KR20140039622A - New compounds and organic electro luminescence device using the same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescent device using the same, and more specifically, to an organic electroluminescent device which improves luminous efficiency, driving voltage and lifetime characteristics by including a novel indole carbazole compound with improved hole transporting performance and electron transporting performance in one or more organic layers. The present invention provides the organic electroluminescent device which includes an anode, a cathode, and one or more organic layers placed between the anode and the cathode.

Description

Novel compound and organic electroluminescent device including same TECHNICAL FIELD

TECHNICAL FIELD The present invention relates to a novel compound and an organic electroluminescent device including the same and more particularly to a compound used in an organic material layer of an organic electroluminescent device.

A study on the electroluminescent (EL) devices that led to the blue electroluminescence using the anthracene single crystal in 1965 based on the observation of the organic thin film emission of the Bernanose in the 1950s was carried out by Tang in 1987, An organic electroluminescent device having a laminated structure divided by functional layers has been proposed. In order to improve the efficiency and lifetime of the organic electroluminescent device, the organic electroluminescent device has been developed to introduce characteristic organic layers in the device.

In the organic electroluminescent device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic layer, and the injected holes and electrons meet to form an exciton. When the exciton formed drops to a ground state The light comes out. The material used as the organic material layer may be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

The luminescent material can be classified into blue, green and red luminescent materials according to luminescent colors and yellow and orange luminescent materials necessary for realizing better natural colors. In addition, in order to increase luminous efficiency through increase in color purity and energy transfer, a host / dopant system may be used as a light emitting material.

Here, the dopant, which is a light emitting material, is a phosphorescent material and a carbazole-based compound is used as a host capable of maximizing the light emitting property of the dopant, but further improvement is required.

JP Special Flat 5-208957

The present invention has been made to solve the above problems and it is an object of the present invention to provide a novel compound capable of improving the efficiency, lifetime and stability of the organic electroluminescent device and an organic electroluminescent device using the compound.

In order to achieve the above object, the present invention provides a compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

Y ₁ to Y ₃ Any one is N and the other is N, O or S, wherein the number of N is 2 or less, and each ring containing X ₁ to X ₃ is independently an aryl group or a nuclear atom of C ₆ ~ C ₄₀ A heteroaryl group of 5 to 40, R ₁ To R ₃ are each independently hydrogen, deuterium, cyano group, aryl group of C ₆ ~ C ₄₀ , heteroaryl group of 5 to 40 nuclear atoms, aryloxy group of C ₆ ~ C ₄₀ , alkyl group of C ₁ ~ C ₄₀ , C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ An arylamine group, C ₃ ~ C ₄₀ cycloalkyl group and 3 to 40 heterocycloalkyl group selected from the group consisting of a, b And c are integers of 0 or 1, respectively.

It is Y ₁ to Y ₃ that the number of N is 2 or less. Any one is N, but containing less than two N (Y ₁ to Y ₃ Except when all are N).

The present invention also provides an organic electroluminescent device comprising an anode, a cathode and one or more organic material layers interposed between the anode and the cathode, wherein at least one of the organic material layers comprises a compound represented by Formula 1 of the present invention. An organic electroluminescent device is provided.

In the present invention, 'alkyl (ene)' means a straight or branched saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, Hexyl etc. are mentioned.

In addition, in the present invention, 'aryl (ene)' means an aromatic moiety having 6 to 40 carbon atoms in which a single ring or two or more rings are combined, and a form in which two or more rings are simply attached or fused to each other. It may be.

In the present invention, "heteroaryl (ene)" means a 5-membered and / or 6-membered ring compound having 2 to 40 carbon atoms or 5 to 40 nuclear atoms, and at least one carbon in the ring is N (nitrogen). It means substituted with a hetero atom such as O (oxygen), S (sulfur) or Se (selenium). In this case, a form in which two or more rings are simply attached or fused to each other and a form condensed with an aryl group may be included.

Here, the "fused form" means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

When the compound represented by the general formula (1) of the present invention is used for an organic material layer (preferably, a light emitting material of a light emitting layer) of an organic electroluminescent device, efficiency (luminous efficiency and messaging efficiency), lifetime, Voltage and the like can be improved. Accordingly, the present invention can improve the performance and lifetime of a full-color organic electroluminescent panel.

Hereinafter, the present invention will be described.

1, a novel compound

The novel compound according to the present invention is a compound in which carbazole (carbazole) and an aromatic compound are condensed to form a basic skeleton, and various substituents (R ₁ to R ₃ ) are represented by Chemical Formula 1 above. Such a compound represented by Chemical Formula 1 of the present invention has various substituents bonded to a basic skeleton of a carbazole and an aromatic compound condensed, and thus a conventional organic electroluminescent device material (for example, CBP (4,4-dicarbazolybiphenyl) It has a higher molecular weight than) and is characterized by a wide energy band gap (sky blue ~ red). In addition, the compound represented by the formula (1) of the present invention significantly increases the molecular weight, the glass transition temperature is improved, and thus may have a higher thermal stability than conventional materials.

Therefore, when the compound represented by Formula 1 of the present invention is used as a material for an organic electroluminescent device, not only the phosphorescence characteristics of the device, but also the electron and / or hole transporting ability, luminous efficiency, driving voltage, . In this case, the compound represented by Formula 1 of the present invention may be used as a material of the organic material layer of the organic electroluminescent device, preferably a hole injection layer, a hole transport layer or a light emitting layer.

The compound represented by the formula (1) of the present invention is preferably selected from the group consisting of compounds represented by the following formula (C-1 to C-5).

In Formulas C-1 to C-5, R ₁ and R ₂ are the same as described above.

In addition, R ₁ of the compound represented by the formula (1) of the present invention R ₃ to R ₃ are each independently selected from the group consisting of hydrogen, an aryl group having ₆ to ₄₀ carbon atoms and a heteroaryl group having 5 to 40 nuclear atoms such that the compound has a high molecular weight and exhibits a wide energy band gap. Do. Here, non-limiting examples of the aryl group include phenyl, naphthyl, indene, indenyl, fluorene fluorenyl, phenanthrene phenanthryl, anthracenyl, triphenyl, and the like, and non-limiting examples of the heteroaryl. Examples include pyrrole, pyran, imidazole, thiophene, furan, pyridine, pyrimidine, triazine, pyridazine, indole, benzimidazole, benzothiazole, purine, quinoline, isoquinoline, quinoxaline, dibenzofuran, Dibenzothiophene, carbazole, phenanthroline, acridine, phenothiazine and the like.

Meanwhile, the R ₁ To the R ₃ heavy hydrogen, a cyano group, an aryl group, a heteroaryl group, an aryloxy group, an alkyl group, an alkyloxy group, an arylamine group, a cycloalkyl group and a heterocycloalkyl group are, each independently, a heavy hydrogen, C ₁ ~ C ₄₀ of alkyl group, C ₁ ~ C ₄₀ alkyloxy group of, C ₃ ~ C ₄₀ cycloalkyl group, C ₆ ~ C ₄₀ aryl group, C ₆ ~ C ₄₀ of the aryloxy group, the number of nuclear atoms of 5 to 40 heteroaryl group , C ₆ ~ C ₆₀ It may be substituted with one or more selected from the group consisting of an arylamine group and a heterocycloalkyl group having 3 to 40 nuclear atoms.

The compound represented by Chemical Formula 1 of the present invention may be synthesized by various synthetic methods, and for example, may be synthesized by the following Process 1 and Process 2.

Referring to the process 1 and process 2, the position of the substituent in the final compound (compounds 9 and 14) may be different depending on the position of the coupling compound Nitro phenyl boronic acid in compound 4 (see Figure 1 below) .

[Figure 1]

Here, when compound 4 is synthesized as compound 5, the position of the carbazole ring is determined in one direction only. When compound 4 is synthesized as compound 10, the position of carbazole ring is again in two directions as shown in Figure 2 below. Divided by. In this case, when compd A is synthesized, the compound is difficult to be synthesized as the compound represented by Formula 1 of the present invention, and the compound represented by Formula 1 of the present invention may be synthesized only when compound 11 is synthesized.

[Figure 2]

Specific examples of the compound represented by Formula 1 of the present invention include the following compounds (Compd 1 ~ Compd 60), but is not limited thereto.

2. Organic Field  Light emitting element

The present invention provides an organic electroluminescent device comprising an anode, a cathode and at least one organic layer interposed between the anode and the cathode, wherein at least one of the organic layers is a compound represented by Formula 1 It provides an organic electroluminescent device comprising a. In this case, the compound represented by Formula 1 may include one kind or two or more kinds.

Preferably, the organic material layer including the compound represented by Formula 1 of the present invention may be any one or more of a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer and an electron injection layer, more preferably a light emitting layer, a hole transport layer or an electron It may be a transport layer.

On the other hand, the organic electroluminescent device according to the present invention has a structure in which one or two or more layers of organic material layers are laminated between the electrodes, for example, (i) anode, light emitting layer, cathode, (ii) anode, hole injection layer, hole transport layer And a light emitting layer, an electron transport layer, an electron injection layer, a cathode, and (iii) an anode, a hole injection layer, a hole transport layer, a light emitting layer, and a cathode.

In addition, the organic electroluminescent device according to the present invention may not only have a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted between an electrode and an organic material layer interface.

In this case, the organic material layer including the compound represented by Formula 1 may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

On the other hand, the organic electroluminescent device according to the present invention may be made of a material known in the art, except that at least one layer of the organic material layer is formed to include the compound represented by the formula (1) of the present invention.

Specifically, a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet may be used as the substrate.

Examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but is not limited thereto.

Examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

A hole injection layer, a hole transport layer and an electron transport layer may also be used materials known in the art.

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

[ Synthetic example  One] Compd  Synthesis of 2

Step  1. Compound C1  synthesis

2-Nitro phenyl boronic acid (16.69 g, 100 mmol), 1.3.5-tribromobenzene (31.48 g, 100 mmol) and Pd (PPh ₃ ) ₄ (1.58 g, 5 w%) were added to the flask. Add 200 ml of Toluene and 100 ml of THF and add K ₂ CO ₃ (41.5 g, 300 mmol) was added to an aqueous solution of 100 ml of distilled water, followed by heating and stirring for 12 hours. After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 100 ml of ethyl acetate. The solvent was removed with a rotary evaporator and then crystallized with MeOH to give compound C1 (23.20 g, yield 65%).

Elemental Analysis: C, 40.37; H, 1.98; Br, 44.76; N, 3.92; O, 8.96

HRMS [M] ⁺ : 357

Step  2. Compound C2  synthesis

Compound C1 (23.20 g, 65 mmol) was added to 100 mL of 1.2-dichlorobenzene at room temperature. Triphenyl phosphine (51.15 g, 195 mmol) was slowly added thereto, and the mixture was heated and stirred for 8 hours. Thereafter, the solvent was evaporated under reduced pressure and purified by column chromatography to obtain a compound C2 (19.01 g, 90% yield).

Elemental Analysis: C, 44.35; H, 2. 17; Br, 49.17; N, 4.31

HRMS [M] ⁺ : 325

Step  3. Compound C3  synthesis

Compound C2 (19.01 g, 58.49 mmol), bromobenzene (9.18 g, 58.49 mmol), Pd (OAc) ₂ (0.75 g, 5 w%), K ₃ PO ₄ (37.25 g, 175.5 mmol) was dissolved in 100 mL of toluene. Tri-t-butyl phosphine 50% and toluene solution 1.Oml were added, followed by heating and stirring for 12 hours. After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 100 ml of ethyl acetate. The solvent was removed with a rotary evaporator and then purified by column chromatography to obtain a compound C3 (18.76g, yield 80%).

Elemental Analysis: C, 53.90; H, 2.76; Br, 39.84; N, 3.49

HRMS [M] ⁺ : 401

Step  4. Compound C4  synthesis

Compound C3 (18.76 g, 46.80 mmol), 2-Nitro phenyl boronic acid (7.82 g, 46.80 mmol) and Pd (PPh ₃ ) ₄ (1.11 g, 5 w%) were added to the flask. Add 100 ml of Toluene and 50 ml of THF and add K ₂ CO ₃ 19.38 g of an aqueous solution dissolved in 50 ml of distilled water was added thereto, followed by heating and stirring for 12 hours. After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 100 ml of ethyl acetate. The solvent was removed using a rotary evaporator, and then purified by column chromatography to obtain a compound C4 (8.30g, 40% yield).

Elemental Analysis: C, 65.03; H, 3.41; Br, 18.03; N, 6. 32; O, 7.22

HRMS [M] ⁺ : 443

Step  5. Compound C5  synthesis

Compound C4 (8.30 g, 18.72 mmol) was added to 50 mL of 1.2-dichlorobenzene at room temperature. Triphenyl phosphine (14.73 g, 56.16 mmol) was slowly added thereto, and the mixture was heated and stirred for 8 hours. Thereafter, the solvent was evaporated under reduced pressure and purified by column chromatography to obtain Compound C5 (2.31 g, yield 30%).

Elemental Analysis: C, 70.09; H, 3.68; Br, 19.43; N, 6.81

HRMS [M] ⁺ : 411

Step  6. Compound C6  synthesis

Compound C5 (2.31 g, 5.62 mmol), iodo benzene (1.14 g, 5.62 mmol), Pd (OAc) ₂ (0.055 g, 5 w%), K ₃ PO ₄ (3.58 g, 16.86 mmol) was dissolved in 40 mL of toluene. Tri-t-butyl phosphine 50% and 0.2 ml of toluene solution were added, followed by heating and stirring for 10 hours. After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 50 ml of ethyl acetate. The solvent was removed with a rotary evaporator and then purified by column chromatography to obtain a compound C6 (2.47g, 90% yield).

Elemental Analysis: C, 73.93; H, 3.93; Br, 16.39; N, 5.75

HRMS [M] ⁺ : 487

Step  7. Compound C7  synthesis

Compound C6 (2.47 g, 5.06 mmol) and 2-Hydroxy phenyl boronic acid (0.70 g, 5.06 mmol) Pd (PPh ₃ ) ₄ (0.14 g, 5 w%) were added to the flask. Put 30 ml of toluene and 15 ml of THF and add K ₂ CO ₃ 2.1 g of the aqueous solution dissolved in 15 ml of distilled water was added, followed by heating and stirring for 7 hours. After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 30 ml of ethyl acetate. The solvent was removed with a rotary evaporator, and then purified by column chromatography to obtain a compound C7 (2.28g, 90% yield).

Elemental Analysis: C, 86.38; H, 4.83; N, 5.60; O, 3.20

HRMS [M] ⁺ : 500

Step  8. Compd  2 synthesis

Compound C7 (2.28g, 4.55mmol), C ₆ F ₆ 30ml, DMI (N, N`-dimethylimidazolidinone) 20ml was added to Schlenk tube and replaced with N ₂ . Here Pd (OAc) ₂ (0.11 g, 5w%), 2-nitropyridine (0.11 g, 5w%), PhCO ₂ -O ^t Bu (1.77g, 9.00mmol) added slowly and the resulting mixture was stirred under heating at 90 ℃ for 5 hours. After completion of the reaction by TLC, the solvent was evaporated under reduced pressure and purified by column chromatography to obtain Compd 2 (1.81 g, yield 80%) as a target compound.

Elemental Analysis: C, 86.72; H, 4. 45; N, 5.62; O, 3.21

HRMS [M] ⁺ : 498

[ Synthetic example  2] Compd  Synthesis of 4

Step  1. Compound C8  synthesis

Compound C2 (19.01 g, 58.49 mmol), 2-Iodo-naphthalene (14.86 g, 58.49 mmol), Pd (OAc) ₂ (0.75 g, 5 w%), K ₃ PO ₄ (37.25 g, 175.5 mmol) was dissolved in 100 mL of toluene. Tri-t-butyl phosphine 50% and toluene solution 1.Oml were added, followed by heating and stirring for 12 hours. After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 100 ml of ethyl acetate. The solvent was removed with a rotary evaporator and then purified by column chromatography to obtain a compound C8 (21.11g, 80% yield).

Elemental Analysis: C, 58.57; H, 2. 90; Br, 35.42; N, 3.10

HRMS [M] ⁺ : 451

Step  2. Compound C9  synthesis

Compound C8 (21.11 g, 46.80 mmol), 2-Nitro phenyl boronic acid (7.82 g, 46.80 mmol) and Pd (PPh ₃ ) ₄ (1.11 g, 5 w%) were added to the flask. Add 100 ml of Toluene and 50 ml of THF and add K ₂ CO ₃ 19.38 g of an aqueous solution dissolved in 50 ml of distilled water was added thereto, followed by heating and stirring for 12 hours. After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 100 ml of ethyl acetate. The solvent was removed using a rotary evaporator, and then purified by column chromatography to obtain a compound C9 (9.23g, 40% yield).

Elemental Analysis: C, 68.17; H, 3.47; Br, 16.20; N, 5.68; O, 6.49

HRMS [M] ⁺ : 493

Step  3. Compound C10  synthesis

Compound C9 (9.23 g, 18.72 mmol) was added to 50 mL of 1.2-dichlorobenzene at room temperature. Triphenyl phosphine (14.73 g, 56.16 mmol) was slowly added thereto, and the mixture was heated and stirred for 8 hours. Thereafter, the solvent was evaporated under reduced pressure and purified by column chromatography to obtain a compound C10 (2.59g, yield 30%).

Elemental Analysis: C, 72.89; H, 3.71; Br, 17.32; N, 6.07

HRMS [M] ⁺ : 461

Step  4. Compound C11  synthesis

Compound C10 (2.59 g, 5.62 mmol), iodo benzene (1.14 g, 5.62 mmol), Pd (OAc) ₂ (0.055 g, 5 w%), K ₃ PO ₄ (3.58 g, 16.86 mmol) was dissolved in 40 mL of toluene. Tri-t-butyl phosphine 50% and 0.2 ml of toluene solution were added, followed by heating and stirring for 10 hours. After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 50 ml of ethyl acetate. The solvent was removed with a rotary evaporator and then purified by column chromatography to obtain a compound C11 (2.72g, 90% yield).

Elemental Analysis: C, 75.98; H, 3.94; Br, 14.87; N, 5.21

HRMS [M] ⁺ : 537

Step  5. Compound C12  synthesis

Compound C11 (2.72 g, 5.06 mmol), Methylsulfanylbenzene-2-boronic acid (0.85 g, 5.06 mmol), and Pd (PPh ₃ ) ₄ (0.14 g, 5 w%) were added to the flask. Put 30 ml of toluene and 15 ml of THF and add K ₂ CO ₃ 2.1 g of the aqueous solution dissolved in 15 ml of distilled water was added, followed by heating and stirring for 7 hours. After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 30 ml of ethyl acetate. The solvent was removed using a rotary evaporator, and then purified by column chromatography to obtain a compound C12 (2.61g, 90% yield).

Elemental Analysis: C, 84.79; H, 4.86; N, 4.82; S, 5.52

HRMS [M] ⁺ : 580

Step  6. Compd  4 synthetic

The compound (C12 2.61 g, 4.55 mmol) was added to 20 mL AcOH at room temperature. AgOAc (1.52 g, 9.10 mmol) and PdCl ₂ (0.65 g, 25 mol%) were slowly added thereto, followed by heat stirring for 2 hours. Thereafter, the solvent was evaporated under reduced pressure and purified by column chromatography to obtain the title compound compd 4 (2.05 g, yield 80%).

Elemental Analysis: C, 85.08; H, 4.28; N, 4.96; S, 5.68

HRMS [M] ⁺ : 564

[ Synthetic example  3] Compd  5, synthesis.

Step  1. Compound C13  synthesis

Compound C2 (19.01 g, 58.49 mmol), 3-Bromo-9-phenyl carbazole (18.83 g, 58.49 mmol), Pd (OAc) ₂ (0.75 g, 5 w%), K ₃ PO ₄ (37.25 g, 175.5 mmol) was dissolved in 100 mL of toluene. Tri-t-butyl phosphine 50% and toluene solution 1.Oml were added, followed by heating and stirring for 12 hours. After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 100 ml of ethyl acetate. The solvent was removed using a rotary evaporator, and then purified by column chromatography to obtain a compound C13 (26.50g, yield 80%).

Elemental Analysis: C, 63.63; H, 3. 20; Br, 28.22; N, 4.95

HRMS [M] ⁺ : 564

Step  2. Compound C14  synthesis

Compound C13 (26.50 g, 46.80 mmol), 2-Nitro phenyl boronic acid (7.82 g, 46.80 mmol) and Pd (PPh ₃ ) ₄ (1.11 g, 5 w%) were added to the flask. Add 100 ml of Toluene and 50 ml of THF and add K ₂ CO ₃ 19.38 g of an aqueous solution dissolved in 50 ml of distilled water was added thereto, followed by heating and stirring for 12 hours. After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 100 ml of ethyl acetate. The solvent was removed using a rotary evaporator, and then purified by column chromatography to obtain a compound C14 (11.39g, 40% yield).

Elemental Analysis: C, 71.06; H, 3. 64; Br, 13.13; N, 6.91; O, 5.26

HRMS [M] ⁺ : 608

Step  3. Compound C15  synthesis

Compound C14 (11.39 g, 18.72 mmol) was added to 50 mL of 1.2-dichlorobenzene at room temperature. Triphenyl phosphine (14.73 g, 56.16 mmol) was slowly added thereto, and the mixture was heated and stirred for 8 hours. Thereafter, the solvent was evaporated under reduced pressure and purified by column chromatography to obtain Compound C15 (3.23 g, yield 30%).

Elemental Analysis: C, 72.98; H, 3. 74; Br, 13.49; N, 7.09; O, 2.70

HRMS [M] ⁺ : 576

Step  4. Compound C16  synthesis

Compound C15 (3.23 g, 5.62 mmol), iodo benzene (1.14 g, 5.62 mmol), Pd (OAc) ₂ (0.055 g, 5 w%), K ₃ PO ₄ (3.58 g, 16.86 mmol) was dissolved in 40 mL of toluene. Tri-t-butyl phosphine 50% and 0.2 ml of toluene solution were added, followed by heating and stirring for 10 hours. After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 50 ml of ethyl acetate. The solvent was removed using a rotary evaporator, and then purified by column chromatography to obtain a compound C16 (3.30g, 90% yield).

Elemental Analysis: C, 76.22; H, 3.94; Br, 13.00; N, 6.84

HRMS [M] ⁺ : 652

Step  5. Compound C17  synthesis

Compound C16 (3.30 g, 5.06 mmol), Methylsulfanylbenzene-2-boronic acid (0.85 g, 5.06 mmol), and Pd (PPh ₃ ) ₄ (0.14 g, 5 w%) were added to the flask. Put 30 ml of toluene and 15 ml of THF and add K ₂ CO ₃ 2.1 g of the aqueous solution dissolved in 15 ml of distilled water was added, followed by heating and stirring for 7 hours. After confirming that the reaction was terminated by TLC, the reaction solution was filtered and extracted twice with 30 ml of ethyl acetate. The solvent was removed using a rotary evaporator, and then purified by column chromatography to obtain a compound C17 (3.18g, 90% yield).

Elemental Analysis: C, 84.33; H, 5.05; N, 6.02; S, 4.59

HRMS [M] ⁺ : 697

Step  6. Compd  5 synthetic

The compound C17 (3.18 g, 4.55 mmol) was added to 20 mL of AcOH at room temperature. AgOAc (1.52 g, 9.10 mmol) and PdCl ₂ (0.65 g, 25 mol%) were slowly added thereto, followed by heat stirring for 2 hours. Thereafter, the solvent was evaporated under reduced pressure and purified by column chromatography to obtain the title compound compd 5 (2.48 g, yield 80%).

Elemental Analysis: C, 84.44; H, 4.82; N, 6.09; S, 4.65

HRMS [M] ⁺ : 681

[ Synthetic example  4] Compd  7, composite

Step  1. Compound C18  synthesis

Compound C18 was obtained by coupling the compound C2 with 2-bromoquinoline.

Step  2. Compound C19  synthesis

Suzuki coupling of the compound C18 and 2-Nitro phenyl boronic acid afforded compound C19.

Step  3. Compound C20  synthesis

Compound C19 was added to 1.2-dichlorobenzene at room temperature. Triphenyl phosphine was slowly added thereto and heated and stirred for 12 hours. Thereafter, the solvent was evaporated under reduced pressure and purified by column chromatography to obtain a compound C20.

Step  4. Compound C21  synthesis

Compound C20 and iodo benzene, Pd (OAc) ₂ and K ₃ PO ₄ were dissolved in Toluene. Tri-t-butyl phosphine 50% and toluene solution were added, followed by heating and stirring for 16 hours to obtain compound C21.

Step  5. Compound C22  synthesis

Compound C22 was obtained by Suzuki coupling the compound C21 with Methylsulfanylbenzene-2-boronic acid.

Step  6. Compd  7 synthetic

Compound C22 was added to AcOH at room temperature. AgOAc and PdCl ₂ were slowly added thereto, and the mixture was heated and stirred for 2 hours. Thereafter, the solvent was evaporated under reduced pressure and purified by column chromatography to obtain the title compound compd 7.

Elemental Analysis: C, 83.88; H, 4.09; N, 6.82; S, 5.21

HRMS [M] ⁺ : 615

[ Synthetic example  5] Compd  9, synthesis

Step  1. Compound C23  synthesis

Compound C23 was obtained by coupling the compound C2 with 2-bromonaphthalene.

Step  2. Compound C24  synthesis

Compound C24 was obtained by the same procedure as Steps 4 and 5 of Synthesis Example 1, except that Compound C23 was used instead of Compound C3.

Step  3. Compound C25  synthesis

Compound C25 was obtained by coupling Compound C24 with 7-bromo-1H-phenalene.

Step  4. Compound C26  synthesis

Compound C26 was obtained by Suzuki coupling the compound C25 with (2-hydroxynaphthalen-1-yl) boronic acid.

Step  5. Compd  9 synthetic

Compound C26, C ₆ F ₆ , DMI (N, N`-dimethylimidazolidinone) was added to Schlenk tube and substituted with N ₂ . Pd (OAc) ₂ , 2-nitropyridine, PhCO ₂ -O ^t Bu was added slowly and stirred at 90 ° C. for 5 hours to obtain compd 9 as the target compound.

Elemental Analysis: C, 89.19; H, 4.40; N, 4.08; O, 2.33

HRMS [M] ⁺ : 686

[ Synthetic example  6] Compd  11 Synthesis

Step  1. Compound C27  synthesis

Compound C27 was obtained by coupling the compound C2 with 2-bromothiophene.

Step  2. Compound C28  synthesis

Compound C28 was obtained by the same process as Steps 4 and 5 of Synthesis Example 1, except that Compound C27 was used instead of Compound C3.

Step  3. Compound C29  synthesis

Compound C29 was obtained by coupling Compound C28 with 3-bromopyridine.

Step  4. Compound C30  synthesis

Compound C30 was obtained by suzuki coupling the compound C29 with 2-hydroxy phenylboronic acid.

Step  5. Compd  11 synthetic

Compound C30, C ₆ F ₆ , DMI (N, N`-dimethylimidazolidinone) was added to Schlenk tube and substituted with N ₂ . Pd (OAc) ₂ , 2-nitropyridine, PhCO ₂ -O ^t Bu was added slowly and stirred at 90 ° C. for 5 hours to obtain compd 11 as the target compound.

Elemental Analysis: C, 78.08; H, 4. 17; N, 8. 28; 0, 3.15; S, 6.32

HRMS [M] ⁺ : 507

[ Synthetic example  7] Compd  14 Synthesis

Step  1 compound C31  synthesis

Compound C31 was obtained by coupling the compound C5 with 2-chloro-4,6-diphenyl-1,3,5-triazine.

Step  2. Compound C32  synthesis

Compound C32 was obtained by Suzuki coupling the compound C31 and Methylsulfanylbenzene-2-boronic acid.

Step  3. Compd  14 synthetic

Compound C32 was added to AcOH at room temperature. AgOAc and PdCl ₂ were slowly added thereto, and the mixture was heated and stirred for 5 hours. Then, the solvent was evaporated under reduced pressure and purified by column chromatography to obtain the title compound compd 14.

Elemental Analysis: C, 80.69; H, 4.06; N, 10.46; S, 4.79

HRMS [M] ⁺ : 669

[ Synthetic example  8] Compd  26 composites

Step  1. Compound C33  synthesis

Compound C33 was obtained by coupling the compound C2 with 2-chloro-4,6-diphenyl-1,3,5-triazine.

Step  2. Compound C34  synthesis

Compound C34 was obtained by Suzuki coupling the compound C33 and Methylsulfanylbenzene-2-boronic acid.

Step  3. Compd  26 synthetic

Compound C34 was added to AcOH at room temperature. AgOAc, PdCl ₂ Was added slowly and stirred for 8 hours. Thereafter, the solvent was evaporated under reduced pressure and purified by column chromatography to obtain the title compound compd 26.

Elemental Analysis: C, 76.70; H, 3.63; N, 9.17; S, 10.50

HRMS [M] ⁺ : 610

[ Synthetic example  9] Compd  25 composites

Step  1. Compound C35  synthesis

Compound C35 was obtained by coupling the compound C2 with 2-bromonaphthalene.

Step  2. Compound C36  synthesis

Compound C36 was obtained by Suzuki coupling the compound C35 and Methylsulfanylbenzene-2-boronic acid.

Step  3. Compound C37  synthesis

Compound C36 was added to AcOH at room temperature. AgOAc and PdCl ₂ were slowly added thereto, followed by heating and stirring for 5 hours to obtain compound C37.

Step  4. Compound C38  synthesis

Compound C38 was obtained by Suzuki coupling the compound C37 and 2-hydroxy phenylboronic acid.

Step  5. Compd  25 synthetic

Compound C38, C ₆ F ₆ , DMI (N, N`-dimethylimidazolidinone) was added to Schlenk tube and substituted with N ₂ . Pd (OAc) ₂ , 2-nitropyridine, PhCO ₂ -O ^t Bu was added slowly and stirred at 90 ° C. for 4 hours to obtain compd 25 as the target compound.

Elemental Analysis: C, 83.41; H, 3.91; N, 2.86; 0, 3.27; S, 6.55

HRMS [M] ⁺ : 489

[ Synthetic example  10] Compd  Synthesis of 27

Step  1. Compound C39  synthesis

Compound C39 was obtained by coupling the compound C2 with 3-bromo-9-phenyl-9H-carbazole.

Step  2. Compound C40  synthesis

Compound C40 was obtained by suzuki coupling the compound C39 with 2-Hydroxy phenyl boronic acid.

Step  3. Compd  27 synthetic

Compound C40, C ₆ F ₆ , DMI (N, N`-dimethylimidazolidinone) was added to Schlenk tube and substituted with N ₂ . Pd (OAc) ₂ , 2-nitropyridine, PhCO ₂ -O ^t Bu was added slowly and stirred at 90 ° C. for 5 hours to obtain compd 27, the target compound.

Elemental Analysis: C, 85.70; H, 4.11; N, 4.76; O, 5.44

HRMS [M] ⁺ : 588

[ Synthetic example  11] Compd  30 synthetic

Step  1. Compound C41  synthesis

Compound C41 was obtained by coupling the compound C2 with 2- (3-bromophenyl) -1-phenyl benzoimidazole.

Step  2. Compound C42  synthesis

Compound C42 was obtained by Suzuki coupling 3 equivalents of Compound C41 and 2-Hydroxy phenyl boronic acid.

Step  3. Compd  30 synthetic

Compound C42, C ₆ F ₆ , DMI (N, N`-dimethylimidazolidinone) was added to Schlenk tube and substituted with N ₂ . Pd (OAc) ₂ , 2-nitropyridine, PhCO ₂ -O ^t Bu was added slowly and stirred at 90 ° C. for 5 hours to obtain compd 30, the target compound.

Elemental Analysis: C, 83.88; H, 4.09; N, 6.83; O, 5.20

HRMS [M] ⁺ : 615

[ Synthetic example  12] Compd  Synthesis of 31

Step  1. Compound C43  synthesis

Compound C43 was obtained by coupling the compound C2 with 2- (3-bromophenyl) -1-phenyl-1H-benzoimidazole.

Step  2. Compound C44  synthesis

Compound C44 was obtained by Suzuki coupling the compound C43 and Methylsulfanylbenzene-2-boronic acid.

Step  3. Compound C45  synthesis

Compound C44 was added to AcOH at room temperature. AgOAc and PdCl ₂ were slowly added thereto, followed by heating and stirring for 5 hours to obtain compound C45.

Step  4. Compound C46  synthesis

Compound C46 was obtained by Suzuki coupling the compound C45 and 2-hydroxy phenylboronic acid.

Step  5. Compd  31 synthetic

Compound C46, C ₆ F ₆ , DMI (N, N`-dimethylimidazolidinone) was added to Schlenk tube and substituted with N ₂ . Pd (OAc) ₂ , 2-nitropyridine, PhCO ₂ -O ^t Bu was added slowly and stirred at 90 ° C. for 4 hours to obtain compd 31 as the target compound.

Elemental Analysis: C, 81.75; H, 3.99; N, 6.65; 0, 2.53; S, 5.08

HRMS [M] ⁺ : 631

[ Synthetic example  13] Compd  Synthesis of 35

Step  1. Compound C47  synthesis

Compound C47 was obtained by coupling the compound C6 with (3- (methylthio) pyridin-2-yl) boronic acid.

Step  2. Compd  35 synthetic

Compound C47 was added to AcOH at room temperature. AgOAc and PdCl ₂ were slowly added thereto, and the mixture was heated and stirred for 4 hours to obtain compd 35, a target compound.

Elemental Analysis: C, 81.53; H, 4.11; N, 8. 15; S, 6.22

HRMS [M] ⁺ : 515

[ Synthetic example  14] Compd  Synthesis of 46

Step  1. Compound C48  synthesis

Compound C48 was obtained by coupling the compound C2 with 1-bromopyrene.

Step  2. Compound C49  synthesis

Compound C49 was obtained by coupling the compound C48 with 2-Nitro phenyl boronic acid.

Step  3. Compound C50  synthesis

Compound C49 was added to 1.2-dichlorobenzene at room temperature. Triphenyl phosphine was slowly added thereto and heated and stirred for 6 hours to obtain compound C50.

Step  4. Compound C51  synthesis

Compound C51 was obtained by coupling the compound C50 and 2-bromonaphthalene.

Step  5. Compound C52  synthesis

Compound C52 was obtained by coupling the compound C51 with Methylsulfanylbenzene-2-boronic acid.

Step  6. Compd  46 synthetic

Compound C52 was added to AcOH at room temperature. AgOAc and PdCl ₂ were slowly added thereto, and the mixture was heated and stirred for 5 hours to obtain compd 46 as a target compound.

Elemental Analysis: C, 87.04; H, 4. 34; N, 4.02; S, 4.60

HRMS [M] ⁺ : 688

[ Synthetic example  15] Compd  56 composites

Step  1. Compound C53  synthesis

Compound C53 was obtained by coupling the compound C2 with 2-bromonaphthalene.

Step  2. Compound C54  synthesis

Compound C54 was obtained by the same process as Steps 4 and 5 of Synthesis Example 1, except that Compound C53 was used instead of Compound C3.

Step  3. Compound C55  synthesis

Compound C55 was obtained by coupling the compound C54 with 2-bromo spirobifluorene.

Step  4. Compound C56  synthesis

Compound C56 was obtained by Suzuki coupling the compound C55 and Methylsulfanylbenzene-2-boronic acid.

Step  5. Compd  56 synthetic

Compound C56, C ₆ F ₆ , DMI (N, N`-dimethylimidazolidinone) was added to the Schlenk tube and substituted with N ₂ . Pd (OAc) ₂ , 2-nitropyridine, PhCO ₂ -O ^t Bu was added slowly and stirred at 90 ° C. for 5 hours to obtain compd 56, the target compound.

Elemental Analysis: C, 88.12; H, 4. 47; N, 3.45; S, 3.95

HRMS [M] ⁺ : 802

 [ Example  1 to 15] green organic Field  Fabrication of light emitting device

Compounds synthesized above (Synthesis Example 1-15) were subjected to high purity sublimation purification by a conventionally known method, and then green organic EL devices were manufactured according to the following procedure.

First, a glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1500 Å was washed with distilled water ultrasonic waves. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

M-MTDATA (60 nm) / TCTA (80 nm) / Synthesis Examples 1-15 + 10% Ir (ppy) ₃ (300nm) / BCP (10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm) was laminated in order to fabricate an organic EL device.

[ Comparative Example  One]

A green organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of compd 2 of Synthesis Example 1 as a light emitting host material when forming the emission layer.

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ , CBP, and BCP used in Examples 1 to 15 and Comparative Example 1 are as follows.

[ Evaluation example  One]

For each of the green organic electroluminescent devices fabricated in Examples 1 to 15 and Comparative Example 1, the driving voltage, current efficiency, and emission (EL) peak at a current density of 10 mA / cm 2 were measured, and the results are shown in Table 1 below. Shown in

Sample Host The driving voltage (V) EL peak (nm) Current efficiency (cd / A) Example 1 Compd 2 6.63 515 41.3 Example 2 Compd 4 6.55 520 40.4 Example 3 Compd 5 6.71 519 40.9 Example 4 Compd 7 6.70 519 41.7 Example 5 Compd 9 6.77 516 42.0 Example 6 Compd 11 6.30 515 40.8 Example 7 Compd 14 6.57 511 41.1 Example 8 Compd 26 6.81 517 40.2 Example 9 Compd 25 6.79 521 41.3 Example 10 Compd 27 6.86 515 41.5 Example 11 Compd 30 6.89 514 40.4 Example 12 Compd 31 6.91 516 41.2 Example 13 Compd 35 6.76 514 41.5 Example 14 Compd 46 6.84 514 42.3 Example 15 Compd 56 6.81 518 40.9 Comparative Example 1 CBP 6.93 516 38.2

As shown in Table 1, when the compound according to the present invention is used as the light emitting layer of the green organic electroluminescent device (Examples 1 to 15), the current efficiency is higher than that of the conventional green organic electroluminescent device (Comparative Example 1) using CBP. And it can be seen that the excellent performance in terms of driving voltage.

[ Example  16 ~ 30] Blue Organic Field  Manufacturing of light emitting device

After the high purity sublimation purification of the compound synthesized above (Synthesis Example 1-15) by a commonly known method, a blue organic EL device was manufactured according to the following procedure.

First, a glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1500 Å was washed with distilled water ultrasonic waves. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

CuPc (10 nm) / TPAC (30 nm) / Synthesis Examples 1 to 15 + 7% Flrpic (30 nm) / Alq ₃ (30 nm) / LiF (0.2 nm) / Al (150 nm) on the thus prepared ITO transparent electrode The organic electroluminescent device was manufactured by laminating with.

[ Comparative Example  2]

A blue organic electroluminescent device was manufactured in the same manner as in Example 16, except that CBP was used instead of compd 2 of Synthesis Example 1 as a light emitting host material.

The structures of CuPc, TPAC and Flrpic used in Examples 16 to 30 and Comparative Example 2 are as follows.

[ Evaluation example  2]

For each of the blue organic electroluminescent devices fabricated in Examples 16 to 30 and Comparative Example 2, the driving voltage, current efficiency, and emission (EL) peak at a current density of 10 mA / cm 2 were measured, and the results are shown in Table 2 below. Shown in

Sample Host The driving voltage (V) EL peak (nm) Current efficiency (cd / A) Example 16 Compd 2 7.31 471 5.85 Example 17 Compd 4 7.13 473 5.86 Example 18 Compd 5 7.21 475 6.31 Example 19 Compd 7 7.27 475 5.88 Example 20 Compd 9 7.25 474 6.21 Example 21 Compd 11 7.21 477 6.11 Example 22 Compd 14 7.26 475 5.84 Example 23 Compd 26 7.25 476 5.98 Example 24 Compd 25 7.31 476 6.09 Example 25 Compd 27 7.21 478 6.03 Example 26 Compd 30 7.23 479 6.22 Example 27 Compd 31 7.15 471 6.12 Example 28 Compd 35 7.23 473 6.23 Example 29 Compd 46 7.24 475 5.97 Example 30 Compd 56 6.81 518 6.90 Comparative Example 2 CBP 7.80 474 5.80

As shown in Table 2, when the compound according to the present invention is used as the light emitting layer of the blue organic electroluminescent device (Examples 16 to 30), the current efficiency compared to the blue organic electroluminescent device (Comparative Example 2) using the conventional CBP And it can be seen that the excellent performance in terms of driving voltage.

Claims (6)

A compound represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
Y ₁ to Y ₃ One is N and the other is N, O or S, wherein the number of N is 2 or less,
Each ring including X ₁ to X ₃ is independently an aryl group having ₆ to ₄₀ carbon atoms or a heteroaryl group having 5 to 40 nuclear atoms,
R ₁ To R ₃ are each independently, hydrogen, deuterium, a cyano group, an aryloxy group of C ₆ ~ C ₄₀ aryl group, nuclear atoms aryl of from 5 to 40 heteroaryl _{group, C 6 ~ C 40, C} 1 ~ C 40 Is selected from the group consisting of an alkyl group, C ₁ to C ₄₀ alkyloxy group, C ₆ to C ₆₀ arylamine group, C ₃ to C ₄₀ cycloalkyl group, and a nuclear atom having 3 to 40 heterocycloalkyl group,
a, b and c are each an integer of 0 or 1. The method of claim 1,
The compound represented by Formula 1 is selected from the group consisting of compounds represented by the following formula C-1 to C-5.

In Formulas C-1 to C-5, R ₁ and R ₂ are the same as defined in claim 1. The method of claim 1,
The R ₁ R ₃ to R ₃ are each independently selected from hydrogen, an aryl group having ₆ to ₄₀ carbon atoms and a heteroaryl group having 5 to 40 nuclear atoms. The method of claim 1,
The R ₁ To the R ₃ heavy hydrogen, a cyano group, an aryl group, a heteroaryl group, an aryloxy group, an alkyl group, an alkyloxy group, an arylamine group, a cycloalkyl group and a heterocycloalkyl group are, each independently, a heavy hydrogen, C ₁ ~ C ₄₀ of alkyl group, C ₁ ~ C ₄₀ alkyloxy group of, C ₃ ~ C ₄₀ cycloalkyl group, C ₆ ~ C ₄₀ aryl group, C ₆ ~ C ₄₀ of the aryloxy group, the number of nuclear atoms of 5 to 40 heteroaryl group , C ₆ ~ C ₆₀ An arylamine group and a heterocyclic alkyl group of 3 to 40 nuclear atoms, characterized in that substituted with one or more selected from the group consisting of. An organic electroluminescent device comprising an anode, a cathode, and at least one organic material layer interposed between the anode and the cathode,
At least one of the organic layer is an organic electroluminescent device comprising the compound according to any one of claims 1 to 4. 6. The method of claim 5,
An organic material layer comprising the compound according to any one of claims 1 to 4 is an emission layer, an electron transport layer or a hole transport layer.