KR20120020816A - Novel compounds for organic electronic material and organic electroluminescent device using the same - Google Patents

Abstract

PURPOSE: An organic compound for organic electronic material is provided to have high electron transport efficiency, thereby preventing crystallization at manufacturing device, and to have good layer formation ability, thereby improving current properties, reducing the driving voltage of device, and to improve the electricity efficiency. CONSTITUTION: An organic compound for organic electronic material is in chemical formula 1. The organic electroluminescent device comprises a first electrode, a second electrode, and one or more organic material layers inserted between the first electrode and the second electrode. The organic material layer comprises one or more of the organic compound for organic electronic material, and one or more phosphorescent dopant. The organic layer additionally comprises: one or more amine based compound selected from an arylamine compound or a styrylarylamine based compound one or more metal or complex compounds selected from family 1, family 2, period 4 and period 5 transition metals, lanthanum series metals, and organic metals of d-transition atom.

Description

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

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

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

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

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

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

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

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

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

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

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

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

[Formula 1]

[In Formula 1,

L ₁ to L ₅ are each independently a chemical bond, (C6-C30) arylene or (C3-C30) heteroarylene;

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

R ^a and R ^b are independently of each other (C6-C30) aryl or (C3-C30) heteroaryl;

The arylene, heteroarylene of L ₁ to L ₅ and the alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of R ₁ to R ₅ are each independently deuterium, (C1-C30 ) Alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C6-C30) ar (C1-C30) alkyl, (C6-C30) arylthio , Mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C1- C30) alkyldi (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro and hydroxy may be further substituted with one or more selected from the group consisting of;

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

이 수소인 경우는 제외된다.]
only,

This hydrogen is excluded.]

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

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

The compound for an organic electronic material according to the present invention may be selected from the following Chemical Formulas 2 to 7, but is not limited thereto.

[Formula 2]

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Wherein L ₁ and L ₅ are independently of each other (C6-C30) arylene or (C3-C30) heteroarylene; R ₁ is (C6-C30) aryl or (C3-C30) heteroaryl; R ₅ independently of one another is hydrogen, (C6-C30) aryl, (C3-C30) heteroaryl, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6 -C30) arylsilyl, -P (= 0) R ^a R ^b or -P (= S) R ^a R ^b ; R ^a and R ^b are independently of each other (C6-C30) aryl; The arylene, heteroarylene of L ₁ and L ₅ and the aryl and heteroaryl of R ₁ and R ₅ are independently of each other (C1-C30) alkyl, halo (C1-C30) alkyl, (C6-C30) aryl , (C3-C30) heteroaryl, (C6-C30) ar (C1-C30) alkyl, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C1-C30 ) Alkyldi (C6-C30) arylsilyl and tri (C6-C30) arylsilyl may be further substituted with one or more selected from the group consisting of.]

,

,

및

는 서로 독립적으로 하기 구조로부터 선택될 수 있으며, 이에 한정되지는 않는다.Specifically, the substituent

,

,

And

May be selected from the following structures independently from each other, but is not limited thereto.

는 하기 구조로부터 선택될 수 있으며, 이에 한정되지는 않는다.Specifically, the substituent

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

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

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

Scheme 1

[In Reaction Formula 1, in Formula 1, L ₁ to L ₅ and R ₁ to R ₅ are the same as defined in Formula 1, and X is halogen.]

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

When the compound for the organic electronic material of Formula 1 is used as a host in the light emitting layer is characterized in that it comprises at least one phosphorescent dopant. The phosphorescent dopant applied to the organic electroluminescent device of the present invention is not particularly limited, but the phosphorescent dopant applied to the organic electroluminescent device of the present invention is preferably selected from a compound represented by the following formula (8).

[Formula 8]

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 Formula 8,

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

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

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

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

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

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

,

또는

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

,

or

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

The phosphorescent dopant compound of Formula 8 may be exemplified as a compound having the following structure, but is not limited thereto.

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

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

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

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

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

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

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

Preparation Example 1 Preparation of Compound 2

compound 1-1 Manufacture

25 g (123.6 mmol) of fluoranthene are added to 400 mL of PhNO ₂ and dissolved. After cooling the solution to 0 ° C., Br ₂ dissolved in 80 mL of PhNO ₂ was added dropwise over 1 hour. The reaction solution was stirred overnight, and then quenched with Na ₂ S ₂ O ₃ aqueous solution. Extracted with MC and water. The organic layer was dried over anhydrous MgSO ₄ , and then the solvent MC was removed by a rotary evaporator, and distilled to remove PhNO ₂ . Resulting crude mixture (crude mixture) is purified by column chromatography and an MC and hexane as a developing solvent to give the compound 1- 1 (25g, yield 72%, ivory solid).

compound 1-2 Manufacture

450 mL of THF was added to 24.5 g (87.1 mmol) of Compound 1-1 under nitrogen atmosphere. After the reaction solution was cooled to -78 ° C, n-BuLi 45mL (2.5M in hexane, 113 mmol) was added thereto, stirred for 1 hour, and then 15 mL (131 mmol) of trimethoxyborate was added thereto. Stir for hours. After the dry ice / acetone bath was removed, the mixture was further stirred for 1 hour. The reaction mixture was quenched with aqueous NH ₄ Cl solution and extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO ₄ , and then the solvent was removed using a rotary evaporator, and then recrystallized with MC and hexane to obtain Compound 1-2 (14 g, yield 65%, yellow solid).

compound 1-3 Manufacture

Compound 1-2 14 g (57 mmol), 10 g (50 mmol) _2- bromonitetrobenzene, 2.2 g ( ₂ mmol) Pd (PPh ₃ ) ₄ , 17 g (120 mmol) K ₂ CO ₃ , 180 mL toluene, 60 mL EtOH and 60 mL of H ₂ O was mixed and stirred at 90 ° C. for 2 hours. Extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO ₄ , and then the solvent was removed using a rotary evaporator, and then recrystallized with MC and hexane to obtain compound 1-3 (13.2g, yield 82%).

compound 1-4 Manufacture

13 g (40 mmol) of Compound 1-3 , 100 mL of P (OEt) _{3, and} 100 mL of 1,2-dichlorobenzene were mixed and then stirred at 150 ° C. overnight. The reaction solution was distilled, dissolved in THF, adsorbed onto silica, and recrystallized from MC and hexane to give compound 1-4 (5.5 g, yield 48%, yellow solid).

compound 1-5 Manufacture

After dissolving 50 g (91 mmol) of cyanuric chloride in 1.3 L of THF, the mixture was cooled to 0 ° C., and 225 mL (3 M solution in diethyl ether, 675 mmol) of phenylmagnesium bromide was slowly added dropwise. The reaction solution was stirred for 3 hours and then extracted with distilled water and ethyl acetate. The organic layer was dried over anhydrous MgSO ₄ , and then the solvent was removed using a rotary evaporator, and then silica filter was carried out using MC as a developing solvent to obtain 37 g (yield 63%) of the crude product of Compound 1-5 . The crude product showed a purity suitable for the next reaction.

compound 2 Manufacture

5.3 g (18.2 mmol) of Compound 1-4 were dissolved in 90 mL of DMF, and 0.87 g (21.8 mmol) of NaH was added thereto, followed by stirring for 15 minutes. The solution was added to a solution of 5.4 g (20 mmol) of Compound 1-5 dissolved in 50 mL of DMF. The reaction mixture was stirred at room temperature overnight. The reaction mixture was quenched with water and the resulting solid was washed with MeOH and hexanes. The crude product was triturated with DMF to give 6.5 g (68%) of solid compound 2 .

MS / FAB: 522.18 (found), 522.60 (calculated)

Preparation Example 2 Preparation of Compound 44

compound 1-6 Manufacture

Compound 1-2 15 g (60.1 mmol), 1,4-dibromo-2-nitrobenzene 14 g (50.0 mmol), Pd (PPh ₃ ) ₄ 2.9 g (2.50 mmol), 2 M Na ₂ CO ₃ 60 mL and toluene 300 The mL was mixed and stirred at 100 ° C. for 4 hours. After cooling to room temperature, distilled water was added and extracted with EA. It was dried over anhydrous MgSO ₄ and distilled under reduced pressure. MC and hexane were purified by column chromatography using a developing solvent (MC: HEX = 1: 1) to give compound 1-6 (13 g, yield 62%).

compound 1-7 Manufacture

13 g (39.3 mmol) of Compound 1-6 were mixed with 100 mL of triethylphosphite, and stirred at 150 ° C. for 12 hours. Cooled to room temperature and distilled under reduced pressure. Extracted with EA and washed with distilled water. It was dried over anhydrous MgSO ₄ and distilled under reduced pressure. Recrystallization from hexane gave compound 1-7 (5.5 g, yield 48%).

compound 1-8 Manufacture

4 g (11.8 mmol) of compound 1-7 , 2.7 mL (23.7 mmol) of iodobenzene, 1.1 g (5.9 mmol) of CuI, 7.7 g (35.6 mmol) of K ₃ PO ₄ and 60 mL of toluene were mixed and heated to 80 ° C. 0.8 mL (11.9 mmol) of ethylenediamine was added thereto. It was stirred at reflux for 12 hours. Cooled to room temperature, extracted with EA, and washed with NaHCO ₃ aqueous solution. It was dried over anhydrous MgSO ₄ and distilled under reduced pressure. MC and hexane were purified by column chromatography with developing solvent (MC: HEX = 1: 6) to give compound 1-8 (2.5 g, yield 47%).

compound 1-9 Manufacture

2.5 g (5.6 mmol) of Compound 1-8 were dissolved in THF, and 3.4 mL (8.40 mmol, 2.5 M in hexane) of n-buLi was slowly added at -78 ° C. After an hour, 2.6 mL (11.2 mmol) of triisopropylborate was added. After stirring for 12 hours at room temperature, distilled water was added. Extracted with EA and dried over anhydrous MgSO ₄ . Distillation under reduced pressure and recrystallization with EA and hexane gave Compound 1-9 (2.3 g, yield 90%).

compound 1-5 Manufacture

2,4,6-trichloro-1,3,5-triazine 30 g (164 mmol), phenylboronic acid 44 g (360.8 mmol), Pd (PPh ₃ ) ₄ 5.7 g (4.9 mmol), 2M Na ₂ CO ₃ 250 mL And toluene 1.8L was added and stirred at 100 ℃ for 4 hours. After cooling to room temperature, distilled water was added and extracted with EA. It was dried over anhydrous MgSO ₄ and distilled under reduced pressure. MC and hexane were purified by column chromatography with developing solvent (MC: HEX = 1: 2) to give compound 1-5 (26 g, yield 60%).

compound 44 Manufacture

Compound 1-5 1.3g (4.85mmol), Compound 1-9 2.3g (5.83mmol), Pd (PPh ₃ ) ₄ 224.6mg (0.1944mmol), 2M K ₂ CO ₃ 7mL and toluene 24mL were added to 4 at 100 ℃ Stir for hours. After cooling to room temperature, distilled water was added and extracted with EA. It was dried over anhydrous MgSO ₄ and distilled under reduced pressure. MC and hexane were purified by column chromatography with developing solvent (MC: HEX = 1: 1) to give compound 44 (2.5 g, yield 86%).

MS / FAB: 598.22 (found), 598.69 (calculated)

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

An OLED device having a structure using the light emitting material of the present invention was produced. First, a transparent electrode ITO thin film (15 Ω / □) obtained from OLED glass (manufactured by Samsung Corning Corporation) was subjected to ultrasonic cleaning using trichloroethylene, acetone, ethanol and distilled water sequentially, and then placed in isopropanol. It was used after. Next, the ITO substrate is installed in the substrate folder of the vacuum deposition apparatus, and 2-TNATA (4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine) is installed in the cell in the vacuum deposition apparatus. 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. ( '-bis (α-naphthyl) - N, N' N, N -diphenyl-4,4'-diamine) NPB to another cell of the vapor deposition devices placed to evaporate NPB to apply a current to the cell, the hole injection layer A 20 nm-thick hole transport layer was deposited on one side of the vacuum deposition equipment, and the compound 3 according to the present invention was vacuum sublimated under 10 ^-6 torr as a host material, and the other cell (piq) was used as a light emitting dopant. ) of _{2 Ir (acac) [bis- (} 1-phenylisoquinolyl) iridium (III) acetylacetonate] after loading, respectively, the two materials were evaporated at different rates from 4 to 20 A light emitting layer having a thickness of 30 nm was deposited on the hole transport layer by doping at%, followed by deposition of Alq (tris (8-hydroxyquinoline) -aluminum (III)) having a thickness of 20 nm as an electron transport layer, followed by an electron injection layer. After depositing Liq (lithium quinolate) to a thickness of 1 to 2 nm, an Al cathode was deposited to a thickness of 150 nm using another vacuum deposition equipment to manufacture an OLED.

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

As a result, red light emission of 7.2 cd / A was confirmed at a voltage of 6.8 V.

[Example 2]

An OLED device was manufactured in the same manner as in Example 1, except that Compound 45 was used as the host material in the emission layer.

As a result, red light emission of 6.9 cd / A was observed at a voltage of 7.0 V.

Example 3

An OLED device was manufactured in the same manner as in Example 1, except that Compound 4 was used as the host material in the light emitting layer.

As a result, red light emission of 7.3 cd / A was confirmed at a voltage of 6.6 V.

Example 4

An OLED device was manufactured in the same manner as in Example 1, except that Compound 42 was used as the host material in the light emitting layer.

As a result, 7.2 cd / A red light emission was observed at a voltage of 6.9V.

Comparative Example 1

An OLED device was manufactured in the same manner as in Example 1, except that 4,4′-bis (carbazol-9-yl) biphenyl (CBP) was used instead of the compound of the present invention as a host material in the emission layer.

As a result, red light of 6.5 cd / A was confirmed at a voltage of 7.5 V.

The organic light emitting compounds developed in the present invention were found to exhibit similar or superior light emission characteristics as the conventional light emitting materials as red light emitting materials. In addition, the electroluminescent compound according to the present invention was able to lower the driving voltage and increase the luminous efficiency by 0.4 to 0.8 cd / A without using the hole blocking layer used in the device structure of the conventional light emitting material.

Claims (10)

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

[In the above formula (1)
L ₁ to L ₅ are each independently a chemical bond, (C6-C30) arylene or (C3-C30) heteroarylene;
R ₁ to R ₅ are independently of each other hydrogen, deuterium, (C1-C30) alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl , (C2-C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C6- C30) Ar (C1-C30) alkyl, (C6-C30) arylthio, mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro, -P (= O) R ^a R ^b , -P (= S) R ^a R ^b or hydroxy Is;
R ^a and R ^b are independently of each other (C6-C30) aryl or (C3-C30) heteroaryl;
The arylene, heteroarylene of L ₁ to L ₅ and the alkyl, cycloalkyl, heterocycloalkyl, alkenyl, alkynyl, aryl and heteroaryl of R ₁ to R ₅ are each independently deuterium, (C1-C30 ) Alkyl, halo (C1-C30) alkyl, halogen, cyano, (C3-C30) cycloalkyl, 5- to 7-membered heterocycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C6-C30) aryl, (C1-C30) alkoxy, (C6-C30) aryloxy, (C3-C30) heteroaryl, (C6-C30) ar (C1-C30) alkyl, (C6-C30) arylthio , Mono or di (C1-C30) alkylamino, mono or di (C6-C30) arylamino, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C1- C30) alkyldi (C6-C30) arylsilyl, tri (C6-C30) arylsilyl, nitro and hydroxy may be further substituted with one or more selected from the group consisting of;
The heteroarylene, heterocycloalkyl and heteroaryl include one or more heteroatoms selected from B, N, O, S, P (= 0), Si and P;
only,

This hydrogen is excluded.] The method of claim 1,
A compound for an organic electronic material selected from the following Chemical Formulas 2 to 7.
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Wherein L ₁ and L ₅ are independently of each other (C6-C30) arylene or (C3-C30) heteroarylene; R ₁ is (C6-C30) aryl or (C3-C30) heteroaryl; R ₅ independently of one another is hydrogen, (C6-C30) aryl, (C3-C30) heteroaryl, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6 -C30) arylsilyl, -P (= 0) R ^a R ^b or -P (= S) R ^a R ^b ; R ^a and R ^b are independently of each other (C6-C30) aryl; The arylene, heteroarylene of L ₁ and L ₅ and the aryl and heteroaryl of R ₁ and R ₅ are independently of each other (C1-C30) alkyl, halo (C1-C30) alkyl, (C6-C30) aryl , (C3-C30) heteroaryl, (C6-C30) ar (C1-C30) alkyl, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C1-C30 ) Alkyldi (C6-C30) arylsilyl and tri (C6-C30) arylsilyl may be further substituted with one or more selected from the group consisting of.] The method of claim 1,
The substituent

,

,

And

Are compounds independently selected from the following structures for organic electronic materials.

The method of claim 1,
The substituent

The compound for an organic electronic material, characterized in that selected from the following structure.

The method of claim 1,
A compound for organic electronic materials selected from the following compounds.

An organic electroluminescent device comprising the compound for organic electronic material according to any one of claims 1 to 5. 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 comprises at least one compound for an organic electronic material and at least one phosphorescent dopant. The method of claim 7, wherein
At least one amine compound selected from the group consisting of an arylamine compound or a styrylarylamine compound or an organic metal of Group 1, Group 2, 4 cycle, 5 cycle transition metal, lanthanide series metal and d-transition element in the organic layer An organic electroluminescent device further comprising at least one metal or complex compound selected from the group consisting of: 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. The method of claim 7, wherein
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.