KR20220081550A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to a novel organic light emitting compound represented by [Formula I], which is employed in 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 .
[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 electron transport layer material in an organic light emitting device, and by employing the same, light emitting characteristics such as low voltage driving and excellent luminous efficiency of the device are significantly improved It relates to an organic 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, a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. 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 improvement is 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 electron transport 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], the compound implemented thereby, and Y, A ₁ to A ₃ will be described later.

When the organic light-emitting compound according to the present invention is employed in the electron transport layer in the organic light-emitting device, it is possible to realize light-emitting characteristics such as low voltage driving and excellent light-emitting efficiency of the device, and thus 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] that can achieve light emitting characteristics such as low voltage driving and excellent luminous efficiency of the device of an organic light emitting device, and structurally a dibenzo represented by the following [Formula I] In the furan or dibenzothiophene skeleton structure, a structure represented by the following [Formula 1] is bonded to one position selected from A ₁ to A ₂ .

[Formula Ⅰ]

In the [Formula I],

Y is O or S.

Any one of A ₁ and A ₃ is represented by the following [Structural Formula 1], and the rest is hydrogen.

[Structural Formula 1]

In the [Structural Formula 1],

L is a divalent linking group, and is any one selected from the structures represented by the following [Structural Formula 2], and * represents a connected moiety.

[Structural Formula 2]

Each X is independently CH or N, and at least one of the plurality of Xs is N.

Ar ₁ To Ar ₂ are the same as or different from each other, and 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, It is selected from a substituted or unsubstituted C6-C30 aryl group and a substituted or unsubstituted C3-C30 heteroaryl group.

On the other hand, in the definition of L, Ar ₁ to Ar ₂ , 'substituted or unsubstituted' means deuterium, deuterium, halogen group, cyano group, nitro group, hydroxyl group, silyl group, alkyl group, halogenated alkyl group, deuterated 1 or 2 or more substituents selected from the group consisting of an 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, 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 in the organic light emitting device due to its structural specificity, preferably used as an electron transport layer material.

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, the organic light emitting device may further include a light efficiency improving layer (Capping layer) structure, The present invention 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

1-Bromo-2-chloronaphthalene (10.0 g, 0.041 mol), 2,6-Diphenylpyridin-4-ylboronic acid (13.7 g, 0.050 mol), K ₂ CO ₃ (17.2 g, 0.124 mol), Pd(PPh ₃ ) ₄ (1.0 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 under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 11.4 g (yield 70.3%) of <Intermediate 1-1>.

(2) production example 2: Synthesis of compound 1

Dibenzo[b,d]furan-1-ylboronic acid (10.0 g, 0.047 mol), Intermediate 1-1 (22.2 g, 0.057 mol), K ₂ CO ₃ (19.6 g, 0.142 mol), Catalyst Pd(OAc) ₂ (2.7 g, 0.002 mol), ligand X-Phos (2.2 g, 0.005 mol), 200 mL of THF, 50 mL of H ₂ O, and 50 mL of ethanol were added, and the mixture was reacted by stirring under reflux at 90° C. for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 15.9 g (yield 64.4%) of <Compound 1>.

LC/MS: m/z=523[(M+1) ⁺ ]

Synthesis example 2: Synthesis of compound 38

(One) production example 1: Synthesis of intermediate 38-1

DMF was added to 2-Bromonaphthalene-1-carboxaldehyde (10.0 g, 0.043 mol), 1-Naphthalenecarboximidamide hydrochloride (17.6 g, 0.085 mol), K ₂ CO ₃ (11.8 g, 0.085 mol) and stirred at 120 °C for 18 hours. reacted. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 13.4 g (yield 58.5%) of <Intermediate 38-1>.

(2) production example 2: Synthesis of compound 38

Dibenzo[b,d]furan-1-ylboronic acid (10.0 g, 0.047 mol), intermediate 38-1 (30.5 g, 0.057 mol), K ₂ CO ₃ (19.6 g, 0.142 mol), Pd(PPh ₃ ) ₄ 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to (1.1 g, 0.001 mol), and the reaction was stirred under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 21.2 g (yield 71.8%) of <Compound 38>.

LC/MS: m/z=625[(M+1) ⁺ ]

Synthesis example 3: Synthesis of compound 58

(One) production example 1: Synthesis of intermediate 58-1

2,6-Dibromo-4-chloropyridine (10.0 g, 0.037 mol), 2-Naphthaleneboronic acid (15.2 g, 0.088 mol), K ₂ CO ₃ (30.6 g, 0.221 mol), Pd(PPh ₃ ) ₄ (0.9 g , 0.001 mol) was added 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, followed by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column to obtain 10.2 g (yield 75.7%) of <Intermediate 58-1>.

(2) production example 2: Synthesis of intermediate 58-2

Intermediate 58-1 (10.0 g, 0.027 mol), Bis(pinacolato)diboron (8.3 g, 0.033 mol), KOAc (5.4 g, 0.055 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 to obtain 8.4 g (yield: 67.2%) of <Intermediate 58-2>.

(3) production example 3: Synthesis of intermediate 58-3

2-Bromo-1-chloronaphthalene (10.0 g, 0.041 mol), intermediate 58-2 (22.7 g, 0.050 mol), K ₂ CO ₃ (17.2 g, 0.124 mol), Pd(PPh ₃ ) ₄ (1.0 g, 0.001) mol) was added 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, and the mixture was reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 14.4 g (yield 70.7%) of <Intermediate 58-3>.

(4) production example 4: Synthesis of compound 58

Dibenzo[b,d]furan-2-ylboronic acid (10.0 g, 0.047 mol), intermediate 58-3 (27.9 g, 0.057 mol), K ₂ CO ₃ (19.6 g, 0.142 mol), catalyst Pd(OAc) ₂ (2.7 g, 0.002 mol), ligand X-Phos (2.2 g, 0.005 mol), 200 mL of THF, 50 mL of H ₂ O, and 50 mL of ethanol were added, and the mixture was reacted by stirring under reflux at 90° C. for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 17.8 g (yield: 60.5%) of <Compound 58>.

LC/MS: m/z=623 [(M+1) ⁺ ]

Synthesis example 4: Synthesis of compound 75

(One) production example 1: Synthesis of intermediate 75-1

DMF was added to 1-Bromo-2-naphthaldehyde (10.0 g, 0.043 mol), 4-Cyanobenzimidamide hydrochloride (15.5 g, 0.085 mol), K ₂ CO ₃ (11.8 g, 0.085 mol) and stirred at 120 ° C for 18 hours. reacted. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 12.2 g (yield 58.7%) of <Intermediate 75-1>.

(2) production example 2: Synthesis of compound 75

Dibenzo[b,d]furan-1-ylboronic acid (10.0 g, 0.047 mol), intermediate 75-1 (27.6 g, 0.057 mol), K ₂ CO ₃ (19.6 g, 0.142 mol), Pd(PPh ₃ ) ₄ 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to (1.1 g, 0.001 mol), and the reaction was stirred under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 18.8 g (yield: 69.2%) of <Compound 75>.

LC/MS: m/z=575[(M+1) ⁺ ]

Synthesis example 5: Synthesis of compound 132

(One) production example 1: Synthesis of intermediate 132-1

DMF was added to 3-Bromo-2-naphthaldehyde (10.0 g, 0.043 mol), Benzamidine hydrochloride (13.3 g, 0.085 mol), K ₂ CO ₃ (11.8 g, 0.085 mol), and the reaction was stirred at 120 ° C. for 18 hours. . After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 11.8 g (yield 63.3%) of <Intermediate 132-1>.

(2) production example 2: Synthesis of compound 132

Dibenzo[b,d]furan-2-ylboronic acid (10.0 g, 0.047 mol), intermediate 132-1 (24.8 g, 0.057 mol), K ₂ CO ₃ (19.6 g, 0.142 mol), Pd(PPh ₃ ) ₄ (1.1 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 under reflux at 100 °C for 6 hours. After completion of the reaction, 17.2 g (yield 69.4%) of <Compound 132> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=525[(M+1) ⁺ ]

Synthesis example 6: Synthesis of compound 171

(One) production example 1: Synthesis of intermediate 171-1

2,6-Dibromo-4-chloropyridine (10.0 g, 0.037 mol), [4-(4-cyanophenyl)phenyl]boronic acid (19.7 g, 0.088 mol), K ₂ CO ₃ (30.6 g, 0.221 mol), Pd (PPh ₃ ) ₄ (0.9 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 under reflux at 100 °C for 6 hours. After completion of the reaction, 12.8 g (yield 74.2%) of <Intermediate 171-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 171-2

Intermediate 171-1 (10.0 g, 0.021 mol), Bis(pinacolato)diboron (6.5 g, 0.026 mol), KOAc (4.2 g, 0.043 mol), dioxane 200 in Pd(dppf)Cl ₂ (0.5 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 8.1 g (yield 67.8%) of <Intermediate 171-2>.

(3) production example 3: Synthesis of intermediate 171-3

1-Bromo-2-chloronaphthalene (10.0 g, 0.041 mol), intermediate 171-2 (27.8 g, 0.050 mol), K ₂ CO ₃ (17.2 g, 0.124 mol), Pd(PPh ₃ ) ₄ (1.0 g, 0.001) mol), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 17.6 g (yield 71.6%) of <Intermediate 171-3>.

(4) production example 4: Synthesis of compound 171

Dibenzo[b,d]furan-1-ylboronic acid (10.0 g, 0.044 mol), intermediate 171-3 (31.3 g, 0.053 mol), K ₂ CO ₃ (18.2 g, 0.132 mol), catalyst Pd(OAc)2 (2.5 g, 0.002 mol), ligand X-Phos (2.1 g, 0.004 mol), THF 200 mL, H ₂ O 50 mL, and ethanol 50 mL were added, and the reaction was stirred at 90 ° C. under reflux for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 20.4 g (yield 62.7%) of <Compound 171>.

LC/MS: m/z=741 [(M+1) ⁺ ]

Synthesis example 8: Synthesis of compound 189

(One) production example 1: Synthesis of intermediate 189-1

4,6-Dibromo-2-chloropyrimidine (10.0 g, 0.037 mol), 1-Naphthaleneboronic acid (15.2 g, 0.08 8mol), K ₂ CO ₃ (30.5 g, 0.220 mol), Pd(PPh ₃ ) ₄ (0.9 g , 0.001 mol), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed to obtain 9.2 g (yield: 68.3%) of <Intermediate 189-1>.

(2) production example 2: Synthesis of intermediate 189-2

Intermediate 189-1 (10.0 g, 0.027 mol), Bis(pinacolato)diboron (8.3 g, 0.033 mol), KOAc (5.4 g, 0.055 mol), dioxane 200 in Pd(dppf)Cl ₂ (0.6 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 7.1 g (yield 56.8%) of <Intermediate 189-2>.

(3) production example 3: Synthesis of intermediate 189-3

1-Bromo-2-chloronaphthalene (10.0 g, 0.041 mol), Intermediate 189-2 (22.8 g, 0.050 mol), K ₂ CO ₃ (17.2 g, 0.124 mol), Pd(PPh ₃ ) ₄ (1.0 g, 0.001) mol), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 14.2 g (yield 69.6%) of <Intermediate 189-3>.

(4) production example 4: Synthesis of compound 189

Dibenzo[b,d]thiophen-2-ylboronic acid (10.0 g, 0.044 mol), intermediate 189-3 (25.9 g, 0.053 mol), K ₂ CO ₃ (18.2 g, 0.132 mol), catalyst Pd(OAc) ₂ (2.5 g, 0.002 mol), ligand X-Phos (2.1 g, 0.004 mol), 200 mL of THF, 50 mL of H ₂ O, and 50 mL of ethanol were added, and the mixture was reacted by stirring under reflux at 90 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 16.2 g (yield: 57.7%) of <Compound 189>.

LC/MS: m/z=640[(M+1) ⁺ ]

Synthesis example 8: Synthesis of compound 196

(One) production example 1: Synthesis of intermediate 196-1

DMF was added to 2-Bromo-1-naphthaldehyde (10.0 g, 0.043 mol), 2-Naphthimidamide hydrochloride (17.6 g, 0.085 mol), K ₂ CO ₃ (11.8 g, 0.085 mol) and stirred at 120 ° C for 18 hours. reacted. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 13.3 g (yield: 58.1%) of <Intermediate 196-1>.

(2) production example 2: Synthesis of compound 196

Dibenzo[b,d]thiophen-1-ylboronic acid (10.0 g, 0.044 mol), Intermediate 196-1 (28.3 g, 0.053 mol), K ₂ CO ₃ (18.2 g, 0.132 mol), Pd(PPh ₃ ) ₄ (1.0 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. under reflux for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 19.4 g (yield 68.9%) of <Compound 196>.

LC/MS: m/z=641 [(M+1) ⁺ ]

Synthesis example 9: Synthesis of compound 210

(One) production example 1: Synthesis of intermediate 210-1

2,6-Dibromo-4-chloropyridine (10.0 g, 0.037 mol), 4-Biphenylboronic acid (17.5 g, 0.088 mol), K ₂ CO ₃ (30.6 g, 0.221 mol), Pd(PPh ₃ ) ₄ (0.9 g , 0.001 mol), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed to obtain 10.8 g (yield 70.1%) of <Intermediate 210-1>.

(2) production example 2: Synthesis of intermediate 210-2

Intermediate 210-1 (10.0 g, 0.024 mol), Bis(pinacolato)diboron (7.3 g, 0.029 mol), KOAc (4.7 g, 0.048 mol), dioxane 200 in Pd(dppf)Cl ₂ (0.5 g, 0.001 mol) mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, extraction was performed, followed by concentration and column to obtain 8.1 g (yield: 66.5%) of <Intermediate 210-2>.

(3) production example 3: Synthesis of intermediate 210-3

2-Bromo-1-chloronaphthalene (10.0 g, 0.041 mol), Intermediate 210-2 (25.3 g, 0.050 mol), K ₂ CO ₃ (17.2 g, 0.124 mol), Pd(PPh ₃ ) ₄ (1.0 g, 0.001) mol), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 16.8 g (yield 74.6%) of <Intermediate 210-3>.

(4) production example 4: Synthesis of compound 210

Dibenzo[b,d]thiophen-2-ylboronic acid (10.0 g, 0.044 mol), intermediate 210-3 (28.6 g, 0.053 mol), K ₂ CO ₃ (18.2 g, 0.132 mol), catalyst Pd(OAc) ₂ (2.5 g, 0.002 mol), ligand X-Phos (2.1 g, 0.004 mol), 200 mL of THF, 50 mL of H ₂ O, and 50 mL of ethanol were added, and the mixture was reacted by stirring under reflux at 90 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 18.1 g (yield: 59.7%) of <Compound 210>.

LC/MS: m/z=691 [(M+1) ⁺ ]

Synthesis example 10: Synthesis of compound 254

(One) production example 1: Synthesis of Intermediate 254-1

2,6-Dibromo-4-chloropyridine (10.0 g, 0.037 mol), 2-Naphthaleneboronic acid (15.2 g, 0.088 mol), K ₂ CO ₃ (30.6 g, 0.221 mol), Pd(PPh ₃ ) ₄ (0.8 g , 0.001 mol), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column to obtain 8.1 g (yield 60.1%) of <Intermediate 254-1>.

(2) production example 2: Synthesis of intermediate 254-2

Intermediate 254-1 (10.0 g, 0.027 mol), Bis(pinacolato)diboron (8.3 g, 0.033 mol), KOAc (5.4 g, 0.055 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 to obtain 8.1 g (yield 64.8%) of <Intermediate 254-2>.

(3) production example 3: Synthesis of intermediate 254-3

9-Bromo-10-chlorophenanthrene (10.0 g, 0.034 mol), Intermediate 254-2 (18.8 g, 0.041 mol), K ₂ CO ₃ (14.2 g, 0.103 mol), Pd(PPh ₃ ) ₄ (0.8 g, 0.001) mol), toluene 200 mL, ethanol 50 mL, H ₂ O 50 mL, and reacted by stirring under reflux at 100 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 13.1 g (yield 70.5%) of <Intermediate 254-3>.

(4) production example 4: Synthesis of compound 254

Dibenzo[b,d]thiophen-1-ylboronic acid (10.06 g, 0.044 mol), intermediate 254-3 (28.5 g, 0.053 mol), K ₂ CO ₃ (18.2 g, 0.132 mol), catalyst Pd(OAc) ₂ (2.5 g, 0.002 mol), ligand X-Phos (2.1 g, 0.004 mol), THF 200 mL, H ₂ O 50 mL, and ethanol 50 mL were added, and the reaction was stirred at 90 ° C. under reflux for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 17.8 g (yield 58.9%) of <Compound 254>.

LC/MS: m/z=689[(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 33

The compound implemented according to the present invention was used as an electron transport layer, and a blue organic light emitting device having the following device structure was manufactured, 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 chemical formula 1, 18, 35, 38, 39, 42, 58, 75, 78, 87, 91, 118, 123, 125, 132, 133, 134, 149, 159, 165, 171 implemented by the present invention. , 182, 189, 196, 199, 210, 227, 245, 250, 288, 301, 323, 341 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 ET 1 was used instead of the compound embodied in the present invention for the electron transport layer in the device structures of Examples 1 to 33.

Device Comparative Example 2

The organic light emitting device for Device Comparative Example 2 was manufactured in the same manner except that ET 2 was used instead of the compound embodied in the present invention for the electron transport layer in the device structures of Examples 1 to 33.

Device Comparative Example 3

The organic light emitting device for Device Comparative Example 3 was prepared in the same manner as in Examples 1 to 33 except that 201 was used instead of the compound embodied in the present invention for the electron transport layer in the device structure.

Experimental Example 1: Light emitting characteristics of Device Examples 1 to 33

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 4.1 7.0 0.134 0.150 2 Formula 18 4.2 7.2 0.132 0.149 3 Formula 35 3.9 7.1 0.133 0.145 4 Formula 38 4.0 7.2 0.131 0.151 5 Formula 39 4.0 7.1 0.133 0.150 6 Formula 42 3.9 7.3 0.131 0.149 7 Formula 58 4.2 7.3 0.134 0.149 8 Formula 75 4.0 7.4 0.133 0.150 9 Formula 78 3.9 7.1 0.131 0.151 10 Formula 87 4.1 7.0 0.134 0.150 11 Formula 91 4.0 7.2 0.131 0.152 12 Formula 118 4.0 7.2 0.134 0.150 13 Formula 123 4.1 7.2 0.132 0.148 14 Formula 125 4.0 7.3 0.133 0.151 15 Formula 132 3.9 7.1 0.133 0.150 16 Formula 133 4.1 7.3 0.132 0.147 17 Formula 134 4.0 7.4 0.134 0.150 18 Formula 149 3.9 7.3 0.133 0.149 19 Formula 159 4.2 7.0 0.132 0.148 20 Formula 165 4.1 7.2 0.134 0.150 21 Formula 171 3.9 7.2 0.130 0.149 22 Formula 182 4.1 7.1 0.133 0.150 23 Formula 189 4.0 7.3 0.131 0.147 24 Formula 196 3.9 7.3 0.134 0.151 25 Formula 199 4.1 7.0 0.131 0.150 26 Formula 210 4.1 7.2 0.134 0.153 27 Formula 227 3.9 7.2 0.132 0.148 28 Formula 245 4.2 7.1 0.131 0.149 29 Formula 250 4.1 7.3 0.134 0.142 30 Formula 288 3.9 7.3 0.131 0.150 31 Formula 301 4.1 7.2 0.133 0.149 32 Formula 323 4.2 7.4 0.131 0.143 33 Formula 341 4.0 7.2 0.134 0.151 Comparative Example 1 ET 1 4.8 6.1 0.136 0.141 Comparative Example 2 ET 2 4.2 6.4 0.138 0.144 Comparative Example 3 201 4.7 6.6 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, the low voltage driving characteristics and , it can be confirmed that the luminous properties such as luminous efficiency and quantum efficiency are remarkably excellent.

[HAT_CN] [α-NPB] [BH1] [BD1] [EBL1]

[201] [ET 1] [ET 2]

Claims (6)

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

In the above [Formula I]
Y is O or S;
Any one of A ₁ and A ₃ is represented by the following [Structural Formula 1], the rest is hydrogen,
[Structural Formula 1]

In the [Structural Formula 1],
L is a divalent linking group, and is any one selected from the structures represented by the following [Structural Formula 2] (* denotes each connected portion),
[Structural Formula 2]

X is each independently CH or N, at least one of the plurality of X is N,
Ar ₁ to Ar ₂ are the same as or different from each other, and 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, It is selected from a substituted or unsubstituted C6-C30 aryl group and a substituted or unsubstituted C3-C30 heteroaryl group. The method of claim 1,
In the definition of Ar ₁ to Ar ₂ , 'substituted or unsubstituted' means deuterium, a halogen group, a cyano group, a nitro group, a hydroxyl group, a silyl group, an alkyl group, a halogenated alkyl group, a deuterated alkyl group, a cycloalkyl group, It is substituted with one or more substituents selected from the group consisting of 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, or the substituents An organic light-emitting compound, characterized in that it 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 342]:

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.