KR20120038060A - Novel compounds for organic electronic material and organic electroluminescent device using the same - Google Patents

Abstract

상기 화학식 1에서, L₁, L₂, A고리, X₁, X₂ 및 R₁ 내지 R₃는 각각 발명의 상세한 설명에서 정의한 바와 같다.
본 발명에 따른 유기 전자재료용 화합물은 전자전달 효율이 높아 소자 제작시 결정화를 방지할 뿐만 아니라 층 형성이 양호하여 소자의 전류특성을 개선시킴으로서 소자의 구동전압을 저하시키고 동시에 전력효율이 향상된 OLED 소자를 제조할 수 있는 장점이 있다.The present invention relates to a novel compound for an organic electronic material, and an organic electroluminescent device including the same. Specifically, the compound for an organic electronic material according to the present invention is represented by the following Chemical Formula 1.
[Formula 1]

In Formula 1, L ₁ , L ₂ , A ring, X ₁ , X ₂ and R ₁ to R ₃ are as defined in the detailed description of the invention, respectively.
The compound for an organic electronic material according to the present invention has a high electron transfer efficiency, which not only prevents crystallization during device fabrication but also has a good layer formation to improve the current characteristics of the device, thereby lowering the driving voltage of the device and at the same time improving the power efficiency. There is an advantage to manufacture.

Description

Novel compounds for organic electronic material and organic electroluminescent device using the same

The present invention relates to a novel compound for organic electronic materials and an organic electroluminescent device comprising the same.

Among the display elements, an electroluminescence device (EL device) is a self-luminous display element that has a wide viewing angle, excellent contrast, and high response speed.Eastman Kodak Co., Ltd. in 1987 An organic EL device using a low molecular aromatic diamine and an aluminum complex as a light emitting layer formation material was first developed [Appl. Phys. Lett. 51, 913, 1987].

The organic EL element injects charge into an organic film formed between the electron injection electrode (cathode) and the hole injection electrode (anode) to generate excitons by pairing electrons and holes. Light is emitted by using light emission (phosphorescence or fluorescence) when the excitons are inactive. The organic EL device emits polarized light with a voltage of about 10V and a high luminance of about 100 to 10,000 cd / m 2, and emits light in a spectrum from blue to red by simply selecting a fluorescent material. The device can be formed on a flexible transparent substrate such as plastic, and can be driven at a lower voltage (less than 10V) compared to a plasma display panel or an inorganic EL display, and has a relatively low power consumption. It has a small and excellent color.

In organic EL devices, the most important factor that determines the performance of light emission efficiency, lifetime, etc. is a light emitting material. Some characteristics required for such a light emitting material include high quantum fluorescence yield in solid state, and mobility of electrons and holes. It should be high, not easily decomposed during vacuum deposition, and form a stable thin film.

Organic light emitting materials can be classified into high molecular materials and low molecular materials. Low molecular materials include pure organic light emitting materials that do not contain metal complexes and metals in terms of molecular structure. As such light emitting materials, light emitting materials such as chelate complexes such as tris (8-quinolinolato) aluminum complexes, coumarin derivatives, tetraphenylbutadiene derivatives, bisstyrylarylene derivatives and oxadiazole derivatives are known. Has been reported to obtain visible region luminescence from blue to red.

In order to realize a full color OLED display, three kinds of RGB light emitting materials are used, and development of high efficiency long life RGB light emitting materials is an important task to improve the characteristics of the entire organic EL. The light emitting material can be classified into a host material and a dopant material in terms of its function. In general, a device structure having excellent EL characteristics is known to make a light emitting layer by doping a host with a dopant. Recently, the development of high efficiency and long life organic EL devices has emerged as an urgent task, and considering the level of EL characteristics required in medium and large OLED panels, it is urgent to develop materials that are much superior to existing light emitting materials. In this respect, the development of host materials is one of the most important factors to be solved. In this case, the desirable properties of the host material serving as a solvent and energy transporter in the solid state should be high in purity and have an appropriate molecular weight to enable vacuum deposition. In addition, high glass transition temperature and pyrolysis temperature should ensure thermal stability, high electrochemical stability is required for long life, easy to form amorphous thin film, good adhesion with other adjacent materials, Should not.

When an organic EL device is manufactured using a doping technique, energy transfer from the host molecule to the dopant in the excited state is less than 100%, and not only the dopant but also the host material emits light. In particular, in the case of a red light emitting device, since the host material emits light in a wavelength range where visibility is greater than that of the dopant, color purity is deteriorated by light emission of the host material. In addition, the light emission life and the sustainability need to be improved in practical application.

On the other hand, CBP is the most widely known host material for phosphorescent emitters, and high-efficiency OLEDs using a hole blocking layer such as BCP and BAlq are known, and high-performance OLEDs using BAlq derivatives as a host are known in Pioneer, Japan. Is known.

However, existing materials have advantages in terms of luminescence properties, but the glass transition temperature is low and the thermal stability is not very good, and thus has a disadvantage such that the material changes when undergoing a high temperature deposition process under vacuum. Since power efficiency = (π / voltage) × current efficiency in OLEDs, power efficiency is inversely proportional to voltage. However, low power consumption of OLEDs requires high power efficiency. Actually, OLEDs using phosphorescent materials have significantly higher current efficiency (cd / A) than OLEDs using fluorescent materials.However, when a conventional material such as BAlq or CBP is used as a host of phosphorescent materials, OLEDs using fluorescent materials Compared with the higher driving voltage, there was no significant advantage in terms of power efficiency (lm / w). In addition, in terms of lifespan in OLED devices, they are never satisfactory, and development of a more stable and more excellent host material is required.

Accordingly, an object of the present invention is to firstly provide a compound for organic electronic material having a good skeleton having an excellent luminous efficiency and device life, and having an appropriate color coordinate, in order to solve the above problems. It is to provide a high efficiency and long life organic electroluminescent element employing a compound for a material as a light emitting material.

The present invention relates to a compound for an organic electronic material represented by the following formula (1) and an organic electroluminescent device comprising the same, the compound for an organic electronic material according to the present invention has better luminous efficiency and excellent life characteristics of the material than the conventional material The driving life of the device is very excellent and there is an advantage of manufacturing an OLED device with improved power consumption by inducing an increase in power efficiency.

[Formula 1]

[In Formula 1,

L ₁ and L ₂ are independently of each other a chemical bond, (C6-C30) arylene or (C3-C30) heteroarylene;

X ₁ and X ₂ are independently of each other CR ₄ or N and at the same time not CR ₄ ;

Ring A is a monocyclic or polycyclic (C6-C30) aromatic ring;

R ₁ to R ₄ are each independently hydrogen, deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl , (C2-C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C6- C30) Ar (C1-C30) alkyl, (C6-C30) arylthio, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro or hydroxy;

The aromatic ring of arylene, heteroarylene, and ring A of L ₁ and L ₂ and alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, and heteroaryl of R ₁ to R ₄ are independently of each other. Deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30) alkenyl, (C2 (C3-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C1-C30) alkyl substituted (C3-C30) Heteroaryl, (C6-C30) aryl substituted (C3-C30) heteroaryl, (C6-C30) ar (C1-C30) alkyl, (C6-C30) arylthio, mono or di (C1-C30) alkyl Amino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C1-C30) alkyldi (C6-C30) aryl May be further substituted with one or more selected from the group consisting of silyl, tri (C6-C30) arylsilyl, nitro and hydroxy ;

The heteroarylene, heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P;

가 수소인 경우는 제외한다.]
only,

Except when is hydrogen.]

Substituents including the "alkyl", "alkoxy" and other "alkyl" moieties described herein include all linear or pulverized forms, and "cycloalkyl" is not only a monocyclic system but also substituted or unsubstituted adamantyl Or several ring-based hydrocarbons such as substituted or unsubstituted (C7-C30) bicycloalkyl. "Aryl" described in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, and a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms in each ring as appropriate. It includes a system, including a form in which a plurality of aryl is connected by a single bond. Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthasenyl, fluoranthenyl, and the like. It is not limited to this. Said naphthyl includes 1-naphthyl and 2-naphthyl, anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and fluorenyl is 1-fluorenyl, 2- Fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl. The "heteroaryl" described in the present invention contains 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si, and P as aromatic ring skeleton atoms, and the remaining aromatic ring skeleton atoms are carbon. Meaning an aryl group which is 5 to 6 membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, which may be partially saturated. In addition, the heteroaryl in the present invention also includes a form in which one or more heteroaryls are linked by a single bond. Such heteroaryl groups include divalent aryl groups in which heteroatoms in the ring are oxidized or quaternized to form, for example, N-oxides or quaternary salts. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetra Monocyclic heteroaryl such as zolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothia Zolyl, Benzoisoxazolyl, Benzoxazolyl, Isoindoleyl, Indolyl, Indazolyl, Benzothiadiazolyl, Quinolyl, Isoquinolyl, Cinolinyl, Quinazolinyl, Quinoxalinyl, Carbazolyl, Phenantridinyl , Polycyclic heteroaryls such as benzodioxolyl and the like, and their corresponding N-oxides (eg, pyridyl N-oxides, quinolyl N-oxides), quaternary salts thereof, and the like. .

In addition, the '(C1-C30) alkyl' groups described herein include (C1-C20) alkyl or (C1-C10) alkyl, and the '(C6-C30) aryl' group is a (C6-C20) aryl or (C6-C12) aryl. '(C3-C30) heteroaryl' group includes (C3-C20) heteroaryl or (C3-C12) heteroaryl, and the '(C3-C30) cycloalkyl' group is (C3-C20) cycloalkyl or (C3- C7) cycloalkyl. '(C2-C30) alkenyl or alkynyl' groups include (C2-C20) alkenyl or alkynyl, (C2-C10) alkenyl or alkynyl.

L ₁ and L ₂ are each independently a chemical bond, (C6-C30) arylene or (C3-C30) heteroarylene; X ₁ and X ₂ are independently of each other CR ₄ or N and at the same time not CR ₄ ; Ring A is a monocyclic or polycyclic (C6-C30) aromatic ring; R ₁ to R ₄ are independently of each other hydrogen, deuterium, (C6-C30) aryl or (C3-C30) heteroaryl; The aromatic ring of arylene, heteroarylene, and ring A of L ₁ and L ₂ and the aryl and heteroaryl of R ₁ to R ₄ are each independently of deuterium, (C 1 -C 30) alkyl, and halo (C 1 -C 30). Alkyl, (C6-C30) aryl, (C3-C30) heteroaryl, (C1-C30) alkyl substituted (C3-C30) heteroaryl, (C6-C30) aryl substituted (C3-C30) heteroaryl And it may be further substituted with one or more selected from the group consisting of (C6-C30) ar (C1-C30) alkyl.

는

,

또는

이고;More specifically

Is

,

or

ego;

R _a and R _b are independently of each other (C1-C7) alkyl or (C6-C12) aryl;

R _c to R _e are each independently hydrogen, deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, (C6-C30) aryl, (C3-C30) heteroaryl, (C1-C30) alkyl Substituted (C3-C30) heteroaryl, (C6-C30) aryl are substituted (C3-C30) heteroaryl and (C6-C30) ar (C1-C30) alkyl;

및

는 서로 독립적으로 수소 또는 하기 구조에서 선택되며, 단

이 수소인 경우는 제외된다.

And

Are independently selected from hydrogen or the following structures, provided

This hydrogen is excluded.

The compound for an organic electronic material according to the present invention may be more specifically exemplified as the following compound, but the following compound is not intended to limit the present invention.

The compound for an organic electronic material according to the present invention may be prepared as shown in Scheme 1, but is not limited thereto and may be prepared using a known organic synthesis method.

Scheme 1

[Formula 1 in Scheme 1, X ₁ , X ₂ , L ₁ , L ₂ , A ring And R ₁ to R ₃ are the same as defined in Chemical Formula 1, and X is a halogen.]

In addition, the present invention provides an organic electroluminescent device, the organic electroluminescent device according to the present invention comprises a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes at least one compound for an organic electronic material of Chemical Formula 1. The organic material layer includes a light emitting layer, and the compound for the organic electronic material of Chemical Formula 1 is used as a host material in the light emitting layer.

When the compound for the organic electronic material of Formula 1 is used as a host in the light emitting layer is characterized in that it comprises at least one phosphorescent dopant. The phosphorescent dopant applied to the organic electroluminescent device of the present invention is not particularly limited, but the phosphorescent dopant applied to the organic electroluminescent device of the present invention is preferably selected from compounds represented by the following Chemical Formula 2.

[Formula 2]

M ¹ L ¹⁰¹ L ¹⁰² L ¹⁰³

Wherein M ¹ is selected from the group consisting of metals of Groups 7, 8, 9, 10, 11, 13, 14, 15 and 16, and the ligands L ¹⁰¹ , L ¹⁰² and L ¹⁰³ Are independently selected from the following structures.

[In the formula (2)

R ₂₀₁ to R ₂₀₃ are independently of each other hydrogen, deuterium, (C1-C30) alkyl with or without halogen, (C6-C30) aryl or halogen with or without (C1-C30) alkyl;

R ₂₀₄ to R ₂₁₉ are each independently hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, Substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted mono or substituted or unsubstituted di- (C1-C30) alkylamino, substituted or unsubstituted Substituted mono or di- (C6-C30) arylamino, SF ₅ , substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl , Substituted or unsubstituted tri (C6-C30) arylsilyl, cyano or halogen;

R ₂₂₀ to R ₂₂₃ are each independently hydrogen, deuterium, (C1-C30) alkyl with or without halogen, or (C6-C30) aryl with or without (C1-C30) alkyl;

R ₂₂₄ and R ₂₂₅ are each independently hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen, or R ₂₂₄ and R ₂₂₅ are fused to Linked with (C3-C12) alkylene or (C3-C12) alkenylene with or without formation to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;

R ₂₂₆ is substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C5-C30) heteroaryl or halogen;

R ₂₂₇ to R ₂₂₉ are each independently hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen;

,

또는

이며, R₂₃₁ 내지 R₂₄₂는 서로 독립적으로 수소, 중수소, 할로겐이 치환되거나 치환되지 않은 (C1-C30)알킬, (C1-C30)알콕시, 할로겐, 치환 또는 비치환된(C6-C30)아릴, 시아노, 치환 또는 비치환된(C5-C30)시클로알킬이거나, 인접한 치환체와 알킬렌 또는 알케닐렌으로 연결되어 스피로 고리 또는 융합고리를 형성할 수 있거나, R₂₀₇ 또는 R₂₀₈과 알킬렌 또는 알케닐렌으로 연결되어 포화 또는 불포화의 융합고리를 형성할 수 있다.]Q is

,

or

R ₂₃₁ to R ₂₄₂ are each independently of the other hydrogen, deuterium, (C1-C30) alkyl, (C1-C30) alkoxy, halogen, substituted or unsubstituted (C6-C30) aryl, Cyano, substituted or unsubstituted (C5-C30) cycloalkyl, or may be linked to adjacent substituents with alkylene or alkenylene to form a spiro ring or fused ring, or with R ₂₀₇ or R ₂₀₈ and alkylene or alkenylene To form a saturated or unsaturated fused ring.]

The phosphorescent dopant compound of Formula 2 may be exemplified as a compound having the following structure, but is not limited thereto.

In the organic electroluminescent device of the present invention, it may include at least one compound selected from the group consisting of a compound for an organic electronic material of formula (1) and at the same time an arylamine compound or styrylarylamine compound. The arylamine-based compound or styrylarylamine-based compound is exemplified in Patent Application Nos. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but is not limited thereto.

In addition, in the organic electroluminescent device of the present invention, in the organic material layer, in addition to the compound for the organic electronic material of Formula 1, Group 1, Group 2, 4 cycle, 5 cycle transition metals, lanthanum series metals and organic metal of d-transition element It may further include one or more metals or complex compounds selected from the group consisting of, the organic material layer may include a light emitting layer and a charge generating layer.

In addition, an organic electroluminescent device that emits white light may be formed by simultaneously including one or more organic light emitting layers including blue, red, or green light emitting compounds in addition to the organic electronic material compound. The compound emitting blue, green, or red light is exemplified in Application Nos. 10-2008-0123276, 10-2008-0107606, or 10-2008-0118428, but is not limited thereto.

In the organic electroluminescent device of the present invention, one layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer (hereinafter referred to as "surface layer ") is formed on the inner surface of at least one of the pair of electrodes, Or more. Concretely, it is preferable to dispose a halogenated metal layer or a metal oxide layer on the surface of the anode on the side of the light emitting medium layer and on the surface of the cathode on the side of the light emitting medium layer, with a chalcogenide (including oxide) layer of a metal of silicon and aluminum Do. Thus, stabilization of the drive can be obtained. Examples of the chalcogenide include SiO _x (1 ≦ _X ≦ ₂ ), AlO _X (1 ≦ _X ≦ 1.5), SiON, SiAlON, and the like, and examples of the metal halide include LiF, MgF ₂ , CaF ₂ , and fluoride. Rare earth metals and the like are preferable. Examples of the metal oxides include Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO and the like.

Further, in the organic electroluminescent device of the present invention, disposing a mixed region of an electron transfer compound and a reducing dopant or a mixed region of a hole transfer compound and an oxidative dopant on at least one surface of the pair of electrodes thus produced desirable. In this way, the electron transfer compound is reduced to an anion, thereby facilitating injection and transfer of electrons from the mixed region into the light emitting medium. In addition, since the hole transport compound is oxidized to become a cation, it is easy to inject and transfer holes from the mixed region to the light emitting medium. Preferred oxidative dopants include various Lewis acids and acceptor compounds. Preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals and mixtures thereof. In addition, the reducing dopant layer The white organic electroluminescent device having two or more light emitting layers may be manufactured using the charge generating layer.

The compound for an organic electronic material according to the present invention has an advantage of being able to manufacture an OLED device having good luminous efficiency and lowering driving voltage of the device and at the same time improving power efficiency.

Hereinafter, for the detailed understanding of the present invention, a compound for an organic electronic material according to the present invention, a method for preparing the same, and a light emitting property of the device will be described with reference to a representative compound of the present invention, but only for the purpose of illustrating the embodiments thereof. It does not limit the scope of the present invention.

Preparation Example 1 Preparation of Compound 1

compound 1-1 Manufacture

10 g (49.5 mmol) of 1-bromo-2-nitrobenzene and 10.2 g (59.3 mmol) of 1-naphthalene boronic acid were dissolved in 200 mL of toluene, 50 mL of ethanol, and 50 mL of water, and then 2.9 g (2.5) of Pd (PPh ₃ ) ₄ mmol) and 20.5 g (148.3 mmol) of potassium carbonate are added. The mixture is stirred at 120 ° C. for 5 hours. The reaction is cooled to room temperature and the reaction is terminated with 40 mL of aqueous ammonium chloride solution. The mixture was extracted with EA 500 mL, and the obtained organic layer was washed with distilled water 100 mL. The organic layer was dried over anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel column chromatography to obtain compound 1-1 (10 g, 81%).

compound 1-2 Manufacture

10 g (40.1 mmol) of Compound 1-1 is dissolved in 100 mL of 1,2-dichlorobenzene, and 100 mL of triethoxyphosphine is added thereto. The reaction mixture is stirred at 150 ° C. for 20 hours. The reaction mixture is cooled to room temperature and the solvents 1,2-dichlorobenzene and triethoxyphosphine are removed by distillation under reduced pressure. The remaining organics are extracted with EA 300mL, and the obtained organic layer is washed with 40mL of distilled water. The organic layer was dried over anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel column chromatography to obtain compound 1-2 (7 g, 80%).

compound 1-3 Manufacture

Dissolve 7g (32.2 mmol) of Compound 1-2 in 150 mL of DMF and then add 5.74 g (32.2 mmol) of NBS. The reaction mixture is stirred at room temperature for 12 hours. The reaction mixture was terminated with 30 mL of saturated sodium thiosulfate aqueous solution, extracted with 200 mL of EA, and the obtained organic layer was washed with 20 mL of distilled water. The organic layer was dried over anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel column chromatography to obtain compound 1-3 (9 g, 94%).

compound 1-4 Manufacture

Compound 1-3 9 g (30.4 mmol) and 8.8 mL (61 mmol) of iodinebenzene were dissolved in 150 mL of toluene, followed by 2.9 g (15.2 mmol) of CuI, 1 mL (15.2 mmol) of 1,2-diaminoethane, and 29.7 g (91.2) of cesium carbonate. mmol) is added. The reaction mixture is refluxed for 20 hours. After the reaction mixture was cooled to room temperature, the reaction was terminated with 10% aqueous hydrochloric acid solution, extracted with EA 300 mL, and the obtained organic layer was washed with 40 mL of distilled water. The organic layer was dried over anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel column chromatography to obtain compound 1-4 (8.5 g, 75%).

compound 1-5 Manufacture

10 g (26.9 mmol) of Compound 1-4 are dissolved in 120 mL of THF, and the solution is then cooled to -78 ° C. 13 mL of n-BuLi (2.5M in hexane) is added at -78 ° C. After stirring the mixture at -78 ° C for 1 hour, 4.5 ml of trimethoxyborane compound is added thereto. After stirring the whole reaction for 2 hours, the reaction was terminated with 30 mL of ammonium chloride aqueous solution, extracted with EA 300 mL, and the obtained organic layer was washed with 50 mL of distilled water. The organic layer was dried over anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. The obtained solid was separated by recrystallization to give compound 1-5 (6.7 g, 74%).

compound 1-6 Manufacture

110 g (466 mmol) of 1,4-dibromobenzene and 40 g (233 mmol) of 1-naphthalene boronic acid were dissolved in a mixture of 2 L of toluene, 500 mL of ethanol and 500 mL of water, and then 13.4 g (11.6 mmol) of Pd (PPh ₃ ) ₄ and sodium carbonate. Add 74g (698mmol). The mixture is stirred at 120 ° C. for 5 hours. The reaction is cooled to room temperature and the reaction is terminated with 500 mL of aqueous ammonium chloride solution. The mixture was extracted with 3 L of ethyl acetate, and the obtained organic layer was washed with 1 L of distilled water. The organic layer was dried over anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel filter and recrystallized to obtain compound 1-6 (50 g, 50%).

compound 1-7 Manufacture

60 g (0.21 mol) of Compound 1-6 was dissolved in 1 L of THF, and the solution was then cooled to -78 ° C. 102 mL of n-BuLi (2.5M in hexane) is added at -78 ° C. The mixture is stirred at -78 ° C for 1 hour and then 35.1 mL of B (OMe) ₃ is added. After stirring the entire reaction for 2 hours, the reaction was terminated with 300 mL of ammonium chloride aqueous solution, extracted with EA 2L, and the obtained organic layer was washed with 500 mL of distilled water. The organic layer was dried over anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. The obtained solid was isolated by recrystallization to give compound 1-7 (34 g, 65%).

compound 1-8 Manufacture

27.1 g (136 mmol) of 2,4-dichloroquinazoline and 33.8 g (136 mmol) of Compound 1-7 were dissolved in a mixed solution of 800 mL of toluene, 200 mL of ethanol, and 200 mL of water, followed by 6.3 g (5.45 mmol) of Pd (PPh ₃ ) ₄ and sodium carbonate. Add 43.3 g (409 mmol). The mixture is stirred at 120 ° C. for 5 hours. The reaction was cooled to room temperature and the reaction was terminated with 200 mL of aqueous ammonium chloride solution. The mixture was extracted with EA 1.5L, and the obtained organic layer was washed with 500 mL of distilled water. The organic layer was dried over anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel filter and recrystallized to obtain compound 1-8 (21 g, 42%).

compound One Manufacture

5 g (13.6 mmol) of Compound 1-8 and 6.7 g (19.9 mmol) of Compound 1-5 were dissolved in 100 mL of toluene, 20 mL of ethanol, and 20 mL of water, followed by 1.6 g (1.4 mmol) of Pd (PPh ₃ ) ₄ and potassium carbonate. g (41.2 mmol) is added. The mixture is stirred at 120 ° C. for 5 hours. The reaction is cooled to room temperature and the reaction is terminated with 50 mL of aqueous ammonium chloride solution. The mixture was extracted with EA 500 mL, and the obtained organic layer was washed with 50 mL of distilled water. The organic layer was dried over anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel filter and recrystallized to obtain compound 1 (8.2 g, 96%).

MS / FAB: 623.74 (found), 623.24calculated)

Preparation Example 2 Preparation of Compound 20

compound 2-1 Manufacture

In the same manner as in the synthesis of Compound 1-1 in Preparation Example 1, except that 17.7 g (74.3 mmol) of 9,9-dimethyl- 9H -fluoren-2-yl boronic acid was used instead of 1-naphthalene boronic acid Compound 2-1 (13 g, 83%) was obtained.

compound 2-2 Manufacture

Using Compound 2-1 13g (41.2mmol), Compound 2-2 (4.2 g, 36%) was obtained in the same manner as the synthesis of Compound 1-2 in Preparation Example 1.

compound 2-3 Manufacture

6.8 g (24 mmol) of Compound 2-2 and 13.6 g (48 mmol) of 1-bromo-4-iodinebenzene were dissolved in 240 mL of toluene, followed by 270 mg (1.2 mmol) of Pd (OAc) ₂ , 50% P (i-Bu) ₃ Add 1.6 mL (2.4 mmol) and 4.6 g (48 mmol) NaOt-Bu. The reaction mixture is refluxed for 2 days. After the reaction mixture was cooled to room temperature, the reaction was terminated with 50 mL of saturated aqueous ammonium chloride solution, extracted with EA 300 mL, and the obtained organic layer was washed with 40 mL of distilled water. The organic layer was dried over anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel column chromatography to obtain compound 2-3 (4.3 g, 41%).

compound 2-4 Manufacture

Compound 2-4 (2.5 g, 63%) was prepared in the same manner as in the synthesis of Compound 1-5 in Preparation Example 1, except that 4.3 g (9.8 mmol) of Compound 2-3 was used instead of 1-naphthalene boronic acid. Got it.

compound 2-5 Manufacture

33 g (139 mmol) of 2,4-dichloroquinazolin in place of 1,4-dibromobenzene and 9,9-dimethyl- 9H -fluoren-2-yl boronic acid in place of 1-naphthalene boronic acid Compound 2-5 (16.5 g, 37%) was obtained by the same method as the synthesis of compound 1-6 in Preparation Example 1, except that 25 g (126 mmol) was used.

compound 20 Manufacture

1.5 g (4.2 mmol) of Compound 2-5 was used instead of Compound 1-8 , and 2 g (5.0 mmol) of Compound 2-4 was used instead of Compound 1-5 . Compound 20 (1.7 g, 60%) was obtained in the same manner as the synthesis.

MS / FAB: 679.85found), 679.30 (calculated)

Preparation Example 3 Preparation of Compound 23

compound 23 Manufacture

Compound 23 (1.8 g, 62%) was obtained by the same method as the synthesis of Compound 1 in Preparation Example 1, except that 2 g (5.0 mmol) of Compound 2-4 was used instead of Compound 1-5 .

MS / FAB: 689.84 (found), 689.28calculated)

Preparation Example 4 Preparation of Compound 25

compound 4-1 Manufacture

157 g (554 mmol) of 2-naphthalene boronic acid is used instead of 1-naphthalene boronic acid, and 100 g (581.7 mmol) of 1-bromo-4-iodobenzene is used instead of 1,4-dibromobenzene Compound 4-1 (94 g, 60%) was obtained by the same method as the synthesis of compound 1-6 in Preparation Example 1.

compound 4-2 Manufacture

Compound 4-2 (57g, 67.0%) was obtained by the same method as the synthesis of Compound 1-7, except that Compound 4-1 94g (332 mmol) was used instead of Compound 1-6 .

compound 4-3 Manufacture

Compound 4-3 (51g, 99.9%) was obtained by the same method as the synthesis of Compound 1-8, except that Compound 4-2 57g (230 mmol) was used instead of Compound 1-7 .

compound 25 Manufacture

NaH 706 mg (17.6 mmol) was dissolved in 200 mL of DMF and Compound 2-2 dissolved in 200 mL of DMF was added. After stirring for 1 hour at room temperature, the reaction was slowly added to 4.3 g (11.8 mmol) of Compound 4-3 dissolved in 170 mL of DMF. Stirred at room temperature overnight. After quenching with 30 mL of MeOH and 30 mL of distilled water, the mixture was filtered under reduced pressure and washed with distilled water and MeOH. The obtained solid was triturated with MeOH / EA, triturated with DMF, and triturated with EA / THF. After dissolving with chloroform and filtering with silica, trituration with MeOH / EA gave compound 25 (5.5 g, 76.4%).

MS / FAB: 613.75 (found), 613.25 (calculated)

Preparation Example 5 Preparation of Compound 26

compound 5-1 Manufacture

Compound 1-2 30 g (0.138 mol), 98 g (3 eq) of 1,4-dibromobenzene, 13.1 g (0.5 eq) of CuI, 90 g (3 eq) of K ₃ PO ₄ , 9.3 mL (1 eq) of ethylenediamine and 700 mL of toluene Add and stir at reflux for 12 hours at 100 ℃. After completion of the reaction, the mixture was extracted with EA, and then purified by column chromatography to obtain a white compound 5-1 (39 g, 56%).

compound 5-2 Manufacture

39 g of Compound 5-1, 50.3 mL (1.2 eq) of n-BuLi, and 500 mL of THF were added and stirred at -78 ° C for 30 minutes. After stirring was completed, B (OMe) ₃ 36mL (1.5eq) was added and stirred for 12 hours, extracted with EA to give a white compound 5-2 (25g, 71%) using column chromatography.

compound 26 Manufacture

Compound 2-5 6.8g (0.019mol) and compound 5-2 9.64g (1.5eq) and _{2M K 3 PO 4 12.4g (3eq} ) and _{Pd (OAC) 2 0.43g (0.1eq} ) and P (t-Bu ₃ ) Add 3.8 mL (0.3eq), 120 mL of toluene and 60 mL of EtOH, and stir for 12 hours. After reaction, the mixture was extracted with EA, and then purified by column chromatography to obtain a white compound 26 (5.8 g, 50%).

MS / FAB: 613.75 (found), 613.25 (calculated)

Preparation Example 6 Preparation of Compound 9

Compound 1-3 6 g (0.016 mol), Compound 5-3 8.3 g (1.5 eq), 2 M K ₂ CO ₃ 6.8 g (3 eq), Pd (PPh ₃ ) ₄ 1.9 g (0.1 eq), 100 mL of toluene and 50 mL EtOH Add and stir at 100 ° C for 12 hours. After the reaction, the mixture was extracted with EA, and then purified by column chromatography to obtain a white compound 9 (7 g, 70%).

MS / FAB: 623.74 (found), 623.24 (calculated)

Preparation Example 7 Preparation of Compound 21

compound 7-1 Manufacture

Compound 5- in Preparation Example 5, except that 15.3 g (53.99 mmol) of 11,12-dihydro-12,12-dimethylindeno [2,1-a] carbazole was used instead of compound 1-2 Compound 7-1 (11 g, 44%) was obtained in the same manner as in the synthesis of 2.

compound 7-2 Manufacture

Compound 7-2 ( 5.8g, 57%) was obtained by the same method as the synthesis of Compound 5-3 in Preparation Example 5, except that 11 g (0.025 mol) of Compound 7-1 was used instead of Compound 5-1 .

compound 21 Manufacture

Compound 21 (3.3 g, 45%) was obtained in the same manner as the synthesis of Compound 26 in Preparation Example 5, except that 5.1 g (12.77 mmol) of Compound 7-2 was used instead of Compound 5-2 .

MS / FAB: 679.85 (found), 679.30 (calculated)

Preparation Example 8 Preparation of Compound 13

compound 8-1 Manufacture

Compound 8-1 (18.4) in the same manner as in the synthesis of Compound 1-6 in Preparation Example 1, except that 25 g (0.14 mol) of 1,3-dibromobenzene was used instead of 1,4-dibromobenzene. g, 45%).

compound 8-2 Manufacture

Compound 8-2 (10g, 63%) was obtained by the same method as the synthesis of Compound 1-7 in Preparation Example 1, except that 18.4 g (0.065 mol) of Compound 8-1 was used instead of Compound 1-6 .

compound 8-3 Manufacture

Compound 8-3 (4.5 g, 37%) was obtained by the same method as the synthesis of Compound 1-8 in Preparation Example 1, except that 8.8 g (85.48 mmol) of Compound 8-2 was used instead of Compound 1-7 . .

compound 13 Manufacture

In Preparation Example 1, except that 4.5 g (0.012 mol) of Compound 8-3 was used instead of Compound 1-8 , and 4.9 g (0.014 mol) of Compound 5-2 was used instead of Compound 1-5 . Compound 13 (4.3 g, 56%) was obtained in the same manner as the synthesis.

MS / FAB: 623.74 (found), 623.24 (calculated)

Preparation Example 9 Preparation of Compound 10

compound 9-1 Manufacture

50 g (0.155 mol) of 3-bromo-9-phenyl-9H-carbazole was dissolved in THF and slowly added 75 mL (0.186 mol, 2.5 M in hexane) of n-buLi at -78 ° C. After one hour, 53.5 mL (0.233 mol) of triisopropylborate was added. After stirring for 12 hours at room temperature, distilled water was added. Extracted with EA and dried over magnesium sulfate. Distillation under reduced pressure and recrystallization with MC and hexane gave Compound 9-1 (33 g, 0.115 mol, 74%).

compound 10 Manufacture

Compound 10 (5.7 g, 9.94 mmol, 73%) was obtained by the same method as the synthesis of compound 1 in Preparation Example 1, except that 5.87 g (20.44 mmol) of compound 9-1 was used instead of compound 1-5 .

MS / FAB: 573.68 (found), 573.22 (calculated)

Preparation Example 10 Preparation of Compound 14

Compound 4-3 5 g (13.63 mmol), Compound 5-2 6.9 g (20.45 mmol), Pd (PPh ₃ ) ₄ 1.58 g (1.36 mmol), 2M K ₂ CO ₃ 5.65 g (40.9 mmol), toluene 80 mL, ethanol 40 mL was mixed and stirred for 5 hours at 120 ° C. Cooled to room temperature and distilled water was added. Extraction with EA and distillation under reduced pressure recrystallized with EA and MeOH. Recrystallization again with THF and EA gave compound 14 (2.7 g, 4.43 mmol, 32%).

MS / FAB: 623.74 (found), 623.24 (calculated)

Preparation Example 11 Preparation of Compound 24

3.9 g (10.7 mmol) of Compound 4-3, 5.2 g (12.9 mmol) of Compound 7-2 and 3.4 g (32.1 mmol) of sodium carbonate were dissolved in a mixed solution of 50 mL of toluene, 20 mL of ethanol and 20 mL of distilled water, and then Pd (PPh ₃ ) ₄ 0.6 g (0.6 mmol) is added. The mixture is stirred at 120 ° C. for 5 hours. The reaction was cooled to room temperature, extracted with EA 300mL, and the obtained organic layer was washed with 50mL of distilled water. The organic layer was dried over anhydrous magnesium sulfate, and the organic solvent was removed under reduced pressure. The obtained solid was separated by silica gel column chromatography and recrystallization to give compound 24 (2.3g, 31%).

MS / FAB: 689.84 (found), 689.28 (calculated)

Example 1 Fabrication of an OLED Device Using a Compound for Organic Electronic Materials According to the Present Invention

An OLED device having a structure using the light emitting material of the present invention was produced. First, a transparent electrode ITO thin film (15? It was used after. Next, the ITO substrate is placed in the substrate folder of the vacuum deposition equipment, and the 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) tree having the following structure is installed in the cell in the vacuum deposition equipment. Phenylamine (2-TNATA) was added and evacuated until the vacuum in the chamber reached 10 ^-6 torr. Then, a current was applied to the cell to evaporate 2-TNATA to inject a 60 nm thick hole injection layer onto the ITO substrate. Subsequently, N , N' -bis (α-naphthyl) -N , N' -diphenyl-4,4'-diamine (NPB) was added to another cell in the vacuum deposition apparatus, and a current was applied to the cell. NPB was evaporated to deposit a 20 nm-thick hole transport layer on the hole injection layer, and then the light emitting layer was deposited on the hole injection layer as follows: One cell in the vacuum deposition apparatus. into a compound (1) according to the present invention as a host to another cell, the _{Ir (piq) 3 [tris (} 1-phenylisoquinoline) iridium (III)] as a dopant After each addition, the two materials were evaporated at different rates and doped at 4 to 10% by weight to deposit a 30 nm thick light emitting layer on the hole transport layer, followed by tris (8-hydroxyquinoline) -aluminum as an electron transport layer on the light emitting layer. (III) After depositing (Alq) to a thickness of 20 nm, and then depositing lithium quinolate (Liq) to a thickness of 1 to 2 nm with an electron injection layer, using another vacuum deposition equipment to the Al cathode to a thickness of 150 nm The deposition produced an OLED device.

For each material, the compound was vacuum sublimated under 10-6 torr and used as an OLED light emitting material.

As a result, a current of 14.3 mA / cm ² flowed at a voltage of 6.8 V, and red light emission of 1050 cd / m ² was confirmed.

[Example 2]

An OLED device was manufactured in the same manner as in Example 1, except that Compound 18 was used as the host material in the light emitting layer.

As a result, a current of 15.1 mA / cm ² flowed at a voltage of 6.5 V, and red light emission of 1040 cd / m ² was confirmed.

Example 3

An OLED device was manufactured in the same manner as in Example 1, except that Compound 9 was used as the host material in the light emitting layer.

As a result, a current of 13.9 mA / cm ² flowed at a voltage of 6.5 V, and red emission of 1060 cd / m ² was confirmed.

Example 4

An OLED device was manufactured in the same manner as in Example 1, except that Compound 20 was used as the host material in the light emitting layer.

As a result, a current of 14.5 mA / cm ² flowed at a voltage of 6.9 V, and red light emission of 1030 cd / m ² was confirmed.

[Example 5]

An OLED device was manufactured in the same manner as in Example 1, except that Compound 25 was used as the host material in the light emitting layer.

As a result, a current of 14.2 mA / cm ² flowed at a voltage of 7.0 V, and red light emission of 1050 cd / m ² was confirmed.

Comparative Example 1

4,4'-bis (carbazol-9-yl) biphenyl (CBP) was used as a host material in the light emitting layer instead of the compound of the present invention, and bis (2-methyl-8-quinolinate) (p) was used as the hole blocking layer. An OLED device was manufactured in the same manner as in Example 1, except that -phenylphenolrato) aluminum (III) (Balq) was used.

As a result, a current of 15.3 mA / cm ² flowed at a voltage of 7.5 V, and red light emission of 1000 cd / m ² was confirmed.

It was confirmed that the luminescence properties of the organic light emitting compounds developed in the present invention showed superior properties compared to the conventional materials. In addition, the device using the organic light emitting compound according to the present invention as a light emitting host material is excellent in light emission characteristics, and also has an effect of lowering the driving voltage, thereby inducing an increase in power efficiency, thereby improving power consumption.

Claims (10)

Compound for an organic electronic material represented by the formula (1).
[Formula 1]

[In the above formula (1)
L ₁ and L ₂ are independently of each other a chemical bond, (C6-C30) arylene or (C3-C30) heteroarylene;
X ₁ and X ₂ are independently of each other CR ₄ or N and at the same time not CR ₄ ;
Ring A is a monocyclic or polycyclic (C6-C30) aromatic ring;
R ₁ to R ₄ are each independently hydrogen, deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl , (C2-C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C6- C30) Ar (C1-C30) alkyl, (C6-C30) arylthio, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro or hydroxy;
The aromatic ring of arylene, heteroarylene, and ring A of L ₁ and L ₂ and alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl, and heteroaryl of R ₁ to R ₄ are independently of each other. Deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30) alkenyl, (C2 (C3-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C1-C30) alkyl substituted (C3-C30) Heteroaryl, (C6-C30) aryl substituted (C3-C30) heteroaryl, (C6-C30) ar (C1-C30) alkyl, (C6-C30) arylthio, mono or di (C1-C30) alkyl Amino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C1-C30) alkyldi (C6-C30) aryl May be further substituted with one or more selected from the group consisting of silyl, tri (C6-C30) arylsilyl, nitro and hydroxy ;
The heteroarylene, heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P;
only,

Except when is hydrogen.] The method of claim 1,
L ₁ and L ₂ are each independently a chemical bond, (C6-C30) arylene or (C3-C30) heteroarylene; X ₁ and X ₂ are independently of each other CR ₄ or N and at the same time not CR ₄ ; Ring A is a monocyclic or polycyclic (C6-C30) aromatic ring; R ₁ to R ₄ are independently of each other hydrogen, deuterium, (C6-C30) aryl or (C3-C30) heteroaryl; The aromatic ring of arylene, heteroarylene, and ring A of L ₁ and L ₂ and the aryl and heteroaryl of R ₁ to R ₄ are each independently of deuterium, (C 1 -C 30) alkyl, and halo (C 1 -C 30). Alkyl, (C6-C30) aryl, (C3-C30) heteroaryl, (C1-C30) alkyl substituted (C3-C30) heteroaryl, (C6-C30) aryl substituted (C3-C30) heteroaryl And (C6-C30) ar (C1-C30) alkyl, which may be further substituted with one or more selected from the group consisting of organic electronic materials. The method of claim 2,
remind

Is

,

or

ego;
R _a and R _b are independently of each other (C1-C7) alkyl or (C6-C12) aryl;
R _c to R _e are each independently hydrogen, deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, (C6-C30) aryl, (C3-C30) heteroaryl, (C1-C30) alkyl Substituted (C3-C30) heteroaryl, (C6-C30) aryl are substituted (C3-C30) heteroaryl and (C6-C30) ar (C1-C30) alkyl;

And

Are independently selected from hydrogen or the following structures, provided

The case for this hydrogen is excluded, The compound for organic electronic materials characterized by the above-mentioned.

The method of claim 3, wherein
A compound for organic electronic materials selected from the following compounds.

An organic electroluminescent device comprising the compound for organic electronic material according to any one of claims 1 to 4. 6. The method of claim 5,
The organic electroluminescent device includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer comprises at least one compound for an organic electronic material and at least one phosphorescent dopant. The method according to claim 6,
An organic electroluminescent device further comprising at least one amine compound selected from the group consisting of an arylamine compound or a styrylarylamine compound in the organic layer. The method according to claim 6,
An organic electric field further comprising at least one metal or a complex compound selected from the group consisting of Group 1, Group 2, 4, 5 cycle transition metals, lanthanum series metals and organic metals of d-transition elements in the organic layer. Light emitting element. The method according to claim 6,
The organic material layer is an organic electroluminescent device comprising a light emitting layer and a charge generating layer. The method according to claim 6,
The organic light emitting device of claim 1, further comprising at least one organic light emitting layer for emitting blue, red or green light to the organic material layer.