KR101813692B1 - pyrimidine derivatives substituted with heteroaryl-substituted phenyl group, and organic electroluminescent device including the same - Google Patents

Abstract

There is provided a pyrimidine derivative represented by the following formula (1).
[Chemical Formula 1]

[In the formula 1,
Ar ₁ and Ar ₂ are each independently C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl;
Each of X ₁ to X _{4 is} independently CH or N (provided that at least one is N);
A has any one of the structures represented by the following formula (2)
(2)

Description

(Pyrimidine derivatives substituted with heteroaryl-substituted phenyl groups, and organic electroluminescent devices including the same) having a heteroaryl group substituted phenyl group,

The present invention relates to a specific heteroaryl group substituted pyrimidine derivative and an organic electroluminescent device including the heteroaryl group substituted pyrimidine derivative. In particular, the present invention relates to an organic electroluminescent device having a high light emitting efficiency and a specific heteroaryl group substituted phenyl group bonded thereto 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 Publication No. 10-2014-0009263 Korean Patent Publication No. 10-1317495

As a result of intensive studies, the inventors of the present invention have found that a pyrimidine derivative compound having a specific aryl group or a heteroaryl group-substituted phenyl group bonded thereto is used as a material for forming an organic material layer of an organic electronic device, A driving voltage drop and an increase in stability can be exhibited.

The present invention provides a pyrimidine derivative compound to which the above-mentioned specific aryl group or heteroaryl group substituted phenyl group is bonded, and an organic electronic device using the same.

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

[Chemical Formula 1]

Wherein Ar ₁ and Ar ₂ are each independently C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl;

A has any one of the structures represented by the following formula (2)

(2)

Wherein X ₁ to X ₈ are each independently CH, CR or N;

Each R is independently hydrogen, halogen, amino, nitro, cyano, hydroxy, diphenyl phosphine group, diphenylphosphino pook oxide group, C ₁ -C ₁₀ alkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C _30-silyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryloxy, C ₁ -C ₂₀ alkylthio, C ₆ -C ₃₀ aryl, C ₆ -C ₃₀ aralkyl, C ₁ -C ₁₀ heteroalkyl, C ₂ -C ₈ heterocycloalkyl, C ₅ -C ₃₀ heteroaryl, C ₅ -C ₃₀ heteroaralkyl, C ₆ -C ₂₀ arylthio, C ₆ -C _40, or a mono- or diaryl amino, Z is O, S or CR'R ", wherein R 'and R "are C ₆ -C ₃₀ aryl or C ₁ -C ₅ alkyl.

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

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

According to another aspect of the present invention, the aryl group or the heteroaryl group-substituted phenyl group-bonded pyrimidine derivative functions as an electron blocking layer, an electron transport layer, an electron injection layer, an electron transport function and an electron injection function A light emitting layer, a light emitting layer, a light emitting layer, and a light emitting layer.

The specific aryl group or heteroaryl group-substituted phenyl group-bonded pyrimidine derivative compound according to the present invention may be prepared by introducing a specific aryl group or heteroaryl group into the phenyl group to form an organic layer material of an organic electronic device including an organic light- Can be used. 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 structural diagram of a pyrimidine derivative 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, pyreneyl, perylenyle, It is not limited.

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.

The pyrimidine derivative to which an aryl group or a heteroaryl group substituted phenyl group is bonded according to an embodiment of the present invention may be represented by the following general formula (1).

[Chemical Formula 1]

Wherein Ar ₁ and Ar ₂ are each independently C ₆ -C ₃₀ aryl or C ₅ -C ₃₀ heteroaryl;

A has any one of the structures represented by the following formula (2)

(2)

[In the formula (2)

X ₁ to X ₈ are each independently CH, CR or N;

Each R is independently hydrogen, halogen, amino, nitro, cyano, hydroxy, diphenyl phosphine group, diphenylphosphino pook oxide group, C ₁ -C ₁₀ alkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C _30-silyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryloxy, C ₁ -C ₂₀ alkylthio, C ₆ -C ₃₀ aryl, C ₆ -C ₃₀ aralkyl, C ₁ -C ₁₀ heteroalkyl, C ₂ -C ₈ heterocycloalkyl, C ₅ -C ₃₀ heteroaryl, C ₅ -C ₃₀ heteroaralkyl, C ₆ -C ₂₀ arylthio, C ₆ -C _40, or a mono- or diaryl amino, Z is O, S or CR'R ", wherein R 'and R "are C ₆ -C ₃₀ aryl or C ₁ -C ₅ alkyl.

Specifically, R in formula (2) has a structure represented by the following formula (3)

(3)

Specific examples of the compound represented by the formula (1) of the present invention include those represented by the following formula (7). However, the compound represented by the formula (1) of the present invention is not limited to the compounds of the following formula (7).

[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 using a pyridyl group represented by the 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.

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

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 intended to illustrate the present invention and the scope of the present invention is not limited thereto.

[Example]

Intermediate Synthesis Example 1: Synthesis of Intermediate (3)

(Synthesis of Intermediate (1)

50.0 g (189 mmol) of 3, 5-dibromobenzaldehyde and 37.2 g (189 mmol) of 4-acetylbiphenyl are placed in 1.2 L of ethanol and stirred at room temperature. 70 mL (350 mmol) of a 5M aqueous sodium hydroxide solution is slowly added dropwise to the reaction solution. After stirring overnight at room temperature, the precipitate was filtered, washed with water and ethanol, and purified to obtain 78.3 g (yield: 93.5%) of a solid compound (Intermediate (1)).

(Synthesis of Intermediate (2)

78.3 g (177 mmol) of Intermediate (1) and 28.6 g (182 mmol) of benzamidine hydrochloride were added to 890 mL of ethanol and stirred. 14.2 g (354 mmol) of sodium hydroxide are added in small portions at room temperature. Thereafter, the reaction solution was refluxed overnight. After cooling the reaction mixture to room temperature, the precipitate was filtered, washed with water and methanol and purified to obtain 58.7 g (yield: 61.1%) of a solid compound (intermediate (2)).

(Synthesis of Intermediate (3)

Intermediate (4) 15.0 21.1 g (83 mmol) of (PIN) ₂ B ₂ , 1.13 g (1.38 mmol) of Pd (dppf) Cl ₂ .CH ₂ Cl ₂ , 16.3 g (166 mmol) of KOAc and 276 mL of dioxane And the mixture was refluxed and stirred at 90 ° C for 12 hours. After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 17 g (yield: 96.6%) of a white solid compound (intermediate (3)).

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

Example 1: Synthesis of Compound 7-1 (WS15-30-134)

Intermediate (3) 8.5 g (13.4 mmol ) and Int.1 7.62 g (26.7 mmol) was dissolved in 70 mL toluene and 30 mL of ethanol and water _{30 mL Pd (PPh 3) 4} 772 mg (668 μmol) and K ₃ PO ₄ 17.0 g (80.1 mmol) were added thereto, followed by stirring at 80 ° C for 12 hours. After the temperature of the reaction mixture was lowered to room temperature, the precipitate was filtered, washed with water and MeOH, and then dried. The dried solid was dissolved in chloroform and then purified by silica gel column chromatography to obtain 2.46 g of a white solid compound 7-1 (WS15-30-134) (yield: 23.2%).

Example 2: Synthesis of Compound 7-3 (WS15-30-237)

4.0 g (6.29 mmol) of Intermediate (3) and 3.51 g (18.9 mmol) of 3-bromo-2,6-dimethylpyridine were dissolved in toluene Ethanol (15 mL) and water (15 mL). 726 mg (629 μmol) of Pd (PPh ₃ ) ₄ and 8.0 g (37.7 mmol) of K ₃ PO ₄ were added together and stirred at 80 ° C. for 12 hours. After the temperature of the reaction mixture was lowered to room temperature, 150 mL of dichloromethane and 60 mL of water were added to separate the organic layer, and the organic layer was washed with water and concentrated under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography to obtain 1.66 g of a white solid compound 7-3 (WS15-30-237) (yield: 44.4%).

Example 3: Synthesis of Compound 7-32 (WS15-30-207)

3.2 g (18.9 mmol) of 2-bromo-4-methylpyridine and 4.0 g (6.29 mmol) of the intermediate compound (3) were dissolved in toluene (40 mL) and ethanol And 722 mg (629 μmol) of Pd (PPh ₃ ) ₄ and 8.01 g (37.7 mmol) of K ₃ PO ₄ were added thereto, followed by stirring at 80 ° C. for 12 hours. After the temperature of the reaction mixture was lowered to room temperature, 150 mL of DCM and 60 mL of water were added thereto, and the organic layer was washed with water and concentrated under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography to obtain 1.30 g (yield: 36.5%) of a white solid compound 7-32 (WS15-30-207).

Example 4: Synthesis of Compound 7-36 (WS15-30-206)

Intermediate (2) 4.0 g (7.38 mmol ) and Int.2 5.15 g (18.4 mmol) in toluene 40 mL, dissolved in ethanol, 20 mL water and _{20 mL Pd (PPh 3) 4} 426 mg (369 μmol) and K ₃ PO ₄ 7.83 g (36.9 mmol) were added thereto, followed by stirring at 80 ° C for 12 hours. After the temperature of the reaction mixture was lowered to room temperature, the precipitate was filtered, washed with water and MeOH, and then dried. The dried solid was dissolved in chloroform and then purified by silica gel column chromatography to obtain 3.14 g (yield: 62%) of a white solid compound 7-36 (WS15-30-206).

Example 5: Synthesis of Compound 7-39 (WS15-30-208)

Intermediate (2) 4.0 g (7.38 mmol ) with 8-quinolinyl boronic acid (8-quinolinylboronic acid) 3.19 g (18.4 mmol) in toluene 40 mL, dissolved in ethanol, 20 mL water and 20 mL Pd (PPh _{3) 4} 426 mg (369 μmol) of K ₃ PO _{4 and} 7.83 g (36.9 mmol) of K ₃ PO ₄ were added thereto, followed by stirring at 80 ° C. for 12 hours. After the temperature of the reaction mixture was lowered to room temperature, the precipitate was filtered, washed with water and MeOH, and then dried. The dried solid was dissolved in chloroform and then purified by silica gel column chromatography to obtain 2.12 g (yield: 45%) of a white solid compound 7-39 (WS15-30-208).

Example 6: Synthesis of compound 7-42 (KO-11-48)

Intermediate (3) 4.0 g (6.29 mmol ) and Int.3 3.57 g (13.8 mmol) in toluene 40 mL, dissolved in ethanol, 15 mL water and _{15 mL Pd (PPh 3) 4} 726 mg (629 μmol) and K ₃ PO ₄ 8.01 g (37.7 mmol) were added thereto, followed by stirring at 80 ° C for 12 hours. After the temperature of the reaction mixture was lowered to room temperature, 150 mL of DCM and 60 mL of water were added thereto, and the organic layer was washed with water and concentrated under reduced pressure. The resulting reaction mixture was purified by silica gel column chromatography to obtain 1.18 g of a white solid compound 7-42 (KO-11-48) (yield: 25.4%).

Example 7: Synthesis of Compound 7-55 (WS15-30-110)

1 250 mL delta flask -carbamic Boleyn (δ-carboline) 7.44 g ( 44.3 mmol), intermediate (2) 8.00 g (14.8 mmol ), Cu 187 mg (2.95 mmol), K 2 CO 3 6.12 g (44.3 mmol ), 6.29 g (44.3 mmol) of Na ₂ SO ₄ and 73 mL of nitrobenzene, and then stirred at 170-180 overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, solidified with MeOH, and filtered. The solid was dissolved in chloroform and then purified by silica gel column chromatography (CHCl ₃ ) to obtain 5.13 g (yield: 48.5%) of a white solid compound 7-55 (WS15-30-110).

Example 8: Synthesis of Compound 7-57 (WS15-30-113)

1 seed to obtain 250 mL flask benzo carbazole (C-benzocarbazole) 9.62 g ( 44.3 mmol), intermediate (2) 8.00 g (14.8 mmol ), Cu 469 mg (7.38 mmol), K 2 CO 3 6.12 g (44.3 mmol), 6.29 g (44.3 mmol) of Na ₂ SO ₄ and 73 mL of nitrobenzene, and then stirred at 170-180 overnight. After the reaction was completed, the reaction mixture was cooled to room temperature, solidified with MeOH, and filtered. The solid was dissolved in chloroform and then purified by silica gel column chromatography (CHCl ₃ ) to obtain 2.80 g of a white solid compound 7-57 (WS15-30-113) (yield: 23.3%).

Example 9: Synthesis of Compound 7-59 (WS15-30-152)

One seed in 100 mL flask Ben Nephew Boleyn (C-benzocarboline) 8.45 g ( 38.7 mmol), intermediate (2) 7.00 g (12.9 mmol ), Pd (dba) 2 1.48 g (2.58 mmol), 50% P ( t-Bu) ₃ 2.09 g (5.16 mmol), NaO ^t Bu 5.58 g (58.1 mmol) and Toluene 129 mL and then refluxed. After the reaction was completed, the reaction mixture was cooled to room temperature, solidified with MeOH, and filtered. The solid was purified by silica gel column chromatography (MC: HEX), solidified with EA and filtered to obtain 2.63 g (yield: 24.9%) of a yellow solid compound 7-59 (WS15-30-152).

≪ 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 results division compound UV (nm) * 1 PL (nm, room temperature) * 2 Example 1 7-1
(WS15-30-134) 269, 319 409 Example 2 7-3
(WS15-30-237) 254, 276 378 Example 3 7-32
(WS15-30-207) 279 375.5 Example 4 7-36
(WS15-30-206) 262, 309 383 Example 5 7-39
(WS15-30-208) 287 379, 450 Example 6 7-42
(KO-11-48) 236, 267 482, 503.5 Example 7 7-55
(WS15-30-110) 259, 298, 329 432.5 Example 8 7-57
(WS15-30-113) 265, 325, 363 507.5 Example 9 7-59
(WS15-30-152) 256, 327 465 * 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) / -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 deposition of the organic material, the ITO electrode was subjected to oxygen plasma treatment at 125 W for 2 minutes at 2 × 10 ^-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.

Test Example 1 ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / WS15-30-237 (30 nm) / Liq Al (100 nm)

In the comparative test examples, and the element was manufactured in the same manner as in Comparative Test Example, except that instead of using a 7-3 (WS15-30-237) compound prepared in Example 2, the electron transport layer using Alq ₃ .

Test Example 2: ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / WS15-30-207 (30 nm) / Liq Al (100 nm)

In the above comparative test example, a device was fabricated in the same manner as in the above comparative test except that the 7-32 (WS15-30-207) compound prepared in Example 3 was used as an electron transport layer instead of using Alq ₃ .

Test Example 3 ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / WS15-30-206 (30 nm) / Liq Al (100 nm)

In the Comparative Test Example, an element was fabricated in the same manner as in the Comparative Test Example, except that the 7-36 (WS15-30-206) compound prepared in Example 4 was used as an electron transport layer instead of using Alq ₃ .

Test Example 4 ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / WS15-30-208 (30 nm) / Liq Al (100 nm)

In the above comparative test example, a device was fabricated in the same manner as in the Comparative Test Example except that Alq ₃ was used instead of 7-39 (WS 15-30-208) compound prepared in Example 5 as the electron transport layer .

Test Example 5 ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / WS15-30-110 (30 nm) / Liq Al (100 nm)

In the comparative test example, a device was fabricated in the same manner as in the comparative test except that Alq ₃ was used instead of 7-55 (WS 15-30-110) compound prepared in Example 7 as an electron transport layer .

Test Example 6 ITO / 2-TNATA (60 nm) / NPB (20 nm) / -ADN: 10% Pyrene-CN (30 nm) / WS15-30-113 (30 nm) / Liq (100 nm)

In the comparative test example, a device was fabricated in the same manner as in the comparative test except that Alq ₃ was used instead of 7-57 (WS 15-30-113) compound prepared in Example 8 as an electron transport layer .

Test Example 7: ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / WS15-30-152 (30 nm) / Liq Al (100 nm)

In the comparative test example, a device was fabricated in the same manner as in the comparative test except that Alq ₃ was used instead of 7-59 (WS 15-30-152) compound prepared in Example 9 as an electron transport layer .

division compound Driving voltage
[V] efficiency
[cd / A] life span
(%) Comparative Example Alq ₃ 6.60 5.10 91.78 Test Example 1 WS15-30-237 3.89 5.53 94.54 Test Example 2 WS15-30-207 4.36 8.52 95.48 Test Example 3 WS15-30-206 4.22 5.45 97.94 Test Example 4 WS15-30-208 4.89 6.03 99.53 Test Example 5 WS15-30-110 4.71 5.72 97.47 Test Example 6 WS15-30-113 4.81 6.65 95.99 Test Example 7 WS15-30-152 4.98 5.27 97.73

From the results shown in the above Table 2, the specific aryl group or the heteroaryl group-substituted phenyl group-bonded pyrimidine derivative compound according to the present invention can be used as a material of an organic material layer of an organic electronic device including an organic light emitting device, It can be seen that organic electronic devices including devices exhibit excellent characteristics in terms of efficiency, driving voltage, and stability. 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 (9)

A pyrimidine derivative having a heteroaryl group-substituted phenyl group bonded thereto represented by the following formula (1).
[Chemical Formula 1]

[In the formula 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenyl or naphthyl;
Each of X ₁ to X _{4 is} independently CH or N (provided that at least one is N);
A has any one of the structures represented by the following formula (2)
(2)

[In the formula (2)
Each of X ₅ to X _{8 is} independently CH, CR ₅ or N;
R ₁ to R ₅ are each independently selected from the group consisting of hydrogen, halogen, amino, nitro, cyano, hydroxy, diphenylphosphine group, diphenylphosphoroxide group, C ₁ -C ₁₀ alkyl, C ₃ -C ₈ cycloalkyl, C ₆ -C ₃₀ alkylsilyl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryloxy, C ₁ -C ₂₀ alkylthio, C ₆ -C ₃₀ aryl, C ₆ -C ₃₀ aralkyl, C ₁ -C ₁₀ and heteroaryl alkyl, C ₂ -C ₈ heterocycloalkyl, C ₅ -C ₃₀ heteroaryl, C ₅ -C ₃₀ heteroaralkyl, C ₆ -C ₂₀ arylthio, or C ₆ -C ₄₀ mono- or diaryl amino,
Z is O, S or CR'R "(R 'and R" are methyl or phenyl groups). delete delete The method according to claim 1,
Wherein the compound of formula (1) is selected from the group consisting of the following formula (4).
[Chemical Formula 4]

6. An organic electroluminescent device comprising a pyrimidine derivative to which a heteroaryl group-substituted phenyl group according to any one of claims 1 to 4 is bonded. 6. The method of claim 5,
Wherein the heteroaryl group-substituted phenyl group-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,
Wherein the organic layer comprises a pyrimidine derivative to which the heteroaryl group-substituted phenyl group of claim 1 or 4 is bonded. 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,
Wherein the heteroaryl group-substituted phenyl group-bonded pyrimidine derivative is selected from the group consisting of an electron blocking layer, an electron transport layer, an electron injection layer, a functional layer having both an electron transport function and an electron injection function and a light emitting layer constituting the organic film 1 < / RTI >

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