred for 18 hours while heating and refluxing. After the reaction was completed, the solvent was distilled off under reduced pressure, diluted with 50 mL of CHCl ₃ , and filtered using celite. After washing with 100 mL of CHCl _{3, the} solution was concentrated and purified by silica gel column chromatography to obtain 1.8 g (yield: 62.5%) of a white solid compound 4-56 (WS15-30-327).

Example 30: Synthesis of compound 4-57 (WS15-30-312)

Intermediate (4) 2.5 g (4.5 mmol ), intermediate (27) 1.30 g (4.5 mmol ), Pd (PPh 3) 4 0.16 g (0.14 mmol), 2M K 2 CO 3 5 mL (10 mmol), toluene 13 mL And 5 mL of ethanol was refluxed and stirred for 12 hours. The reaction mixture was cooled to room temperature and the resulting precipitate was filtered under reduced pressure and washed with toluene, water, and methanol. The filtered precipitate was dried under reduced pressure, and recrystallized from dichloromethane and methanol to obtain 2.03 g (yield: 73%) of solid compound 4-57 (WS15-30-312).

Example 31: Synthesis of Compound 4-62 (WS15-30-282)

1 intermediate necked 250 mL flask, (4) 3.0 g (5.45 mmol ), intermediate (18) 1.43 g (5.45 mmol ), Pd (PPh 3) 4 0.19 g (0.16 mmol), K 2 CO 3 1.51 g (10.90 mmol ), 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and stirred for 18 hours while heating and refluxing. After the reaction was completed, the solvent was distilled off under reduced pressure, diluted with 50 mL of CHCl ₃ , and filtered using celite. After washing with 100 mL of CHCl ₃ , the residue was purified by silica gel column chromatography to obtain 2.07 g (yield: 65.7%) of a white solid compound 4-62 (WS15-30-282).

Example 32: Synthesis of compound 4-66 (WS15-30-308)

1 intermediate necked 250 mL flask, (4) 2.5 g (4.54 mmol ), intermediate (23) 1.59 g (4.54 mmol ), Pd (PPh 3) 4 0.16 g (0.14 mmol), K 2 CO 3 1.26 g (9.08 mmol ), 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and stirred for 14 hours while heating to reflux. After the reaction was completed, the solvent was distilled off under reduced pressure, diluted with 50 mL of CHCl ₃ , and filtered using celite. Washed with 100 mL of CHCl ₃ , concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 1.50 g (yield: 42.9%) of a white solid compound 4-66 (WS15-30-308).

Example 33: Synthesis of compound 4-67 (WS15-30-328)

To a 250 ml one-necked flask was added 2.5 g (4.54 mmol) of intermediate (4), 1.21 g (4.54 mmol) of 2-chloro-4,6-diphenylpyrimidine, Pd ₃ ) 0.16 g (0.14 mmol) of ₄ , 1.26 g (9.08 mmol) of K ₂ CO ₃ , 50 mL of toluene, 20 mL of ethanol and 10 mL of water were mixed and stirred for 16 hours while heating to reflux. After the reaction was completed, the solvent was distilled off under reduced pressure, diluted with 50 mL of CHCl ₃ , and filtered using celite. After washing with 100 mL of CHCl _{3, the} solution was concentrated and purified by silica gel column chromatography to obtain 1.80 g (yield: 60.6%) of solid compound 4-67 (WS15-30-328) as a white solid.

Example 34: Synthesis of compound 4-69 (WS15-30-302)

1.3 g (4.856 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine was added to one 250 mL flask. , intermediate (4) 2.7 g (4.856 mmol ), Pd (PPh 3) 4 0.2 g (0.146 mmol), while stirring as the toluene 80 mL ethanol, _{40 mL, K 2 CO 3 1.0} g (7.284 mmol) / H 2 O was added thereto, and the mixture was stirred under reflux for 7 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added thereto, and the mixture was extracted with DCM. The organic phase was dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to obtain 1.6 g of white solid compound 4-69 (WS15-30-302) : 49%).

Example 35: Synthesis of compound 4-73 (WS15-35-21)

In a one-necked 100 mL flask, Int. 9 (3.0 g, 16.3 mmol) and methanol (30 mL) were added, and 7.4 g (16.3 mmol) of Intermediate (5) was slowly added thereto at room temperature. After 1 hour, the reaction was completed and the reaction mixture was concentrated under reduced pressure to obtain a liquid intermediate having a high viscosity.

The thus obtained intermediate and 100 mL of DCM were added, and 4.1 g (17.9 mmol) of DDQ was slowly added thereto at room temperature and stirred for 1 hour. After completion of the reaction was confirmed, the solution was filtered through a silica plug, and the filtrate was concentrated under reduced pressure. The concentrate was purified in EtOA / methanol to obtain 4.54 g (yield: 45.2%) of Compound 4-73 (WS15-35-21) as a white solid.

&Lt; Test Example 1 >

The UV / VIS spectra of the compounds of the present invention were measured using a Jasco V-630 instrument and PL (photoluminescence) spectra were measured using a Jasco FP-8500 instrument.

UV / VIS And PL result division compound UV (nm) * 1 PL (nm, room temperature) * 2 One 4-1 (WS15-30-317) 241, 336 380.5 2 4-2 (WS15-30-303) 265, 353 420 3 4-3 (WS15-30-326) 352 420 4 4-4 (WS15-30-280) 254, 344 404 5 4-7 (WS15-30-278) 243, 359 424.5 6 4-8 (WS15-30-276) 251, 346 424 7 4-9 (WS15-30-318) 262, 340, 376, 397 438.5 8 4-10 (WS15-30-313) 241, 352 427 9 4-11 (WS15-30-279) 240, 349 414 10 4-14 (WS15-30-309) 256, 350 422 11 4-15 (WS15-30-307) 255, 285, 349 413.5 12 4-16 (WS15-30-332) 254, 263, 351 425 13 4-17 (WS15-30-338) 243, 363 404, 422.5 14 4-18 (MK-26-05) 241, 352 427 15 4-19 (WS15-30-301) 255, 356 421.5 16 4-20 (WS15-30-311) 235, 361 405, 424.5 17 4-21 (WS16-30-036) 251, 344 394.5 18 4-22 (WS15-30-314) 248, 287, 351 408, 544 19 4-23 (WS15-30-334) 240, 358 400, 419 20 4-26 (WS15-30-300) 243, 346 410 21 4-33 (WS15-30-306) 356 420.5 22 4-36 (WS15-30-281) 355 406, 418.5 23 4-39 (WS16-30-035) 256, 350 422 24 4-42 (WS15-30-305) 286, 348 409 25 4-43 (WS16-30-063) 255, 285, 349 413.5 26 4-45 (KBS-17-37) 243, 346 410 27 4-50 (WS15-30-304) 251, 344 394.5 28 4-51 (WS15-30-299) 242, 344 400 29 4-56 (WS15-30-327) 370 410.5, 429 30 4-57 (WS15-30-312) 245, 367 404, 424 31 4-62 (WS15-30-282) 348 402.5 32 4-66 (WS15-30-308) 251, 267, 348 387.5, 402.5 33 4-67 (WS15-30-328) 255, 349 399.5 34 4-69 (WS15-30-302) 267, 353, 366 388.5, 403.5 35 4-73 (WS15-35-21) 356 420.5 * 1: 1.0 x 10 ^-5 M in Methylene Chloride
* 2: 5.0 x 10 ^-6 M in Methylene Chloride

Device fabrication test example

2-TNATA is a hole injecting layer, NPB is a hole transporting layer, αβ-ADN is a host of a light emitting layer, Pyene-CN is a blue fluorescent dopant, Liq is an electron injecting layer , And Al was used as a cathode. The structures of these compounds are shown below.

Comparative Example: ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / Alq ₃ (30 nm) / Liq (2 nm) / Al (100 nm)

The blue fluorescent organic light-emitting device was prepared in the same manner as in Example 1 except that ITO (180 nm) / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: Pyrene-CN 10% (30 nm) / electron transport layer nm) / Al (100 nm) in this order. Before depositing the organic substance is applied to the ITO electrodes 2 × 10 ^- was for 2 minutes plasma treatment to 125W at ² Torr. Organic materials were deposited at a vacuum of 9 × 10 ^-7 Torr. Simultaneously, Pyrene-CN was co-deposited with 0.02 Å / sec on the basis of Liq and 0.18 Å / sec for αβ-ADN. / sec. < / RTI > The electron transport layer material used in the experiment was Alq ₃ . After fabricating the device, it was sealed in a glove box filled with nitrogen gas to prevent air and moisture contact of the device. Barium oxide (Barium Oxide), which is a hygroscopic agent capable of removing moisture and so on, was put into a glass plate after 3M's adhesive tape was formed.

&Lt; Test Examples 1 to 32 >

In the comparative test examples, elements were prepared in the same manner as in the comparative test except that each compound shown in Table 2 below was used instead of Alq ₃ .

Table 2 shows the electroluminescent characteristics of the organic light-emitting devices prepared in the above comparative test examples and Test Examples 1 to 32.

division compound Driving voltage
[V] efficiency
[cd / A] life span
(%) Comparative Example Alq ₃ 6.60 5.10 91.78 Test Example 1 WS15-30-317 4.62 6.70 98.87 Test Example 2 WS15-30-303 3.93 6.07 105.43 Test Example 3 WS15-30-326 3.81 5.65 98.79 Test Example 4 WS15-30-280 3.64 5.40 94.23 Test Example 5 WS15-30-278 3.61 6.65 98.85 Test Example 6 WS15-30-276 4.05 5.72 108.17 Test Example 7 WS15-30-318 3.77 5.50 97.38 Test Example 8 WS15-30-313 4.06 6.42 104.94 Test Example 9 WS15-30-279 3.97 5.65 99.91 Test Example 10 WS15-30-309 4.17 7.37 100.51 Test Example 11 WS15-30-307 4.00 6.37 106.42 Test Example 12 WS15-30-332 4.14 6.97 99.52 Test Example 13 WS15-30-338 3.66 5.57 95.67 Test Example 14 WS15-30-301 3.93 5.77 101.48 Test Example 15 WS15-30-311 3.60 6.25 103..34 Test Example 16 WS16-30-036 3.77 5.50 96.15 Test Example 17 WS15-30-334 3.55 5.58 95.81 Test Example 18 WS15-30-300 3.96 6.81 104.71 Test Example 19 WS15-30-306 3.95 9.00 97.57 Test Example 20 WS15-30-281 3.71 5.87 99.30 Test Example 21 WS16-30-035 4.02 8.62 97.60 Test Example 22 WS15-30-305 4.10 6.31 101.86 Test Example 23 WS16-30-063 4.00 7.11 97.23 Test Example 24 WS15-30-304 4.44 8.09 98.42 Test Example 25 WS15-30-299 3.77 5.89 101.03 Test Example 26 WS15-30-327 4.49 5.53 98.61 Test Example 27 WS15-30-312 4.13 6.56 97.10 Test Example 28 WS15-30-282 4.10 8.50 97.75 Test Example 29 WS15-30-308 4.00 8.61 97.89 Test Example 30 WS15-30-328 3.55 6.02 96.88 Test Example 31 WS15-30-302 4.08 6.43 98.79 Test Example 32 WS15-35-21 3.95 9.00 97.57

From the results of the above Table 2, the specific aryl group or the heteroaryl group substituted fluorene-bonded pyrimidine derivative compound according to the present invention can be used as a material of the organic material layer of the organic electronic device including the organic light emitting device, The organic electronic device including the light emitting device exhibits excellent characteristics in terms of efficiency, driving voltage, stability, and the like. In particular, the compounds according to the present invention exhibited high efficiency characteristics because of their excellent electron hole balancing ability and electron transporting ability.

Claims

An aryl group or a heteroaryl group substituted fluorene represented by the following formula (1).
[Chemical Formula 1]

[In the formula 1, Ar ₁ And Ar < ₂ _> are each independently hydrogen, methyl or phenyl,
L is C ₆ -C ₂₄ aryl or C ₃ -C ₂₄ heteroaryl,
n is an integer of 0 or 1,
Ar ₃ is C ₆ -C ₃₀ aryl or C ₃ -C ₃₀ heteroaryl]

The method according to claim 1,
Wherein L in the above formula (1) is any one selected from the group consisting of the following formula (2).
(2)

,

Wherein Ar ₃ in the formula (1) is any one selected from the group consisting of the following formula (3).
(3)
H, CN, CH _3,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

In Formula 3,
Z is O or S
X ₁ to X ₆ are each independently CH or N,
R ₁ to R ₂ are each independently H, CH ₃ or CN.

The method according to claim 1,
Wherein the pyrimidine derivative of Formula 1 is an aryl or heteroaryl group substituted fluorene bonded to a pyrimidine derivative selected from the group consisting of the following Formula 4.
[Chemical Formula 4]

An organic electroluminescent device comprising a pyrimidine derivative according to any one of claims 1 to 4, wherein the pyrimidine derivative is bonded to an aryl group or a heteroaryl group substituted fluorene.

6. The method of claim 5,
Wherein the aryl group or the heteroaryl group substituted fluorene-bonded pyrimidine derivative is used as an electron transport layer material.

A first electrode, a second electrode, and at least one organic film disposed between the electrodes,
The organic electroluminescent device according to any one of claims 1 to 4, wherein the organic film comprises a pyrimidine derivative having an aryl group or a heteroaryl group substituted fluorene bonded thereto.

8. The method of claim 7,
The organic layer includes a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, And at least one functional layer having at least one functional group at the same time.

8. The method of claim 7,
The pyrimidine derivative in which the aryl group or the heteroaryl group substituted fluorene is bonded includes an electron blocking layer, an electron transporting layer, an electron injecting layer, a functional layer having both an electron transporting function and an electron injecting function, and a light emitting layer The organic electroluminescent device comprising: a substrate;