KR20120042633A - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents

Abstract

PURPOSE: An organic electroluminescence compound is provided to have excellent luminous efficiency especially in phosphorescence, by enlarging blocking in order to stay triplet excitons in a light emitting layer, thereby offering an OLED having very excellent driving life time, and improved power consumption. CONSTITUTION: An organic electroluminescence compound is in chemical formula 1. In here, A ring and C ring is respectively a functional group in chemical formula 1-a, and B ring is a functional group in chemical formula 1-b, X1 and X2 is respectively CR3 or N, and Y1 and Y2 is respectively a chemical bond, -O-, -S-, -C(R11R12)-, -Si(R13R14)- or -N(R15)-. An organic electroluminescence device comprises a first electrode, a second electrode, and one or more organic material layers inserted between the first and the second electrodes. The organic material layer comprises one or more layers including the organic electroluminescence compound in chemical formula 1.

Description

Novel organic electroluminescent compounds and organic electroluminescent device using the same

The present invention relates to a novel organic light emitting compound and an organic electroluminescent device comprising the same, and more particularly to a novel organic light emitting compound used as a hole transport material or a hole injection material and an organic electroluminescent device employing the same. It is about.

Liquid crystal display (LCD), which is the most widely used at present, is a non-light emitting display device, which consumes little power and is light. However, the device driving system is complicated and characteristics such as response time and contrast are not satisfactory. Therefore, research on organic electroluminescent devices, which are recently attracting attention as a next-generation flat panel display, is being actively conducted.

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].

In the light emitting mechanism of the organic EL device, when charge is injected into the organic film formed between the electron injection electrode (cathode) and the hole injection electrode (anode), electrons and holes are paired and then disappear to emit light. 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.

Organic materials in organic EL devices can be roughly divided into light emitting materials and charge transport materials. The luminescent material is directly related to the emission color and the luminous efficiency. Some of the required properties are that the fluorescence quantum yield should be high in the solid state, the mobility of electrons and holes should be high, and not easily decomposed during vacuum deposition. It should be stable, forming a uniform thin film.

Hole injection and transport materials include copper phthalocyanine (CuPc), NPB, TPD, MTDATA (4, 4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine), etc. These materials are included in the hole injection and transport layer. The device has a problem in that the efficiency and lifespan are lowered, because when the organic EL device is driven at a high current, thermal stress is generated between the anode and the hole injection layer. In addition, since the organic material used in the hole injection layer has a very high hole mobility, the hole-electron charge balance between the holes and the electrons is broken, and thus the quantum efficiency (cd / A) becomes low.

In order to increase the durability of the organic EL device, it is reported that the compound having good thin film stability and the compound having high amorphousness have higher thin film stability. At this time, the glass transition point (Tg) is used as an index of amorphousness. MTDATA's glass transition temperature is 76 ℃, which means that its amorphousness is not high. These materials did not obtain satisfactory characteristics in terms of durability of the organic EL element and also in luminous efficiency due to the characteristics of hole injection and transport.

 Appl. Phys. Lett. 51, 913, 1987

Accordingly, an object of the present invention is to provide an organic light emitting compound having an excellent luminescence efficiency and device life better than the existing hole injection or hole transport material in order to solve the above problems, and to provide a novel organic light emitting compound in the hole injection layer or An organic electroluminescent element employed in a hole transport layer is provided.

The present invention relates to an organic light emitting compound represented by Chemical Formula 1, and an organic electroluminescent device comprising the same, wherein the organic light emitting compound according to the present invention is included in the hole injection layer or the hole transport layer of the organic electroluminescent device The luminous efficiency can be improved while lowering the driving voltage.

[Formula 1]

[In Formula 1,

이며;Ring A and Ring C are each independently

Is;

이고;B ring

ego;

X ₁ and X ₂ are each independently CR ₃ or N;

Y ₁ and Y ₂ are each independently a chemical bond, —O—, —S—, —C (R ₁₁ R ₁₂ ) —, —Si (R ₁₃ R ₁₄ ) — or —N (R ₁₅ ) — Except when Y ₁ and Y ₂ are at the same time a chemical bond;

R ₁ to R ₃ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) hetero Aryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30) ar (C1-C30) alkyl, substituted or Unsubstituted (C1-C30) alkylsilyl, cyano, nitro or hydroxyl, and when there are a plurality of R ₁ or R ₂ , each of R ₁ and R ₂ may combine with each other to form a cyclic structure;

L is substituted or unsubstituted (C6-C30) arylene or substituted or unsubstituted (C2-C30) heteroarylene, provided that when L is plural, they may combine with each other to form a cyclic structure;

이며;Ar ₁ and Ar ₂ are each independently substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) heteroaryl

Is;

Y ₃ and Y ₄ are each independently a chemical bond, —O—, —S—, —C (R ₁₆ R ₁₇ ) —, —Si (R ₁₈ R ₁₉ ) — or —N (R ₂₀ ) — Except that Y ₃ and Y ₄ are simultaneously chemical bonds;

R ₁₁ to R ₂₀ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (C2-C30) hetero A cycloaliphatic ring and a monocyclic ring or a polycyclic ring which is connected to a substituted or unsubstituted (C3-C30) alkylene or a substituted or unsubstituted (C3-C30) alkenylene, which is aryl or does not include or include a fused ring with adjacent substituents. Can form an aromatic ring of a ring;

m and n are each independently integers of 0 to 4, and when m and n are integers of 2 or more, each of R ₁ and L may be the same or different from each other;

p is an integer from 0 to 2, and when p is 2, each R ₂ may be the same or different from each other;

Wherein said heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.]

Substituents comprising the 'alkyl' and other 'alkyl' moieties described herein include both straight and pulverized forms, and 'cycloalkyl' is substituted or unsubstituted adamantyl or substituted or unsubstituted as well as a single ring system It also includes several ring-based hydrocarbons such as cyclic (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, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like. Including but not limited to. The naphthyl includes 1-naphthyl and 2-naphthyl, anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and phenanthryl is 1-phenanthryl, 2-phenanthryl , 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, naphthasenyl includes 1-naphthacenyl, 2-naphthacenyl, 9-naphthacenyl, pyrenyl is 1-pyrenyl, 2-pyrene 1, 4-pyrenyl, biphenyl includes 2-biphenyl, 3-biphenyl, 4-biphenyl, terphenyl is a p-terphenyl-4-yl group, p-terphenyl-3- Diary, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, fluorenyl is 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl. "Heteroaryl" described in the present invention contains 1 to 4 heteroatoms selected from B, N, O, S, P, P (= O), Si and Se as aromatic ring skeleton atoms, and the remaining aromatic ring skeletons. Means an aryl group whose atoms are carbon, 5-6 membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, which may be partially saturated. 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, fura Monocyclic heteroaryl such as residue, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, isobenzofuranyl, benzoimidazolyl, Benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzooxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinolinyl, quinazolinyl, quinoxalinyl , Polycyclic heteroaryls such as carbazolyl, phenantridinyl, benzodioxolyl, acridinyl, phenanthrolinyl, phenazinyl, phenthiazininyl, phenoxazinyl, and their corresponding N-oxides (e.g., Pyridyl N-oxide, quinolyl N-oxide), Of the like, but a quaternary salt, and the like. The pyrrolyl comprises 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, pyridyl includes 2-pyridyl, 3-pyridyl, 4-pyridyl, and indolyl is 1-indolyl , 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, isoindoleyl includes 1-isoindoleyl, 2-isoindoleyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolinyl, 7-isoindolinyl, furyl includes 2-furyl, 3-furyl, benzofuranyl is 2 -Benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, isobenzofuranyl is 1-isobenzofuranyl, 3 Isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl, 7-isobenzofuranyl, and quinolyl is 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, wherein isoquinolyl includes 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl groups, quinoxalinyl includes 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl Carbazolyl includes 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl, 9-carbazolyl, and phenantridinyl is 1-phenanthridinyl, 2-phenanthridinyl, 3 Phenanthridinyl, 4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl, and acridinyl is 1- Acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-acridinyl, wherein phenanthrolinyl is a 1,7-phenanthroline-2-yl group, 1,7 -Phenanthroline-3-yl, 1,7-phenanthroline-4-yl, 1,7-phenanthroline-5-diary, 1,7-phenanthroline-6-diary, 1,7-phenan Troolin-8-Diary, 1,7-phenanthroline-9-diary, 1,7-phenanthroline-10-diary, 1,8-phenanthroline-2-yl, 1,8-phenanthroline -3-diary, 1,8-pe Troolin-4-yl, 1,8-phenanthroline-5-diary, 1,8-phenanthroline-6-diary, 1,8-phenanthroline-7-diary, 1,8-phenanthroline -9-diary, 1,8-phenanthroline-10-diary, 1,9-phenanthroline-2-yl, 1,9-phenanthroline-3-yl, 1,9-phenanthroline-4 -Diary, 1,9-phenanthroline-5-diary, 1,9-phenanthroline-6-diary, 1,9-phenanthroline-7-diary, 1,9-phenanthroline-8-diary , 1,9-phenanthroline-10- diary, 1,10-phenanthroline-2-yl, 1,10-phenanthroline-3-yl, 1,10-phenanthroline-4-yl, 1 , 10-phenanthroline-5- diary, 2,9-phenanthroline-1-yl, 2,9-phenanthroline-3-yl, 2,9-phenanthroline-4-yl, 2,9 -Phenanthroline-5-diary, 2,9-phenanthroline-6-diary, 2,9-phenanthroline-7-diary, 2,9-phenanthroline-8-diary, 2,9-phenan Trolline-10- diary, 2,8-phenanthroline-1-yl, 2,8-phenanthroline-3-yl, 2,8-phenanthroline-4-yl, 2,8-phenanthroline -5-diary, 2,8-phenanthroline-6-diary, 2,8-phenanthroline-7-diary, 2,8-phenanthroline-9-diary, 2,8-phenan Rollin-10- Di, 2,7-Phenanthroline-1-yl, 2,7-Phenanthroline-3-yl, 2,7-Phenanthroline-4-yl, 2,7-Phenanthroline- 5-diary, 2,7-phenanthroline-6-diary, 2,7-phenanthroline-8-diary, 2,7-phenanthroline-9-diary, 2,7-phenanthroline-10- Diary, phenazinyl includes 1-phenazinyl, 2-phenazinyl, phenoxyazinyl, 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenosycin Azinyl, 10-phenothiazinyl, phenoxazinyl includes 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phenoxazinyl, 10-phenoxazinyl, Oxazolyl includes 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, oxadiazoles include 2-oxazolyl, 5-oxazozolyl, furazanyl includes 3-furazanyl, , Dibenzofuranyl includes 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl, 4-dibenzofuranyl, and dibenzofuranyl EO phenyl includes all of 1-dibenzo thiophenyl, 2-benzo thiophenyl, 3-benzo diode thiophenyl, 4-benzo diode thiophenyl.

In addition, the alkyl of the '(C1-C30) alkyl or (C6-C30) ar (C1-C30) alkyl' group described in the present invention includes (C1-C20) alkyl or (C1-C10) alkyl, Aryl of the '(C6-C30) aryl and (C6-C30) ar (C1-C30) alkyl' groups includes (C6-C20) aryl or (C6-C12) aryl. '(C2-C30) heteroaryl' group includes (C2-C20) heteroaryl or (C2-C12) heteroaryl, and the '(C3-C30) cycloalkyl' group is a (C3-C20) cycloalkyl or (C3- C7) cycloalkyl. '(C3-C30) alkylene or alkenylene' groups include (C3-C20) alkylene or alkenylene, (C3-C10) alkylene or alkenylene.

, 시아노, 카바졸릴, (C6-C30)아르(C1-C30)알킬, (C1-C30)알킬(C6-C30)아릴, -OR₂₁, -SR₂₂, -NR₂₃R₂₄, -PR₂₅R₂₆, -SiR₂₇R₂₈R₂₉, 나이트로 및 하이드록실로 이루어진 군으로부터 선택되는 하나 이상이고, Y₁₁ 및 Y₁₂는 각각 독립적으로 화학결합, -C(R₃₁R₃₂)-, -O-, -S- 또는 -N(R₃₃)-이고, 단 Y₁₁ 및 Y₁₂가 동시에 화학결합인 경우는 제외하며; R₂₁ 내지 R₃₃은 서로 독립적으로 (C1-C30)알킬, (C6-C30)아릴, (C2-C30)헤테로아릴 또는 (C3-C30)시클로알킬인 것을 특징으로 한다.In addition, in the description of "substituted or unsubstituted" described in the present invention, "substituted" means a case where is further substituted with an unsubstituted substituent, the R _1, R _2, R _3, L, Ar ₁ , Ar ₂ And Substituents further substituted with R ₁₁ to R ₂₀ are independently substituted or unsubstituted with deuterium, halogen, or halogen-substituted (C1-C30) alkyl, (C6-C30) aryl, or (C6-C30) aryl. Fused (C2-C30) heteroaryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused at least one aromatic ring, (C3-C30) cycloalkyl, at least one fused ring (C6-C30) cycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl,

, Cyano, carbazolyl, (C6-C30) ar (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, -OR ₂₁ , -SR ₂₂ , -NR ₂₃ R ₂₄ , -PR ₂₅ R ₂₆ , -SiR ₂₇ R ₂₈ R ₂₉ , at least one selected from the group consisting of nitro and hydroxyl, Y ₁₁ and Y ₁₂ are each independently a chemical bond, -C (R ₃₁ R ₃₂ )-, -O -, -S- or -N (R ₃₃ )-, except that Y ₁₁ and Y ₁₂ are at the same time a chemical bond; R ₂₁ to R ₃₃ are independently from each other (C1-C30) alkyl, (C6-C30) aryl, (C2-C30) heteroaryl or (C3-C30) cycloalkyl.

으로, 인돌린 고리에 융합되어 있고 6원의 방향족고리 또는 6원의 질소 함유 헤테로방향족고리이고, B고리는

으로, A고리에 융합되어 있고 5원 또는 6원의 고리이고, C고리는

으로, B고리에 융합되어 있고 6원의 방향족고리 또는 6원의 질소 함유 헤테로방향족고리이다.In Formula 1, A ring

Ring is fused to an indolin ring and is a six-membered aromatic ring or a six-membered nitrogen-containing heteroaromatic ring, and the B ring

Which is fused to ring A and is a 5 or 6 membered ring, and ring C is

Or a 6-membered aromatic ring or a 6-membered nitrogen-containing heteroaromatic ring fused to ring B.

은 하기 구조에서 선택되나, 이에 한정되지는 않는다.Specifically, of Formula 1

Is selected from the following structures, but is not limited thereto.

[In the above structure, R ₂ , R ₁₁ to R ₁₅ and p are the same as defined in Formula 1 above.]

또는

이고; Y₃ 및 Y₄는 서로 독립적으로 -O-, -S-, -C(R₁₆R₁₇)- 또는 -N(R₂₀)-이고; R₁₆, R₁₇ 및 R₂₀은 서로 독립적으로 (C1-C30)알킬, (C6-C30)아릴 또는 (C2-C30)헤테로아릴이거나, R₁₆과 R₁₇은 융합고리를 포함하거나 포함하지 않는 치환 또는 비치환된 (C3-C30)알킬렌 또는 치환 또는 비치환된 (C3-C30)알케닐렌으로 연결되어 지환족 고리 및 단일환 또는 다환의 방향족 고리를 형성할 수 있으며; R₁는 수소, (C6-C30)아릴 또는 (C2-C30)헤테로아릴이거나, 인접한 치환체와

,

또는

으로 연결되어 고리를 형성할 수 있고; 상기 L의 아릴렌, Ar₁ 및 Ar₂의 아릴, 헤테로아릴, R_{16 ,} R₁₇ 및 R₂₀의 알킬, 아릴 또는 헤테로아릴, R₁의 아릴 또는 헤테로아릴은 각각 중수소, 할로겐, 할로겐이 치환 또는(C6-C30)아릴, 비치환된 (C1-C30)알킬, (C6-C30)아릴이 치환 또는 비치환된 (C2-C30)헤테로아릴, 5원 내지 7원의 헤테로시클로알킬, 방향족고리가 하나이상 융합된 5원 내지 7원의 헤테로시클로알킬,

, 카바졸릴, -NR₂₃R₂₄로 이루어진 군으로부터 선택되는 하나 이상으로 더 치환될 수 있고, 상기 Y₁₁ 및 Y₁₂는 각각 독립적으로 -C(R₃₁R₃₂)-, -O-, -S- 또는 -N(R₃₀)-이고; R₂₃, R₂₄, R₃₁, R₃₂ 및 R₃₃은 서로 독립적으로 (C1-C30)알킬, (C6-C30)아릴 또는 (C2-C30)헤테로아릴이다.More specifically, L is (C6-C30) arylene; Ar ₁ and Ar ₂ are each independently of the other (C6-C30) aryl, (C2-C30) heteroaryl,

or

ego; Y ₃ and Y ₄ are independently of each other -O-, -S-, -C (R ₁₆ R ₁₇ )-or -N (R ₂₀ )-; R ₁₆ , R ₁₇ and R ₂₀ independently of one another are (C 1 -C 30) alkyl, (C 6 -C 30) aryl or (C 2 -C 30) heteroaryl, or R ₁₆ and R ₁₇ are substituted with or without a fused ring Or may be linked with an unsubstituted (C3-C30) alkylene or a substituted or unsubstituted (C3-C30) alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring; R ₁ is hydrogen, (C6-C30) aryl or (C2-C30) heteroaryl, or

,

or

To form a ring; Arylene of L, aryl, heteroaryl of Ar ₁ and Ar ₂ , alkyl, aryl or heteroaryl of R _{16 ,} R ₁₇ and R ₂₀ , aryl or heteroaryl of R ₁ are each substituted with deuterium, halogen, halogen or (C6-C30) aryl, unsubstituted (C1-C30) alkyl, (C6-C30) aryl substituted or unsubstituted (C2-C30) heteroaryl, 5- to 7-membered heterocycloalkyl, aromatic ring One or more fused 5- to 7-membered heterocycloalkyl,

, Carbazolyl, -NR ₂₃ R ₂₄ can be further substituted with one or more selected from the group consisting of, wherein Y ₁₁ and Y ₁₂ are each independently -C (R ₃₁ R ₃₂ )-, -O-, -S -Or -N (R ₃₀ )-; R ₂₃ , R ₂₄ , R ₃₁ , R ₃₂ and R ₃₃ are independently of each other (C1-C30) alkyl, (C6-C30) aryl or (C2-C30) heteroaryl.

The organic light emitting compound according to the present invention may be more specifically exemplified as the following compound, but the following compound does not limit the present invention.

The organic light emitting compound according to the present invention may be prepared, for example, as shown in Scheme 1 below, but is not limited thereto.

Scheme 1

[In Scheme 1, A, B, C, R ₁ , L, Ar ₁ , Ar ₂ , m and n are the same as defined in Formula 1 above.]

In another aspect, the present invention provides an organic electroluminescent device, characterized in that the organic light emitting compound according to the invention is used as a hole injection material or a hole transport material.

When the organic light emitting compound of Formula 1 is used in the hole injection layer or the hole transport layer according to the present invention, there is an advantage of manufacturing an OLED device having improved power consumption by inducing an increase in power efficiency.

The organic electroluminescent device according to the present invention comprises a first electrode; A second electrode; And at least one organic layer interposed between the first electrode and the second electrode, wherein the organic material layer includes at least one layer including the organic light emitting compound of Formula 1.

In addition, the organic material layer may further include at least one light emitting layer in addition to the layer containing the organic light emitting compound of Formula 1, the light emitting layer further comprises at least one dopant or host, the organic field of the present invention The dopant or host applied to the light emitting device is not particularly limited, but is preferably selected from the following Chemical Formulas 2 to 6.

[Formula 2]

M ^One L ¹⁰¹ L ¹⁰² L ¹⁰³

In Chemical Formula 2,

Wherein M ¹ is selected from the group consisting of Ir, Pt, Pd and Os,

The ligands L ¹⁰¹ , L ¹⁰² and L ¹⁰³ are independently selected from the following structures.

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 di- (C1-C30) alkylamino, substituted or unsubstituted 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 independently of each other hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen, or R ₂₂₄ and R ₂₂₅ contain fused rings 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 (C2-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(C3-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 (C3-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.]

(3)

[In Formula 3,

Z is -O-, -S-, -C (R ₄₁ R ₄₂ )-, -Si (R ₄₃ R ₄₄ )-or -N (R ₄₅ )-;

이며;D ring and F ring each independently

Is;

이고;E ring

ego;

Y ₂₁ to Y ₂₂ are each independently CH or N;

Y ₂₃ to Y ₂₄ are each independently a chemical bond, —O—, —S—, —C (R ₄₁ R ₄₂ ) —, —Si (R ₄₃ R ₄₄ ) — or —N (R ₄₅ ) —; Provided that Y ₂₃ and Y ₂₄ are simultaneously a chemical bond;

R ₃₁ and R ₃₂ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) hetero Aryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30) ar (C1-C30) alkyl, substituted or Unsubstituted (C1-C30) alkylsilyl group, substituted or unsubstituted (C1-C30) arylsilyl group, substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylsilyl group, cyano, nitrate Cycloaliphatic ring and monocyclic or polycyclic aromatic, which is hydroxy and is linked to a substituted or unsubstituted (C3-C30) alkylene or (C3-C30) alkenylene, which may or may not include adjacent substituents and fused rings. May form a ring;

R ₄₁ to R ₄₅ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) hetero Aryl, substituted or unsubstituted 5 to 7 membered heterocycloalkyl, substituted or unsubstituted (C3-C30) cycloalkyl, or adjacent substituents may combine to form a ring;

r and q are each independently integers of 0 to 4; when r or q is an integer of 2 or more, each of R ₃₁ and R ₃₂ may be the same or different from each other, and adjacent substituents may combine with each other to form a ring;

Wherein said heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.]

[Formula 4]

( Cz - L ₂ ) _a -M

[Chemical Formula 5]

( Cz ) _b - L ₂ -M

[In Formula 4 and Formula 5,

Cz is selected from the structure

Ring G is a (C6-C30) aliphatic ring, a (C6-C30) aromatic ring or a (C2-C30) heteroaromatic ring;

R ₅₁ to R ₅₃ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) hetero Aryl, substituted or unsubstituted 5 to 7 membered heterocycloalkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted To 7-membered heterocycloalkyl fused with one or more aromatic rings, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted aromatic rings with one or more fused (C3-C30) cycloalkyl , Substituted or unsubstituted (C6-C30) ar (C1-C30) alkyl, cyano, nitro, hydroxy, -BR ₆₁ R ₆₂ , -PR ₆₃ R ₆₄ , -P (= O) R ₆₅ R ₆₆ , R ₆₇ R ₆₈ R ₆₉ Si _- , _- NR ₇₀ R ₇₁ , -YR ₇₂ Substituted or unsubstituted (C3-C30) alkylene or substituted or unsubstituted (C3) with or without adjacent substituents and fused ring -C30) may be linked to alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, wherein the carbon atoms of the formed alicyclic ring and monocyclic or polycyclic aromatic ring are selected from nitrogen, oxygen and sulfur May be substituted with one or more heteroatoms; Each R ₅₂ or R ₅₃ may be the same or different;

Y is O or S;

R ₆₁ to R ₇₂ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) hetero Aryl, substituted or unsubstituted 5 to 7 membered heterocycloalkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted To 7-membered heterocycloalkyl fused with one or more aromatic rings, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted aromatic rings with one or more fused (C3-C30) cycloalkyl , Substituted or unsubstituted (C6-C30) ar (C1-C30) alkyl, cyano, nitro or hydroxy;

L ₂ is a chemical bond, a substituted or unsubstituted (C6-C30) aryl, or a substituted or unsubstituted (C2-C30) heteroaryl;

M is substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (C2-C30) heteroaryl;

a to d are each independently an integer of 0 to 4;

[Formula 6]

[In Formula 6,

A ₁ to A ₁₉ are each independently CR ₈₁ Or N;

X is -C (R ₈₂ R ₈₃ )-, -N (R ₈₄ )-, -S-, -O-, -Si (R ₈₅ ) (R ₈₆ )-, -P (R ₈₇ )-, -P (═O) (R ₈₈ ) — or —B (R ₈₉ ) —;

Ar ₁₁ is substituted or unsubstituted (C6-C40) arylene, or substituted or unsubstituted (C2-C40) heteroarylene, provided that when e is 0 and A ₁₅ to A ₁₉ are CR ₈₁ at the same time Exclude;

R ₈₁ to R ₈₉ are each independently Substituted or unsubstituted fused with one or more hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) cycloalkyl Substituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, or substituted or unsubstituted aromatic ring 5 1-7 membered heterocycloalkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted aromatic ring (C3-C30) cycloalkyl, cyano, trifluoromethyl,- NR ₉₁ R ₉₂ , -BR ₉₃ R ₉₄ , -PR ₉₅ R ₉₆ , -P (= O) R ₉₇ R ₉₈ , R ₉₉ R ₁₀₀ R ₁₀₁ Si-, R ₁₀₂ Y _21- , R ₁₀₃ C (= O) R ₁₀₄ C (= 0) O-, substituted or unsubstituted (C6-C30) ar (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C2 -C30) alkynyl, carboxyl, nitro, hydroxy or adjacent teeth It does not contain a fused ring, or comprises a body (C3-C30) alkylene or (C3-C30) alkenylene with an alicyclic ring, or a monocyclic or polycyclic, and may form an aromatic ring or heteroaromatic ring;

R ₉₁ to R ₉₈ are each independently substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (C2-C30) heteroaryl;

R ₉₉ to R ₁₀₁ are independently of each other substituted or unsubstituted (C1-C30) alkyl, or substituted or unsubstituted (C6-C30) aryl;

Y ₂₁ is S or O;

R ₁₀₂ is substituted or unsubstituted (C1-C30) alkyl, or substituted or unsubstituted (C6-C30) aryl;

R ₁₀₃ is substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (C6-C30) Aryloxy;

R ₁₀₄ is substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (C6-C30) Aryloxy;

e is an integer from 0 to 2;

Wherein said heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.]

In the description of "substituted or unsubstituted" described in Formulas 2 to 6, 'substituted' refers to a case where the substituent is further substituted with an unsubstituted substituent, and at least one substituent selected from the same group as in Formula 1 above. it means.

Specifically, the formulas 2 to 6 preferably use the following compounds.

In the organic electroluminescent device of the present invention, it may include one or more compounds selected from the group consisting of an organic light emitting compound of formula (1), and at the same time an arylamine compound or a styrylarylamine compound, an arylamine compound Or specific examples of the styrylarylamine-based compound are exemplified in the identification number <212> to <224> of Patent Application No. 10-2008-0060393, 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 organic light emitting compound of Chemical Formula 1, a group consisting of Group 1, Group 2, 4 cycle, 5 cycle transition metal, lanthanide series metal and organic metal of d-transition element It may further comprise one or more metals or complex compounds selected from, the organic material layer may include a light emitting layer and a charge generating layer at the same time.

An organic electroluminescent device comprising an organic light emitting compound of Formula 1 of the present invention is a subpixel, and includes Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au, and An organic electroluminescent device having an independent light emitting pixel structure in which at least one subpixel including at least one metal compound selected from the group consisting of Ag is simultaneously patterned in parallel may be implemented.

In addition, an organic light emitting device that emits white light may be formed by simultaneously including one or more organic light emitting layers including red, green, or blue light emitting compounds in addition to the organic electroluminescent 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 &quot;) 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, a white organic electroluminescent device having two or more light emitting layers may be manufactured using a reducing dopant layer as a charge generation layer.

The organic electroluminescent device using the organic light emitting compound according to the present invention as a hole transporting material or a hole injection material has a good luminous efficiency and excellent life characteristics of the material, the driving life of the device is very excellent, leading to an increase in power efficiency, power consumption There is an advantage to manufacture this improved OLED device.

Hereinafter, the organic light emitting compound according to the present invention, a method for preparing the same and a light emitting property of the device are described for the detailed understanding of the present invention, but the present invention is only intended to illustrate the embodiments of the present invention. It does not limit the scope of the invention.

Preparation Example 1 Preparation of Compound 1

compound 1-1 Manufacture

30 g (120.4 mmol) of 2-iodobenzene, 26 g (132.5 mmol) of 4-bromophenylboronic acid, 6.9 g (6.02 mmol) of Pd (PPh ₃ ) ₄ , 150 mL of 2M Na ₂ CO ₃ , 500 mL of toluene Heated at ° C. After 4 hours, the mixture was cooled to room temperature and extracted with ethyl acetate. The mixture was washed with distilled water, dried over MgSO ₄ , distilled under reduced pressure, and column separated to obtain compound 1-1 28g (100.68 mmol, 83,33%).

compound 1-2 Manufacture

28 g (100.68 mmol) of Compound 1-1 were mixed with 300 mL of triethylphosphite and stirred at 150 ° C. for 6 hours. After cooling to room temperature, the mixture was distilled under reduced pressure, extracted with ethyl acetate, and washed with distilled water. After drying over MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 1-2 (11 g, 44.69 mmol, 44.38%).

compound 1-3 Manufacture

Compound 1-2 30g (101.29mmol), iodobenzene 41.3g (202.59mmol), CuI 9.6g (50.64mmol), Cs ₂ CO ₃ 82.5g (253.2mmol), toluene 600mL was mixed and heated at 50 ℃, 6.8 mL (101.29 mmol) of ethylenediamine was added thereto, and the mixture was stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extraction with ethyl acetate, drying with MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 1-3 (32 g, 85.96 mmol, 84.86%).

compound 1-4 Manufacture

32 g (85.96 mmol) of Compound 1-3 were dissolved in 300 mL of THF, and 37.8 mL (94.55 mmol, 2.5 M in hexane) of n-butyllithium was slowly added at -78 ° C. After 1 hour trimethyl borate 12.4 mL (111.7 mmol) was added. After stirring for 12 hours at room temperature, distilled water was added. Extraction with ethyl acetate, drying with MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 1-4 20g (59.31 mmol, 69.00%).

compound 1-5 Manufacture

Compound 1-4 20 g (59.31 mmol), 1-bromo-2-nitrobenzene 14.3 g (71.17 mmol), Pd (PPh ₃ ) ₄ 2.7 g (2.37 mmol), 2 M Na ₂ CO ₃ 75 mL, toluene 300 mL, ethanol 70 mL was mixed and stirred at reflux. After 5 hours, cooled to room temperature and distilled water was added. Extraction with ethyl acetate, drying with MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 1-5 20g (48.25mmol, 81.36%).

compound 1-6 Manufacture

To 20 g (48.25 mmol) of Compound 1-5 , add 200 mL of triethylphosphite. After stirring for 6 hours at 150 ℃, cooled to room temperature and distilled under reduced pressure. Extracted with ethyl acetate and washed with distilled water. MgSO _{4 was} dried and distilled under reduced pressure, followed by column separation to obtain compound 1-6 7g (18.30 mmol, 37.93%).

compound One Manufacture

Compound 1-6 7 g (18.30 mmol), 4-bromo-N, N-diphenylaniline 11.9 g (36.60 mmol), CuI 1.7 g (9.15 mmol), K ₃ PO ₄ 11.6 g (54.90 mmol), toluene 100 mL Was mixed and heated at 50 ° C. 1.2 mL (18.30 mmol) of ethylenediamine was added thereto, and the mixture was stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extraction with ethyl acetate, drying of MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 1 (8 g, 17.44 mmol, 95.33%).

MS / FAB found 576, calculated 575.70

Preparation Example 2 Preparation of Compound 15

compound 2-1 Manufacture

15 g (0.074 mol) of 1-bromo-2-nitrobenzene was added to 1 L 2-neck RBF, and 23 g (0.096 mol) of 9,9-dimethyl-9H-fluorene-2-ylboronic acid and Pd (PPh ₃ ) ₄ 4.2 g (0.003 mol), 111 mL of Na ₂ CO ₃ (2M) and 111 mL of ethanol were added thereto, and 200 mL of toluene was added thereto, followed by heating and stirring at 120 ° C. for 3 hours. After the reaction was terminated, washed with distilled water and extracted with ethyl acetate. The organic layer was dried over MgSO ₄ and the solvent was removed using a rotary evaporator, and then purified by column chromatography to obtain 22 g (95%) of Compound 2-1 .

compound 2-2 Manufacture

24 g (0.076 mol) of Compound 2-1 was added to 1 L 2-sphere RBF, 200 mL of triethylphosphite and 200 mL of 1,2-dichlorobenzene were added thereto, followed by heating and stirring at 140 ° C. for 12 hours. After the reaction was completed, the solvent was distilled off, washed with distilled water and extracted with ethyl acetate. The organic layer was dried over MgSO ₄ and the solvent was removed using a rotary evaporator, and then purified by column chromatography to obtain compound 2-2 7g (33%).

compound 15 Manufacture

Compound 2-2 7 g (18.30 mmol), N- (4-bromophenyl) -N-phenylnaphthalen-2-amine (N- (4-bromophenyl) -N-phenylnaphthalen-2-amine) 13.7 g (36.60 mmol) ), 1.7 g (9.15 mmol) of CuI, 11.6 g (54.90 mmol) of K ₃ PO ₄ , and 100 mL of toluene were mixed and heated at 50 ° C. Ethylenediamine 1.2 mL (18.30 mmol) was added thereto, and the mixture was stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extraction with ethyl acetate, drying with MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 15 (8 g, 17.44 mmol, 95.33%).

MS / FAB found 577, calculated 576.73

Preparation Example 3 Preparation of Compound 22

compound 3-1 Manufacture

Compound 2-bromo-9H-carbazole 7 g (18.30 mmol), N- (4- (9H-carbazol-9-yl) phenyl) -4-bromo-N-phenylaniline (N- (4- ( 9H-carbazol-9-yl) phenyl) -4-bromo-N-phenylaniline) 13.7g (36.60mmol), CuI 1.7g (9.15mmol), K ₃ PO ₄ 11.6g (54.90mmol), mix 100mL toluene 50 Heated at ° C. 1.2 mL (18.30 mmol) of ethylenediamine was added thereto, and the mixture was stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extraction with ethyl acetate, drying of MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 3-1 8 g (17.44 mmol, 95.33%).

compound 3-2 Manufacture

Compound 3-1 12 g (37.42 mmol), 2- (methylthio) phenylboronic acid 7.5 g (44.69 mmol), Pd (PPh ₃ ) ₄ 2.15 g (1.6 mmol), 2 M 45 mL of Na ₂ CO ₃ aqueous solution and 200 mL of THF were mixed and stirred under reflux. After 5 hours, the mixture was cooled to room temperature, extracted with ethyl acetate, and washed with distilled water. After drying over MgSO ₄ and distillation under reduced pressure, column separation was performed to obtain 10 g (27.36 mmol, 73.47%) of compound 3-2 .

compound 3-3 Manufacture

10 g (27.36 mmol) of Compound 3-2 was added to 100 mL of acetic acid, and 2.65 mL (30.09 mmol, 35%) of H ₂ O ₂ was slowly added thereto. After stirring for 12 hours at room temperature, acetic acid was distilled under reduced pressure. Extracted with dichloromethane and neutralized with aqueous NaHCO ₃ solution. Drying with MgSO ₄ and distillation under reduced pressure yielded 10 g (26.21 mmol, 95.79%) of compound 3-3 .

compound 22 Manufacture

10 g (26.21 mmol) of Compound 3-3 were mixed with 70 mL of trifluoromethanesulfonic acid and stirred at 100 ° C. for 5 hours. Cooled to room temperature and added to 100 mL of the mixture (pyridine: distilled water = 1: 5). After stirring for 1 hour at reflux, the mixture was cooled to room temperature and the resulting solid was filtered under reduced pressure. Compound 22 (6g, 17.16mmol, 65.47%) was obtained by column separation.

MS / FAB found 682, calculated 681.84

Preparation Example 4 Preparation of Compound 32

compound 4-1 Manufacture

10 g (43.84 mmol) of dibenzo [b, d] thiophen-4-ylboronic acid, 8.85 g (43.84 mmol) of bromonitrobenzene, 2 M Na ₂ CO 70 mL of ₃ aqueous solution, 200 mL of toluene, and 70 mL of ethanol were mixed, and it stirred under reflux. After 5 hours, the mixture was cooled to room temperature, extracted with ethyl acetate, and washed with distilled water. After drying over MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 4-1 10 g (32.74 mmol, 74.68%).

compound 4-2 Manufacture

10 g (32.74 mmol) of Compound 4-1 were mixed with 100 mL of triethylphosphite and stirred at 150 ° C. for 7 hours. After cooling to room temperature, distillation under reduced pressure and recrystallization with ethyl acetate yielded Compound 4-2 7g (25.60 mmol, 78.19%).

compound 32 Manufacture

Compound 4-2 7 g (25.60 mmol), N- (4-bromophenyl) -N, 9-diphenyl-9H-carbazole-3-amine (N- (4-bromophenyl) -N, 9-diphenyl- 9H-carbazol-3-amine) 10.44g (51.21mmol), CuI 2.5g (12.80mmol), K ₃ PO ₄ 16.30g (76.82mmol) and 200mL of toluene were added and heated to 50 ℃, followed by 1.72mL of ethylenediamine (25.60 mmol) was added. After stirring for 12 hours at reflux, the mixture was cooled to room temperature and extracted with ethyl acetate, followed by NaHCO ₃ It was washed with an aqueous solution. After drying over MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 32 (8 g, 22.89 mmol, 89.41%).

MS / FAB found 682, calculated 681.84

Preparation Example 5 Preparation of Compound 41

compound 5-1 Manufacture

50 g (0.23 mol) of 2- (phenylamino) benzoic acid was dissolved in 1 L of MeOH, and placed in an ice bath containing ice and stirred at 0 ° C. for 10 minutes. 60 mL (0.58 mol) of SOCl ₂ was slowly added at 0 ° C., followed by stirring under reflux at 90 ° C. for 12 hours. When the reaction was terminated, washed with distilled water and extracted with ethyl acetate. The organic layer was dried over MgSO ₄ , and the solvent was removed using a rotary evaporator. The mixture was purified by column chromatography with ethyl acetate as a developing solvent, to obtain compound 5-1 47 g (92%).

compound 5-2 Manufacture

90 g (0.3 mol) of Compound 5-1 was added to 1.5 L of THF, and 462 mL (1.38 mol) of MeMgBr (3.0M) was added slowly, followed by stirring at room temperature for 12 hours. After the reaction was completed, the mixture was neutralized with distilled water and extracted with ethyl acetate. The organic layer was dried over MgSO ₄ , and the solvent was removed using a rotary evaporator. Purification by column chromatography using ethyl acetate as a developing solvent gave 80 g (90%) of the compound 5-2 .

compound 5-3 Manufacture

80 g (0.35 mol) of Compound 5-2 was added to 1.7 L of H ₃ PO _4, followed by stirring at room temperature for 12 hours. When the reaction was terminated, the mixture was neutralized with distilled water and filtered while washing the resulting solid with water. The solid was extracted by dissolving with dichloromethane and neutralized with NaOH. The organic layer was dried over MgSO ₄ , the solvent was removed with a rotary evaporator, and recrystallized with hexane to obtain 64 g (87%) of compound 5-3 .

compound 5-4 Manufacture

Compound 5-3 64 g (0.30 mol), Bromobenzene 52.8 g (0.33 mol), Pd (OAc) ₂ 1.37 g (6.11 mmol), P (t-Bu) ₃ 50% 7.3 mL (15.28 mmol) ) And 58 g (0.61 mol) of NaOt-Bu were dissolved in 1.2 L of toluene and stirred at 120 ° C. for 12 hours. After the reaction was completed, the mixture was neutralized with distilled water and extracted with ethyl acetate. The organic layer was dried over MgSO ₄ , and the solvent was removed using a rotary evaporator. The mixture was purified by column chromatography with ethyl acetate as a developing solvent to obtain 71 g (81%) of the compound 5-4 .

compound 5-5 Manufacture

20 g (0.07 mol) of Compound 5-4 were dissolved in 800 mL of DMF and stirred at 0 ° C. for 10 minutes. A solution of 12.5 g (0.07 mol) of NBS dissolved in 350 mL of DMF was slowly added thereto, followed by stirring at 0 ° C. for 6 hours. After the reaction was completed, the mixture was neutralized with distilled water and extracted with ethyl acetate. The organic layer was dried over MgSO ₄ , and the solvent was removed using a rotary evaporator. The mixture was purified by column chromatography with ethyl acetate as a developing solvent, to obtain 21 g (84%) of the compound 5-5 .

compound 5-6 Manufacture

Compound 5-5 20 g (0.054 mol), 2-chloroaniline 8.4 g (0.065 mol), Pd (OAc) ₂ 370 mg (1.64 mmol), P (t-Bu) ₃ 50% 3.6 mL (5.49 mmol) and 35.7 g (0.109 mol) of Cs ₂ CO ₃ were dissolved in 300 mL of toluene and stirred at 120 ° C. for 4 hours. After the reaction was completed, the mixture was neutralized with distilled water and extracted with ethyl acetate. The organic layer was dried over MgSO ₄ , and the solvent was removed using a rotary evaporator. Purification by column chromatography using ethyl acetate as a developing solvent gave 13.6 g (60%) of compound 5-6 .

compound 5-7 Manufacture

Compound 5-6 12.6 g (0.03 mol), Pd (OAc) ₂ 1.37 mg (6.13 mmol), Di-tert-butyl (methyl) phosponium tetrafluoroborate 3 g (12.26 mmol) and 50 g (0.15 mol) of Cs ₂ CO ₃ were dissolved in 240 mL of DMA and stirred at 190 ° C. for 4 hours. After the reaction was completed, the mixture was neutralized with distilled water and extracted with ethyl acetate. The organic layer was dried over MgSO ₄ , and the solvent was removed using a rotary evaporator. The mixture was purified by column chromatography with ethyl acetate as a developing solvent, to obtain compound 5-7 7 g (70%).

compound 41 Manufacture

Compound 5-7 7g (25.60mmol), N- (biphenyl-4-yl) -N- (4-bromophenyl) -9,9-dimethyl-9H-fluoren-2-amine (N- (biphenyl -4-yl) -N- (4-bromophenyl) -9,9-dimethyl-9H-fluoren-2-amine) 10.44 g (51.21 mmol), CuI 2.5 g (12.80 mmol), K ₃ PO ₄ 16.30 g ( 76.82 mmol) and 200 mL of toluene were added thereto, followed by heating to 50 ° C., followed by adding 1.72 mL (25.60 mmol) of ethylenediamine. After stirring for 12 hours under reflux, the mixture was cooled to room temperature, extracted with ethyl acetate, and washed with NaHCO ₃ aqueous solution. After drying over MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 41 (8 g, 22.89 mmol, 89.41%).

MS / FAB found 811, calculated 810.04

Preparation Example 6 Preparation of Compound 51

compound 6-1 Manufacture

8.1 g (0.028 mol) of Compound 2-2 were added to 1 L 2-neck RBF, 300 mL of DMF was added thereto, and the mixture was stirred at reflux for 10 minutes at 0 ° C. 5.08 g (0.028 mol) of NBS was added to 300 mL of DMF, and then slowly added to the reaction. The mixture was stirred at reflux for 6 hours at 0 ° C. After the reaction was completed, the mixture was neutralized with distilled water and extracted with ethyl acetate. The organic layer was dried over MgSO ₄ , the solvent was removed using a rotary evaporator, and purified by column chromatography using ethyl acetate as a developing solvent to obtain compound 6-1 9g (87%).

compound 6-2 Manufacture

Compound 6-1 7 g (18.30 mmol), N- (4-bromophenyl) -N-phenylnaphthalen-2-amine (N- (4-bromophenyl) -N-phenylnaphthalen-2-amine) 13.7 g (36.60 mmol) ), 1.7 g (9.15 mmol) of CuI, 11.6 g (54.90 mmol) of K ₃ PO ₄ , and 100 mL of toluene were mixed and heated at 50 ° C. 1.2 mL (18.30 mmol) of ethylenediamine was added thereto, and the mixture was stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extraction with ethyl acetate, drying of MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 6-2 8 g (17.44 mmol, 95.33%).

compound 51 Manufacture

Compound 6-2 7 g (18.30 mmol), 9H-carbazole 13.7 g 36.60 mmol), CuI 1.7 g (9.15 mmol), K ₃ PO ₄ 11.6 g (54.90 mmol), and 100 mL of toluene were mixed and heated at 50 ° C. 1.2 ml (18.30 mmol) of ethylenediamine was added thereto, and the mixture was stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extraction with ethyl acetate, drying with MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 51 (8 g, 17.44 mmol, 95.33%).

MS / FAB found 742, calculated 741.92

Preparation Example 7 Preparation of Compound 53

compound 7-1 Manufacture

2-bromodibenzo [b, d] thiophene 74 g (216.3 mmol) was dissolved in 1.5 L of THF, and 86.5 mL (216.3 mmol, 2.5 M in hexane) of n-butyllithium was slowly added at -78 ° C. After 1 hour, 28.9 ml (259.6 mmol) of trimethylborate was added and stirred at room temperature for 12 hours, followed by distilled water. Extraction with ethyl acetate, drying with MgSO ₄ , distillation under reduced pressure, and recrystallization with ethyl acetate and hexane gave compound 7-1 40g (136.8 mmol, 62.96%).

compound 7-2 Manufacture

Compound 7-1 40g (136.8mmol), iodonitrobenzene 37.4g (150.5mmol), Pd (PPh ₃ ) ₄ 6.32g (5.47mmol), 2M Na ₂ CO ₃ 170mL, toluene 700mL was added for 4 hours at 100 ℃ Was stirred. After cooling to room temperature, distilled water was added and extracted with ethyl acetate. After drying over MgSO ₄ , distillation under reduced pressure, and column separation yielded Compound 7-2 28g (72.86mmol, 52.94%).

compound 7-3 Manufacture

28 g (72.86 mmol) of Compound 7-2 were mixed with 300 mL of triethylphosphite and stirred at 150 ° C. for 12 hours. The mixture was cooled to room temperature, distilled under reduced pressure, extracted with ethyl acetate, and washed with distilled water. After drying over MgSO ₄ , distillation under reduced pressure, and column separation were carried out to obtain compound 7-3 11g (31.22mmol, 43.05%).

compound 53 Manufacture

Compound 7-3 7g (18.30 mmol), 4-bromo-N- (4- (dibenzo [b, d] thiophen-4-yl) phenyl) -N-phenylaniline (4-bromo-N- ( 4- (dibenzo [b, d] thiophen-4-yl) phenyl) -N-phenylaniline) 13.7 g 36.60 mmol), CuI 1.7 g (9.15 mmol), K ₃ PO ₄ 11.6 g (54.90 mmol), 100 mL of toluene Mix and heat at 50 ° C. 1.2 ml (18.30 mmol) of ethylenediamine was added thereto, and the mixture was stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extraction with ethyl acetate, drying of MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 53 (8 g, 17.44 mmol, 95.33%).

MS / FAB found 699, calculated 698.90

Preparation Example 8 Preparation of Compound 54

compound 8-1 Manufacture

50 g (177.99 mol) of compound 2,5-dibromonitrobenzene, 36.7 g (213.59 mmol) of 1-naphthalene boronic acid, 10.28 g (8.89 mmol) of Pd (PPh ₃ ) ₄ , 2M Na ₂ CO ₃ 533.97 mmol) toluene 700 mL and 200 mL of ethanol were mixed and stirred at 100 ° C. for 5 hours. After cooling to room temperature, distilled water was added, extraction was performed with ethyl acetate and dried over MgSO ₄ . Distillation under reduced pressure and column separation yielded 50 g (152.36 mmol, 85.60%) of compound 8-1 .

compound 8-2 Manufacture

50 g (152.36 mmol) of Compound 8-1 and 500 mL of triethyl phosphite were added thereto, followed by stirring at 150 ° C. for 7 hours. After cooling to room temperature and distillation under reduced pressure, the mixture was extracted with ethyl acetate and washed with distilled water. Drying with MgSO ₄ and distillation under reduced pressure followed by column separation yielded Compound 8-2 30g (101.29 mmol, 66.64%).

compound 8-3 Manufacture

Compound 8-2 30 g (101.29 mmol), N- (4- (9H-carbazol-9-yl) phenyl) -4-bromo-N- (4-tert-butylphenyl) aniline (N- (4- (9H-carbazol-9-yl) phenyl) -4-bromo-N- (4-tert-butyl-

phenyl) aniline) 41.3 g (202.59 mmol), CuI 9.6 g (50.64 mmol), Cs ₂ CO ₃ 82.5 g (253.2 mmol), 600 mL of toluene were mixed and heated at 50 ° C., 6.8 mL (101.29 mmol) of ethylenediamine Was added and stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extraction with ethyl acetate, drying with MgSO ₄ , reduced pressure distillation and column separation yielded Compound 8-3 32g (85.96mmol, 84.86%).

compound  8-4 Manufacture

32 g (85.96 mmol) of Compound 8-3 was dissolved in 300 mL of THF, and 37.8 mL (94.55 mmol, 2.5 M in hexane) of n-butyllithium was slowly added at -78 ° C. After 1 hour trimethyl borate 12.4 mL (111.7 mmol) was added. After stirring for 12 hours at room temperature, distilled water was added. Extraction with ethyl acetate, drying with MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 8-4 20g (59.31 mmol, 69.00%).

compound 8-5 Manufacture

Compound 8-4 20 g (59.31 mmol), 1-bromo-2-nitrobenzene 14.3 g (71.17 mmol), Pd (PPh ₃ ) ₄ 2.7 g (2.37 mmol), 2 M Na ₂ CO ₃ 75 ml, toluene 300 mL, ethanol 70 mL was mixed and stirred at reflux. After 5 hours, cooled to room temperature and distilled water was added. Extraction with ethyl acetate, drying with MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 8-5 20 g (48.25 mmol, 81.36%).

compound 8-6 Manufacture

20 g (48.25 mmol) of Compound 8-5 were mixed with 200 mL of triethyl phosphite, stirred at 150 ° C. for 6 hours, cooled to room temperature, and distilled under reduced pressure. Extracted with ethyl acetate and washed with distilled water. MgSO _{4 was} dried and distilled under reduced pressure, followed by column separation to obtain compound 8-6 7g (18.30 mmol, 37.93%).

compound 54 Manufacture

30 g (101.29 mmol) of compound 8-6 , 41.3 g (202.59 mmol) of iodobenzene, 9.6 g (50.64 mmol) of CuI, 82.5 g (253.2 mmol) of Cs ₂ CO ₃ , 600 mL of toluene were mixed and heated at 50 ° C., 6.8 ml (101.29 mmol) of ethylenediamine were added and stirred under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extraction with ethyl acetate, drying with MgSO ₄ , distillation under reduced pressure and column separation yielded Compound 54 32 g (85.96 mmol, 84.86%).

MS / FAB found 848, calculated 847.06

Preparation Example 9 Preparation of Compound 58

compound 9-1 Manufacture

10.2 g (59.4 mmol) of 1-naphthaleneboronic acid, 10.0 g (49.5 mmol) of 1-bromo-2-nitrobenzene, 1.7 g (1.4 mmol) of Pd (PPh ₃ ) ₄ , 2M K ₂ CO ₃ 70 mL of aqueous solution, 200 mL of toluene and 100 mL of ethanol were added thereto, and the mixture was stirred under reflux for 12 hours. The mixture was washed with distilled water, extracted with ethyl acetate, dried over anhydrous MgSO ₄ and distilled under reduced pressure to obtain a compound 9-1 9.0 g (73.7%) by column separation.

compound 9-2 Manufacture

9.0 g (36.1 mmol) of Compound 9-1 and 7.6 g (43.3 mmol) of N-bromosuccinimide were dissolved in 300 mL of dichloromethane and stirred at room temperature for 12 hours. After distillation under reduced pressure, the obtained solid was washed successively with distilled water, methanol and hexane to obtain 9.6 g (81.3%) of Compound 9-2 .

compound 9-3 Manufacture

Compound 9-2 9.6 g (29.3 mmol) and 72.2 g (175.5 mmol) of Fe [C ₂ O ₄ ]? 2H ₂ O (iron oxalate dihydrate) were mixed and heated at 205 ° C. for 30 minutes, then cooled to room temperature and ethyl acetate Extracted with and washed with distilled water. Recrystallization from toluene gave 5.2 g (60.5%) of compound 9-3 .

compound 9-4 Manufacture

Compound 9-3 30 g (101.29 mmol), 4-bromo-N-phenyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) aniline) (4-bromo-N-phenyl -N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) aniline) 41.3 g (202.59 mmol), CuI 9.6 g (50.64 mmol), Cs ₂ CO ₃ 82.5 g (253.2 mmol), toluene After mixing 600 mL and heating at 50 ° C, 6.8 mL (101.29 mmol) of ethylenediamine was added thereto, followed by stirring under reflux. After 14 hours, cooled to room temperature and distilled water was added. Extraction with ethyl acetate and drying over MgSO ₄ , distillation under reduced pressure and column separation yielded 32 g (85.96 mmol, 84.86%) of compound 9-4 .

compound 9-5 Manufacture

23.1 g (62.07 mmol) of Compound 9-4 was dissolved in 500 mL in THF, and 29.79 mL (74.48 mmol, 2.5 M in Hexane) of n-butyllithium was slowly added at -78 ° C. After 1 hour trimethylborate 10.38ml (93.10mmol) was added. After stirring for 12 hours at room temperature, distilled water was added and extracted with ethyl acetate and dried over MgSO ₄ . Distillation under reduced pressure and recrystallization with ethyl acetate and hexane gave compound 9-5 14g (67%).

compound 9-6 Manufacture

Compound 9-5 14 g (41.79 mmol), methyl-2-bromobenzoate 13.51 g (45.97 mmol), Pd (PPh ₃ ) ₄ 1.9 g (1.67 mmol), 2M Na ₂ CO ₃ 60 mL and toluene 200 mL were mixed and stirred under reflux. After 12 hours, the mixture was cooled to room temperature and distilled water was added. Extraction with ethyl acetate, drying with MgSO ₄ , distillation under reduced pressure and column separation yielded 8.8 g (42%) of compound 9-6 .

compound  9-7 Manufacture

8.8 g (17.53 mmol) of Compound 9-6 was dissolved in 200 mL of THF, and 14.60 mL (43.82 mmol, 3.0 M in diethyl ether) of methylmagnesium bromide was added thereto. Heated to 60 ℃ and cooled to room temperature after 6 hours. Distilled water was added and extracted with ethyl acetate. After drying over MgSO ₄ and distillation under reduced pressure, column separation was performed to obtain 6.6 g (74%) of Compound 9-7 .

compound 58 Manufacture

6.6 g (13.14 mmol) of Compound 9-7 , 50 mL of acetic acid and 50 mL of phosphoric acid were mixed and stirred at 50 ° C. for 5 hours. Cooled to room temperature and neutralized with aqueous NaOH solution. Extraction with ethyl acetate, drying with MgSO ₄ and distillation under reduced pressure followed by column separation yielded Compound 58 (5.1 g, 80%).

MS / FAB found 819, calculated 818.01

Preparation Example 10 Preparation of Compound 122

compound 10-1 Manufacture

60 g (0.219 mol) of 2-bromo-9,9-dimethyl-9H-fluorene, 56 g (0.439 mol) of 2-chloroaniline, 1.5 g (0.006 mol) of Pd (OAc) ₂ , P (t-Bu) ₃ 14mL (0.021mol) and 143g (0.439mol) of CsCO ₃ were mixed and 600mL of toluene was added thereto, followed by stirring at 120 ° C for 12 hours. After the reaction, the mixture was washed with distilled water, extracted with ethyl acetate, the organic layer was dried over MgSO ₄ , the solvent was removed by rotary evaporation, and column purification was carried out to obtain compound 10-1 65g (92%).

compound 10-2 Manufacture

Compound 10-1 65 g (0.20 mol), Pd (OAc) ₂ 2.3 g (0.01 mol), di-tert-butyl (methyl) phosphonium tetrafluoroborate 5.9 g (0.02 mol) and Na ₂ CO ₃ 64 g (0.60) mol) to 1000 ml of DMA was added and stirred at 190 ° C. for 16 hours. After the reaction, the mixture was washed with distilled water, extracted with ethyl acetate, the organic layer was dried over MgSO ₄ , the solvent was removed by rotary evaporation, and column purified to obtain compound 10-2 31g (54%).

compound 10-3 Manufacture

Compound 10-2 17 g (0.061 mol), CuI 2.3 g (0.012 mol), 130 mL of toluene was added to a mixture of 3.3 mL (0.049 mol) of ethylenediamine and 16 g (0.074 mol) of K ₃ PO ₃ , followed by 12 at 120 ° C. Stir for hours. After the reaction, the mixture was washed with distilled water, extracted with ethyl acetate, the organic layer was dried over MgSO ₄ , the solvent was removed with a rotary evaporator, and column purified to obtain 7.8 g (72%) of compound 10-3 .

compound 122 Manufacture

Compound 10-3 4 g (0.009 mol), 4- (diphenylamino) phenylboronic acid 3.1 g (0.010 mol), Pd (PPh ₃ ) ₄ 527 mg (0.4 mmol), K ₂ CO ₃ (2M) 14 mL, EtOH 14 mL And a mixture of 28 mL of toluene was stirred at 120 ° C. for 8 hours. After the reaction, the mixture was washed with distilled water, extracted with ethyl acetate, the organic layer was dried over MgSO ₄ , the solvent was removed with a rotary evaporator, and purified by a column to obtain compound 122 (2.6 g, 47%).

MS / FAB found 603. calculated 602.76

Preparation Example 11 Preparation of Compound 132

compound 11-1 Manufacture

10 g (36.6 mmol) of Compound 4-2 , 20 g (73.2 mmol) of iodo-4-bromobenzene, 3.5 g (18.3 mmol) of CuI, 4.5 mL (73.2 mmol) of ethylenediamine, 99.4 g of K ₃ PO ₄ (91.5) mmol) and toluene 200 mL were stirred at 120 ° C. overnight. After the reaction, the mixture was washed with distilled water, extracted with ethyl acetate, the organic layer was dried over MgSO ₄ , the solvent was removed with a rotary evaporator, and purified by column to obtain compound 11-1 7.7g (49%).

compound 132 Manufacture

Compound 11-1 7 g (16.3 mmol), 4- (diphenylamino) phenylboronic acid 5.6 g (19.6 mmol), Pd (PPh ₃ ) ₄ 0.95 g (0.82 mmol), K ₂ CO ₃ A mixture of 6 g (40.8 mmol), 60 mL toluene, 20 mL EtOH and 20 mL H ₂ O was stirred at 100 ° C. overnight. After the reaction, the mixture was washed with distilled water, extracted with ethyl acetate, the organic layer was dried over MgSO ₄ , the solvent was removed with a rotary evaporator, and purified by a column to obtain compound 132 (5.4 g, 56%).

MS / FAB found 593, calculated 592.75

The following compounds were prepared using the method of Preparation Examples 1 to 11.

Example 1 Fabrication of an OLED Device Using an Organic Light Emitting Compound 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 installed in the substrate folder of the vacuum deposition equipment, and 2-TNATA [4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine] is installed in the cell in the vacuum deposition equipment. And evacuated until the vacuum in the chamber reached 10 ⁻⁶ torr, followed by applying a current to the cell to evaporate 2-TNATA to deposit a 60 nm thick hole injection layer on the ITO substrate. Compound 1 according to the present invention was placed in another cell in the deposition equipment, and a current was applied to the cell to evaporate compound 1 to deposit a 20 nm thick hole transport layer on the hole injection layer, after forming the hole injection layer and the hole transport layer. The light emitting layer was deposited thereon as follows: CBP [4,4'-N, N'-dicarbazole-biphenyl] as a host was added to one cell in a vacuum deposition apparatus and (piq) ₂ as a dopant in another cell. After adding Ir (acac) [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate], the two substances A light emitting layer having a thickness of 30 nm was deposited on the hole transport layer by evaporation at a rate of 4% by weight, followed by bis (2-methyl-8-quinolinate) ( p -phenylphenolate) as a hole blocking layer on the light emitting layer. Aluminium (III) (BAlq) was deposited to a thickness of 10 nm, and then Alq [tris (8-hydroxyquinoline) -aluminum (III)] was deposited to a thickness of 20 nm as the electron transport layer, Liq [lithium quinolate] to the electron injection layer. ] Was deposited to a thickness of 1nm, and the Al cathode was deposited to a thickness of 150nm using another vacuum deposition equipment to produce an OLED device.

Each compound was vacuum sublimated and purified under 10 ^-6 torr to be used as an OLED light emitting material.

As a result, a current of 13.8 mA / cm ² flowed at a voltage of 6.9 V, and red light emission of 1020 cd / m ² was confirmed.

Example 2 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

An OLED device was manufactured in the same manner as in Example 1, except that Compound 19 of the present invention was used as a hole transport material.

As a result, a current of 14.3 mA / cm ² flowed at a voltage of 6.7 V, and red light emission of 1060 cd / m ² was observed.

Example 3 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

An OLED device was manufactured in the same manner as in Example 1, except that Compound 31 of the present invention was used as a hole transport material.

As a result, a current of 13.9 mA / cm ² flowed at a voltage of 6.7 V, and red light emission of 1044 cd / m ² was confirmed.

[ Example  4] using the organic light emitting compound according to the present invention OLED  Device fabrication

An OLED device was manufactured in the same manner as in Example 1, except that Compound 69 of the present invention was used as the hole transport material.

As a result, a current of 14.2 mA / cm ² flowed at a voltage of 6.8 V, and red light emission of 1015 cd / m ² was confirmed.

Example 5 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

Example 1, except that compound 1 of the present invention was used as a hole transporting material, and the organic iridium complex Ir (ppy) ₃ [tris (2-phenylpyridine) iridium] was doped at 15% by weight as a light emitting dopant in the light emitting layer. An OLED device was manufactured in the same manner as in Example 1.

As a result, a current of 3.8 mA / cm ² flowed at a voltage of 6.6 V, and green light emission of 1065 cd / m ² was confirmed.

Example 6 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

An OLED device was manufactured in the same manner as in Example 5, except that Compound 20 of the present invention was used as a hole transport material.

As a result, a current of 3.9 mA / cm ² flowed at a voltage of 6.6 V, and green light emission of 1070 cd / m ² was confirmed.

[ Example  7] using the organic light emitting compound according to the present invention OLED  Device fabrication

An OLED device was manufactured in the same manner as in Example 5, except that Compound 31 of the present invention was used as a hole transport material.

As a result, a current of 3.7 mA / cm ² flowed at a voltage of 6.7 V, and green light emission of 1085 cd / m ² was confirmed.

Example 8 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

An OLED device was manufactured in the same manner as in Example 5, except that Compound 42 of the present invention was used as the hole transport material.

As a result, a current of 3.5 mA / cm ² flowed at a voltage of 6.6 V, and green light emission of 1055 cd / m ² was confirmed.

Example 9 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

An OLED device was manufactured in the same manner as in Example 5, except that Compound 43 of the present invention was used as the hole transport material.

As a result, a current of 3.6 mA / cm ² flowed at a voltage of 6.6 V, and green light emission of 1080 cd / m ² was confirmed.

Example 10 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

2-TNATA [4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) as hole injection material

triphenylamine] in the same manner as in Example 5 except for using Compound 14 of the present invention instead of

As a result, a current of 3.7 mA / cm ² flowed at a voltage of 6.6 V, and green light emission of 1050 cd / m ² was confirmed.

Example 11 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

N ¹ , N ^{1 ′} -([1,1′-biphenyl] -4,4′-diyl) bis (N 1-(naphthalen- ¹ -yl) -N ⁴ , N ⁴ -die as the hole injection material Phenylbenzene-1,4-diamine) (N ¹ , N ^{1 '} -([1,1'-biphenyl] -4,4'-diyl) bis (N ^1- (naphthalen-1-yl) -N ⁴ , N ⁴ -diphenylbenzene-1,4-diamine)), evacuated until the vacuum in the chamber reached 10 ^-6 torr, and applied to the cell to evaporate to evaporate 60 nm thick holes on the ITO substrate. The injection layer was deposited. Subsequently, Compound 122 according to the present invention was placed in another cell in the vacuum deposition equipment, and a current was applied to the cell to evaporate Compound 122 to deposit a 20 nm thick hole transport layer on the hole injection layer. After the hole injection layer and the hole transport layer were formed, the light emitting layer was deposited thereon as follows. Put H-31 as a host in one cell and D-58 as a dopant in another cell in the vacuum deposition equipment, and then evaporate the two materials at different rates at a rate of 15% by weight to 30 nm on the hole transport layer. A light emitting layer of thickness was deposited. Then, as an electron transporting layer, 2- (4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole (2- ( Add 4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole), and add Liq (Lithium quinolate) to each other cell. After the addition, the two materials were evaporated at the same rate and doped at 50% by weight to deposit an electron transport layer of 30 nm. After depositing Liq (lithium quinolate) with a thickness of 1 nm as an electron injection layer, an Al cathode was deposited to a thickness of 150 nm using another vacuum deposition equipment to manufacture an OLED device.

Each compound was vacuum sublimated and purified under 10 ^-6 torr to be used as an OLED light emitting material.

As a result, a current of 11.5 mA / cm ² flowed at a voltage of 5.4 V, and green light emission of 6200 cd / m ² was confirmed.

Example 12 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

An OLED device was manufactured in the same manner as in Example 11, except that Compound 132 of the present invention was used as a hole transport material, and H-1 and D-71 were used as dopants for the host.

As a result, a current of 6.32 mA / cm ² flowed at a voltage of 4.0 V, and green light emission of 3300 cd / m ² was confirmed.

Example 13 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

An OLED device was manufactured in the same manner as in Example 11, except that Compound 138 of the present invention was used as a hole transport material, and D-31 was used as a H-34 dopant as a host.

As a result, a current of 2.8 mA / cm ² flowed at a voltage of 3.6 V, and green light emission of 1500 cd / m ² was confirmed.

[ Example  14] using the organic light emitting compound according to the present invention OLED  Device fabrication

An OLED device was manufactured in the same manner as in Example 11, except that Compound 149 of the present invention was used as a hole transport material, and D-31 was used as a H-39 dopant as a host.

As a result, a current of 1.59 mA / cm ² flowed at a voltage of 3.1 V, and green light emission of 500 cd / m ² was confirmed.

Example 15 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

An OLED device was manufactured in the same manner as in Example 11, except that Compound 109 of the present invention was used as a hole transport material, and H-45 and D-6 were doped with 4 wt% of a dopant as a host.

As a result, a current of 7.5 mA / cm ² flowed at a voltage of 4.0 V, and red light emission of 1065 cd / m ² was confirmed.

Example 16 Fabrication of OLED Device Using Organic Light Emitting Compound According to the Present Invention

An OLED device was manufactured in the same manner as in Example 15, except that Compound 141 of the present invention was used as a hole transport material, and H-49 and D-6 were used as dopants as a host.

As a result, a current of 17.0 mA / cm ² flowed at a voltage of 5.2 V, and red light emission of 2210 cd / m ² was confirmed.

[ Example  17] using the organic light emitting compound according to the present invention OLED  Device fabrication

An OLED device was manufactured in the same manner as in Example 15, except that Compound 142 of the present invention was used as a hole transport material, and H-52 and D-6 were used as dopants for the host.

As a result, a current of 32.1 mA / cm ² flowed at a voltage of 5.6 V, and red light emission of 3700 cd / m ² was confirmed.

[ Example  18] using the organic light emitting compound according to the present invention OLED  Device fabrication

An OLED device was manufactured in the same manner as in Example 15, except that Compound 149 of the present invention was used as a hole transport material, and H-53 and D-9 were used as dopants for the host.

As a result, a current of 12.9 mA / cm ² flowed at a voltage of 6.0 V, and red light emission of 1710 cd / m ² was confirmed.

[ Comparative Example 1] Light emission characteristics of OLED devices using conventional light emitting materials

Except for using NPB [N, N'-bis (α-naphthyl) -N, N'-diphenyl-4,4'-diamine] instead of the compound of the present invention as a hole transport material in one cell in the vacuum deposition equipment. An OLED device was manufactured in the same manner as in Example 1.

As a result, a current of 20.0 mA / cm ² flowed at a voltage of 8.2 V, and red light emission of 1000 cd / m ² was confirmed.

[Comparative Example 2] Light-emitting characteristics of the OLED device using a conventional luminescent material

, Except that the - [ 'N, N -bis ( α-naphthyl)'-diphenyl-4,4'-diamine N, N] to the one cell of the vacuum vapor-deposit device as a hole-transporting material NPB instead of the compound of the invention An OLED device was manufactured in the same manner as in Example 5.

As a result, a current of 5.0 mA / cm 2 flowed at a voltage of 6.0 V, and green light emission of 1183 cd / m 2 was confirmed.

[ Comparative Example 3] Light emission characteristics of the OLED device using a conventional light emitting material

An OLED device was manufactured in the same manner as in Example 11, except that NPB was used as the hole transport material and H-30 and D-30 was used as the dopant.

As a result, a current of 4.62 mA / cm ² flowed at a voltage of 3.0 V, and green light emission of 1000 cd / m ² was confirmed.

[ Comparative Example 4] Light emission characteristics of the OLED device using a conventional light emitting material

An OLED device was manufactured in the same manner as in Example 15, except that NPB was used as the hole transport material and H-46 and D-9 was used as the dopant.

As a result, a current of 13.2 mA / cm ² flowed at a voltage of 4.6 V, and red light emission of 1000 cd / m ² was observed.

The organic light emitting compounds developed in the present invention was confirmed that the light emitting properties are superior to the conventional material. The organic light emitting compound of the present invention has a large triplet (triplet) to increase the effective blocking of the triplet exciter present in the light emitting layer to stay in the light emitting layer well (especially excellent in the luminous efficiency in phosphorescence to produce a very excellent OLED device There is an advantage to this.

Claims (10)

An organic light emitting compound represented by Formula 1 below.
[Formula 1]

[In the above formula (1)
Ring A and Ring C are each independently

Is;
B ring

ego;
X ₁ and X ₂ are each independently CR ₃ or N;
Y ₁ and Y ₂ are each independently a chemical bond, —O—, —S—, —C (R ₁₁ R ₁₂ ) —, —Si (R ₁₃ R ₁₄ ) — or —N (R ₁₅ ) — Except when Y ₁ and Y ₂ are at the same time a chemical bond;
R ₁ to R ₃ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) hetero Aryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30) ar (C1-C30) alkyl, substituted or Unsubstituted (C1-C30) alkylsilyl, cyano, nitro or hydroxyl, and when there are a plurality of R ₁ or R ₂ , each of R ₁ and R ₂ may combine with each other to form a cyclic structure;
L is substituted or unsubstituted (C6-C30) arylene or substituted or unsubstituted (C2-C30) heteroarylene, provided that when L is plural, they may combine with each other to form a cyclic structure;
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) heteroaryl

Is;
Y ₃ and Y ₄ are each independently a chemical bond, —O—, —S—, —C (R ₁₆ R ₁₇ ) —, —Si (R ₁₈ R ₁₉ ) — or —N (R ₂₀ ) — Except that Y ₃ and Y ₄ are simultaneously chemical bonds;
R ₁₁ to R ₂₀ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (C2-C30) hetero A cycloaliphatic ring and a monocyclic ring or a polycyclic ring which is connected to a substituted or unsubstituted (C3-C30) alkylene or a substituted or unsubstituted (C3-C30) alkenylene, which is aryl or does not include or include a fused ring with adjacent substituents. Can form an aromatic ring of a ring;
m and n are each independently integers of 0 to 4, and when m and n are integers of 2 or more, each of R ₁ and L may be the same or different from each other;
p is an integer from 0 to 2, and when p is 2, each R ₂ may be the same or different from each other;
Wherein said heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P.] The method of claim 1,
Substituents further substituted with R _{1 ,} R _{2 ,} R _{3 ,} L, Ar ₁ , Ar _2, and R ₁₁ to R ₂₀ are each independently deuterium, halogen, (C1-C30) alkyl unsubstituted or substituted with halogen, (C6-C30) aryl, (C2-C30) heteroaryl substituted or unsubstituted, 5- to 7-membered heterocycloalkyl, 5- to 7-membered fused at least one aromatic ring Heterocycloalkyl, (C3-C30) cycloalkyl, (C6-C30) cycloalkyl fused with one or more aromatic rings, (C2-C30) alkenyl, (C2-C30) alkynyl,

, Cyano, carbazolyl, (C6-C30) ar (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, -OR ₂₁ , -SR ₂₂ , -NR ₂₃ R ₂₄ , -PR ₂₅ R ₂₆ , -SiR ₂₇ R ₂₈ R ₂₉ , at least one selected from the group consisting of nitro and hydroxyl, Y ₁₁ and Y ₁₂ are each independently a chemical bond, -C (R ₃₁ R ₃₂ )-, -O -, -S- or -N (R ₃₃ )-, except that Y ₁₁ and Y ₁₂ are at the same time a chemical bond; R ₂₁ to R ₃₃ are independently of each other (C1-C30) alkyl, (C6-C30) aryl, (C2-C30) heteroaryl or (C3-C30) cycloalkyl. The method of claim 1,
Of Formula 1

Is an organic light emitting compound, characterized in that selected from the following structure.

[In the above structure, R ₂ , R ₁₁ to R ₁₅ and p are the same as defined in claim 1.] The method of claim 1,
An organic light emitting compound, which is selected from the following compounds.

An organic electroluminescent device comprising the organic light emitting compound according to any one of claims 1 to 4. 6. The method of claim 5,
The organic light emitting device is an organic electroluminescent device, characterized in that used as a hole injection or hole transport material. The method of claim 6,
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 includes at least one layer including the organic light emitting compound of Formula 1. 3. The method of claim 7, wherein
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 of claim 7, wherein
The organic material layer is an organic electroluminescent device comprising a light emitting layer and a charge generating layer at the same time. The method of claim 7, wherein
An organic electroluminescent device for emitting white light, further comprising at least one organic light emitting layer emitting red, green, or blue light to the organic material layer.