KR20110032373A - Novel anthracene derivative and organic electroluminescence device using the same - Google Patents

Abstract

PURPOSE: A novel anthracene derivative is provided to ensure excellent luminous efficiency, brightness, power efficiency, driving voltage and lifetime according to the increase of electron transport ability. CONSTITUTION: A novel anthracene derivative is represented by chemical formula 1. In chemical formula 1, Z^1 - Z^5 are C or N; Ar^1 and Ar^2 are hydrogen, deuterium, substituted or unsubstituted C6~60 aromatic group; X^1 and X^2 are hydrogen, deuterium, substituted or unsubstituted C6~60 aromatic group, substituted or unsubstituted C5~60 aromatic heterocycle, substituted or unsubstituted C1~60 alkyl, substituted or unsubstituted C3~60 cycloalkyl, substituted or unsubstituted C1~60 alkoxy, substituted or unsubstituted C3~60 cycloalkyl, substituted or unsubstituted C1~60 alkyloxy, substituted or unsubstituted C5~60 aryloxy, and substituted or unsubstituted C5~60 heteroaryl; a and b are integers of 0~4; and n is an integer of 1~3.

Description

Novel anthracene derivative and organic electroluminescent device using the same {NOVEL ANTHRACENE DERIVATIVE AND ORGANIC ELECTROLUMINESCENCE DEVICE USING THE SAME}

The present invention relates to an anthracene derivative and an organic electroluminescent device using the same, and more particularly, heteroaryl group containing N (nitrogen), non-limiting examples such as pyridinyl group, pyrazinyl group, pyrimidinyl group, or Novel anthracene derivatives in which a pyridazinyl group and the like are substituted with an anthracene moiety; And an organic material layer containing the anthracene derivative (preferably a light emitting layer in which the anthracene derivative of the present invention is contained as a green and / or blue light emitting material) is interposed between the anode and the cathode so that luminous efficiency, brightness, thermal stability, driving The present invention relates to an organic EL device having improved characteristics such as voltage and lifetime.

Currently, organic electroluminescent devices (organic EL devices) have excellent characteristics such as low driving voltage, wide viewing angle, high-speed response, and high contrast compared to plasma display panel (PDP) or inorganic electroluminescent device display. It can be used as a pixel of a graphic display, as a pixel of a television image display or a surface light source. The device can be formed on a bendable transparent substrate, can be made very thin and light, and has good color, which is emerging as a suitable device for the next generation flat panel display. In 1987, Eastman Kodak developed for the first time an organic EL device using a low molecular aromatic diamine and an aluminum complex as a material for forming a light emitting layer.

When a forward voltage is applied to the device, holes and electrons are injected from the anode and the cathode, respectively, and they are recombined in the emission layer to form an exciton, an electron-hole pair. Excitons, whose structures are excited by the pi-electron excited state, return to the ground and convert their energy into light.

Recently, a method of doping a small amount of fluorescent dyes or phosphorescent dyes to the light emitting layer forming the exciton in order to increase the color purity and efficiency of the light emitted is known. The principle is that when a small amount of fluorescent or phosphorescent dye (hereinafter, referred to as 'dopant') in the light emitting layer is mixed with a smaller energy band gap than the molecules forming the light emitting layer, excitons generated in the light emitting layer are transferred to the dopant, thereby providing high efficiency light. It is a principle to pay.

Diphenylvinylbiphenyl of idemis-high acid (4,4'-bis (2,2-diphenylvinyl) biphenyl), dinaphthylanthracen of Eastman Kodak, tetra (tibutyl) perylene (tetra (t- The butyl) perlyene) system is widely known as a blue material, and much research and development is still in progress. Although the system of Idemitsu high acid distrile compound, which is known to be the most efficient to date, has a device life of more than 30,000 hours, its lifetime is only a few thousand hours when applied to a full color display due to the deterioration of color purity according to the driving time. Do. Therefore, it is an urgent part to research and develop a material having good color purity (high blue color), high efficiency, and excellent thermal stability.

The present invention is a novel anthracene in which a heteroaryl group (for example, pyridinyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, etc.) containing N (nitrogen) is substituted with anthracene, unlike the existing anthracene aryl derivatives. It is aimed at the development of derivatives. In addition, an object of the present invention is to provide an organic electroluminescent device having improved luminous efficiency, brightness, low voltage driving, and excellent thermal stability by applying the anthracene derivative as a material of an organic layer, preferably a light emitting layer in the device. .

The present invention provides a compound, preferably an anthracene derivative represented by the following formula (1) to solve the problems described above.

[Formula 1]

In Chemical Formula 1, Z ¹ to Z ⁵ are the same as or different from each other, and each independently C or N, and at least one of Z ¹ to Z ⁵ is N;

Ar ¹ and Ar ² are the same as or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted C ₆ -C ₆₀ aromatic group;

X ¹ and X ² are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C ₆ ~ C ₆₀ aromatic group, a substituted or unsubstituted C ₅ ~ C ₆₀ aromatic heterocyclic group, substituted or unsubstituted A substituted C ₁ to C ₆₀ alkyl group, a substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group, a substituted or unsubstituted C ₁ to C ₆₀ alkoxy group, a substituted or unsubstituted C ₆ to C ₆₀ aryl Alkyl group, substituted or unsubstituted C ₁ to C ₆₀ alkyloxy group, substituted or unsubstituted C ₅ to C ₆₀ aryloxy group, substituted or unsubstituted C ₅ to C ₆₀ aryl group, or substituted or unsubstituted Ring C ₅ ~ C ₆₀ Heteroaryl group;

a and b are the integers of 0-4 each independently, and n is an integer of 1-3.

In Ar ¹ , Ar ² , X ¹ and X ² of Formula 1, a substituted or unsubstituted C ₆ ~ C ₆₀ aromatic group, a substituted or unsubstituted C ₅ ~ C ₆₀ aromatic heterocyclic group, substituted or unsubstituted A C ₁ to C ₆₀ alkyl group, a substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group, a substituted or unsubstituted C ₁ to C ₆₀ alkoxy group, a substituted or unsubstituted C ₆ to C ₆₀ arylalkyl group , Substituted or unsubstituted C ₁ ~ C ₆₀ alkyloxy group, substituted or unsubstituted C ₅ ~ C ₆₀ aryloxy group, substituted or unsubstituted C ₅ ~ C ₆₀ aryl group, or substituted or unsubstituted The above substitution of the C ₅ to C ₆₀ heteroaryl group is independently deuterium, halogen, nitrile group, nitro group, C ₁ to C ₆₀ alkyl group, C ₂ to C ₆₀ alkenyl group, C ₁ to C ₆₀ An alkoxy group, a C ₁ to C ₆₀ amino group, a C ₃ to C ₆₀ cycloalkyl group, a C ₃ to C ₆₀ heterocycloalkyl group, a C ₆ to C ₆₀ aryl group, or a C ₅ to C ₆₀ heteroaryl group Substituted Or, and the like.

In addition, the present invention, the anode; cathode; And one or more organic material layers interposed between the anode and the cathode.

At least one of the at least one organic material layer provides an organic electroluminescent device, characterized in that the organic material layer containing a compound represented by the formula (1) according to the present invention.

In the organic electroluminescent device of the present invention, the organic material layer including the compound represented by Chemical Formula 1 is preferably a light emitting layer.

When the compound represented by Chemical Formula 1 of the present invention is adopted as a light emitting layer material of an organic EL device, light emission efficiency, luminance, power efficiency, driving voltage and It exhibits excellent characteristics in terms of lifespan, and therefore has a great effect in maximizing performance and improving lifetime in full color organic EL panels.

Compound represented by the formula (1) of the present invention is a heteroaryl group containing N (nitrogen), non-limiting examples, such as pyridinyl (pyridinyl), pyrazinyl group, pyrimidinyl group, pyrimidin A pyridazinyl group and the like are anthracene derivatives substituted with an anthracene moiety. The compound represented by Formula 1 of the present invention is a material having green and / or blue light emitting ability, and may be used as a material of an organic material layer of an organic electroluminescent device, preferably a material of a light emitting layer, and more preferably a host material of a light emitting layer. .

The compounds represented by Formula 2 below are representative examples of the compound represented by Formula 1 of the present invention, but the compound represented by Formula 1 of the present invention is not limited to those illustrated below.

[Formula 2]

Hereinafter, the structure of the organic electroluminescent element of this invention is demonstrated.

The organic electroluminescent device (hereinafter referred to as 'organic EL device') of the present invention comprises an anode; cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is an organic material layer comprising the compound represented by Formula 1 according to the present invention. Is characteristic.

As a typical element structure of the organic electroluminescent element of this invention, (1) anode / light emitting layer / cathode; (2) anode / hole injection layer / light emitting layer / cathode; (3) anode / light emitting layer / electron injection layer / cathode; (4) anode / hole injection layer / light emitting layer / electron injection layer / cathode; (5) anode / organic semiconductor layer / light emitting layer / cathode; (6) anode / organic semiconductor layer / electron barrier layer / light emitting layer / cathode; (7) anode / organic semiconductor layer / light emitting layer / adhesion improving layer / cathode; (8) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode; (9) anode / insulating layer / light emitting layer / insulating layer / cathode; (10) anode / inorganic semiconductor layer / insulating layer / light emitting layer / insulating layer / cathode; (11) anode / organic semiconductor layer / insulating layer / light emitting layer / insulating layer / cathode; (12) anode / insulation layer / hole injection layer / hole transport layer / light emitting layer / insulation layer / cathode; Or (13) an anode / insulating layer / hole injection layer / hole transporting layer / light emitting layer / electron injection layer / cathode. Although the structure of (8) is normally used preferably among these, it is not limited to this.

In the organic EL device of the present invention, the light emitting layer contains a host material. It is preferable that the said host material contains the organic electroluminescent element material of this invention, ie, the compound represented by the said General formula (1), and it is still more preferable that the said host material consists of the organic electroluminescent element material of this invention. As such, when the light emitting layer contains the compound represented by Chemical Formula 1, the electron transport ability is increased, so that the electron and the electron make a better bond in the light emitting layer, so that the light emitting efficiency is not only excellent, but also the luminance, power efficiency, driving voltage, and lifetime characteristics. It is also possible to provide an improved organic EL device.

As the method for forming the light emitting layer in the present invention, a known method such as a vapor deposition method, a spin coating method, or an LB method can be applied.

In addition, other well-known light emitting materials (for example, PVK, PPV, CBP, Alq, BAlq, a known complex, etc.) other than the material for organic electroluminescent elements of this invention are provided in the range which does not impair the objective of this invention. It can also be mixed in a light emitting layer.

The organic EL device of the present invention may be provided with a hole injection layer having a thickness of 5 nm to 5 mu m. When the hole injection layer is provided, the hole injection into the light emitting layer becomes good, so that high light emission luminance can be obtained or low voltage driving can be performed. In addition, in such a hole injection layer, the hole mobility measured when a voltage in the range of 1 × 10 ⁴ to 1 × 10 ⁶ V / cm is applied is 1 × 10 ⁻⁶ cm 2 / V · sec or more, and ionization energy is 5.5. Preference is given to using compounds which are below eV.

Examples of such a hole injection layer material include a porphyrin compound, an aromatic tertiary amine compound, a styrylamine compound, an aromatic dimethylidine compound and a condensed aromatic ring compound. (1-naphthyl) -N-phenylamino] biphenyl (commonly referred to as' NPD ') and 4,4', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine ( Organic compounds such as commonly referred to as 'MTDATA', etc. Also, in some cases, it is more preferable to stack two or more hole injection layers, in which case the anode / hole injection layer 1 (hole injection material 1). ) / Hole injection layer 2 (hole injection material 2) /.../ When stacked in the order of the light emitting layer, the ionization energy Ip of the hole injection material is Ip (hole injection material 1) <Ip (hole injection material 2) Satisfying the relationship is in reducing the drive voltage of the device. It is preferable to come.

It is also preferable to use an inorganic compound such as p-type Si or p-type SiC as a constituent of the hole injection layer. It is also preferable to provide an organic semiconductor layer having a conductivity of 1 × 10 ⁻¹⁰ s / cm or more between the hole injection layer and the anode, or between the hole injection layer and the light emitting layer. By providing such an organic semiconductor layer, hole injection into the light emitting layer becomes better.

The organic EL device of the present invention may be provided with an electron injection layer having a thickness of 5 nm to 5 mu m. When such an electron injection layer is provided, electron injection into the light emitting layer becomes good, so that high light emission luminance can be obtained or low voltage driving can be performed. In addition, in such an electron injection layer, the electron mobility measured when a voltage in the range of 1 × 10 ⁴ to 1 × 10 ⁶ V / cm is applied is 1 × 10 ⁻⁶ cm 2 / V · sec or more and the ionization energy is 5.5. Preference is given to using compounds exceeding eV. As an example of such an electron injection layer material, the metal complex of 8-hydroxyquinoline (Al chelate: Alq) or its derivative (s), an oxadiazole derivative, etc. are mentioned. In addition, incorporation of an alkali metal into the electron injection layer can significantly reduce the voltage and extend the life.

In the organic EL device of the present invention, a hole barrier layer having a thickness of 5 nm to 5 m can be provided between the light emitting layer and the cathode. By providing such a hole barrier layer, the performance of confining holes in the organic light emitting layer is improved, so that high emission luminance is obtained or low voltage driving is possible.

Examples of such hole barrier layers are 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and 2,9-diethyl-4,7-diphenyl-1,10-phenanthroline Although an alkali metal, for example, Li or Cs is contained further, it is preferable. As described above, incorporation of an alkali metal into the material for the hole barrier layer can significantly reduce the voltage for driving the organic EL element and at the same time extend the life of the element. On the other hand, when the alkali metal is contained, the content thereof is preferably 0.01 to 30% by weight, more preferably 0.05 to 20% by weight, even more preferably 0.1 when the total amount of the hole barrier layer is defined as 100% by weight. To 15% by weight. The reason is that when the content of the alkali metal is 0.01% by weight or more, the effect of adding the alkali metal is exerted, whereas when the content is 30% by weight or less, the dispersibility of the alkali metal is uniform and the luminescence brightness does not change.

In the present invention, as the method for forming the hole injection layer, the electron injection layer or the hole barrier layer, a known method such as a vapor deposition method, spin coating method or LB method can be applied.

In the organic EL device of the present invention, it is preferable that a reducing dopant is added to the interface region between the cathode and the organic thin film layer. Examples of the reducing dopant include at least one selected from alkali metals, alkali metal complexes, alkali metal compounds, alkaline earth metals, alkaline earth metal complexes, alkaline earth metal compounds, rare earth metals, rare earth metal complexes, rare earth metal compounds, and halogen compounds and oxides thereof. Can be mentioned.

Examples of the alkali metal include Li (work function: 2.93 eV), Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), Cs (work function: 1.95 eV), and the like. And alkali metals having a work function of 3.0 eV or less are particularly preferable. Of course, Li, K, Rb and Cs are preferred.

Examples of the alkaline earth metal include Ca (work function: 2.9 eV), Sr (work function: 2.0 to 2.5 eV), Ba (work function: 2.52 eV), and the like. desirable.

Examples of the rare earth metal include Sc, Y, Ce, Tb and Yb, and a rare earth metal having a work function of 3.0 eV or less is particularly preferable.

Preferred metals among the above metals have particularly high reducing ability, and therefore, by adding a relatively small amount of metal to the electron injection region, the light emission intensity of the organic EL device can be improved and the life can be extended.

Examples of the alkali metal compound include alkali oxides such as Li ₂ O, Cs ₂ O or K ₂ O, and alkali halides such as LiF, NaF, CsF or KF, and the like, and examples thereof include LiF, Li ₂ O or NaF. Alkali oxides or alkali fluorides are preferred.

Examples of the alkaline earth metal compound include BaO, SrO, CaO, and mixtures thereof, such as Ba _x Sr _1-x O (0 <x <1) and Ba _x Ca _1-x O (0 <x <1) and the like. These include BaO, SrO and CaO.

Examples of the rare earth metal compound include YbF ₃ , ScF ₃ , ScO ₃ , Y ₂ O ₃ , Ce ₂ O ₃ , GdF ₃ and TbF ₃ , and among these, YbF ₃ , ScF ₃ and TbF ₃ are preferable.

The alkali metal complex, alkaline earth metal complex and rare earth metal complex are not particularly limited as long as they each contain one or more alkali metal ions, alkaline earth metal ions and rare earth metal ions as metal ions. In addition, preferred examples of the ligand include quinolinol, benzoquinolinol, akyridinol, phenantridinol, hydroxyphenyl oxazole, hydroxyphenyl thiazole, hydroxy diaryl oxadiazole, and hydroxy diaryl thiazole. , Hydroxyphenylpyridine, hydroxyphenylbenzoimidazole, hydroxybenzotriazole, hydroxyflubolane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, β-diketones, azomethines , And derivatives thereof, and the like, but are not limited thereto.

As a form of addition of the reducing dopant, it is preferable that the reducing dopant is formed in a layered or island shape in the interface region. As a preferable formation method, there is a method of dispersing a reducing dopant in an organic material by depositing a reducing dopant by a resistive heating deposition method and simultaneously depositing an organic material which is a light emitting material or an electron injection material that forms an interface region. The dispersion concentration as the molar ratio of organic compound: reducing dopant is 100: 1 to 1: 100, preferably 5: 1 to 1: 5.

In the case of forming the reducing dopant in the form of a layer, after forming the light emitting material or the electron injecting material serving as the organic layer in the interface in the form of a layer, the reducing dopant is deposited by resistive heating evaporation alone, preferably 0.05 to 1 nm. Form an island with a thickness.

The anode in the organic EL device of the present invention corresponds to the lower electrode or the counter electrode depending on the structure of the organic EL display device, but is a metal, alloy, or electrically conductive compound having a large (for example, 4.0 eV or more) work function. Or a mixture thereof is preferably used for the positive electrode. Specifically, electrode materials such as indium tin oxide (ITO), indium zinc oxide (IZO), copper iodide (CuI), tin oxide (SnO ₂ ), zinc oxide (ZnO), gold, platinum, palladium and the like are used alone. Or it is preferable to use these electrode materials in combination of 2 or more type. By using such an electrode material, a method capable of forming a film in a dry state such as vacuum deposition, sputtering, ion plating, electron beam deposition, chemical vapor deposition (CVD), metal oxide chemical vapor deposition (MOCVD), or plasma CVD It can be used to form a positive electrode having a uniform thickness.

On the other hand, when extracting EL light emission from an anode, it is necessary to make the anode into a transparent electrode. In such a case, it is preferable to use a conductive transparent material such as ITO, IZO, CuI, SnO ₂ or ZnO so that the transmittance value of EL light emission is 70% or more.

Further, the thickness of the anode is not particularly limited either, but these thickness values are preferably in the range of 10 to 1,000 nm, more preferably in the range of 10 to 200 nm. The reason is that when the thickness of the anode has a value within this range, a uniform film thickness distribution and transmittance of EL light emission of 70% or more are obtained, while the sheet resistance value is preferably 1,000 Ω / A or less, more preferably. This is because it can be kept below 100 Ω / A.

On the other hand, the anode (lower electrode), the organic light emitting medium, and the cathode (counter electrode) are sequentially provided, and the lower electrode and the counter electrode are configured in an XY matrix shape to emit any pixel in the light emitting surface. That is, by forming an anode or the like as described above, various information can be easily displayed in the organic EL element.

In addition, the cathode in the organic EL device of the present invention also corresponds to the lower electrode or the counter electrode depending on the structure of the organic EL device, but has a small (for example, less than 4.0 eV) metal, alloy, or electrical conductivity. Preference is given to using the compounds or mixtures thereof or inclusions containing them. Specifically, sodium, sodium-potassium alloys, cesium, magnesium, lithium, magnesium-silver alloys, aluminum, aluminum oxide, aluminum-lithium alloys, indium, and rare earth metals; Mixtures of these metals and materials for organic thin film layers; And it is preferable to use the electrode material which consists of a mixture of these metals and the material for an electron injection layer alone, or to use these electrode materials in combination of 2 or more types.

Further, the film thickness of the cathode is not particularly limited as in the case of the anode, but the film thickness of the cathode is preferably in the range of 10 to 1,000 nm, more preferably in the range of 10 to 200 nm. In addition, in the case of drawing the EL light emission from the cathode, the cathode should be a transparent electrode, and in such a case, it is preferable that the transmittance value of the EL light emission is 70% or more. In the case of the cathode, on the other hand, as in the case of the anode, it is preferable to form the cathode by using a method capable of film formation in a dry state such as vacuum deposition or sputtering.

It is preferable that the support substrate in the organic electroluminescent element of this invention is excellent in mechanical strength, and has little water and oxygen permeability. Specific examples of such support substrates include glass sheets, metal sheets, ceramic sheets and plastic sheets (eg, polycarbonate resins, acrylic resins, vinyl chloride resins, polyethylene terephthalate resins, polyimide resins, polyester resins, epoxy resins, A sheet made of a phenol resin, a silicone resin, a fluororesin, or the like). In addition, it is preferable that the supporting substrate made of these materials is further formed with an inorganic film on the supporting substrate or coated with a fluorine resin to provide moisture proof or hydrophobic treatment in order to prevent moisture from entering the organic EL element. In addition, in order to prevent the ingress of moisture into the organic thin film layer, it is particularly desirable to reduce the moisture content and the gas permeability coefficient in the support substrate. Specifically, the water content and gas permeability coefficient of the support substrate are preferably 0.0001 wt% or less and 1 × 10 ⁻¹ Pa · cm / cm 2 · sec · cmHg or less, respectively.

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the present invention and the present invention is not limited by the following examples.

Synthesis Example 1 Preparation of 5-bromo-2- (naphthalen-1-yl) pyridine

2,5-dibromopyridine (82.6 g, 348.7 mmol) and naphthalen-1-ylboronic acid (50.0 g, 290.6 mmol) were dissolved in 800 mL of toluene and Pd (PPh ₃ ) ₄ (10.1 g, 8.7 mmol) was added under nitrogen. . And Na ₂ CO ₃ (92.4 g, 871.7 mmol) was dissolved in 240 mL of distilled water was added. And additional EtOH (240 mL) was added. The reaction solution was stirred at reflux for 5 hours. After the reaction was terminated and extracted using dichloromethane and distilledwater, and was filtered through a thin silica gel pad to remove the palladium. The organic solvent layer was distilled under reduced pressure to almost remove the solvent, followed by filtration to obtain a brown solid product. The filtrate was dissolved in a small amount of dichloromethane and then cooled to recrystallization and filtered to give a white solid (74.5 g, 91% yield).

¹ H NMR: 7.35 (m, 3H), 7.71 (t, 2H), 7.83 (d, 2H), 8.10 (d, 1H), 8.49 (t, 1H), 8.81 (s, 1H).

Synthesis Example 2 Preparation of 2- (naphthalen-1-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine

5-bromo-2- (naphthalen-1-yl) pyridine (64.5 g, 227.8 mmol), Bis (pinacolate) diboron (69.4 g, 273.4 mmol), CH ₃ COOK (67.1 g, 683.5 mmol) After dissolving in 1000 mL of dioxane, Pd (dppf) Cl ₂ (5.0 g, 0.8 mmol) was added under nitrogen. The reaction solution was stirred at reflux for 12 hours. After the reaction was terminated and extracted using dichloromethane and distilledwater, and filtered through a thin pad of silica gel to remove palladium. The organic solvent layer was distilled under reduced pressure to almost remove the solvent, followed by filtration to obtain a brown solid product. The filtrate was dissolved in a small amount of dichloromethane and then silicacolumn to give a light brown solid (67.9 g, yield 90%).

¹ H NMR: 1.31 (s, 12H), 7.36 (m, 3H), 7.46 (t, 2H), 7.78 (d, 2H), 8.06 (d, 1H), 8.47 (t, 1H), 8.55 (s, 1H).

Synthesis Example 3 Preparation of 2-bromo-6- (naphthalen-1-yl) pyridine

2,6-dibromopyridine (82.6 g, 348.7 mmol) and naphthalen-1-ylboronic acid (50.0 g, 290.6 mmol) were dissolved in 800 mL of toluene and Pd (PPh ₃ ) ₄ (10.1 g, 8.7 mmol) was added under nitrogen. . And Na ₂ CO ₃ (92.4 g, 871.7 mmol) was dissolved in 240 mL of distilled water was added. And additional EtOH (240 mL) was added. The reaction solution was stirred at reflux for 5 hours. After the reaction was terminated and extracted using dichloromethane and distilledwater, and was filtered through a thin silica gel pad to remove the palladium. The organic solvent layer was distilled under reduced pressure to almost remove the solvent, followed by filtration to obtain a brown solid product. The filtrate was dissolved in a small amount of dichloromethane and then cooled down to recrystallize and filtered to give a white solid (71.5 g, 87% yield).

¹ H NMR: 7.33 (m, 4H), 7.58 (m, 4H), 8.01 (d, 1H), 8.47 (d, 1H).

Synthesis Example 4 Preparation of 2- (naphthalen-1-yl) -6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine

2-bromo-6- (naphthalen-1-yl) pyridine (64.5 g, 227.8 mmol), Bis (pinacolate) diboron (69.4 g, 273.4 mmol), CH ₃ COOK (67.1 g, 683.5 mmol) After dissolving in 1000 mL of dioxane, Pd (dppf) Cl ₂ (5.0 g, 0.8 mmol) was added under nitrogen. The reaction solution was stirred at reflux for 12 hours. After the reaction was terminated and extracted using dichloromethane and distilledwater, and filtered through a thin pad of silica gel to remove palladium. The organic solvent layer was distilled under reduced pressure to almost remove the solvent, followed by filtration to obtain a brown solid product. The filtrate was dissolved in a small amount of dichloromethane and silicacolumn to give a light brown solid (60.4 g, yield 80%).

¹ H NMR: 1.34 (s, 12H), 7.12 (t, 1H), 7.31 (m, 2H), 7.51 (m, 5H), 8.05 (d, 1H), 8.45 (d, 1H).

Example 1 Preparation of Inv-1

9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2- (naphthalen-1-yl) -5- (4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl) pyridine (10.4 g, 31.4 mmol) was dissolved in 200 mL of toluene and Pd (PPh ₃ ) ₄ (0.6 g, 0.5 mmol) was added under nitrogen. And Na ₂ CO ₃ (8.3 g, 78.5 mmol) was dissolved in 100 mL of distilled water was added. The reaction solution was stirred at reflux for 6 hours. After the reaction was terminated and extracted using dichloromethane and distilledwater, and was filtered through a thin silica gel pad to remove the palladium. The organic solvent layer was distilled under reduced pressure to almost remove the solvent, followed by filtration to obtain a brown solid product. The filtrate was dissolved in a small amount of dichloromethane and silicacolumn to give a pale yellow solid (10.9 g, yield 82%).

¹ H NMR: 7.37 (t, 2H), 7.38 (t, 2H), 7.48 (dd, 2H), 7.52 (t, 2H), 7.58 (d, 1H), 7.62 (m, 4H), 7.71 (d, 2H), 7.81 (m, 4H), 7.98 (m, 4H), 8.53 (t, 1H), 8.85 (d, 1H); FD-MS: m / z 508 (M ⁺ ).

Example 2 Preparation of Inv-3

9-bromo-10-phenylanthracene (9.0 g, 27.1 mmol), 2- (naphthalen-1-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) Pyridine (10.8 g, 32.5 mmol) was dissolved in 200 mL of toluene. Inv-3 (10.2 g, yield 82%) was obtained by synthesis in the same manner as in Example 1. FD-MS: m / z 408 (M ⁺ ).

Example 3 Preparation of Inv-4

9- (biphenyl-4-yl) -10-bromoanthracene (10.0 g, 24.5 mmol), 2- (naphthalen-1-yl) -5- (4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl) pyridine (9.7 g, 29.4 mmol) was dissolved in 200 mL of toluene. Synthesis was carried out in the same manner as in Example 1 to obtain Inv-4 (11.2 g, yield 86%). FD-MS: m / z 534 (M ⁺ ).

Example 4 Preparation of Inv-11

9-bromo-10-phenylanthracene (9.0 g, 27.1 mmol), 2- (naphthalen-2-yl) -5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) Pyridine (10.8 g, 32.5 mmol) was dissolved in 200 mL of toluene. Synthesis was carried out in the same manner as in Example 1 to obtain Inv-11 (9.9 g, 80% yield). FD-MS: m / z 458 (M ⁺ ).

Example 5 Preparation of Inv-17

9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2-phenyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl pyridine (8.8 g, 31.4 mmol) was dissolved in 200 mL of toluene. Inv-17 (11.0 g, yield 92%) was obtained by synthesis in the same manner as in Example 1. FD-MS: m / z 458 (M ⁺ ).

Example 6 Preparation of Inv-20

9- (biphenyl-4-yl) -10-bromoanthracene (10.0 g, 24.5 mmol), 2-phenyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine (8.3 g, 29.4 mmol) was dissolved in 200 mL of toluene. Synthesis was carried out in the same manner as in Example 1 to obtain Inv-20 (10.4 g, yield 88%). FD-MS: m / z 484 (M ⁺ ).

Example 7 Preparation of Inv-25

9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2- (naphthalen-1-yl) -6- (4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl) pyridine (10.4 g, 31.4 mmol) was dissolved in 200 mL of toluene. Synthesis was carried out in the same manner as in Example 1 to obtain Inv-25 (12.1 g, 91% yield). FD-MS: m / z 508 (M ⁺ ).

Example 8 Preparation of Inv-33

9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2- (naphthalen-2-yl) -6- (4,4,5,5-tetramethyl-1,3,2 -dioxaborolan-2-yl) pyridine (10.4 g, 31.4 mmol) was dissolved in 200 mL of toluene. Synthesis was carried out in the same manner as in Example 1 to obtain Inv-33 (11.8 g, 89% yield). FD-MS: m / z 508 (M ⁺ ).

Example 9 Preparation of Inv-41

9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl pyridine (8.8 g, 31.4 mmol) was dissolved in 200 mL of toluene. Inv-41 (10.7 g, yield 84%) was obtained by synthesis in the same manner as in Example 1. FD-MS: m / z 458 (M ⁺ ).

Example 10 Preparation of Inv-50

9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyrazine (6.5 g, 31.4 mmol) was dissolved in 200 mL of toluene. Inv-50 (7.5 g, yield 75%) was obtained by synthesis in the same manner as in Example 1. FD-MS: m / z 383 (M ⁺ ).

Example 11 Preparation of Inv-62

9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyrimidine (6.5 g, 31.4 mmol) was dissolved in 200 mL of toluene. Synthesis was carried out in the same manner as in Example 1 to obtain Inv-62 (7.0 g, yield 70%). FD-MS: m / z 383 (M ⁺ ).

Example 12 Preparation of Inv-65

9-bromo-10- (naphthalen-2-yl) anthracene (10.0 g, 26.2 mmol), 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5- (thiophen-2-yl) pyridine (9.0 g, 31.4 mmol) was dissolved in 200 mL of toluene. Inv-65 (9.0 g, yield 74%) was obtained by synthesis in the same manner as in Example 1. FD-MS: m / z 464 (M ⁺ ).

Example 13 Preparation of Inv-69

9-bromo-10- (naphthalen-2-yl) -2-phenylanthracene (10.0 g, 21.8 mmol), 2- (naphthalen-1-yl) -5- (4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl) pyridine (8.7 g, 26.2 mmol) was dissolved in 200 mL of toluene. Inv-69 (10.2 g, yield 80%) was obtained by synthesis in the same manner as in Example 1. FD-MS: m / z 584 (M ⁺ ).

Examples 14 to 27 Fabrication and Evaluation of Organic EL Device

Each product (Inv-x) synthesized through Examples 1 to 13 was used as a green or blue host material to configure devices as shown in Tables 1 and 2, and the evaluation results are shown in Table 3 below.

Green-emitting dopant material is DS-501 (Doosan Corporation), which is a material that we have previously applied, and DS-405 (Doosan Corporation), which is a material we have previously used, is used.

Comparative Example 1 Fabrication and Evaluation of Organic EL Device

The evaluation results are shown in Table 3 after configuring the same type of device as in Table 2 except for using the conventional C545T as a green host material instead of the product (Inv-x) synthesized in Examples 1 to 13.

Comparative Example 2 Fabrication and Evaluation of Organic EL Device

The evaluation results are shown in Table 3 after configuring the same type of device as in Table 1 except for using ADN as a blue host material instead of the product (Inv-x) synthesized in Examples 1 to 13.

[Table 1] Blue Device Structure

Table 2 Green and Device Structure

At this time, the structure of NPB, ADN and C545T is as follows.

NPB

C545T

ADN

[Table 3] Device Characteristics

Compounds Current
Density
(mA / ㎠) Voltage
(V) Luminance
(cd / ㎡) Efficiency
(cd / A) color device
rescue
Example 14 (Inv-1) 10 5.1 513 5.1 Sky blue Table 1 Example 15 (Inv-1) 10 4.7 2205 22.1 Green Table 2 Example 16 (Inv-3) 10 4.9 568 5.6 Blue Table 1 Example 17 (Inv-4) 10 5.3 487 4.9 Sky blue Table 1 Example 18 (Inv-11) 10 5 524 5.2 Blue Table 1 Example 19 (Inv-17) 10 5.2 1873 18.7 Green Table 2 Example 20 (Inv-20) 10 5 503 5 Sky blue Table 1 Example 21 (Inv-25) 10 5.1 2121 21.2 Green Table 2 Example 22 (Inv-33) 10 5.1 2164 21.6 Green Table 2 Example 23 (Inv-41) 10 5.2 1898 19 Green Table 2 Example 24 (Inv-50) 10 4.9 499 5 Sky blue Table 1 Example 25 (Inv-62) 10 5 501 5 Sky blue Table 1 Example 26 (Inv-65) 10 5.5 453 4.5 Sky blue Table 1 Example 27 (Inv-69) 10 5.2 2168 21.7 Green Table 2 Comparative Example 1 10 6.9 953 9.5 Green Table 2 Comparative Example 2 10 5.6 481 4.8 blue Table 1

As described above, the organic EL device (Examples 13 to 27) using the compound according to the present invention has a voltage and efficiency when compared with the organic EL device (Comparative Examples 1 and 2) using conventional C545T and ADN for each host material. It was confirmed that the performance was excellent in terms of.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention. It is natural to belong.

Claims (4)

Compound represented by the following formula (1): [Formula 1]

In Chemical Formula 1, Z ¹ to Z ⁵ are the same as or different from each other, and each independently C or N, and at least one of Z ¹ to Z ⁵ is N; Ar ¹ and Ar ² are the same as or different from each other, and are each independently hydrogen, deuterium, a substituted or unsubstituted C ₆ -C ₆₀ aromatic group; X ¹ and X ² are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C ₆ ~ C ₆₀ aromatic group, a substituted or unsubstituted C ₅ ~ C ₆₀ aromatic heterocyclic group, substituted or unsubstituted A substituted C ₁ to C ₆₀ alkyl group, a substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group, a substituted or unsubstituted C ₁ to C ₆₀ alkoxy group, a substituted or unsubstituted C ₆ to C _{60 group} Arylalkyl group, substituted or unsubstituted C ₁ ~ C ₆₀ alkyloxy group, substituted or unsubstituted C ₅ ~ C ₆₀ aryloxy group, substituted or unsubstituted C ₅ ~ C ₆₀ aryl group, or substituted or Unsubstituted C ₅ ~ C ₆₀ Heteroaryl group; a and b are each independently an integer of 0-4, n is an integer of 1-3. The method of claim 1, In Ar ¹ , Ar ² , X ¹ and X ² of Formula 1, a substituted or unsubstituted C ₆ ~ C ₆₀ aromatic group, a substituted or unsubstituted C ₅ ~ C ₆₀ aromatic heterocyclic group, substituted or unsubstituted A C ₁ to C ₆₀ alkyl group, a substituted or unsubstituted C ₃ to C ₆₀ cycloalkyl group, a substituted or unsubstituted C ₁ to C ₆₀ alkoxy group, a substituted or unsubstituted C ₆ to C ₆₀ arylalkyl group , Substituted or unsubstituted C ₁ ~ C ₆₀ alkyloxy group, substituted or unsubstituted C ₅ ~ C ₆₀ aryloxy group, substituted or unsubstituted C ₅ ~ C ₆₀ aryl group, or substituted or unsubstituted The above substitution of the C ₅ to C ₆₀ heteroaryl group is independently deuterium, halogen, nitrile group, nitro group, C ₁ to C ₆₀ alkyl group, C ₂ to C ₆₀ alkenyl group, C ₁ to C ₆₀ An alkoxy group, a C ₁ to C ₆₀ amino group, a C ₃ to C ₆₀ cycloalkyl group, a C ₃ to C ₆₀ heterocycloalkyl group, a C ₆ to C ₆₀ aryl group, or a C ₅ to C ₆₀ heteroaryl group Substituted Characterized by a compound represented by the formula (I). anode; cathode; And one or more organic material layers interposed between the anode and the cathode. At least one of the one or more organic material layer is an organic electroluminescent device, characterized in that the organic material layer containing a compound represented by the formula (1) according to claim 1 or 2. The method of claim 3, The organic light emitting device comprising the compound represented by the formula (1) is a light emitting layer.