KR20120050557A - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents

Abstract

PURPOSE: An organic electroluminescent compound is provided to have excellent device life time because of excellent luminous efficiency, and to manufacture an organic light emitting diode device with improved power efficiency by improving power efficiency. CONSTITUTION: An organic electroluminescent compound is in chemical formula 1. An organic electroluminescent device comprises a first electrode, a second electrode, and one or more of organic material layers inserted between the first electrode and the second electrode. The organic material layer comprises one or more of the organic electroluminescent compound and one or more phosphorescent dopant. And the organic material layer comprises a light-emitting layer and a charge-generating layer, and conducting white light emission by comprising one or more organic electroluminescent layer capable of blue, red, or green light emitting.

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.

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 most important factor determining the luminous efficiency in OLEDs is the luminous material. Fluorescent materials are widely used as the light emitting materials to date, but the development of phosphorescent materials is one of the best ways to improve the luminous efficiency theoretically up to 4 times. To date, iridium (III) complexes are widely known as phosphorescent materials, and for each RGB, materials such as (acac) Ir (btp) ₂ , Ir (ppy) _3, and Firpic are known. In particular, many phosphorescent materials have recently been studied in Japan and Europe.

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. In OLED, power efficiency = (π / voltage) ㅧ current efficiency, so power efficiency is inversely proportional to voltage. 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 an organic light emitting compound having excellent luminous efficiency and device life, and having an appropriate color coordinate, in order to solve the above problems, and secondly, to solve the above organic light emitting compound. It is to provide a high efficiency and long life organic electroluminescent element employed as a light emitting material.

The present invention relates to an organic light emitting compound represented by the following Chemical Formula 1 and an organic electroluminescent device comprising the same, the organic light emitting compound according to the present invention has better light emission efficiency and excellent life characteristics of the material than the existing material, the driving life of the device This is not only very good, but also has an advantage of manufacturing an OLED device with improved power consumption by inducing an increase in power efficiency.

[Formula 1]

[In Formula 1,

R ₁ to R ₆ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-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, cycloalkyl At least one fused substituted or unsubstituted (C6-C30) aryl, a 5 to 7 membered heterocycloalkyl fused at least one substituted or unsubstituted aromatic ring, or at least one fused substituted or unsubstituted aromatic ring With or without fused ring (C3-C30) cycloalkyl, -NR ₁₁ R ₁₂ , -SiR ₁₃ R ₁₄ R ₁₅ , -SR ₁₆ , -OR _17, cyano, nitro or hydroxy or with adjacent substituents Unsubstituted or substituted (C3-C30) alkylene or substituted or unsubstituted (C3-C30) alkenylene An alicyclic ring and a monocyclic or polycyclic aromatic ring may be formed, and the carbon atoms of the formed alicyclic ring and monocyclic or polycyclic aromatic ring may be substituted with one or more heteroatoms selected from nitrogen, oxygen, and sulfur; ;

이고;At least one of R ₁ to R ₆

ego;

L is a chemical bond, a substituted or unsubstituted (C6-C30) arylene, a substituted or unsubstituted (C3-C30) heteroarylene;

Z is selected from the following structures;

Ring A is (C6-C30) aryl, (C5-C30) heteroaryl, (C6-C30) cycloalkyl;

R ₂₁ to R ₂₃ are each independently the same as R ₁ to R ₆ ;

R ₁₁ to R ₁₇ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) hetero Aryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C3-C30) cycloalkyl or substituted or unsubstituted (C3-C30) with or without fused ring with adjacent substituents Alkylene or substituted or unsubstituted (C3-C30) alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, and the alicyclic ring and the monocyclic or polycyclic aromatic ring The carbon atom may be substituted with one or more heteroatoms selected from nitrogen, oxygen and sulfur;

a to b are integers from 1 to 4;

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

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, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like. Including but not limited to. 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. It means an aryl group which is a 5-6 membered monocyclic heteroaryl, and polycyclic heteroaryl condensed with one or more benzene rings, and may be partially saturated. In addition, heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected 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, dibenzofuranyl, dibenzothiophenyl and their corresponding N-oxides (eg pyridyl N-oxides, quinolyl N-oxides), 4 of these Tea salts and the like, but is not limited thereto.

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.

In addition, in the description of "substituted or unsubstituted" described in the present invention, 'substituted' means a case where it is further substituted with an unsubstituted substituent, the R ₁ to R ₆ , R ₁₁ to R ₁₇ and R ₂₁ to R ₂₃ Substituents further substituted with each other independently (C3-C30) substituted or unsubstituted (C1-C30) alkyl, (C6-C30) aryl, or (C6-C30) aryl substituted with deuterium, halogen, or halogen Heteroaryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic rings, (C3-C30) cycloalkyl, (C6-C30) with one or more fused aromatic rings Cycloalkyl, R ^a R ^b R ^c Si-, (C2-C30) alkenyl, (C2-C30) alkynyl, cyano, carbazolyl, -NR ^d R ^e , -BR ^f R ^g , -PR ^h R ⁱ , -P (= 0) R ^j R ^k , (C6-C30) ar (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, R ¹ Z-, R ^m C (= O)-, R ^m C (= 0) O-, one selected from the group consisting of carboxyl, nitro or hydroxy And R ^a to R ^l are independently of each other (C1-C30) alkyl, (C6-C30) aryl or (C3-C30) heteroaryl and may combine with adjacent substituents to form a fused ring; Z is S or O; R ^m means (C1-C30) alkyl, (C1-C30) alkoxy, (C6-C30) aryl or (C6-C30) aryloxy.

More specifically, Z is selected from the following structures, but is not limited thereto.

[Wherein, R ₂₁ to R ₃₅ are the same as defined for R ₁ to R _6. ]

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 reaction scheme for Compound 1 in the organic light emitting compound according to the present invention is shown below, and the organic light emitting compound of the present invention may be prepared by a similar or known organic reaction.

Scheme 1

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 organic light emitting compound of Formula 1. The organic material layer includes a light emitting layer, and the organic light emitting compound of Chemical Formula 1 is used as a host material in the light emitting layer.

When the organic light emitting compound 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 ^One 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 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 (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 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 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 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 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.

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 light emitting 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 organic light emitting compound according to the present invention has the advantage of being able to manufacture an OLED device having good luminous efficiency and excellent driving life of the 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 Manufacturing

After dissolving 2 g (10.0 mmol) of 1,4-dichlorophthalazine in 20 mL of DMF, 3.69 g (22.1 mmol) of carbazole were added and stirred at room temperature for 2 hours. The reaction was terminated by adding water to the reaction, extracted with ethyl acetate and washed with 5% citric acid. Sodium sulfate was used to remove residual moisture, followed by drying and column separation to obtain 2.6 g (79%) of Compound 1-1 .

compound One Manufacturing

Compound 1-1 8.2 g (24.9 mmol), phenylboronic acid 3.6 g (29.9 mmol), Pd (Pph ₃ ) ₄ 1.15 g (0.996 mmol), 87 mL of aqueous sodium carbonate solution and 87 mL of ethanol were dissolved in 180 mL of toluene. Stir at reflux at 120 ^° C. for 3 hours. After the completion of the reaction, the organic layer was extracted with ethyl acetate, magnesium sulfate was used to remove residual moisture, dried, and column separated to obtain compound 1 (5.9 g, 64%).

MS / FAB found 372, calculated 371.43

Preparation Example 2 Preparation of Compound 7

compound 2-1 Manufacturing

15 g (75.36 mmol) of 1,4-dichlorophthalazine, 16.4 g (82.89 mmol) of 4-biphenylboronic acid, 2.4 g (3.76 mmol) of Pd (PPh ₃ ) ₄ , 110 mL of 2M Na ₂ CO _3, and Dissolve 50 mL of ethanol in 300 mL of toluene and stir at reflux at 100 ^o C for 3 hours. After the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, washed with distilled water, residual water was removed using magnesium sulfate, dried, and column separated to obtain compound 2-1 12g (50%).

compound 2-2 Manufacturing

15 g (63.58 mmol) of 1,4-dibromobenzene was dissolved in 300 mL of tetrahydrofuran, and 26.7 mL of n -butyllithium (2.5 M in hexane, 66.76 mmol) was slowly added at −78 ^° C. and stirred for 1 hour. Then, a solution of 20.6 mL of chlorotriphenylsilane dissolved in 70 mL of tetrahydrofuran was added thereto, followed by stirring at room temperature for 12 hours. Upon completion of the reaction, the produced white solid was filtered off, the filtrate was extracted with ethyl acetate, washed with distilled water, residual water was removed using magnesium sulfate, dried and distilled under reduced pressure. After recrystallization with ethyl acetate and methanol to obtain Compound 2-2 17.5g 66%).

compound 2-3 Manufacturing

Dissolve 20 g (48.14 mmol) of Compound 2-2 in 500 mL of tetrahydrofuran, slowly add 23.1 mL of n -butyllithium (2.5 M in hexane, 57.5 mmol) at -78 ^o C, stir for 1 hour, and then 8.5 mL of trimethylborate. (77.03 mmol) was added and the mixture was stirred at room temperature for 12 hours. Then extracted with ethyl acetate and washed with distilled water, and recrystallized with ethyl acetate and n -hexane to give compound 2-3 14g (76%).

compound  2-4 Manufacturing

5 g (24.75 mmol) 2- bromonitrobenzene, 10.35 g (27.22 mmol) compound 2-3 , 1.4 g (1.23 mmol) Pd (PPh ₃ ) ₄ , 35 mL 2M K ₂ CO ₃ , 50 mL ethanol to 100 mL toluene After melting, the mixture was stirred under reflux at 100 ^° C. for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, washed with distilled water, the organic layer was extracted with ethyl acetate, residual water was removed using magnesium sulfate, dried and recrystallized with ethyl acetate and methanol to obtain compound 2-4 11g (97%). .

compound 2-5 Manufacturing

11 g (24.03 mmol) of Compound 2-4 was dissolved in 100 mL of 1,2-dichlorobenzene, 200 mL of triethylphosphite was added thereto, and the mixture was stirred at 150 ^° C. for 15 hours. After distillation under reduced pressure, the solid was dissolved in chloroform and filtered through silica to obtain compound 2-5 (8 g, 78%).

compound 7 Manufacturing

4.8 g (11.36 mmol) of Compound 2-5 were dissolved in 100 mL of dimethylformamide, which was added to a solution of 0.56 g (14.20 mmol) of NaH in 25 mL of DMF, followed by stirring at room temperature for 1 hour. Then, a solution of Compound 2-1 3g (9.47 mmol) dissolved in 50 mL of dimethylformamide was added thereto, followed by stirring at room temperature for 12 hours. The mixture was washed with distilled water, extracted with ethyl acetate, and distilled under reduced pressure. This was dissolved in chloroform and filtered through silica, and recrystallized with methanol, ethyl acetate and dimethylformamide to obtain 2.8 g (58%) of compound 7 .

MS / FAB found 706, calculated 705.92

Preparation Example 3 Preparation of Compound 19

compound 3-1 Manufacturing

40 g (0.198 mol) of 2-bromonitrobene, 37.46 g (0.217 mol) of 1-naphthalene boronic acid, 6.86 g (0.005 mol) of Pd (PPh ₃ ) ₄ , 200 mL of 2M K ₂ CO ₃ and 100 mL of ethanol It was dissolved in 300mL and stirred at reflux for 4 hours at 100 ^° C. After the reaction, the mixture was cooled to room temperature, washed with distilled water, and extracted with ethyl acetate. The organic layer was removed using magnesium sulfate, dried, and distilled under reduced pressure. Thereafter, the obtained compound was dissolved in methylene chloride, silica filtered, and distilled under reduced pressure to obtain 45 g (91%) of compound 3-1 .

compound 3-2 Manufacturing

45 g (0.180 mol) of Compound 3-1 was dissolved in 200 mL of 1,2-dichlorobenzene, 400 mL of triethylphosphite was added thereto, and the mixture was stirred under reflux at 150 ^° C. for 12 hours. After cooling to room temperature and distillation under reduced pressure, to obtain a compound 3-2 32g (81%).

compound  3-3 Manufacturing

Compound 3-2 24.6 g (113.6 mmol), 15 g (75.7 mmol) 1,4-dichlorophthalazine, 28.8 g (151.4 mmol) CuI, 73 g (227.2 mmol) Cs ₂ CO ₃ , trans 1,2-di 2.7 mL (22.72 mmol) of aminocyclohexane and 500 mL of 1,2-dichlorobenzene were added thereto, and the mixture was stirred under reflux at 180 ^° C. for 12 hours. After the reaction, the mixture was cooled to room temperature, washed with distilled water, and extracted with ethyl acetate. The organic layer was removed using magnesium sulfate, dried, and distilled under reduced pressure. This column was separated and 20 g (70%) of compound 3-3 was obtained.

compound 19 Manufacturing

Compound 3-3 20 g (52.79 mmol), 31 g (158.3 mmol) of 4-biphenylboronic acid, 1.18 g (5.27 mmol) Pd (OAc) ₂ , 5.2 mL (50% in toluene) ₃ 10.5 mmol) and 33.6 g (158.3 mmol) of K ₃ PO ₄ were added to 600 mL of 1,4-dioxane and stirred under reflux at 100 ^° C. for 5 hours. After the reaction, the mixture was cooled to room temperature, washed with distilled water, and extracted with ethyl acetate. The organic layer was removed using magnesium sulfate, dried, and distilled under reduced pressure. This column was separated to obtain 15 g (57%) of compound 19 .

MS / FAB found 498, calculated 497.59

Preparation Example 4 Preparation of Compound 24

compound 4-1 Manufacturing

10 g (20.13 mmol) of Compound 19 was dissolved in 300 mL of tetrahydrofuran, and NBS 3.94 g (22.15 mmol) was added at room temperature, followed by stirring at room temperature for 12 hours. After the reaction, the mixture was washed with distilled water, and extracted with ethyl acetate. The organic layer was removed using magnesium sulfate, dried, and distilled under reduced pressure. After column separation 9.5g (82%) of Compound 4-1 .

compound 24 Manufacturing

9-phenyl-9H-carbazol-3-ylboronic acid 6.7 g (23.44 mmol), compound 4-1 20.3 g (35.16 mmol), Pd (oAc) ₂ 790 mg (3.51 mmol), P (t-Bu) ₃ 4.7 mL 46 mL (93.76 mmol) of K ₃ PO ₄ (2M) was added thereto, 46 mL of ethanol and 200 mL of toluene were added thereto, followed by heating to 120 ° C., followed by stirring for 2 hours. After the reaction was washed with distilled water and extracted with EA, the organic layer was dried over anhydrous MgSO4 and the solvent was removed on a rotary evaporator to give a column purified to give compound 24 9.3g (53%).

MS / FAB found 739 calculated 738.87

Preparation Example 5 Preparation of Compound 33

compound 5-1 Manufacturing

15 g (0.074 mol) of 1-bromo-2-nitrobenzene was added, 23 g (0.096 mol) of 9,9-dimethyl-9H-fluorene-2-ylboronic acid, and 4.2 g (0.003 mol) of Pd (PPh ₃ ) ₄ ), 111 mL of Na ₂ CO ₃ (2M), 111 mL of ethanol, and 200 mL of toluene were 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 compound 5-1 22g (95%).

compound 5-2 Manufacturing

24 g (0.076 mol) of Compound 5-1 was added thereto, and 200 ml of triethyl phosphite 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 5-2 7g (33%).

compound 33 Manufacturing

Compound 2-1 6.3 g (20.0 mmol), Compound 5-2 6.8 g (24 mmol), Pd (OAc) ₂ 0.14 g (0.6 mmol), P (t-Bu) ₃ 1.00 mL (2.0 mmol), NaOt- 5.9 g (60 mmol) of Bu and 200 mL of toluene were added thereto, and the mixture was stirred under reflux at 120 ^° C. for 12 hours. After completion of 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 using a rotary evaporator, purified by column chromatography, and recrystallized to obtain Compound 33 (6.3 g, 56%).

MS / FAB found 564, calculated 563.69

Preparation Example 6 Preparation of Compound 29

compound 6-1 Manufacturing

After dissolving 7 g (32.2 mmol) of Compound 3-2 in 150 mL of DMF, 5.74 g (32.2 mmol) of NBS was added thereto. 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 6-1 (9 g, 94%).

compound 6-2 Manufacturing

Compound 6-1 30 g (138 mmol), 82 g (414 mmol) of 4-bromobiphenyl, 13.1 g (6.9 mmol) of CuI, 90 g (414 mmol) of K3PO4, 9.3 mL (138 mmol) of ethylenediamine and 700 mL of toluene were added and 12 at 100 ° C. Stir at reflux for hours. After completion of the reaction, 39 g (56%) of Compound 6-2 was obtained by column chromatography after extraction with EA.

compound 6-3 Manufacturing

10 g (26.9 mmol) of Compound 6-2 was dissolved in 120 mL of THF, and the solution was 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 obtain 6.7 g (74%) of compound 6-3 .

compound 6-4 Manufacturing

15 g (75.36 mmol) 1,4-dichlorophthalazine, 16.4 g (82.89 mmol) phenylboronic acid, 2.4 g (3.76 mmol) Pd (PPh ₃ ) ₄ , 110 mL 2M Na ₂ CO ₃ and 50 mL ethanol It was dissolved in 300 mL of toluene and stirred under reflux at 100 ^o C for 3 hours. After the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, washed with distilled water, residual water was removed using magnesium sulfate, dried, and column separated to obtain compound 6-4 12g (50%).

compound 44 Manufacturing

Compound 6-3 6.7 g (23.44 mmol), Compound 6-4 20.3 g (35.16 mmol), Pd (oAc) ₂ 790 mg (3.51 mmol), P (t-Bu) ₃ 4.7 mL (7.03 mmol), K ₃ PO 46 mL (93.76 mmol) of ₄ (2M) was added thereto, 46 mL of ethanol and 200 mL of toluene were added thereto, and then heated to 120 ° C., followed by stirring for 2 hours. After the reaction, the mixture was washed with distilled water, extracted with EA, the organic layer was dried over anhydrous MgSO 4, and the solvent was removed using a rotary evaporator, and column purification was performed to obtain Compound 44 9.3 g (53%).

MS / FAB found 574, calculated 573.68

Preparation Example 7 Preparation of Compound 47

compound 47 Manufacturing

After dissolving 2 g (10.0 mmol) of 1,4-dichlorophthalazine in 20 mL of DMF, 4.0 g (25 mmol) of Compound 3-2 were added and stirred at room temperature for 2 hours. The reaction was terminated by adding water to the reaction, extracted with ethyl acetate and washed with 5% citric acid. Sodium sulfate was used to remove residual moisture, followed by drying and column separation to obtain 2.6 g (79%) of Compound 47 .

MS / FAB found 561, calculated 560.65

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. NPB to another cell of the vapor-deposit device - into a [N, N '-bis (α -naphthyl) N, N'-diphenyl-4,4'-diamine], to evaporate NPB to apply a current to the cell, the hole injection layer A 20 nm thick hole transport layer was deposited on top of the hole injection layer, and then a light emitting layer was deposited thereon as follows: Compound 19 according to the present invention was used as a host in one cell in a vacuum deposition apparatus. Insert, after again into another cell as a dopant _{(piq) 2 Ir (acac)} [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate] , respectively, A 30 nm thick light emitting layer was deposited on the hole transport layer by evaporating the material at different rates and doping at 4 to 10 wt%, followed by Alq [tris (8-hydroxyquinoline) -aluminum (III) as electron transport layer on the light emitting layer. ] Was deposited to a thickness of 20 nm, and then Liq [lithium quinolate] was deposited to a thickness of 1 to 2 nm using an electron injection layer, and then another Al deposition was deposited to a thickness of 150 nm using another vacuum deposition equipment. Produced.

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 14.8 mA / cm ² flowed at a voltage of 6.7 V, and red light emission of 1105 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 24 according to the present invention was used as a host material in the emission layer.

As a result, a current of 15.0 mA / cm ² flowed at a voltage of 6.4 V, and red light emission of 1120 cd / m ² was confirmed.

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 47 according to the present invention was used as a host material in the emission layer.

As a result, a current of 14.4 mA / cm ² flowed at a voltage of 7.1 V, and red light emission of 1070 cd / m ² was confirmed.

[Comparative Example 1] Light emission characteristics of OLED device using conventional light emitting material

CBP [4,4'-bis (carbazol-9-yl) biphenyl] as a host material in one cell in the vacuum deposition equipment, (piq) ₂ Ir (acac) [bis- (1- phenylisoquinolyl) iridium (III) acetylacetonate], except that bis (2-methyl-8-quinolinate) ( p -phenylphenolrato) aluminum (III) (BAlq) was used as the hole blocking layer. An OLED device was manufactured in the same manner as in Example 1.

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 was not only excellent in the light emission characteristics, but also by lowering the driving voltage to increase the power efficiency to improve the power consumption.

Claims (9)

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

[In the above formula (1)
R ₁ to R ₆ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-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, cycloalkyl At least one fused substituted or unsubstituted (C6-C30) aryl, a 5 to 7 membered heterocycloalkyl fused at least one substituted or unsubstituted aromatic ring, or at least one fused substituted or unsubstituted aromatic ring With or without fused ring (C3-C30) cycloalkyl, -NR ₁₁ R ₁₂ , -SiR ₁₃ R ₁₄ R ₁₅ , -SR ₁₆ , -OR _17, cyano, nitro or hydroxy or with adjacent substituents Unsubstituted or substituted (C3-C30) alkylene or substituted or unsubstituted (C3-C30) alkenylene An alicyclic ring and a monocyclic or polycyclic aromatic ring may be formed, and the carbon atoms of the formed alicyclic ring and monocyclic or polycyclic aromatic ring may be substituted with one or more heteroatoms selected from nitrogen, oxygen, and sulfur; ;
At least one of R ₁ to R ₆

ego;
L is a chemical bond, a substituted or unsubstituted (C6-C30) arylene, a substituted or unsubstituted (C3-C30) heteroarylene;
Z is selected from the following structures;

Ring A is (C6-C30) aryl, (C5-C30) heteroaryl, (C6-C30) cycloalkyl;
R ₂₁ to R ₂₃ are each independently the same as R ₁ to R ₆ ;
R ₁₁ to R ₁₇ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) hetero Aryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C3-C30) cycloalkyl or substituted or unsubstituted (C3-C30) with or without fused ring with adjacent substituents Alkylene or substituted or unsubstituted (C3-C30) alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, and the alicyclic ring and the monocyclic or polycyclic aromatic ring The carbon atom may be substituted with one or more heteroatoms selected from nitrogen, oxygen and sulfur;
a to b are integers from 1 to 4;
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 to R ₆ , R ₁₁ to R ₁₇ and R ₂₁ to R ₂₃ independently of each other, deuterium, halogen, (C1-C30) alkyl unsubstituted or substituted with halogen, (C6-C30) Aryl, (C6-C30) aryl substituted or unsubstituted (C3-C30) heteroaryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused with one or more aromatic rings, ( C3-C30) cycloalkyl, (C6-C30) cycloalkyl fused with one or more aromatic rings, R ^a R ^b R ^c Si-, (C2-C30) alkenyl, (C2-C30) alkynyl, cyano, Carbazolyl, -NR ^d R ^e , -BR ^f R ^g , -PR ^h R ⁱ , -P (= 0) R ^j R ^k , (C6-C30) ar (C1-C30) alkyl, (C1-C30) At least one selected from the group consisting of alkyl (C6-C30) aryl, R ¹ X-, R ^m C (= 0)-, R ^m C (= 0) O-, carboxyl, nitro or hydroxy, R ^a to R ^l are independently of each other (C1-C30) alkyl, (C6-C30) aryl or (C3-C30) heteroaryl and are bonded to each other with adjacent substituents Can form a fusion ring; X is S or O; R ^m is (C1-C30) alkyl, (C1-C30) alkoxy, (C6-C30) aryl or (C6-C30) aryloxy. The method of claim 1,
Z is an organic light emitting compound, characterized in that the substituent selected from the following.

[Wherein, R ₂₁ to R ₃₅ are the same as defined for R ₁ to R _6. ] The method of claim 3, wherein
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 electroluminescent device includes a first electrode; A second electrode; And one or more organic material layers interposed between the first electrode and the second electrode, wherein the organic material layers include one or more organic light emitting compounds and one or more phosphorescent dopants represented by the following Chemical Formula 2. EL device.
[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.

[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;
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 method according to claim 6,
At least one compound (A) selected from the group consisting of an arylamine compound or a styrylarylamine compound in the organic material layer; At least one metal or complex compound (B) selected from the group consisting of Group 1, Group 2, 4 and 5 cycle transition metals, lanthanide series metals and organic metals of d-transition elements; An organic electroluminescent device comprising one selected from (A) and (B). 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.