KR20220084559A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention is a novel organic light emitting compound represented by [Formula I] that is employed in an organic layer such as an electron transport layer in an organic light emitting device to realize light emitting characteristics such as low voltage driving and excellent luminous efficiency of the device, and an organic light emitting device comprising the same is about
[Formula Ⅰ]

Description

An organic light emitting compound and an organic light emitting device comprising the same {An electroluminescent compound and an electroluminescent device comprising the same}

The present invention relates to an organic light emitting compound, and more particularly, to an organic light emitting compound, characterized in that it is employed as an organic layer material in an organic light emitting device, and an organic light emitting property with significantly improved light emitting properties such as low voltage driving and excellent luminous efficiency of the device by employing the same It relates to a light emitting device.

The organic light emitting device can be formed on a transparent substrate as well as being able to drive at a low voltage of 10 V or less compared to a plasma display panel or an inorganic electroluminescent (EL) display, and consume relatively little power. , has the advantage of excellent color, and can represent three colors of green, blue, and red.

However, in order for such an organic light emitting device to exhibit the above characteristics, the material constituting the organic layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material, is supported by stable and efficient materials. However, the development of a stable and efficient organic layer material for an organic light emitting device has not yet been sufficiently developed.

Therefore, in order to realize a more stable organic light emitting device, and to achieve high efficiency, long lifespan, and large size of the device, additional improvements are required in terms of efficiency and lifespan characteristics. It is desperately needed.

Accordingly, an object of the present invention is to provide a novel organic light emitting compound capable of implementing excellent light emitting characteristics such as low voltage driving and improved luminous efficiency of the device by being employed in the organic layer in the organic light emitting device, and an organic light emitting device including the same.

In order to solve the above problems, the present invention provides an organic light emitting compound represented by the following [Formula I].

[Formula Ⅰ]

The characteristic structure of the [Formula I] and the compounds implemented thereby, X, L, Ar ₁ to Ar ₂ will be described later.

When the organic light emitting compound according to the present invention is employed as an organic layer material such as an electron transport layer in an organic light emitting device, it is possible to realize light emitting characteristics such as low voltage driving and excellent luminous efficiency of the device, so that it can be usefully used in various display devices.

Hereinafter, the present invention will be described in more detail.

The present invention relates to an organic light-emitting compound represented by the following [Formula I], which can achieve light-emitting characteristics such as low voltage driving of the organic light-emitting device and excellent light-emitting efficiency,

It is characterized by introducing a triazine derivative through an L linkage into a skeletal structure structurally represented by the following [Formula I], that is, a benzonaphthofuran, benzonaphthothiophene or benzofluorene structure to which a cyano group (CN) is bonded. And, it is possible to improve the low voltage driving characteristics and luminous efficiency characteristics of the organic light emitting diode through these structural features.

[Formula Ⅰ]

In the [Formula I],

X is O, S or C(CH ₃ ) ₂ .

L is a single bond, or is selected from a substituted or unsubstituted C6 to C30 arylene group and a substituted or unsubstituted C3 to C30 heteroarylene group, n is an integer from 0 to 3, and n is 2 or more A plurality of L's are the same as or different from each other.

Ar ₁ To Ar ₂ are each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C It is selected from an aryl group having 6 to 30 and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In addition, according to an embodiment of the present invention, Ar ₁ to Ar ₂ are each selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In addition, according to an embodiment of the present invention, Ar _One To Ar ₂ Each may be a substituted or unsubstituted aryl group to a heteroaryl group having various structures, Ar _One To Ar ₂ Each is benzo the same as the skeleton structure It may be naphthofuran, benzonaphthothiophene or benzofluorene.

Meanwhile, in the definition of L, Ar ₁ to Ar ₂ , 'substituted or unsubstituted' means that L and Ar ₁ to Ar ₂ are deuterium, deuterium, halogen group, cyano group, nitro group, hydroxyl group, silyl group, respectively. , an alkyl group, a halogenated alkyl group, a deuterated alkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkoxy group, a halogenated alkoxy group, a deuterated alkoxy group, an aryl group, a heteroaryl group, an alkylamine group, an arylamine group and a silyl group. It means that it is substituted with one or two or more substituents selected from the group consisting of, or substituted with a substituent to which two or more of the substituents are connected, or does not have any substituents.

For specific examples, the substituted aryl group means that a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, etc. are substituted with other substituents do.

In addition, the substituted heteroaryl group refers to a pyridyl group, a thiophenyl group, a triazine group, a quinoline group, a phenanthroline group, an imidazole group, a thiazole group, an oxazole group, a carbazole group and a condensed heterocyclic group thereof, such as a benzquinoline group. , a benzimidazole group, a benzoxazole group, a benzthiazole group, a benzcarbazole group, a dibenzothiophenyl group, a dibenzofuran group, and the like are substituted with other substituents.

In the present invention, examples of the substituents will be described in detail below, but the present invention is not limited thereto.

In the present invention, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, and the like, but is not limited thereto.

In the present invention, the alkoxy group may be straight-chain or branched. Although the number of carbon atoms of the alkoxy group is not particularly limited, it is preferably 1 to 20 in a range that does not cause steric hindrance. Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, i-propyloxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentyloxy group , neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group , a benzyloxy group, a p-methylbenzyloxy group, etc., but is not limited thereto.

In the present invention, a deuterated alkyl group or alkoxy group, halogenated alkyl group or alkoxy group means an alkyl group or alkoxy group in which the alkyl group or alkoxy group is substituted with deuterium or a halogen group.

In the present invention, the aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 30. Examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and a stilbene group. Examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, and a tetracenyl group. , chrysenyl group, fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthrene group, etc., but the scope of the present invention is not limited to these examples.

,

,

등이 있다.In the present invention, the fluorenyl group is a structure in which two ring organic compounds are connected through one atom, for example,

,

,

etc.

,

등이 있다.In the present invention, the fluorenyl group includes a structure of an open fluorenyl group, wherein the open fluorenyl group is a structure in which one ring compound is disconnected in a structure in which two ring organic compounds are connected through one atom. , for example

,

etc.

,

,

,

등이 있다.In addition, the carbon atom of the ring may be substituted with any one or more heteroatoms selected from N, S and O, for example,

,

,

,

etc.

In the present invention, the heteroaryl group is a heterocyclic group containing O, N, or S as a heteroatom, and the number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, and for a specific example thereof in the present invention, a thiophene group , furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, acridyl group, pyridazine group, pyra Zinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxa Zol group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, dibenzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadia and a zolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, a phenoxazine group, a phenothiazine group, and the like, but are not limited thereto.

In the present invention, the silyl group is an unsubstituted silyl group or a silyl group substituted with an alkyl group, an aryl group, etc., and specific examples of the silyl group include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxy phenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfurylsilyl, and the like, but is not limited thereto.

In the present invention, the amine group may be -NH ₂ , an alkylamine group, an arylamine group, etc., the arylamine group means an amine substituted with an aryl, the alkylamine group means an amine substituted with an alkyl, and an arylamine group Examples of these include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group, and the aryl group in the arylamine group is the same as the definition of the aryl group, , The alkyl group of the alkylamine group is also the same as the definition of the alkyl group.

Specific examples of the halogen group as a substituent used in the present invention include fluorine (F), chlorine (Cl), bromine (Br), and the like.

In the present invention, the cycloalkyl group refers to, and includes, monocyclic, polycyclic and spiro alkyl radicals, and preferably contains 3 to 20 ring carbon atoms, cyclopropyl, cyclopentyl, cyclohexyl, bicyclo heptyl, spirodecyl, spirodecyl, adamantyl, and the like, wherein the cycloalkyl group may be optionally substituted.

In the present invention, heterocycloalkyl groups refer to and include aromatic and non-aromatic cyclic radicals containing one or more heteroatoms, wherein one or more heteroatoms are O, S, N, P, B, Si, and Se , Preferably it is selected from O, N or S, and specifically, when N is included, it may be aziridine, pyrrolidine, piperidine, azepane, azocan, and the like.

The organic light emitting compound according to the present invention represented by the above [Formula I] can be used as various organic layers, including the electron transport layer in the organic light emitting device due to its structural specificity.

Preferred examples of the organic light emitting compound represented by [Formula I] according to the present invention include the following compounds, but is not limited thereto.

As such, the organic light emitting compound according to the present invention can synthesize an organic light emitting compound having various characteristics using a characteristic skeleton exhibiting unique properties and a moiety having intrinsic properties introduced thereto, As a result, the organic light emitting compound according to the present invention can be applied to various organic layer materials such as a light emitting layer, a hole transport layer, an electron transport layer, an electron blocking layer, and a hole blocking layer. can be further improved.

In addition, the compound of the present invention can be applied to a device according to a general method for manufacturing an organic light emitting device.

The organic light emitting device according to an embodiment of the present invention may have a structure including a first electrode and a second electrode and an organic layer disposed therebetween. Except that, it may be manufactured using a conventional device manufacturing method and material.

The organic layer of the organic light emitting device according to the present invention may have a single-layer structure, but may have a multi-layered structure in which two or more organic layers are stacked. For example, it may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, a hole blocking layer, etc., a structure including a light efficiency improving layer (Capping layer) provided in the organic light emitting device may have, but is not limited thereto, and may include a smaller number or a larger number of organic layers.

The organic layer structure of the preferred organic light emitting device according to the present invention will be described in more detail in the following Examples.

In addition, the organic light emitting device according to the present invention uses a PVD (physical vapor deposition) method, such as sputtering or e-beam evaporation, to form a metal or a conductive metal oxide or an alloy thereof on a substrate. It can be prepared by depositing an anode, forming an organic layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate. The organic layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic layer can be formed in a smaller number by a solvent process rather than a vapor deposition method using various polymer materials, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method. It can be made in layers.

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc. Metal oxides, combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT) , a conductive polymer such as polypyrrole and polyaniline, but is not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof, and multilayered materials such as LiF/Al or LiO ₂ /Al Structural materials and the like, but are not limited thereto.

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene, quinacridone-based organic material, perylene-based organic material, Anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer is suitable, and a material having high hole mobility is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together. can be further improved.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazole-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole, benzthiazole and There are benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, rubrene, and the like, but is not limited thereto.

As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline, a complex including Alq ₃ , an organic radical compound, and a hydroxyflavone-metal complex.

The organic light emitting diode according to the present invention may be a top emission type, a back emission type, or a double side emission type depending on the material used.

In addition, the organic light emitting compound according to the present invention can act on a principle similar to that applied to the organic light emitting device in organic electronic devices including organic solar cells, organic photoreceptors, organic transistors, and the like.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for explaining the present invention in more detail, the scope of the present invention is not limited thereby, and it is common in the art that various changes and modifications are possible within the scope and spirit of the present invention. It will be obvious to those with knowledge.

Synthesis example 1: Synthesis of compound 1

(One) production example 1: Synthesis of Intermediate 1-1

Add 150 mL of DMF to 9-Bromo-7,7-dimethyl-7H-benzo[c]fluorene (10.0 g, 0.031 mol) and Copper(I) cyanide (5.5 g, 0.062 mol) and reflux at 150 °C for 12 hours. The reaction was stirred. After completion of the reaction, 7.4 g (yield 88.8%) of <Intermediate 1-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 1-2

180 mL of DMF was added to Intermediate 1-1 (10.0 g, 0.037 mol) and N-Bromosuccinimide (7.9 g, 0.045 mol), and the reaction was stirred at room temperature for 6 hours. After completion of the reaction, 9.1 g (yield 70.4%) of <Intermediate 1-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) production example 3: Synthesis of Intermediate 1-3

Intermediate 1-2 (10.0 g, 0.029 mol), Bis(pinacolato)diboron (8.8 g, 0.035 mol), KOAc (5.6 g, 0.057 mol), Pd(dppf)Cl ₂ (0.6 g, 0.001 mol) in dioxane 200 mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 8.3 g (yield 73.1%) of <Intermediate 1-3>.

(4) production example 4: Synthesis of compound 1

2-Chloro-4,6-diphenyl-1,3,5-triazine (10.0 g, 0.037 mol), Intermediate 1-3 (17.7 g, 0.045 mol), K ₂ CO ₃ (15.5 g, 0.112 mol), Pd 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to (PPh ₃ ) ₄ (0.9 g, 0.001 mol) and stirred at 100 °C for 6 hours to react. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 13.3 g (yield 71.1%) of <Compound 1>.

LC/MS: m/z=500[(M+1) ⁺ ]

Synthesis example 2: Synthesis of compound 4

(One) production example 1: Synthesis of compound 4

2,4-Bis(4-biphenylyl)-6-chloro-1,3,5-triazine (10.0 g, 0.024 mol), Intermediate 1-3 (11.3 g, 0.029 mol), K ₂ CO ₃ (9.9 g, 0.071 mol), Pd(PPh ₃ ) ₄ (0.6 g, 0.001 mol) was added with 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring at 100° C. for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 11.5 g (yield 73.9%) of <Compound 4>.

LC/MS: m/z=652 [(M+1) ⁺ ]

Synthesis example 3: Synthesis of compound 6

(One) production example 1: Synthesis of Intermediate 6-1

Cyanuric chloride (10.0 g, 0.054 mol), 9-Phenanthracenylboronic acid (28.9 g, 0.130 mol), K ₂ CO ₃ (44.9 g, 0.325 mol), Pd(PPh ₃ ) ₄ (1.2 g, 0.001 mol) toluene 200 mL, 50 mL of ethanol, and 50 mL of H ₂ O were added, and the reaction was stirred at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 17.3 g (yield 68.2%) of <Intermediate 6-1>.

(2) production example 2: Synthesis of compound 6

To Intermediate 6-1 (10.0 g, 0.015 mol), Intermediate 1-3 (10.1 g, 0.019 mol), K ₂ CO ₃ (6.4 g, 0.046 mol), Pd(PPh ₃ ) ₄ (0.4 g, 0.001 mol) 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added, and the reaction was stirred at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 7.5 g (yield 69.3%) of <Compound 6>.

LC/MS: m/z=700[(M+1) ⁺ ]

Synthesis example 4: Synthesis of compound 29

(One) production example 1: Synthesis of compound 29

2-(4-Bromophenyl)-4,6-di(naphthalen-2-yl)-1,3,5-triazine (10.0 g, 0.021 mol), Intermediate 1-3 (9.7 g, 0.025 mol), K ₂ 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to CO ₃ (8.5 g, 0.061 mol), Pd(PPh ₃ ) ₄ (0.5 g, 0.0004 mol), and the reaction was stirred at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 9.8 g (yield 70.7%) of <Compound 29>.

LC/MS: m/z=676[(M+1) ⁺ ]

Synthesis example 5: Synthesis of compound 31

(One) production example 1: Synthesis of compound 31

2-(4-Bromophenyl)-4,6-di(naphthalen-1-yl)-1,3,5-triazine (10.0 g, 0.021 mol), Intermediate 1-3 (9.7 g, 0.025 mol), K ₂ 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to CO ₃ (8.5 g, 0.061 mol), Pd(PPh ₃ ) ₄ (0.5 g, 0.0004 mol), and the reaction was stirred at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 9.6 g (yield 69.3%) of <Compound 31>.

LC/MS: m/z=676[(M+1) ⁺ ]

Synthesis example 6: Synthesis of compound 39

(One) production example 1: Synthesis of intermediate 39-1

1-Bromo-4-iodobenzene (10.0 g, 0.035 mol), Intermediate 1-3 (16.8 g, 0.042 mol), K ₂ CO ₃ (14.7 g, 0.106 mol), Pd(PPh ₃ ) ₄ (0.8 g, 0.001) mol) was added 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, and stirred at 100 °C for 6 hours to react. After completion of the reaction, extraction and concentration were performed, followed by column to obtain 7.9 g (yield: 52.7%) of <Intermediate 39-1>.

(2) production example 2: Synthesis of intermediate 39-2

Intermediate 39-1 (10.0 g, 0.024 mol), Bis(pinacolato)diboron (7.2 g, 0.028 mol), KOAc (4.6 g, 0.047 mol), Pd(dppf)Cl ₂ (0.5 g, 0.001 mol) in dioxane 200 mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, extraction and concentration were performed, and then column <Intermediate 39-2> was obtained to obtain 7.9 g (yield 71.1%).

(3) production example 3: Synthesis of intermediate 39-3

Cyanuric chloride (10.0 g, 0.054 mol), 4-(2-Benzo[d]oxazolyl)phenylboronic acid (31.1 g, 0.130 mol), K ₂ CO ₃ (44.9 g, 0.325 mol), Pd(PPh ₃ ) ₄ ( 1.3 g, 0.001 mol) was added to 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring at 100 °C for 6 hours to react. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 17.2 g (yield: 63.2%) of <Intermediate 39-3>.

(4) production example 4: Synthesis of compound 39

To intermediate 39-3 (10.0 g, 0.020 mol), intermediate 39-2 (11.3 g, 0.024 mol), K ₂ CO ₃ (8.3 g, 0.060 mol), Pd(PPh ₃ ) ₄ (0.5 g, 0.001 mol) 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added, and the reaction was stirred at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 11.2 g (yield: 69.3%) of <Compound 39>.

LC/MS: m/z=810[(M+1) ⁺ ]

Synthesis example 7: Synthesis of compound 45

(One) production example 1: Synthesis of compound 45

4,6-Diphenyl-1,3,5-triazine (10.0 g, 0.026 mol), intermediate 39-2 (14.6 g, 0.031 mol), K ₂ CO ₃ (10.7 g, 0.077 mol), Pd(PPh ₃ ) ₄ (0.6 g, 0.001 mol) was added with 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring at 100 °C for 6 hours to react. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 12.4 g (yield 73.8%) of <Compound 45>.

LC/MS: m/z=652 [(M+1) ⁺ ]

Synthesis example 8: Synthesis of compound 116

(One) production example 1: Synthesis of intermediate 116-1

2,7-Dibromo-9,9-dimethyl-9H-fluorene (10.0 g, 0.028 mol), Intermediate 1-3 (13.5 g, 0.034 mol), K ₂ CO ₃ (11.8 g, 0.085 mol), Pd(PPh) ₃ ) 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to ₄ (0.7 g, 0.001 mol) and stirred at 100 °C for 6 hours to react. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 8.1 g (yield 52.8%) of <Intermediate 116-1>.

(2) production example 2: Synthesis of intermediate 116-2

Intermediate 116-1 (10.0 g, 0.019 mol), Bis(pinacolato)diboron (5.6 g, 0.022 mol), KOAc (3.6 g, 0.037 mol), dioxane 200 in Pd(dppf)Cl ₂ (0.4 g, 0.001 mol) mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, extraction and concentration were performed, followed by column to obtain 7.8 g (yield 71.8%) of <Intermediate 116-2>.

(3) production example 3: Synthesis of compound 116

Intermediate 116-2 (10.0 g, 0.017 mol), 2-Chloro-4,6-diphenyl-1,3,5-triazine (5.5 g, 0.020 mol), K ₂ CO ₃ (7.1 g, 0.051 mol), Pd 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to (PPh ₃ ) ₄ (0.4 g, 0.001 mol), and the reaction was stirred at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 8.8 g (yield 74.6%) of <Compound 116>.

LC/MS: m/z=692[(M+1) ⁺ ]

Synthesis example 9: Synthesis of compound 138

(One) production example 1: Synthesis of intermediate 138-1

4,6-Dibromodibenzofuran (10.0 g, 0.031 mol), Intermediate 1-3 (14.6 g, 0.037 mol), K ₂ CO ₃ (12.7 g, 0.092 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.001 mol) 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added thereto, and the reaction was stirred at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 8.5 g (yield 53.9%) of <Intermediate 138-1>.

(2) production example 2: Synthesis of intermediate 138-2

Intermediate 138-1 (10.0 g, 0.019 mol), Bis(pinacolato)diboron (5.9 g, 0.023 mol), KOAc (3.8 g, 0.039 mol), dioxane 200 in Pd(dppf)Cl ₂ (0.4 g, 0.001 mol) mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, extraction and concentration were performed to obtain 8.2 g (yield 75.1%) of <Intermediate 138-2>.

(3) production example 3: Synthesis of compound 138

Intermediate 138-2 (10.0 g, 0.018 mol), 2-Chloro-4,6-diphenyl-1,3,5-triazine (5.7 g, 0.021 mol), K ₂ CO ₃ (7.4 g, 0.053 mol), Pd 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to (PPh ₃ ) ₄ (0.4 g, 0.0004 mol), and the reaction was stirred at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 7.8 g (yield 75.7%) of <Compound 138>.

LC/MS: m/z=666[(M+1) ⁺ ]

Synthesis example 10: Synthesis of compound 151

(One) production example 1: Synthesis of intermediate 151-1

To 4-Bromo-2-naphthol (10.0 g, 0.045 mol), KI (5.2 g, 0.031 mol), KIO ₃ (2.88 g, 0.130 mol), add 375 mL of H ₂ O, 8 mL of H ₂ SO ₄ and 18 at room temperature. time was reacted. After completion of the reaction, 7.6 g (yield 48.7%) of <Intermediate 151-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 151-2

Intermediate 151-1 (10.0 g, 0.029 mol), K ₂ CO ₃ (5.5 g, 0.040 mol) was added with 66 mL of Acetone, slowly added dropwise dimethyl sulfate (4.7 g, 0.037 mol), and stirred at 55 °C for 1 hour. and reacted. After completion of the reaction, 9.5 g (yield 91.3%) of <Intermediate 151-2> was obtained by extraction, concentration, and column.

(3) production example 3: Synthesis of intermediate 151-3

Intermediate 151-2 (10.0 g, 0.028 mol), 4-Chloro-2-fluorophenylboronic acid (5.8 g, 0.033 mol), K ₂ CO ₃ (11.4 g, 0.083 mol), Pd(PPh ₃ ) ₄ (0.6 g, 0.006 mol) into 140 mL of Toluene, 35 mL of EtOH, and 35 mL of H ₂ O, followed by stirring at 100 °C for 6 hours to react. After completion of the reaction, 7.9 g (yield 51.2%) of <Intermediate 151-3> was obtained by extraction, concentration, and column.

(4) production example 4: Synthesis of intermediate 151-4

Intermediate 151-3 (10.0 g, 0.027 mol) was dissolved in anhydrous DCM, and BBr ₃ (in DCM) (17.13 g, 0.068 mol) was added dropwise at 0 °C dropwise. The reaction was stirred at room temperature for 16 hours. After completion of the reaction, 8.2 g (yield 85.3%) of <Intermediate 151-4> was obtained by extraction, concentration, and column.

(5) production example 5: Synthesis of intermediate 151-5

Intermediate 151-4 (10.0 g, 0.030 mol), K ₂ CO ₃ (10.3 g, 0.043 mol) NMP 500 mL was added to the reaction was stirred at 180 ℃ for 24 hours. After completion of the reaction, 5.0 g (yield 53.0%) of <Intermediate 151-5> was obtained by extraction, concentration, and column.

(6) production example 6: Synthesis of intermediate 151-6

Intermediate 151-5 (10.0 g, 0.030 mol), Bis(pinacolato)diboron (9.2 g, 0.036 mol), KOAc (5.9 g, 0.060 mol), dioxane 200 in Pd(dppf)Cl ₂ (0.7 g, 0.001 mol) mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, extraction and concentration were performed, followed by column to obtain 7.7 g (yield 67.4%) of <Intermediate 151-6>.

(7) production example 7: Synthesis of intermediate 151-7

2-Chloro-4,6-diphenyl-1,3,5-triazine (10.0 g, 0.037 mol), Intermediate 151-6 (16.9 g, 0.045 mol), K ₂ CO ₃ (15.5 g, 0.112 mol), Pd 200 ml of toluene, 50 ml of ethanol, and 50 ml of H ₂ O were added to (PPh ₃ ) ₄ (0.9 g, 0.001 mol) and stirred at 100° C. for 6 hours to react. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 11.5 g (yield 63.6%) of <Intermediate 151-7>.

(8) production example 8: Synthesis of compound 151

Intermediate 151-7 (10.0 g, 0.021 mol), Pd(OAc) ₂ (0.07 g, 0.0003 mol), X-Phos (0.3 g, 0.0006 mol), K ₄ [Fe(CN) ₆ ] 3H ₂ O ( 0.55 g, 0.0013 mol), water/1,4 dioxane mixed 1:1 with K ₂ CO ₃ (0.7 g, 0.005 mol) was added, and the reaction was stirred at room temperature for 10 hours. After completion of the reaction, 7.1 g (yield 72.4%) of <Compound 151> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=474[(M+1) ⁺ ]

Synthesis example 11: Synthesis of compound 156

(One) production example 1: Synthesis of Intermediate 156-1

2-(4-Chlorophenyl)-4,6-diphenyl-1,3,5-triazine (10.0 g, 0.029 mol), intermediate 151-6 (13.2 g, 0.035 mol), K ₂ CO ₃ (12.1 g, 0.087) mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.001 mol) was added with 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 9.8 g (yield: 60.2%) of <Intermediate 156-1>.

(2) production example 2: Synthesis of compound 156

Intermediate 156-1 (10.0 g, 0.018 mol), Pd(OAc) ₂ (0.06 g, 0.0003 mol), X-Phos (0.26 g, 0.0005 mol), K ₄ [Fe(CN) ₆ ] 3H ₂ O ( 0.47 g, 0.0011 mol), water/1,4 dioxane mixed 1:1 with K ₂ CO ₃ (0.62 g, 0.004 mol) was added, and the reaction was stirred at room temperature for 10 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 7.1 g (yield 72.2%) of <Compound 156>.

LC/MS: m/z=550[(M+1) ⁺ ]

Device Example (ETL)

In an embodiment according to the present invention, the ITO transparent electrode is patterned so that the light emitting area is 2 mm × 2 mm in size, using an ITO glass substrate to which an ITO transparent electrode is attached, on a glass substrate of 25 mm × 25 mm × 0.7 mm After that, it was washed. After the substrate was mounted in a vacuum chamber and the base pressure was set to 1 × 10 ^-6 torr or more, the organic material and the metal were deposited on the ITO in the following structure.

Device Examples 1 to 30

The compound implemented according to the present invention was used as the electron transport layer. A blue organic light emitting device having the following device structure was fabricated, and light emitting characteristics including current efficiency were measured .

ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (α-NPB, 100 nm) / electron blocking layer (EBL1 10 nm) / light emitting layer (20 nm) / hole blocking layer (HBL1, 50 nm) / Electron transport layer (201:Liq, 30 nm) / LiF (1 nm) / Al (100 nm)

To form a hole injection layer on the ITO transparent electrode, [HAT-CN] was used to deposit 5 nm, and then, the hole transport layer was deposited at 100 nm using α-NPB. The electron blocking layer was deposited to a thickness of 10 nm using [EBL1]. In addition, [BH1] was used as the host compound for the light emitting layer, and [BD1] was used as the dopant compound to be co-deposited to a thickness of 20 nm. The electron transport layer is a compound of Formula 1, 4, 6, 7, 9, 24, 26, 39, 45, 48, 115, 116, 117, 118, 122, 124, 125, 131, 133, 138, 143, 144, 145, 146, 148, 150, 151, 155, 156, and 190 were used to form a film to a thickness of 30 nm (Liq doping). An organic light emitting device was manufactured by forming a film of 1 nm LiF and 100 nm of Al.

Device Comparative Example 1

The organic light emitting device for Device Comparative Example 1 was manufactured in the same manner except that 201 was used instead of the compound embodied in the present invention for the electron transport layer in the device structure of Example 1.

Device Comparative Example 2

The organic light emitting device for Device Comparative Example 2 was manufactured in the same manner except that ET1 was used instead of the compound embodied in the present invention for the electron transport layer in the device structure of Example 1.

Device Comparative Example 3

The organic light emitting device for Device Comparative Example 3 was manufactured in the same manner except that ET2 was used instead of the compound embodied in the present invention for the electron transport layer in the device structure of Example 1.

Device Comparative Example 4

The organic light emitting device for Device Comparative Example 4 was manufactured in the same manner except that ET3 was used instead of the compound embodied in the present invention for the electron transport layer in the device structure of Example 1.

Experimental Example 1: Light emitting characteristics of Device Examples 1 to 30

The organic light emitting device manufactured according to the above Example was measured for voltage, current and luminous efficiency using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and the result value based on 1000 nit was It is shown in [Table 1] below.

Example electron transport layer V cd/A CIEx CIEy One Formula 1 4.2 6.9 0.133 0.148 2 Formula 4 4.0 7.0 0.132 0.149 3 Formula 6 4.2 7.2 0.130 0.151 4 Formula 7 4.1 7.5 0.131 0.151 5 Formula 9 4.2 6.9 0.134 0.149 6 Formula 24 4.3 6.8 0.132 0.148 7 Formula 26 4.1 7.3 0.133 0.149 8 Formula 39 4.0 7.4 0.134 0.152 9 Formula 45 4.1 7.2 0.131 0.152 10 Formula 48 4.0 7.1 0.132 0.150 11 Formula 115 4.2 7.0 0.131 0.148 12 Formula 116 4.2 7.0 0.132 0.148 13 Formula 117 4.3 7.1 0.131 0.149 14 Formula 118 4.2 7.2 0.130 0.151 15 Formula 122 4.3 6.9 0.131 0.150 16 Formula 124 4.2 7.2. 0.134 0.149 17 Formula 125 4.3 6.9 0.132 0.148 18 Formula 131 4.2 7.0. 0.131 0.148 19 Formula 133 4.3 7.1 0.132 0.150 20 Formula 138 4.2 7.0. 0.133 0.148 21 Formula 143 4.2 7.0. 0.133 0.149 22 Formula 144 4.3 6.9 0.133 0.151 23 Formula 145 4.2 7.0. 0.131 0.151 24 Formula 146 4.3 7.1 0.134 0.149 25 Formula 148 4.2 7.0. 0.131 0.148 26 Formula 150 4.3 6.9 0.133 0.147 27 Formula 151 4.4 6.8 0.132 0.152 28 Formula 155 4.0 7.5 0.131 0.152 29 Formula 156 4.1 7.3 0.132 0.146 30 Formula 190 4.4 6.8 0.131 0.148 Comparative Example 1 201 4.7 6.6 0.135 0.151 Comparative Example 2 ET1 4.7 6.6 0.133 0.152 Comparative Example 3 ET2 4.6 6.3 0.132 0.155 Comparative Example 4 ET3 4.8 6.4 0.135 0.151

Looking at the results shown in [Table 1], when the compound according to the present invention is applied to the electron transport layer in the organic light emitting device, a device employing a conventional compound and a compound having no characteristic structure according to the present invention (Comparative Examples 1 to 4) ), it can be seen that the luminescence characteristics such as low voltage driving characteristics, luminous efficiency, and quantum efficiency are significantly superior.

[HAT_CN] [α-NPB] [BH1] [BD1] [EBL1]

[201] [ET1] [ET2] [ET3]

Claims (6)

An organic light emitting compound represented by the following [Formula I]:
[Formula Ⅰ]

In the [Formula I],
X is O, S or C(CH ₃ ) ₂ ,
L is a single bond, or is selected from a substituted or unsubstituted C6 to C30 arylene group and a substituted or unsubstituted C3 to C30 heteroarylene group (n is an integer from 0 to 3, and n is 2 or more a plurality of L's are the same or different from each other),
Ar ₁ To Ar ₂ are each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C It is selected from an aryl group having 6 to 30 and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms,
CN means a cyano group. The method of claim 1,
In the definition of L, Ar ₁ to Ar ₂ , 'substituted or unsubstituted' means that L and Ar ₁ to Ar ₂ are deuterium, a halogen group, a cyano group, a nitro group, a hydroxy group, a silyl group, an alkyl group, a halogenated selected from the group consisting of an alkyl group, a deuterated alkyl group, a cycloalkyl group, a heterocycloalkyl group, an alkoxy group, a halogenated alkoxy group, a deuterated alkoxy group, an aryl group, a heteroaryl group, an alkylamine group, an arylamine group and a silyl group. An organic light-emitting compound, characterized in that it is substituted with one or two or more substituents, or is substituted with a substituent to which two or more of the substituents are connected, or does not have any substituents. The method of claim 1,
The [Formula I] is an organic light emitting compound, characterized in that any one selected from the following [Compound 1] to [Compound 190]:

An organic light emitting device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode,
At least one of the organic layers is an organic light emitting device comprising the organic light emitting compound of [Formula I] according to claim 1. 5. The method of claim 4,
The organic layer is selected from a hole injection layer, a hole transport layer, a layer that performs both hole injection and hole transport functions, an electron transport layer, an electron injection layer, a layer that performs both electron transport and electron injection functions, an electron blocking layer, a hole blocking layer and a light emitting layer including one or more floors that become
At least one of the layers comprises an organic light emitting compound represented by the [Formula I]. 6. The method of claim 5,
An organic light emitting device comprising an organic light emitting compound represented by the above [Formula I] in any one of the electron transport layer, the electron injection layer, and the layer that performs both electron transport and electron injection functions.