TW201302974A - Novel compounds for organic electronic material and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescent device containing the same. Since the compounds for organic electronic materials according to the present invention have high efficiency in transporting electrons, crystallization could be prevented when manufacturing a device. Further, the compounds have good layer formability and improve the current characteristic of the device. Therefore, they can produce an organic electroluminescent device having lowered driving voltages and enhanced power efficiency.

Description

Novel compound for organic electronic materials and organic electric field illuminating device using the same

The present invention relates to novel compounds for organic electronic materials and organic electric field illuminating devices using the same.

An electroluminescence (EL) device is a self-luminous display device that is superior to other types of display devices in that it provides a wider viewing angle, higher contrast, and faster response time. Eastman Kodak first developed an organic EL device using a small molecule aromatic diamine and an aluminum complex as a substance for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].

The most important factor determining the luminous efficiency of an organic EL device is a luminescent material. Fluorescent materials have hitherto been widely used as luminescent materials. However, from the viewpoint of the electric field luminescence mechanism, the phosphorescent material theoretically exhibits a luminous efficiency four times higher than that of the fluorescent material. Therefore, phosphorescent materials have been studied.铱(III) complex is a well-known phosphorescent material, including bis-(2-(2'-benzothienyl)-pyridyl-N,C3') fluorene as a red material, a green material and a blue material, respectively. (Acetylpyruvate) ((acac) Ir(btp) ₂ ), ginseng (2-phenylpyridine) oxime (Ir(ppy) ₃ ) and bis(4,6-difluorophenylpyridinyl-N, C2) Firpic. Specifically, many phosphorescent materials have recently been developed in Japan, Europe, and the United States.

Currently, 4,4'-N,N'-dicarbazole-biphenyl (CBP) is the most widely known host material for phosphorescent materials. Furthermore, it is known to use bathocuproine (BCP) and aluminum (III) bis(2-methyl-8-hydroxyquinoline). (4-phenylphenolate) (BAlq) as a high-efficiency organic EL device for a hole barrier layer, and Pioneer (Japan) has developed a high-performance organic EL device using a BAlq derivative as a host material. .

Although these phosphorus-containing host materials provide good luminescent characteristics, they still have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, they may be degraded during the high temperature deposition process of vacuum. (2) The power efficiency of the organic EL device is obtained from [(Π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage, so high power efficiency is required in order to reduce power consumption. Although an organic EL device including a phosphorescent material provides higher current efficiency (candle/ampere (cd/A)) than an organic EL device including a fluorescent material, when a conventional material such as BAlq or CBP is used as a phosphorescent host material, the phase A significantly higher driving voltage is still required than an organic EL device using a fluorescent material. Therefore, there is no significant advantage in terms of power efficiency (lumens (lm) / watt (W)). (3) Furthermore, the organic EL device has a short operational life, and therefore there is still a need to improve luminous efficiency.

International Patent Publication No. WO2006/049013 discloses a compound for an organic electroluminescent material having a fused bicyclic group as a skeleton structure. However, this patent does not disclose a nitrogen-containing fused bicyclic group compound substituted with a carbazolyl group, wherein the carbazole group is fused to a heterocycloalkyl group or a cycloalkyl group fused to an aromatic ring.

The object of the present invention is to provide a compound for an organic electronic material which has an excellent structure and which has high luminous efficiency and long operation life. And a suitable organic color illuminating device using the compound;

The inventors of the present invention have found that the above object can be attained by the compound represented by the following formula 1: Wherein L ₁ and L ₂ each independently represent a single bond, a substituted or unsubstituted 3 to 30 membered heteroaryl group, a substituted or unsubstituted (C6-C30) extended aryl group, or a substituted or Unsubstituted (C6-C30)cycloalkylene; X ₁ represents CH or N; Y ₁ to Y ₃ each independently represent -O-, -S-, -CR ₆ R ₇ - or -NR ₈ -, limiting The conditions are that Y ₂ and Y _{3 are} not present at the same time; R ₁ to R ₅ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6- C30) aryl, substituted or unsubstituted 3 to 30 membered heteroaryl, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted 5 to 7 membered heterocycloalkane (C6-C30) aryl (C1-C30) alkyl, -NR ₁₁ R ₁₂ , -SiR ₁₃ R ₁₄ R ₁₅ , -SR ₁₆ , -OR ₁₇ , cyano, nitrate Or a hydroxyl group; or each of R ₁ to R ₅ may be bonded to one or more adjacent substituents through a substituted or unsubstituted (C3-C30) alkyl group or a (C3-C30) alkenyl group. Monocyclic or polycyclic lipids substituted with one or more carbon atoms in the ring via at least one hetero atom selected from nitrogen, oxygen and sulfur a ring or an aromatic ring; R ₆ to R ₈ and R ₁₁ to R ₁₇ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6- C30) aryl, substituted or unsubstituted 3 to 30 membered heteroaryl, substituted or unsubstituted 5 to 7 membered heterocycloalkyl, or substituted or unsubstituted (C3-C30) ring Or an alkyl group; or each of R ₆ to R ₈ and R ₁₁ to R ₁₇ may be bonded to one or more phases through a substituted or unsubstituted (C3-C30) alkylene group or a (C3-C30) extended alkenyl group. An ortho-substituent to form a monocyclic or polycyclic alicyclic or aromatic ring in which one or more carbon atoms in the ring may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur; a, b, c and e Each independently represents an integer from 1 to 4, wherein when a, b, c or e is an integer of 2 or more, each R ₁ , each R ₂ , each R ₃ or each R ₅ is the same or Different; d represents an integer of 1 to 3, wherein, when d is an integer of 2 or more, each R ₄ is the same or different; and the heterocycloalkyl and (extended) heteroaryl group contain at least one selected from the group consisting of Heteroatoms of B, N, O, S, P(=O), Si, and P.

The compound for an organic electronic material of the present invention can produce an organic electric field light-emitting device having high luminous efficiency and long operational life.

Further, since the compound for an organic electronic material of the present invention has high electron transport efficiency, it can prevent crystallization at the time of manufacturing a device. again The compound has good layer formability, thus improving the current characteristics of the device. Thereby, the compound can produce an organic electric field light-emitting device having a reduced driving voltage and increased power efficiency.

Hereinafter, the present invention will be described in detail. However, the following description is intended to be illustrative of the invention and is not intended to limit the scope of the invention in any way.

The present invention relates to a compound for an organic electronic material represented by the above formula 1, and an organic electric field light-emitting device comprising the same.

In the present specification, "(C1-C30)(alkyl)alkyl" means a straight or branched alkyl group having 1 to 30 carbon atoms, wherein the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, etc., but is not limited thereto; "(C2- C30) (extended) alkenyl" means a straight or branched (alkenyl) alkenyl group having 2 to 30 carbon atoms, wherein the number of carbon atoms is preferably from 2 to 20, more preferably from 2 to 10. And include, but are not limited to, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, and the like. The "(C2-C30)alkynyl group" is a linear or branched alkynyl group having 2 to 30 carbon atoms, wherein the number of carbon atoms is preferably from 2 to 20, more preferably from 2 to 10. And includes, but is not limited to, an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-methylpent-2-ynyl group, and the like. The "(C1-C30) alkoxy group" is a linear or branched alkoxy group having 1 to 30 carbon atoms, wherein the number of carbon atoms is preferably from 1 to 20, more preferably 1 to 10, and includes methoxy, ethoxy, propoxy, isopropoxy, 1-ethylpropoxy and the like, but is not limited thereto; "(C3-C30)cycloalkyl" has a monocyclic or polycyclic hydrocarbon having 3 to 30 carbon atoms, wherein the number of carbon atoms is preferably from 3 to 20, more preferably from 3 to 7, and comprises a cyclopropyl group, a cyclobutyl group, a cyclopentyl group. , cyclohexyl, and the like, but is not limited thereto; "(C6-C30)cycloalkylene" is formed by removing a hydrogen from a cycloalkyl group, wherein the cycloalkyl group has 6 to 30, Preferably 6 to 20, more preferably 6 or 7 carbon atoms; and "5- to 7-membered heterocycloalkyl" cycloalkyl having at least one selected from the group consisting of B, N, O, S, P(=O), Si and P heteroatoms, preferably N, O and S, and 5 to 7 ring main chain atoms, and comprising tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc. , but is not limited thereto; "(C6-C30) (extended) aryl" is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, wherein the number of carbon atoms is preferably 6 to 20, more preferably 6 to 12, and comprising a phenyl group, a biphenyl group, a terphenyl group, Base, fluorenyl, phenanthryl, fluorenyl, fluorenyl, triphenylenyl, fluorenyl, tetracenyl, fluorenyl, chrysenyl, naphthacenyl, Propylhenyl, etc., but is not limited thereto; "3- to 30-membered (hetero)heteroaryl" has at least one, preferably 1 to 4 heteroatoms, and 3 to 30 An aryl group of a ring backbone atom selected from the group consisting of B, N, O, S, P(=O), Si, and P; which is monocyclic or with at least one benzene ring Condensed fused ring; preferably from 5 to 21, more preferably from 5 to 12 ring backbone atoms; may be partially saturated; at least one heteroaryl group may be passed through one or more single bonds Or an aryl group bonded to a heteroaryl group; and comprises a monocyclic type heteroaryl group, including furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl ,different Azolyl, Azolyl, Diazolyl, three Base, four Base, triazolyl, tetrazolyl, furazolyl, pyridyl, pyridyl Base, pyrimidinyl, oxime Base, and fused ring type heteroaryl, including benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl Benzoisothiazolyl, benzopyrene Azolyl, benzo Azolyl, isodecyl, fluorenyl, oxazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, porphyrinyl, quinazolinyl, quin Orolinyl, carbazolyl, brown Peptidyl, benzodiyl Benzodioxolyl, etc., but is not limited thereto. Further, "halogen" includes F, Cl, Br, and I.

In the present specification, "substituted" in the "substituted or unsubstituted" expression means that a hydrogen atom of a particular functional group is replaced by another atom or group (ie, a substituent).

The substituted (extended) alkyl group, substituted alkenyl group, substituted alkyne in the groups of L ₁ , L ₂ , R ₁ to R ₅ , R ₆ to R ₈ , and R ₁₁ to R ₁₇ a substituted cycloalkyl group, a substituted cycloalkyl group, a substituted heterocycloalkyl group, a substituted (extended) aryl group, a substituted (extended) heteroaryl group, and a substituted aromatic ring Preferably, the substituents are each independently at least one selected from the group consisting of hydrazine, halogen, halogen-substituted or unsubstituted (C1-C30) alkyl, (C6-C30) aryl, C6-C30) aryl-substituted or unsubstituted 3- to 30-membered heteroaryl, (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl, tri(C1-C30)alkyl a decyl group, a tris(C6-C30) aryl decyl group, a di(C1-C30)alkyl (C6-C30) aryl decyl group, a (C1-C30) alkyl bis(C6-C30) aryl decyl group, (C2-C30) alkenyl, (C2-C30)alkynyl, cyano, oxazolyl, di(C1-C30)alkylamino, di(C6-C30)arylamino, (C1-C30) Alkyl (C6-C30) arylamino, bis(C6-C30) arylboronyl, bis(C1-C30)alkylborocarbonyl, (C1-C30)alkyl (C6-C30) aryl Boronylcarbonyl, (C6-C30) aryl (C1-C30) alkyl (C1-C30)alkyl (C6-C30) aryl, carboxy, nitro and hydroxy, more preferably, the substituent is at least one selected from the group consisting of hydrazine, halogen, halogen substituted or Unsubstituted (C1-C30) alkyl, (C6-C30) aryl, (C1-C30)alkyl (C6-C30) aryl, substituted by (C6-C30) aryl or unsubstituted 3 a 30-membered heteroaryl group, a (C3-C30)cycloalkyl group, and a (C6-C30)aryl(C1-C30)alkyl group, and more preferably the substituent group is at least one selected from the group consisting of Group: hydrazine, fluorine, methyl, phenyl and naphthyl.

In the above formula 1, L ₁ and L ₂ preferably each independently represent a single bond, a (C1-C6)alkyl substituted or unsubstituted (C6-C12) extended aryl group or an unsubstituted (C1-C6). The cycloalkyl group is more preferably a single bond, a phenyl group, a phenyl group, a dimethylphenyl group or a cyclohexyl group.

In the above formula 1, Y ₁ to Y ₃ each independently represent -O-, -S-, -CR ₆ R ₇ - or -NR ₈ -, wherein R ₆ and R ₈ are each independently hydrogen, hydrazine, Halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted 3 to 30 membered heteroaryl; or Y ₁ to Y ₃ may each be bonded to one or more adjacent substituents to form a spiro ring or a fused spiro ring; more preferably, Y ₁ to Y ₃ are each independently an anthracene, a halogen, or a (C1-C6)alkyl group. a (C6-C12) aryl-substituted or unsubstituted (C6-C20) aryl group, or a (C6-C12) aryl group substituted or unsubstituted 5 to 21 membered heteroaryl; or Y ₁ to Y ₃ may each be bonded to one or more adjacent substituents to form a spiro or fused spiro ring, or Y ₁ to Y ₃ may each pass through a substituted or unsubstituted (C3-C30) alkyl group or (C3-C30) an alkenyl group bonded to one or more adjacent substituents to form a monocyclic or polycyclic alicyclic or aromatic ring; more preferably, Y ₁ to Y ₃ are each independently methyl, benzene Base, biphenyl, terphenyl, naphthyl, phenyl substituted by fluorene, phenyl substituted by fluorine, fluorenyl substituted by methyl, naphthyl a phenyl group, or a phenyl group substituted with a phenyl group, or each of Y ₁ to Y ₃ may be bonded to one or more adjacent substituents to form a spiro ring or a fused spiro ring; or Y ₁ to Y ₃ may each The mono- or polycyclic alicyclic or aromatic ring is formed by a substituted or unsubstituted (C3-C30)alkylene group or a (C3-C30)alkylene group bonded to one or more adjacent substituents.

In the above formula 1, R ₁ to R _{5 are} preferably each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aromatic. a substituted, unsubstituted 3 to 30 membered heteroaryl group, N-carbazolyl, -NR ₁₁ R ₁₂ , or -SiR ₁₃ R ₁₄ R ₁₅ ; or R ₁ to R _{5 are} preferably permeable Substituted or unsubstituted (C3-C30)alkylene or (C3-C30)alkylene bonded to one or more adjacent substituents to form one or more carbon atoms in the ring may be passed through at least one a monocyclic or polycyclic alicyclic or aromatic ring selected from the group consisting of a hetero atom of nitrogen, oxygen and sulfur, wherein R ₁₁ to R ₁₅ are each independently a substituted or unsubstituted (C1-C30) alkyl group. , substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted 3 to 30 membered heteroaryl, more preferably unsubstituted (C1-C6) alkyl, unsubstituted The (C6-C12) aryl group or the unsubstituted 5 to 21 membered heteroaryl group is more preferably a methyl group, a phenyl group or a carbazolyl group.

In the above formula 1, R ₁ to R _{5 are} preferably each independently an unsubstituted (C6-C20) aryl group, an unsubstituted 5 to 21 membered heteroaryl group, -NR ₁₁ R ₁₂ or -SiR ₁₃ R. ₁₄ R _15; or R ₁ to R ₅ each preferably permeable substituted or non-substituted (C3-C30) alkylene or (C3-C30) alkenylene group bonded to one or more adjacent substituents To form a monocyclic or polycyclic alicyclic or aromatic ring, more preferably a phenyl, oxazolyl, diphenylamino or methyldiphenylalkylene group; or R ₁ to R ₅ each permeable The substituted or unsubstituted (C3-C30)alkylene group or (C3-C30)alkylene group is bonded to one or more adjacent substituents to form a monocyclic or polycyclic alicyclic or aromatic ring.

In the above formula 1, It is selected from the following structures, but is not limited to:

Representative compounds of the invention comprise, but are not limited to, the following:

The compound for organic electronic materials of the present invention can be based on the following Reaction scheme preparation.

Wherein R ₁ to R ₅ , Y ₁ to Y ₃ , X ₁ , L ₁ , L ₂ , a, b, c, d and e are the same as defined in the above formula 1, and X represents a halogen.

Further, the present invention provides an organic electric field light-emitting device comprising the compound of the formula 1. The organic electric field light-emitting device includes a first electrode, a second electrode, and at least one organic layer interposed between the first electrode and the second electrode. The organic layer comprises at least one compound of the formula 1 of the present invention. Further, the organic layer includes a light-emitting layer in which a compound of Formula 1 is included as a host material.

Further, the phosphorescent dopant used in the organic electric field light-emitting device together with the host material of the present invention may be a compound selected from the following formula 2: M ¹ L ¹⁰¹ L ¹⁰² L ¹⁰³ ...

Wherein M ¹ is selected from the group consisting of Ir, Pt, Pd, and Os; and L ¹⁰¹ , L ^{102 ,} and L ¹⁰³ are each independently selected from the following structures: R ₂₀₁ to R ₂₀₃ each independently represent hydrogen, deuterium, unsubstituted or substituted by one or more halogen (C1-C30) alkyl groups, unsubstituted or substituted by one or more (C1-C30) alkyl groups. (C6-C30) aryl, or halogen; R ₂₀₄ to R ₂₁₉ each independently represent 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)alkyldecane, substituted or unsubstituted bis(C1-C30)alkyl(C6-C30)aryldecyl, substituted or unsubstituted tris(C6-C30)aryl Alkyl, cyano or halogen; R ₂₂₀ to R ₂₂₃ each independently represent hydrogen, deuterium, unsubstituted or substituted by one or more halogens (C1-C30) alkyl, or unsubstituted or via one or more (C1-C30)alkyl substituted (C6-C30) aryl; R ₂₂₄ and R ₂₂₅ are each independent Representing hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or halogen, or R ₂₂₄ and R ₂₂₅ permeable with or without The (C3-C12)alkylene group or the (C3-C12)alkylene group of the fused ring is bonded to each other to form a monocyclic or polycyclic alicyclic or aromatic ring; R ₂₂₆ represents substituted or unsubstituted ( C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted 5- or 30-membered heteroaryl or halogen; R ₂₂₇ to R ₂₂₉ each independently represent hydrogen , hydrazine, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen; Q represents R ₂₃₁ to R ₂₄₂ each independently represent hydrogen, deuterium, unsubstituted or substituted by one or more halogens (C1-C30)alkyl, (C1-C30) alkoxy, halogen, substituted or unsubstituted (C6-C30) aryl, cyano, or substituted or unsubstituted (C5-C30) cycloalkyl, or each R ₂₃₁ to R ₂₄₂ permeable (C2-C30) alkyl or (C2- C30) an alkenyl group bonded to an adjacent substituent to form a spiro ring or a fused ring, or a (C2-C30) alkyl group or a (C2-C30) alkenyl group bonded to R ₂₀₇ or R ₂₀₈ A saturated or unsaturated fused ring is formed.

The dopant of Formula 2 includes the following, but is not limited thereto:

The organic electroluminescent device of the present invention may further comprise at least one compound selected from the group consisting of an arylamine-based compound and a styrylarylamine-based compound, in addition to the compound represented by Formula 1.

In the organic electric field light-emitting device of the present invention, the organic layer may include a metal selected from Group 1 of the periodic table, a metal of the second group, a transition metal of the fourth cycle, a transition metal of the fifth cycle, and a lanthanide metal. And at least one metal of the group consisting of group d transition elements, or at least one complex comprising the metal. The organic layer may include a light emitting layer and a charge generating layer.

Furthermore, in addition to the compound of the present invention, the organic electroluminescent device can emit white light by including at least one layer comprising a blue electric field luminescent compound, a red electric field luminescent compound or a green electric field luminescent compound.

Preferably, in the organic electric field light-emitting device according to the present invention, at least one layer selected from the group consisting of a chalcogenide layer, a metal halide layer, and a metal oxide layer (hereinafter referred to as a "surface layer") may be placed. On one or more inner surfaces of a single or two electrodes. Specifically, it is preferable to provide a layer of chalcogenide (including oxide) of bismuth or aluminum on the anode surface of the electric field luminescent medium layer, and to provide a metal halide layer or a metal oxide layer on the cathode of the electric field luminescent medium layer. surface. The surface layers provide operational stability of the organic electric field illuminating device. Preferably, the chalcogenide compound comprises SiO _X (1≦X≦2), AlO _X (1≦X≦1.5), SiON, SiAlON, etc.; the metal halide comprises LiF, MgF ₂ , CaF ₂ , rare earth metal fluoride And a metal oxide comprising Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO, or the like.

Preferably, in the organic electric field light-emitting device of the present invention, a mixed region of the electron transporting compound and the reducing dopant, or a mixed region of the hole transporting compound and the oxidizing dopant may be disposed on at least one surface of the electrode pair. In this case, the electron transporting compound is reduced to an anion, making the electron transporting compound easy to inject and transport electrons from the mixing zone to the electric field illuminating medium. Furthermore, the hole transport compound is oxidized to a cation, making the hole transport compound easy to inject and transport holes from the mixing zone to the electric field luminescent medium. Preferably, the oxidizing dopant comprises a plurality of Lewis acids and an acceptor compound; and the reducing dopant comprises an alkali metal, an alkali metal compound, an alkaline earth metal, a rare earth metal, and a mixture thereof. A reduced doping layer may be used as the charge generating layer to prepare an electric field light-emitting device having two or more layers of an electroluminescent layer and emitting white light.

Hereinafter, the compound for an organic electronic material, the method for producing the compound, and the luminescent properties of the device including the compound of the present invention will be described in detail with reference to the following examples:

Preparation Example 1: Preparation of Compound C-16

Preparation of Compound 1-1

2,4-dichloroquinazoline (30 g (g), 151 mmol (mmol)), 9-phenyl-9H-indazol-3-ylboronic acid (15.6 g, 75.3 mmol), Pd (PPh ₃ ) ₄ (2.6 g, 2.3 mmol) and Na ₂ CO ₃ (16 g, 150 mmol) dissolved in a mixture of toluene (300 mL) and distilled water (75 mL). Stir at 90 ° C for 2 hours. The resulting organic layer was distilled under reduced pressure and then was triturated with MeOH. The obtained solid was dissolved in dichloromethane (MC), filtered through silica gel, and then triturated with MC and hexane to give Compound 1-1 (9.3 g, 51.4%).

Preparation of Compound 1-2

Dibenzo[b,d]furan-4-ylboronic acid (30 g, 142 mmol), 1-bromo-2-nitrobenzene (23.8 g, 118 mmol), K ₂ CO ₃ (39.1克,283mm, and Pd(PPh ₃ ) ₄ (6.8g, 5.8mmol) dissolved in a mixture of toluene (600ml), EtOH (150ml) and purified water (50ml), The reaction mixture was stirred at reflux for 24 hours. After the reaction was terminated, the reaction mixture was allowed to cool to room temperature, and the aqueous layer was removed from the mixture by gravity separation. The obtained organic layer was concentrated, triturated with MC, and then filtered to give Compound 1-2 (34 g, 99.7%).

Preparation of Compound 1-3

Compound 1-2 (34 g, 117.5 mmol) was dissolved in a mixture of P(OEt) ₃ (300 mL) and 1,2-dichlorobenzene (300 mL), and the mixture was stirred at 150 ° C. hour. After the reaction was completed, the reaction mixture was evaporated,jjjjjjjjjjjjjjjj

Preparation of Compound C-16

After dispersing compound 1-1 (6.3 g, 15.5 mmol) and compound 1-3 (4.0 g, 15.5 mmol) in 80 ml of dimethylformamide (DME), 60% NaH at room temperature (930 mg, 23.2 mmol) was added to the mixture. The resulting reaction mixture was stirred for 12 hours. After adding purified water (1 L), the mixture was filtered under reduced pressure. The resulting solid was triturated with MeOH/EA, triturated with DMF and triturated with EtOAc / THF. Dissolved in MC, filtered through silica gel and then triturated with MeOH / EA to afford compound C-16 (6 g, 62%).

MS/FAB measured value 627; calculated value 626.70

Preparation Example 2: Preparation of Compound C-32

Preparation of Compound 2-1

2,4-Dichloroquinazoline (50 g, 251 mmol) and dibenzo[b,d]furan-4-ylboronic acid (53.2 g, 251 mmol) dissolved in toluene (1 liter) and After a mixture of water (200 ml), triphenylphosphine palladium (14.5 g, 12.5 mmol) and sodium carbonate (80 g, 755 mmol) were added to the reaction mixture. The reaction mixture was stirred at 80 ° C for 20 hours and cooled to room temperature. After quenching the reaction with 200 ml of aqueous ammonium chloride solution, the reaction mixture was extracted with 1 liter of ethyl acetate, and the aqueous layer was further extracted with 1 liter of dichloromethane. The obtained organic layer was dried over anhydrous magnesium sulfate and the organic solvent was removed under reduced pressure. The resulting solid was filtered through silica gel and the solvent was removed under reduced pressure. The obtained solid was washed with 100 ml of ethyl acetate to give Compound 2-1 (50 g, 74%).

Preparation of Compound 2-2

Dibenzo[b,d]thiophen-2-ylboronic acid (40 g, 136.8 mmol), iodonitrobenzene (37.4 g, 150.5 mmol) and Pd(PPh ₃ ) ₄ (6.32 g, 5.47) The mixture was dissolved in a mixture of 2M Na ₂ CO ₃ (170 ml) and toluene (700 ml), and the mixture was stirred at 100 ° C for 4 hours. The reaction mixture was cooled to room temperature, distilled water was added, and ethyl acetate was evaporated. Dried over MgSO _4, and distilled under reduced pressure, and filtered through column to give compound 2-2 (28 g, 72.86 mmol, 52.94%).

Preparation of Compound 2-3

After compound 2-2 (28 g, 72.86 mmol) was combined with 300 ml of triethyl phosphite, the reaction mixture was stirred at 150 ° C for 12 hours. The reaction mixture was cooled to room temperature, distilled under reduced pressure, extracted with ethyl acetate and washed with distilled water. Dried MgSO _4, vacuum distillation, and filtered through column to give compound 2-3 (11 g, 31.22 mmol, 43.05%).

Preparation of Compound C-32

After dispersing compound 2-1 (5.1 g, 15.5 mmol) and compound 2-3 (4.2 g, 15.5 mmol) in 80 ml of DMF, 60% NaH (930 mg, 23.2 mmol) at room temperature ) is added to the mixture. The resulting reaction mixture was stirred for 12 hours. After adding purified water (1 L), the mixture was filtered under reduced pressure. The resulting solid was triturated with MeOH/EA, triturated with DMF, and triturated with EA/THF. Dissolved in MC, filtered through silica gel, and then MeOH/EA was triturated to give compound C-32 (5.4 g, 62%).

MS/FAB measured value 568; calculated value 567.66

Preparation 3: Preparation of Compound C-51

Preparation of Compound C-51

After compound 2-1 (5.1 g, 15.5 mmol) and compound 1-3 (4.0 g, 15.5 mmol) were dispersed in 80 ml of DMF, 60% NaH (930 mg, 23.2 mmol) at room temperature. ) was added to the mixture and stirred for 12 hours. After adding purified water (1 liter), the mixture was filtered under reduced pressure. The resulting solid was triturated with MeOH/EA, triturated with DMF, and triturated with EA/THF. Dissolved in MC, filtered through silica gel, and then triturated with MeOH / EA to afford compound C-51 (5.9 g, 69%).

MS/FAB measured value 552; calculated value 551.59

Preparation Example 4: Preparation of Compound C-94

Preparation of Compound 4-1

Compound 1-3 (27.3 g, 106.1 mmol), 1-bromo-4-iodobenzene (45 g, 159.2 mmol), CuI (10 g, 53 mmol), K ₃ PO ₄ (67.5 After gram (318.3 mmol) and ethylenediamine (EDA) (7.2 mL, 106.1 mmol) dissolved in toluene (300 mL), the reaction mixture was stirred under reflux for 24 hours. The mixture was extracted with EA, and the obtained organic layer was evaporated under reduced pressure, and then filtered through a column of EtOAc and hexane to afford compound 4-1 (32 g, 73.2%).

Preparation of Compound C-4-2

After compound 4-1 (30.9 g, 74.9 mmol) was dissolved in (THF) (250 mL), then 2.5 M in n-BuLi (44.9 mL, 112.4 mmol) in hexane was added at -78 °C. The reaction mixture was stirred for 1 hour into the reaction mixture. The reaction mixture was stirred for 2 hours while B (Oi-Pr) ₃ (29.3 mL, 127.3 mmol) was slowly added to the reaction mixture. The reaction mixture was quenched by the addition of 2M HCl and the mixture was extracted with distilled water and EA. The obtained organic layer was evaporated under reduced pressure and then recrystallized from MC and hexane to afford compound 4-2 (22.3 g, 80%).

Preparation of Compound C-94

Compound 2-1 (3.9 g, 11.9 mmol), compound 4-2 (4.0 g, 11.9 mmol), Pd(PPh ₃ ) ₄ (687 mg, 0.59 mmol) and Na ₂ CO ₃ ( After a mixture of toluene (55 ml), EtOH (14 ml) and distilled water (14 ml), the mixture was stirred at 90 ° C for 2 hours. The mixture was extracted with distilled water and EtOAc, and then evaporated and evaporated.

MS/FAB measured value 628; calculated value 627.69

Preparation 5: Preparation of Compound C-96

Preparation of Compound C-96

Compound 1-1 (4.8 g, 11.9 mmol) and compound 4-2 (4.0 g, 11.9 mmol), Pd(PPh ₃ ) ₄ (687 mg, 0.59 mmol) and Na ₂ CO ₃ ( After a mixture of toluene (55 ml), EtOH (14 ml) and distilled water (14 ml), the mixture was stirred at 90 ° C for 2 hours. The mixture was extracted with distilled water and EtOAc, and then evaporated and evaporated.

MS/FAB measured value 703; calculated value 702.80

Example 1: Manufacture of an OLED device using the compound of the present invention

An OLED device is fabricated using the compounds of the invention. Transparent electrode indium tin oxide (ITO) film on a glass substrate for organic light-emitting diode (OLED) device (manufactured by Samsung-Corning, Republic of Korea) using ultrasonic waves in the order of trichloroethylene, acetone, ethanol and distilled water (15 Ω/sq), then stored in isopropanol. Then, the ITO substrate was mounted on a substrate holder of a vacuum vapor deposition apparatus. N ¹ N ^{1 '} -([1,1'-biphenyl]-4,4'-diyl) bis(N ¹ -(naphthalen-1-yl)-N ⁴ ,N ⁴ -diphenylbenzene- 1,4-Diamine is introduced into the cell of the vacuum vapor deposition apparatus, and then the pressure of the chamber of the apparatus is controlled to 10 ^-6 torr. Thereafter, a current is applied to the chamber to evaporate the introduction. a material for forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Thereafter, N,N'-bis(4-biphenyl)-N,N'-bis(4-biphenyl)- 4,4'-diaminobiphenyl is introduced into another chamber of the vacuum vapor deposition apparatus, and is evaporated by applying a current to the chamber, thereby forming a hole having a thickness of 20 nm on the hole injection layer. The transport layer. Thereafter, the compound C-16 is introduced into one chamber of the vacuum vapor deposition apparatus as a host material, and the compound D-7 is introduced into another chamber as a dopant. The two materials are evaporated at different rates. Deposited at a doping amount of 4 wt% to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. Then, 2-(4-(9,10-di(naphthalen-2-yl)anthracene-2) -yl)phenyl)-1-phenyl-1H-benzo[d]imidazole introduced into a chamber and 8-hydroxyl Lithium quinolate is introduced into another chamber. The two materials are evaporated at the same rate and deposited at a doping amount of 50 wt% to form an electron transport layer having a thickness of 30 nm on the luminescent layer. After depositing lithium hydroxyquinolate having a thickness of 2 nm as an electron injecting layer on the electron transporting layer, an Al cathode having a thickness of 150 nm is deposited on the electron injecting layer by another vacuum vapor deposition apparatus. An OLED device was fabricated. All materials used to fabricate the OLED device were purified by vacuum sublimation at 10 ^-6 torr.

The prepared OLED device showed red light having a luminance of 1,030 candelas (cd) per square meter (m ² ) and a current density of 10.0 milliamperes (mA) per square centimeter (cm ² ) at a driving voltage of 4.1V. Furthermore, the minimum time from a brightness of 5,000 nits to 90% brightness is 30 hours.

Example 2: Preparation of an OLED device using the compound of the invention

The OLED device was prepared in the same manner as in Example 1, except that Compound C-48 was used as a host material and Compound D-11 was used as a dopant.

The obtained OLED device showed red light having a luminance of 1,030 cd/m ² and a current density of 12.7 mA/cm ² at a driving voltage of 4.2V. Furthermore, the minimum time from a brightness of 5,000 nit to a 90% brightness is 100 hours.

Example 3: Preparation of an OLED device using the compound of the invention

The OLED device was prepared in the same manner as in Example 1, except that Compound C-51 was used as a host material and Compound D-11 was used as a dopant.

The obtained OLED device showed red light having a luminance of 1,010 cd/m ² and a current density of 13.7 mA/cm ² at a driving voltage of 4.5V. Furthermore, the minimum time from a brightness of 5,000 nit to a 90% brightness is 100 hours.

Example 4: Preparation of an OLED device using the compound of the invention

The OLED device was prepared in the same manner as in Example 1, except that Compound C-94 was used as a host material and Compound D-11 was used as a dopant.

The obtained OLED device showed red light having a luminance of 1,060 cd/m ² and a current density of 12.2 mA/cm ² at a driving voltage of 4.2V. Furthermore, the minimum time from a brightness of 5,000 nit to a 90% brightness is 40 hours.

Example 5: Preparation of an OLED device using the compound of the invention

The OLED device was prepared in the same manner as in Example 1, except that the compound C-96 was used as the host material and the compound D-7 was used as the blend. Miscellaneous.

The obtained OLED device showed red light having a luminance of 1,010 cd/m ² and a current density of 9.8 mA/cm ² at a driving voltage of 3.9V. Furthermore, the minimum time from a brightness of 5,000 nit to a 90% brightness is 20 hours.

Comparative Example 1: Preparation of an OLED device using a conventional electroluminescent compound

An OLED device was prepared in the same manner as in Example 1, except that a light-emitting layer having a thickness of 30 nm deposited on the hole transport layer was changed to use 4,4'-N,N'-dicarbazole-biphenyl (CBP). As a host material and compound D-11 as a dopant and by using bis(2-methyl-8-hydroxyquinolinyl)-4-phenylphenol aluminum (III) to deposit a hole block having a thickness of 10 nm Floor.

The obtained OLED device showed red light having a luminance of 1,000 cd/m ² and a current density of 20.0 mA/cm ² at a driving voltage of 8.2V. Furthermore, the minimum time from a brightness of 5,000 nit to a 90% brightness is 10 hours.

Since the compound for an organic electronic material of the present invention has high electron transport efficiency, it can prevent crystallization at the time of manufacturing a device. Furthermore, the compound has good layer formability, thereby improving the current characteristics of the device. Thereby, the compound can produce an organic electric field light-emitting device having a reduced driving voltage and increased power efficiency. Furthermore, OLED devices using conventional compounds for organic electronic materials require a hole blocking layer, while OLED devices using the compounds of the present invention do not require a hole blocking layer.

Claims (6)

a compound represented by the following formula 1, Wherein L ₁ and L ₂ each independently represent a single bond, a substituted or unsubstituted 3 to 30 membered heteroaryl group, a substituted or unsubstituted (C6-C30) extended aryl group, or a substituted or Unsubstituted (C6-C30)cycloalkylene; X ₁ represents CH or N; Y ₁ to Y ₃ each independently represent -O-, -S-, -CR ₆ R ₇ - or -NR ₈ -, The limitation is that Y ₂ and Y _{3 are} not present at the same time; R ₁ to R ₅ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6 -C30) aryl, substituted or unsubstituted 3 to 30 membered heteroaryl, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted 5 to 7 membered heterocyclic ring Alkyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl, -NR ₁₁ R ₁₂ , -SiR ₁₃ R ₁₄ R ₁₅ , -SR ₁₆ , -OR ₁₇ , cyano, a nitro group, or a hydroxy group; or each of R ₁ to R ₅ may be bonded to one or more adjacent substituents through a substituted or unsubstituted (C3-C30)alkylene group or a (C3-C30)alkylene group. To form a monocyclic or polycyclic ring in which one or more carbon atoms in the ring may be replaced by at least one hetero atom selected from the group consisting of nitrogen, oxygen and sulfur. An alicyclic or aromatic ring; R ₆ to R ₈ and R ₁₁ to R ₁₇ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6 -C30) aryl, substituted or unsubstituted 3 to 30 membered heteroaryl, substituted or unsubstituted 5 to 7 membered heterocycloalkyl, or substituted or unsubstituted (C3-C30) a cycloalkyl group; or each of R ₆ to R ₈ and R ₁₁ to R ₁₇ may be bonded to one or more via a substituted or unsubstituted (C3-C30) alkylene group or a (C3-C30) alkylene group. Adjacent substituents, forming a monocyclic or polycyclic alicyclic or aromatic ring wherein one or more carbon atoms in the ring are replaced by at least one hetero atom selected from nitrogen, oxygen and sulfur; a, b, c and e each independently represents an integer from 1 to 4, wherein when a, b, c or e is an integer of 2 or more, each R ₁ , each R ₂ , each R ₃ or each R ₅ is the same Or different; d represents an integer from 1 to 3, wherein, when d is an integer of 2 or more, each R ₄ is the same or different; and the heterocycloalkyl and (extended) heteroaryl group contain at least one selected from Heteroatoms of B, N, O, S, P(=O), Si, and P. The compound according to claim 1, wherein the substituted group in the groups of L ₁ and L ₂ , R ₁ to R ₅ , R ₆ to R ₈ , and R ₁₁ to R ₁₇ An alkyl group, substituted alkenyl group, substituted alkynyl group, substituted cycloalkylene group, substituted cycloalkyl group, substituted heterocycloalkyl group, substituted (extended) aryl group, substituted The substituents of the (hetero)heteroaryl group and the substituted aromatic ring are each independently at least one selected from the group consisting of hydrazine, halogen, halogen-substituted or unsubstituted (C1-C30) alkane. , (C6-C30) aryl, 3- to 30-membered heteroaryl substituted by (C6-C30) aryl, (C3-C30) cycloalkyl, 5- to 7-membered Cycloalkyl, tri(C1-C30)alkyldecyl, tris(C6-C30)aryldecyl, bis(C1-C30)alkyl(C6-C30)aryldecyl,(C1-C30)alkane Bis(C6-C30)arylalkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, cyano, oxazolyl, bis(C1-C30)alkylamino, di(C6- C30) arylamino group, (C1-C30)alkyl (C6-C30) arylamino group, di(C6-C30) aryl boroncarbonyl group, di(C1-C30)alkyl boroncarbonyl group, (C1-C30 Alkyl (C6-C30) aryl boron Carbonyl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30)alkyl (C6-C30) aryl, carboxyl, nitro and hydroxy. The compound of claim 1, wherein L ₁ and L ₂ each independently represent a single bond, a 3 to 30 member heteroaryl group, a (C6-C30) extended aryl group, or a (C6-C30) extension. Cycloalkyl; X ₁ represents CH or N; Y ₁ to Y ₃ each independently represent -O-, -S-, -CR ₆ R ₇ - or -NR ₈ -, with the limitation that Y ₂ and Y _{3 are} different Existence; R ₁ to R ₅ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or not Substituted 3 to 30 membered heteroaryl, N-carbazolyl, -NR ₁₁ R ₁₂ , -SiR ₁₃ R ₁₄ R ₁₅ ; or R ₁ to R ₅ each permeable or unsubstituted (C3- C30) an alkyl or (C3-C30) alkenyl group bonded to one or more adjacent substituents to form one or more carbon atoms in the ring may be passed through at least one selected from the group consisting of nitrogen, oxygen and sulfur Atomic or monocyclic or polycyclic alicyclic or aromatic ring; R ₆ to R ₈ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted 3 to 30 membered heteroaryl; or R ₆ to R ₈ It may be bonded to one or more adjacent substituents via a substituted or unsubstituted (C3-C30) alkylene group or a (C3-C30) alkenyl group to form a monocyclic or polycyclic alicyclic ring or aroma. R ₁₁ to R ₁₅ each independently represent a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted 3 to a 30-membered heteroaryl; and the aryl, heteroaryl and cycloalkyl group in L ₁ and L ₂ , the alkyl or aryl group in R ₁ to R ₅ and R ₁₁ to R ₁₅ And a heteroaryl group may be substituted with at least one selected from the group consisting of hydrazine, halogen, halogen-substituted or unsubstituted (C1-C30) alkyl, (C6-C30) aryl, (C1- C30) alkyl (C6-C30) aryl, 3 to 30 membered heteroaryl substituted by (C6-C30) aryl, (C3-C30)cycloalkyl and (C6-C30) aryl (C1-C30) alkyl. The compound of claim 1, wherein the following part of formula 1: It is selected from the following structures: The compound of claim 1, wherein the compound represented by the formula 1 is selected from the group consisting of: An organic electric field illuminating device comprising the compound according to claim 1 of the patent application.