KR20230167304A - Organic compound and electroluminescent device comprising the same - Google Patents

Abstract

The present invention is an organic compound represented by the following [Chemical Formula I], and when it is used in an organic layer, preferably an electron blocking layer, in an organic light-emitting device, an organic light-emitting device with excellent luminous properties such as luminous efficiency and quantum efficiency can be realized. possible.
[Formula Ⅰ]

Description

Organic compound and electroluminescent device comprising the same}

The present invention relates to organic compounds, and more specifically, to organic compounds employed in organic layers such as electron blocking layers in organic light-emitting devices, and to organic light-emitting devices whose device characteristics, such as low-voltage operation, long life, and luminous efficiency, are significantly improved by employing the same. It's about.

Organic light emitting devices not only can be formed on transparent substrates, but also can be driven at low voltages of 10 V or less compared to plasma display panels or inorganic electroluminescence (EL) displays, and consume relatively little power. , It has the advantage of excellent color and can display three colors of green, blue, and red, so it has recently been the subject of much attention as a next-generation display device.

In an organic light emitting device, electrons injected from an electron injection electrode (cathode electrode) and holes injected from a hole injection electrode (anode electrode) combine in the light emitting layer to form an exciton, and the exciton produces energy. It is a self-luminous device that emits light while emitting light, and such organic light-emitting devices are attracting attention as next-generation light sources due to the advantages of low driving voltage, high luminance, wide viewing angle, fast response speed, and applicability to full-color flat panel light-emitting displays. .

However, in order for these organic light-emitting devices to exhibit the above characteristics, the structure of the organic layer within the device must be optimized, and the materials that make up each organic layer: hole injection material, hole transport material, hole blocking material, light-emitting material, electron transport material, and electron. Although injection materials, electron blocking materials, etc. must be supported by stable and efficient materials, there is still a need for the development of stable and efficient organic layer structures and materials for organic light-emitting devices.

In particular, in order to achieve higher luminous efficiency, there is a need for the development of materials that can be more appropriately used as an electron blocking layer as well as an increase in hole mobility so that they can be used as a hole injection layer or hole transport layer.

Therefore, the present invention provides an organic compound that can be used as an organic layer material such as an electron blocking layer and a hole transport layer in an organic light emitting device to significantly improve device characteristics such as low voltage driving characteristics, long life, and luminous efficiency, and an organic light emitting device containing the same. We would like to provide.

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

[Formula Ⅰ]

The specific structure of [Chemical Formula I], the specific compounds implemented thereby, and the definitions of X, R ₁ to R ₃ , Ar ₁ to Ar ₄ , D (deuterium), and n will be described later.

The organic compound according to the present invention has excellent hole injection and transport performance, high triplet exciton confinement performance, excellent electron blocking performance, and excellent stability in a thin film state, and is used as an electron blocking layer, hole transport layer, etc. Organic light-emitting devices used in the organic layer have significantly superior device characteristics such as low-voltage operation, long lifespan, and luminous efficiency compared to conventional devices, and can be usefully used in various lighting devices and display devices.

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

The present invention relates to an organic compound represented by the following [Chemical Formula I], which significantly improves device characteristics such as low-voltage driving, long life, and luminous efficiency when employed in various organic layers in an organic light-emitting device, preferably in an electron blocking layer. It is possible to implement organic light emitting devices.

[Formula Ⅰ]

In the above [Chemical Formula I],

X is O or S.

R ₁ to R ₃ are the same as or different from each other, and are each independently hydrogen or deuterium.

Ar ₁ to Ar ₄ are the same or different from each other, and are each independently 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.

D is deuterium, n refers to the number of hydrogens in the formula (I) replaced with deuterium (D), and n is an integer from 0 to 60.

[Formula I] is characterized in that it is a compound in which not only the skeletal structure, but also R ₁ to R ₃ and Ar ₁ to Ar ₄ introduced therein are each partially substituted with deuterium (D), and in an embodiment of the present invention According to this, the deuterium (D) substitution rate may be 10 to 90%.

In this way, the compound according to the present invention replaces some of the hydrogen in the structure of [Formula I] with deuterium, so that the compound represented by [Formula I] according to the present invention may be a compound containing at least one deuterium, and may be a conventional moiety By making up for the shortcomings of the low lifespan of organic light-emitting devices that are identified depending on their structure, it is possible to implement organic light-emitting devices with a longer lifespan.

In addition, according to one embodiment of the present invention, the compound represented by [Formula I] according to the present invention may contain at least one or more deuterium in [Formula I], and accordingly, R ₁ to R ₃ and Ar ₁ to Ar ₄ At least one of them is a substituent having a structure containing deuterium.

According to one embodiment of the present invention, at least one of Ar ₁ to Ar ₄ is selected from the following [Structural Formula 1] to [Structural Formula 6].

[Structural Formula 1] [Structural Formula 2] [Structural Formula 3]

[Structural Formula 4] [Structural Formula 5] [Structural Formula 6]

In [Structural Formula 1] to [Structural Formula 6],

R and R' are each independently selected from hydrogen, deuterium, 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.

R ₄ to R ₆ are the same or different from each other, and each independently represents deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted 6 to 20 carbon atoms. It is selected from an aryl group of 30 and a substituted or unsubstituted heteroaryl group of 3 to 30 carbon atoms.

R ₄ and R ₅ may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring.

The '*-' indicates a linking site, and in [Structural Formula 4], any one of R, R' and R ₆ is '*-'.

According to one embodiment of the present invention, Ar ₄ is any one selected from [Structural Formula 1] to [Structural Formula 6].

Meanwhile, in the definition of R, R', R ₁ to R ₆ and Ar ₁ to Ar ₄ , 'substituted or unsubstituted' refers to R, R', R ₁ to R ₆ and Ar ₁ to Ar ₄ With one or two or more substituents selected from deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, cycloalkyl group, heterocycloalkyl group, aryl group, fluorenyl group, heteroaryl group, silyl group and amine group. It means being substituted, being substituted with a substituent in which two or more of the above substituents are linked, or not having any substituents.

For specific examples, a substituted aryl group refers to a phenyl group, biphenyl group, naphthalene group, fluorenyl group, pyrenyl group, phenanthrenyl group, perylene group, tetracenyl group, anthracenyl group, etc. substituted with another substituent such as deuterium. means, and substituted heteroaryl group refers to pyridyl group, thiophenyl group, triazine group, quinoline group, phenanthroline group, imidazole group, thiazole group, oxazole group, carbazole group and condensed heterocyclic groups thereof, such as This means that benzquinoline group, benzimidazole group, benzoxazole group, benzthiazole group, benzcarbazole group, dibenzothiophenyl group, dibenzofuran group, etc. are also substituted with other substituents such as deuterium.

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

In the present invention, the alkyl group may be straight chain 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, etc., but is not limited to these.

In the present invention, the alkoxy group may be straight chain or branched chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20, which is 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 , benzyloxy group, p-methylbenzyloxy group, etc., but is not limited thereto.

In the present invention, the alkyl group and the alkoxy group may be a deuterated alkyl group or alkoxy group, a halogenated alkyl group or an alkoxy group, respectively, which means an alkyl group or an alkoxy group in which the alkyl group or alkoxy group is substituted with a deuterium or 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. It also includes a polycyclic aryl group structure in which cycloalkyl, etc. are fused, and the monocyclic aryl group Examples of phenyl group (Ph), biphenyl group, terphenyl group, stilbene group, etc. Examples of polycyclic aryl groups include naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, 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.

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

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

Additionally, the carbon atom of the ring may be substituted with one or more heteroatoms selected from N, S, and O, for example , , , etc.

Additionally, in the present invention, the fluorenyl group may have a structure in which a monocyclic or polycyclic aromatic ring and a monocyclic or polycyclic alicyclic ring, etc. are further condensed to the above linked structure or open structure.

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 is preferably 2 to 30 carbon atoms, and is a polycyclic group fused with cycloalkyl or heterocycloalkyl, etc. It contains a heteroaryl group structure, and specific examples thereof in the present invention include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, and bipyridyl group. , pyrimidyl group, triazine group, triazole group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, Dibenzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, phenoxazine group, phenothiazine group, etc., but only these It is not limited.

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. Specific examples of such silyl groups include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, and dimethoxysilyl. Examples include phenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfurylsilyl, etc., but are not limited thereto.

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

In the present invention, cycloalkyl groups refer to and include monocyclic, polycyclic and spiro alkyl radicals, and preferably contain ring carbon atoms having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, and bicyclo. It includes heptyl, spirodecyl, spiroundecyl, adamantyl, etc., and 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, It is preferably selected from O, N or S, and specifically, when it contains N, it may be aziridine, pyrrolidine, piperidine, azepane, azocan, etc.

In the present invention, the amine group may be -NH ₂ , an alkylamine group, an arylamine group, an arylheteroarylamine group, etc., an arylamine group refers to an amine substituted with aryl, and an alkylamine group refers to an amine substituted with alkyl. The arylheteroarylamine group refers to an amine substituted with aryl and heteroaryl groups. Examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or There is an unsubstituted triarylamine group, and the aryl group and heteroaryl group in the arylamine group and arylheteroarylamine group may be a monocyclic aryl group, a monocyclic heteroaryl group, or a polycyclic aryl group or a polycyclic heteroaryl group. and the aryl group, the arylamine group containing two or more heteroaryl groups, and the arylheteroarylamine group include a monocyclic aryl group (heteroaryl group), a polycyclic aryl group (heteroaryl group), or a monocyclic aryl group (heteroaryl group). It may contain both an aryl group) and a polycyclic aryl group (heteroaryl group). In addition, the aryl group and heteroaryl group of the arylamine group and the arylheteroarylamine group may be selected from examples of the above-mentioned aryl group and heteroaryl group.

Additionally, various specific examples of substituents according to the present invention can be clearly identified in the specific compounds described below.

As described above, the organic compound according to the present invention represented by [Chemical Formula I] can be used as an organic layer of an organic light-emitting device due to its structural specificity, and more specifically, electron blocking of the organic layer depending on the characteristics of various substituents introduced. It can be used as a material for layers, etc.

Preferred specific examples of the compound represented by [Chemical Formula I] according to the present invention include the following compounds, but are not limited to these.

Through the above-mentioned characteristic skeletal structure and substituents, organic compounds with unique properties of the skeletal structure and substituents can be synthesized. For example, organic compounds that meet the conditions required for each organic layer, such as the electron blocking layer, when manufacturing an organic light-emitting device. Compound materials can be manufactured, and in particular, when the compound of [Chemical Formula I] according to the present invention is used in the electron blocking layer, etc., device characteristics such as luminous efficiency of the device can be further improved.

The organic compound according to the present invention can be applied to an organic light-emitting device according to a conventional manufacturing method.

The organic light emitting device according to an embodiment of the present invention may have a structure including a first electrode, a second electrode, and an organic layer disposed between them, except that the organic compound according to the present invention is used in the organic layer of the device. It can be manufactured using conventional device manufacturing methods and materials.

The organic layer of the organic light emitting device according to the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic layers are stacked. For example, it may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer, etc. However, it is not limited to this and may include fewer or more organic layers.

As such, the organic light emitting device according to an embodiment of the present invention may include a hole injection layer, a hole transport layer, a light emitting layer, etc. formed on an anode, and may also include a hole blocking layer, an electron injection layer, an electron transport layer, an electron blocking layer, It may include a light emitting auxiliary layer, etc., but is not limited thereto.

Therefore, in the organic light emitting device according to the present invention, the organic layer may include an electron blocking layer, etc., and one or more of the layers may include the organic compound represented by [Chemical Formula I].

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

In addition to this method, an organic light-emitting device can also be made 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 hole blocking layer, a light emitting layer, an electron blocking layer, an electron transport layer, an electron blocking layer, etc., but is not limited to this and may have a single layer structure. In addition, the organic layer uses a variety of polymer materials and is formed using a solvent process rather than a deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, to form a smaller number of layers. It can be manufactured in layers.

The anode is usually preferably a material with a large work function to ensure smooth hole injection into the organic layer. Specific examples of anode materials that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). 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) , conductive polymers such as polypyrrole and polyaniline, but are not limited to these.

The cathode is generally preferably made of a material with a low work function to facilitate electron injection into the organic layer. Specific examples of cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof, multilayers such as LiF/Al or LiO ₂ /Al. Structural materials, etc., but are not limited to these.

The hole injection layer is a material that can easily receive holes from the anode at a low voltage, and it is preferable that the HOMO (highest occupied molecular orbital) 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 hole injection materials include metal porphyrine, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene, quinacridone-based organic substances, perylene-based organic substances, Examples include anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited to these.

The hole transport layer is a material that can transport holes from the anode or hole injection layer and transfer them to the light emitting layer, and a material with high mobility for holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions, but are not limited to these.

The electron blocking layer is a layer that blocks the movement of electrons and can be formed on the hole transport layer. An electron blocking layer that can block the movement of electrons without affecting the transport of holes can be used. Additionally, a light-emitting layer may be formed on the electron blocking layer, and a hole blocking layer, an electron transport layer, and an electron injection layer may be formed.

The hole blocking layer can be used to prevent the movement of holes without affecting the transport of electrons. An example of such a hole blocking layer is TPBi (1,3,5-tri(1-phenyl-1H-benzo). [d]imidazol-2-yl)phenyl), BCP (2,9-dimethyl4,7-diphenyl-1,10-phenanthroline), CBP (4,4-bis(N-carbazolyl)-1,1'-biphenyl ), PBD (2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole), PTCBI (bisbenzimidazo[2,1-a:1',2-b']anthra [2,1,9-def:6,5,10-d'e'f']diisoguinoline-10,21-dione) or BPhen (4,7-diphenyl-1,10-phenanthroline), etc. It is not limited.

The light-emitting layer is a material that can emit light in the visible light range by transporting holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining them, and a material with 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 Examples include benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, and rubrene, but are not limited to these.

The electron injection layer can be one that has high injection efficiency of electrons transferred from the cathode. Examples of such electron injection layers include, but are not limited to, lithium quinolate (Liq).

The electron transport layer is a material that can easily receive electrons from the cathode and transfer them to the light emitting layer, and a material with high electron mobility is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline, a complex containing Alq ₃ , an organic radical compound, and a hydroxyflavone-metal complex.

The organic light emitting device according to the present invention may be a front emitting type, a back emitting type, or a double-sided emitting type depending on the material used.

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

Hereinafter, synthesis examples of preferred compounds and device examples are presented to aid understanding of the present invention. However, the following examples are for illustrating the present invention and are not intended to limit the scope of the present invention.

Synthesis example 1: Synthesis of Compound 1

(One) Manufacturing example 1: Synthesis of intermediate 1-1

(6-phenyldibenzo[b,d]furan-4-yl)boronic acid (10.0 g, 0.031 mol), 3,5-dichlorophenylboronic acid (7.1 g, 0.037 mol), K ₂ CO ₃ (12.8 g, 0.093 mol) , 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to Pd(PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 9.1 g of <Intermediate 1-1> (yield 75.6%).

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

Intermediate 1-1 (10.0 g, 0.026 mol), dibenzo[b,d]furan-4-ylboronic acid (6.5 g, 0.031 mol), K ₂ CO ₃ (10.7 g, 0.077 mol), Pd(OAc) ₂ ( 1.5 g, 1.3 mmol), X-Phos (1.3 g, 2.6 mmol), 200 mL of THF, and 50 mL of H ₂ O were added and stirred at 70°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 6.1 g of <Intermediate 1-2> (yield 47.5%).

(3) Manufacturing example 3: Synthesis of Compound 1

Intermediate 1-2 (10.0 g, 0.019 mol), Bis-biphenyl-4-yl-amine (9.3 g, 0.029 mol), NaOtBu (5.5 g, 0.058 mol), Pd(dba) ₂ (0.4 g, 0.8 mmol) , 150 mL of Xylene was added to t-Bu ₃ P (0.3 g, 1.5 mmol) and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.3 g of <Compound 1> (yield 66.3%).

LC/MS: m/z=805[(M) ⁺ ]

Synthesis example 2: Synthesis of Compound 4

(One) Manufacturing example 1: Synthesis of Compound 4

Intermediate 1-2 (10.0 g, 0.019 mol), N-(biphenyl-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (10.4 g, 0.029 mol), NaOtBu (5.5 g, 0.058 mol) ), Pd(dba) ₂ (0.4 g, 0.8 mmol), and t-Bu ₃ P (0.3 g, 1.5 mmol) were added to 150 mL of Xylene and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized with a column to obtain 10.2 g of <Compound 4> (yield 62.8%).

LC/MS: m/z=845[(M) ⁺ ]

Synthesis example 3: Synthesis of Compound 6

(One) Manufacturing example 1: Synthesis of Compound 6

Intermediate 1-2 (10.0 g, 0.019 mol), N-[1,1'-Biphenyl]-4-yl-3-dibenzofuranamine (9.7 g, 0.029 mol), NaOtBu (5.5 g, 0.058 mol), Pd(dba ) ₂ (0.4 g, 0.8 mmol) and t-Bu ₃ P (0.3 g, 1.5 mmol) were mixed with 150 mL of Xylene and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized with a column to obtain 9.8 g of <Compound 6> (yield 62.3%).

LC/MS: m/z=819[(M) ⁺ ]

Synthesis example 4: Synthesis of Compound 19

(One) Manufacturing example 1: Synthesis of intermediate 19-1

Intermediate 1-1 (10.0 g, 0.026 mol), dibenzo[b,d]furan-2-ylboronic acid (6.5 g, 0.031 mol), K ₂ CO ₃ (10.7 g, 0.077 mol), Pd(OAc) ₂ ( 1.5 g, 1.3 mmol), X-Phos (1.3 g, 2.6 mmol), 200 mL of THF, and 50 mL of H ₂ O were added and stirred at 70°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 8.4 g of <Intermediate 19-1> (yield 62.7%).

(2) Manufacturing example 2: Synthesis of Compound 19

Intermediate 19-1 (10.0 g, 0.019 mol), N-([1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-4-amine (9.7 g, 0.029 mol), NaOtBu (5.5 g, 0.058 mol), Pd(dba) ₂ (0.4 g, 0.8 mmol), and t-Bu ₃ P (0.3 g, 1.5 mmol) were mixed with 150 mL of xylene and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 8.7 g of <Compound 19> (yield 55.3%).

LC/MS: m/z=819[(M) ⁺ ]

Synthesis example 5: Synthesis of Compound 31

(One) Manufacturing example 1: Synthesis of intermediate 31-1

Intermediate 1-1 (10.0 g, 0.026 mol), dibenzothiophene-4-boronic acid (7.0 g, 0.031 mol), K ₂ CO ₃ (10.7 g, 0.077 mol), Pd(OAc) ₂ (1.5 g, 1.3 mmol) , X-Phos (1.3 g, 2.6 mmol), 200 mL of THF and 50 mL of H ₂ O were added and stirred at 70°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized using a column to obtain 7.8 g of <Intermediate 31-1> (yield 56.5%).

(2) Manufacturing example 2: Synthesis of Compound 31

Intermediate 31-1 (10.0 g, 0.019 mol), N-(biphenyl-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (10.1 g, 0.028 mol), NaOtBu (5.4 g, 0.056 mol) ), Pd(dba) ₂ (0.4 g, 0.7 mmol), and t-Bu ₃ P (0.3 g, 1.5 mmol) were added to 150 mL of Xylene and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 9.1 g of <Compound 31> (yield 56.7%).

LC/MS: m/z=861[(M) ⁺ ]

Synthesis example 6: Synthesis of Compound 50

(One) Manufacturing example 1: Synthesis of intermediate 50-1

Intermediate 1-1 (10.0 g, 0.026 mol), dibenzothiophen-1-ylboronic acid (7.0 g, 0.031 mol), K ₂ CO ₃ (10.7 g, 0.077 mol), Pd(OAc) ₂ (1.5 g, 1.3 mmol) , X-Phos (1.3 g, 2.6 mmol), 200 mL of THF and 50 mL of H ₂ O were added and stirred at 70°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 8.3 g of <Intermediate 50-1> (yield 60.1%).

(2) Manufacturing example 2: Synthesis of Compound 50

Intermediate 50-1 (10.0 g, 0.019 mol), N-([1,1'-biphenyl]-4-yl)-9,9'-spirobi[fluoren]-4-amine (13.5 g, 0.028 mol), _Add 150 _mL of . After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 10.5 g of <Compound 50> (yield 57.3%).

LC/MS: m/z=984[(M) ⁺ ]

Synthesis example 7: Synthesis of Compound 52

(One) Manufacturing example 1: Synthesis of intermediate 52-1

(6-phenyldibenzo[b,d]furan-4-yl)boronic acid (10.0 g, 0.031 mol), 5-chloro[1,1'-biphenyl]-3-ylboronic acid (8.6 g, 0.037 mol), K ₂ CO ₃ (12.8 g, 0.093 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.6 mmol) were added with 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, and stirred at 80°C for 6 hours to react. . After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 9.6 g of <Intermediate 52-1> (yield 71.9%).

(2) Manufacturing example 2: Synthesis of Compound 52

Intermediate 52-1 (10.0 g, 0.023 mol), Bis-biphenyl-4-yl-amine (11.2 g, 0.035 mol), NaOtBu (6.7 g, 0.070 mol), Pd(dba) ₂ (0.5 g, 0.9 mmol) , 150 mL of Xylene was added to t-Bu ₃ P (0.4 g, 1.9 mmol) and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted and concentrated, followed by column and recrystallization to obtain 12.7 g of <Compound 52> (yield 76.5%).

LC/MS: m/z=715[(M) ⁺ ]

Synthesis example 8: Synthesis of Compound 62

(One) Manufacturing example 1: Synthesis of intermediate 62-1

Intermediate 1-1 (10.0 g, 0.026 mol), 2-biphenylboronic acid (6.1 g, 0.031 mol), K ₂ CO ₃ (10.7 g, 0.077 mol), Pd(OAc) ₂ (1.5 g, 1.3 mmol), -Phos (1.3 g, 2.6 mmol), 200 mL of THF, and 50 mL of H ₂ O were added and stirred at 70°C for 6 hours to react. After completion of the reaction, it was extracted, concentrated, and recrystallized with a column to obtain 7.2 g of <Intermediate 62-1> (yield 55.2%).

(2) Manufacturing example 2: Synthesis of Compound 62

Intermediate 62-1 (10.0 g, 0.020 mol), Bis(3-biphenylyl)amine (9.5 g, 0.030 mol), NaOtBu (5.7 g, 0.059 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol), t 150 mL of Xylene was added to -Bu ₃ P (0.3 g, 1.6 mmol) and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 10.5 g of <Compound 62> (yield 67.2%).

LC/MS: m/z=791[(M) ⁺ ]

Synthesis example 9: Synthesis of Compound 64

(One) Manufacturing example 1: Synthesis of Compound 64

Intermediate 62-1 (10.0 g, 0.020 mol), N-[1,1'-Biphenyl]-4-yl-3-dibenzofuranamine (9.9 g, 0.030 mol), NaOtBu (5.7 g, 0.059 mol), Pd(dba ) ₂ (0.5 g, 0.8 mmol) and t-Bu ₃ P (0.3 g, 1.6 mmol) were added to 150 mL of Xylene and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 10.2 g of <Compound 64> (yield 64.2%).

LC/MS: m/z=805[(M) ⁺ ]

Synthesis example 10: Synthesis of Compound 86

(One) Manufacturing example 1: Synthesis of intermediate 86-1

Intermediate 1-1 (10.0 g, 0.026 mol), [1,1':3',1"-terphenyl]-5'-ylboronic acid (8.5 g, 0.031 mol), K ₂ CO ₃ (10.7 g, 0.077 mol) ₎ , Pd(OAc) ₂ (1.5 g, 1.3 mmol), After extraction and concentration, column and recrystallization were performed to obtain 6.3 g of <Intermediate 86-1> (yield 42.0%).

(2) Manufacturing example 2: Synthesis of Compound 86

Intermediate 86-1 (10.0 g, 0.017 mol), Bis-biphenyl-4-yl-amine (8.3 g, 0.026 mol), NaOtBu (4.9 g, 0.051 mol), Pd(dba) ₂ (0.4 g, 0.7 mmol) , 150 mL of Xylene was added to t-Bu ₃ P (0.3 g, 1.4 mmol) and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 9.6 g of <Compound 86> (yield 64.5%).

LC/MS: m/z=867[(M) ⁺ ]

Synthesis example 11: Synthesis of Compound 96

(One) Manufacturing example 1: Synthesis of intermediate 96-1

Intermediate 1-1 (10.0 g, 0.026 mol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (7.3 g, 0.031 mol), K ₂ CO ₃ (10.7 g, 0.077 mol), Pd (OAc _{) 2} (1.5 g, 1.3 mmol), After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 5.7 g of <Intermediate 96-1> (yield 40.5%).

(2) Manufacturing example 2: Synthesis of Compound 96

Intermediate 96-1 (10.0 g, 0.018 mol), N-Phenyl-9,9'-spirobi[9H-fluoren]-4-amine (11.2 g, 0.027 mol), NaOtBu (5.3 g, 0.055 mol), Pd( 150 mL of xylene was added to dba) ₂ (0.4 g, 0.7 mmol) and t-Bu ₃ P (0.3 g, 1.5 mmol) and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized with a column to obtain 11.5 g of <Compound 96> (yield 62.6%).

LC/MS: m/z=917[(M) ⁺ ]

Synthesis example 12: Synthesis of compound 113

(One) Manufacturing example 1: Synthesis of intermediate 113-1

4,6-dibromodibenzofuran (10.0 g, 0.031 mol), 2-biphenylboronic acid (7.3 g, 0.037 mol), K ₂ CO ₃ (12.7 g, 0.092 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.0006 mol) Add 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O and stir at 80°C for 6 hours to react. After completion of the reaction, extraction was performed, concentration was performed, and 6.3 g of <Intermediate 113-1> was obtained (yield 51.4%).

(2) Manufacturing example 2: Synthesis of intermediate 113-2

Intermediate 113-1 (10.0 g, 0.025 mol), (3,5-dichlorophenyl)boronic acid (5.7 g, 0.030 mol), K ₂ CO ₃ (10.4 g, 0.075 mol), Pd(PPh ₃ ) ₄ (0.6 g , 0.0005 mol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 7.2 g (yield 61.8%) of <Intermediate 113-2>.

(3) Manufacturing example 3: Synthesis of intermediate 113-3

Intermediate 113-2 (10.0 g, 0.022 mol), dibenzo[b,d]furan-4-ylboronic acid (5.5 g, 0.026 mol), K ₂ CO ₃ (8.9 g, 0.065 mol), Pd(OAc) ₂ ( 1.2 _g , 0.001 mol), After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 6.1 g of <Intermediate 113-3> (yield 47.5%).

(4) Manufacturing example 4: Synthesis of Compound 113

Intermediate 113-3 (10.0 g, 0.017 mol), Bis-biphenyl-4-yl-amine (8.1 g, 0.025 mol), NaOtBu (4.8 g, 0.050 mol), Pd(dba) ₂ (0.4 g, 0.7 mmol) , 150 mL of Xylene was added to t-Bu ₃ P (0.3 g, 1.3 mmol) and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 10.8 g of <Compound 113> (yield 73.1%).

LC/MS: m/z=852[(M) ⁺ ]

Synthesis example 13: Synthesis of compound 123

(One) Manufacturing example 1: Synthesis of intermediate 123-1

4,6-dibromodibenzofuran (10.0 g, 0.031 mol), dibenzo[b,d]furan-2-ylboronic acid (7.8 g, 0.037 mol), K ₂ CO ₃ (12.7 g, 0.092 mol), Pd(PPh ₃ ) _{To 4} (0.7 g, 0.6 mmol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 6.8 g (yield 53.6%) of <Intermediate 123-1>.

(2) Manufacturing example 2: Synthesis of intermediate 123-2

Intermediate 123-1 (10.0 g, 0.024 mol), 5-chloro[1,1'-biphenyl]-3-ylboronic acid (6.8 g, 0.029 mol), K ₂ CO ₃ (10.0 g, 0.073 mol), Pd ( To PPh ₃ ) ₄ (0.6 g, 0.0005 mol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 7.8 g of <Intermediate 123-2> (yield 61.9%).

(3) Manufacturing example 3: Synthesis of Compound 123

Intermediate 123-2 (10.0 g, 0.019 mol), Bis-biphenyl-4-yl-amine (9.3 g, 0.029 mol), NaOtBu (5.5 g, 0.058 mol), Pd(dba) ₂ (0.4 g, 0.8 mmol) , 150 mL of Xylene was added to t-Bu ₃ P (0.3 g, 1.5 mmol) and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 12.2 g of <Compound 123> (yield 78.9%).

LC/MS: m/z=805[(M) ⁺ ]

Synthesis example 14: Synthesis of compound 139

(One) Manufacturing example 1: Synthesis of intermediate 139-1

(6-phenyldibenzo[b,d]furan-4-yl)boronic acid (10.0 g, 0.031 mol), 3-chloro-5-fluorophenylboronic acid (6.5 g, 0.037 mol), K ₂ CO ₃ (12.8 g, 0.093 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.6 mmol) was mixed with 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.1 g (yield 70.1%) of <Intermediate 139-1>.

(2) Manufacturing example 2: Synthesis of intermediate 139-2

DMF was added to Intermediate 139-1 (10 g, 0.027 mol), 9H-Carbazole (5.4 g, 0.032 mol), and Cs ₂ CO ₃ (5.6 g, 0.040 mol), and the mixture was refluxed and stirred at 150°C for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 9.1 g of <Intermediate 139-2> (yield 65.3%).

(3) Manufacturing example 3: Synthesis of Compound 139

Intermediate 139-1 (10.0 g, 0.019 mol), Bis-biphenyl-4-yl-amine (9.3 g, 0.029 mol), NaOtBu (3.7 g, 0.039 mol), Pd(dba) ₂ (0.6 g, 1.0 mmol) , 150 mL of Xylene was added to t-Bu ₃ P (0.4 g, 1.9 mmol) and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 10.2 g of <Compound 139> (yield 65.9%).

LC/MS: m/z=804[(M) ⁺ ]

Synthesis example 15: Synthesis of compound 165

(One) Manufacturing example 1: Synthesis of Compound 165

Intermediate 139-2 (10.0 g, 0.019 mol), N-([1,1'-Biphenyl]-4-yl)-9,9'-spirobi[fluoren]-4-amine (14.0 g, 0.029 mol), Add _{150 mL} of . After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 9.4 g of <Compound 165> (yield 50.6%).

LC/MS: m/z=966[(M) ⁺ ]

Synthesis example 16: Synthesis of Compound 180

(One) Manufacturing example 1: Synthesis of Compound 180

Intermediate 139-1 (10.0 g, 0.019 mol), N-[1,1'-Biphenyl]-4-yl-3-dibenzofuranamine (9.7 g, 0.029 mol), NaOtBu (3.7 g, 0.039 mol), Pd(dba ) ₂ (0.6 g, 1.0 mmol) and t-Bu ₃ P (0.4 g, 1.9 mmol) were mixed with 150 mL of Xylene and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 9.6 g of <Compound 180> (yield 61.0%).

LC/MS: m/z=818[(M) ⁺ ]

Synthesis example 17: Synthesis of Compound 199

(One) Manufacturing example 1: Synthesis of intermediate 199-1

Intermediate 1-1 (10.0 g, 0.026 mol), (9-Phenyl-9H-carbazol-2-yl)boronic acid (8.9 g, 0.031 mol), K ₂ CO ₃ (10.7 g, 0.077 mol), Pd(OAc _{) 2} (1.5 g, 1.3 mmol), After completion of the reaction, the extract was extracted, concentrated, and recrystallized with a column to obtain 8.2 g of <Intermediate 199-1> (yield 53.5%).

(2) Manufacturing example 2: Synthesis of Compound 199

Intermediate 199-1 (10.0 g, 0.017 mol), Bis-biphenyl-4-yl-amine (8.1 g, 0.025 mol), NaOtBu (3.2 g, 0.034 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol) , 150 mL of Xylene was added to t-Bu ₃ P (0.3 g, 1.7 mmol) and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 10.7 g of <Compound 199> (yield 72.4%).

LC/MS: m/z=880[(M) ⁺ ]

Synthesis example 18: Synthesis of compound 221

(One) Manufacturing example 1: Synthesis of intermediate 221-1

Intermediate 1-1 (10.0 g, 0.026 mol), (9-Phenyl-9H-carbazol-3-yl)boronic acid (8.9 g, 0.031 mol), K ₂ CO ₃ (10.7 g, 0.077 mol), Pd(OAc _{) 2} (1.5 g, 1.3 mmol), After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 8.5 g of <Intermediate 221-1> (yield 55.5%).

(2) Manufacturing example 2: Synthesis of Compound 221

Intermediate 221-1 (10.0 g, 0.017 mol), N-[1,1'-biphenyl]-4-yl-9,9'-spiro bi[9H-fluoren]-2-amine (12.2 g, 0.025 mol) , NaOtBu (3.2 g, 0.034 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol), and t-Bu ₃ P (0.3 g, 1.7 mmol) were mixed with 150 mL of I ordered it. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 9.5 g of <Compound 221> (yield 54.3%).

LC/MS: m/z=1042[(M) ⁺ ]

Synthesis example 19: Synthesis of compound 248

(One) Manufacturing example 1: Synthesis of intermediate 248-1

Intermediate 1-1 (10.0 g, 0.026 mol), (9-Phenyl-9H-carbazol-4-yl)boronic acid (8.9 g, 0.031 mol), K ₂ CO ₃ (10.7 g, 0.077 mol), Pd(OAc _{) 2} (1.5 g, 1.3 mmol), After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 7.6 g of <Intermediate 248-1> (yield 49.6%).

(2) Manufacturing example 2: Synthesis of Compound 248

Intermediate 248-1 (10.0 g, 0.017 mol), N-([1,1'-biphenyl]-4-yl)dibenzo[b,d]furan-4-amine (8.4 g, 0.025 mol), NaOtBu (3.2 g, 0.034 mol), Pd(dba) ₂ (0.5 g, 0.8 mmol), and t-Bu ₃ P (0.3 g, 1.7 mmol) were mixed with 150 mL of xylene and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted and concentrated, followed by column and recrystallization to obtain 8.1 g of <Compound 248> (yield 53.9%).

LC/MS: m/z=894[(M) ⁺ ]

Synthesis example 20: Synthesis of compound 254

(One) Manufacturing example 1: Synthesis of intermediate 254-1

4-Bromo-6-phenyldibenzo[b,d]thiophene (10.0 g, 0.030 mol), (3,5-dichlorophenyl)boronic acid (6.8 g, 0.035 mol), K ₂ CO ₃ (12.2 g, 0.089 mol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added to Pd(PPh ₃ ) ₄ (0.7 g, 0.0006 mol) and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 8.1 g of <Intermediate 254-1> (yield 67.8%).

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

Intermediate 254-1 (10.0 g, 0.025 mol), dibenzo[b,d]furan-4-ylboronic acid (6.3 g, 0.030 mol), K ₂ CO ₃ (10.2 g, 0.074 mol), Pd(OAc) ₂ ( 1.4 _g , 0.001 mol), After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 7.1 g of <Intermediate 254-2> (yield 53.6%).

(3) Manufacturing example 3: Synthesis of Compound 254

Intermediate 254-2 (10.0 g, 0.019 mol), Bis-biphenyl-4-yl-amine (9.0 g, 0.028 mol), NaOtBu (5.4 g, 0.056 mol), Pd(dba) ₂ (0.4 g, 0.7 mmol) , 150 mL of Xylene was added to t-Bu ₃ P (0.3 g, 1.5 mmol) and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.8 g of <Compound 254> (yield 77.1%).

LC/MS: m/z=822[(M) ⁺ ]

Synthesis example 21: Synthesis of Compound 338

(One) Manufacturing example 1: Synthesis of intermediate 338-1

4,6-dibromodibenzothiophene (10.0 g, 0.029 mol), 4-biphenylboronic acid (7.0 g, 0.035 mol), K ₂ CO ₃ (12.1 g, 0.088 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.0006 mol) Add 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O and stir at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 6.8 g (yield 56.0%) of <Intermediate 338-1>.

(2) Manufacturing example 2: Synthesis of intermediate 338-2

Intermediate 338-1 (10.0 g, 0.024 mol), (3,5-dichlorophenyl)boronic acid (5.5 g, 0.029 mol), K ₂ CO ₃ (10.0 g, 0.072 mol), Pd(PPh ₃ ) ₄ (0.6 g , 0.0005 mol), 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O were added and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 7.4 g (yield 63.8%) of <Intermediate 338-2>.

(3) Manufacturing example 3: Synthesis of intermediate 338-3

Intermediate 338-2 (10.0 g, 0.021 mol), dibenzo[b,d]furan-4-ylboronic acid (5.3 g, 0.025 mol), K ₂ CO ₃ (8.6 g, 0.062 mol), Pd(OAc) ₂ ( 1.2 _g , 0.001 mol), After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 7.6 g of <Intermediate 338-3> (yield 59.7%).

(4) Manufacturing example 4: Synthesis of compound 338

Intermediate 338-3 (10.0 g, 0.016 mol), Bis-biphenyl-4-yl-amine (7.9 g, 0.025 mol), NaOtBu (4.7 g, 0.049 mol), Pd(dba) ₂ (0.4 g, 0.7 mmol) , 150 mL of Xylene was added to t-Bu ₃ P (0.3 g, 1.3 mmol) and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 11.2 g of <Compound 338> (yield 76.5%).

LC/MS: m/z=898[(M) ⁺ ]

Synthesis example 22: Synthesis of Compound 360

(One) Manufacturing example 1: Synthesis of intermediate 360-1

4-bromo-6-phenyldibenzo[b,d]thiophene (10.0 g, 0.030 mol), 3-chloro-5-fluorophenylboronic acid (6.2 g, 0.035 mol), K ₂ CO ₃ (12.2 g, 0.089 mol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) was added with 200 mL of toluene, 50 mL of ethanol, and 50 mL of H ₂ O, and stirred at 80°C for 6 hours to react. After completion of the reaction, the extract was extracted, concentrated, and columnarized to obtain 6.1 g of <Intermediate 360-1> (yield 53.2%).

(2) Manufacturing example 2: Synthesis of intermediate 360-2

DMF was added to Intermediate 360-1 (10 g, 0.027 mol), 9H-Carbazole (5.4 g, 0.032 mol), and Cs ₂ CO ₃ (5.6 g, 0.040 mol), and the mixture was refluxed and stirred at 150°C for 12 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 9.1 g of <Intermediate 360-2> (yield 68.1%).

(3) Manufacturing example 3: Synthesis of Compound 360

Intermediate 360-2 (10.0 g, 0.019 mol), Bis-biphenyl-4-yl-amine (9.0 g, 0.028 mol), NaOtBu (3.6 g, 0.037 mol), Pd(dba) ₂ (0.5 g, 0.9 mmol) , 150 mL of Xylene was added to t-Bu ₃ P (0.4 g, 1.9 mmol) and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 9.5 g of <Compound 360> (yield 62.0%).

LC/MS: m/z=820[(M) ⁺ ]

Synthesis example 23: Synthesis of compound 375

(One) Manufacturing example 1: Synthesis of Compound 375

Intermediate 360-1 (10.0 g, 0.019 mol), N-([1,1'-Biphenyl]-4-yl)-9,9'-spirobi[fluoren]-4-amine (13.5 g, 0.028 mol), _Add 150 _mL of . After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 8.9 g of <Compound 375> (yield 48.5%).

LC/MS: m/z=982[(M) ⁺ ]

Synthesis example 24: Synthesis of Compound 419

(One) Manufacturing example 1: Synthesis of intermediate 419-1

Intermediate 254-1 (10.0 g, 0.025 mol), (9-([1,1'-biphenyl]-4-yl)-9H-carbazol-4- yl)boronic acid (10.8 g, 0.030 mol), K ₂ Add CO ₃ (10.2 g _, 0.074 mol), Pd(OAc) ₂ (1.4 g, 1.2 mmol), The reaction was stirred for a while. After completion of the reaction, the extract was extracted, concentrated, and then recrystallized with a column to obtain 7.3 g of <Intermediate 419-1> (yield 43.0%).

(2) Manufacturing example 2: Synthesis of Compound 419

Intermediate 419-1 (10.0 g, 0.015 mol), diphenylamine (3.7 g, 0.022 mol), NaOtBu (2.8 g, 0.029 mol), Pd(dba) ₂ (0.4 g, 0.7 mmol), t-Bu ₃ P (0.3 g, 1.5 mmol) was added to 150 mL of xylene and stirred at 110°C for 4 hours to react. After completion of the reaction, the extract was extracted, concentrated, and recrystallized using a column to obtain 8.1 g of <Compound 419> (yield 67.9%).

LC/MS: m/z=820[(M) ⁺ ]

device Example ( EBL )

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 using an ITO glass substrate to which the ITO transparent electrode is attached on a glass substrate of 25 mm × 25 mm × 0.7 mm. and then washed. After the substrate was mounted in a vacuum chamber and the base pressure was set to 1 × 10 ^-6 torr, organic materials and metals were deposited on the ITO in the following structure.

device Example 1 to 80

The compound implemented according to the present invention was employed in the electron blocking layer to manufacture an organic light-emitting device having the following device structure, and then the light emission and driving characteristics of the compound implemented according to the present invention were measured.

ITO / hole injection layer (HAT-CN, 5 nm) / hole transport layer (HT1, 100 nm) / electron blocking layer (10 nm) / emission layer (20 nm) / electron transport layer (ET1:Liq, 30 nm) / LiF ( 1 nm) / Al (100 nm)

[HAT-CN] was deposited to a thickness of 5 nm on the top of the ITO transparent electrode to form a hole injection layer, and then [HT1] was deposited to a thickness of 100 nm to form a hole transport layer. Afterwards, the compound according to the present invention shown in [Table 1] below was deposited to a thickness of 10 nm to form an electron blocking layer, and the emitting layer was formed at a thickness of 20 nm using [BH1] as the host compound and [BD1] as the dopant compound. It was formed by vapor deposition. Afterwards, 30 nm of an electron transport layer (50% doped with [ET1] compound Liq below) was deposited, and then LiF was deposited to a thickness of 1 nm to form an electron injection layer. Afterwards, an organic light emitting device was manufactured by forming Al into a film with a thickness of 100 nm.

device Comparative example One

The organic light emitting device for Comparative Device Example 1 was manufactured in the same manner as the device structures of Examples 1 to 80 except that [EB1] was used instead of the compound according to the present invention in the electron blocking layer.

device Comparative example 2

The organic light emitting device for Device Comparative Example 2 was manufactured in the same manner as the device structures of Examples 1 to 80, except that [EB2] was used instead of the compound according to the present invention in the electron blocking layer.

device Comparative example 3

The organic light emitting device for Device Comparative Example 3 was manufactured in the same manner as the device structures of Examples 1 to 80, except that [EB3] was used in the electron blocking layer instead of the compound according to the present invention.

device Comparative example 4

The organic light-emitting device for Comparative Device Example 4 was manufactured in the same manner as the device structures of Examples 1 to 80, except that [EB4] was used in the electron blocking layer instead of the compound according to the present invention.

Experiment example 1: element Example Luminous properties from 1 to 80

The driving voltage, current efficiency, and color coordinates of the organic light emitting devices manufactured according to the above examples and comparative examples were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and were measured at 1,000 nit. The standard result values are shown in [Table 1] below.

Example electronic low layer V cd/A CIEx CIey One Formula 1 3.89 7.56 0.1361 0.1340 2 Formula 4 4.07 7.46 0.1366 0.1333 3 Formula 6 3.82 7.61 0.1341 0.1359 4 Formula 8 3.96 7.55 0.1340 0.1358 5 Formula 10 3.81 7.66 0.1351 0.1350 6 Formula 12 3.99 7.33 0.1327 0.1376 7 Formula 13 3.81 7.90 0.1351 0.1351 8 Formula 16 4.16 7.48 0.1329 0.1373 9 Formula 18 4.03 7.30 0.1328 0.1374 10 Formula 19 4.01 7.64 0.1317 0.1386 11 Formula 28 3.62 7.56 0.1345 0.1355 12 Formula 31 3.74 7.59 0.1314 0.1392 13 Formula 33 4.20 7.52 0.1316 0.1385 14 Formula 35 4.03 7.38 0.1317 0.1389 15 Formula 37 4.12 7.79 0.1326 0.1378 16 Formula 39 3.66 7.70 0.1329 0.1372 17 Formula 41 3.95 7.35 0.1360 0.1344 18 Formula 48 3.76 7.84 0.1329 0.1382 19 Formula 50 3.91 7.73 0.1307 0.1390 20 Formula 52 3.79 7.80 0.1306 0.1396 21 Formula 55 3.98 7.44 0.1353 0.1363 22 Formula 56 3.77 7.71 0.1306 0.1391 23 Formula 58 3.90 7.37 0.1320 0.1382 24 Formula 60 4.09 7.56 0.1307 0.1395 25 Formula 62 3.97 7.77 0.1310 0.1393 26 Formula 63 3.85 7.91 0.1313 0.1393 27 Formula 64 3.72 7.62 0.1323 0.1382 28 Formula 66 3.66 7.79 0.1339 0.1363 29 Formula 69 3.84 7.72 0.1341 0.1362 30 Formula 71 4.13 7.37 0.1342 0.1363 31 Formula 72 3.78 7.78 0.1326 0.1376 32 Formula 73 4.13 7.37 0.1342 0.1363 33 Formula 74 4.13 7.37 0.1342 0.1363 34 Formula 75 4.13 7.37 0.1342 0.1363 35 Formula 78 3.93 7.57 0.1345 0.1356 36 Formula 79 3.67 7.55 0.1314 0.1391 37 Formula 82 3.80 7.68 0.1328 0.1375 38 Formula 86 4.06 7.87 0.1326 0.1368 39 Formula 90 3.74 7.35 0.1349 0.1354 40 Formula 93 3.81 7.69 0.1346 0.1365 41 Formula 96 3.93 7.51 0.1348 0.1357 42 Formula 99 4.11 7.41 0.1353 0.1350 43 Formula 101 3.86 7.56 0.1328 0.1376 44 Formula 105 4.00 7.50 0.1327 0.1375 45 Formula 113 3.85 7.61 0.1338 0.1367 46 Formula 123 4.03 7.28 0.1314 0.1393 47 Formula 139 3.85 7.85 0.1338 0.1368 48 Formula 165 4.20 7.43 0.1316 0.1390 49 Chemical formula 180 4.07 7.25 0.1315 0.1391 50 Formula 199 4.05 7.59 0.1304 0.1403 51 Chemical formula 201 3.66 7.51 0.1332 0.1372 52 Formula 221 3.78 7.54 0.1301 0.1409 53 Formula 233 4.24 7.47 0.1303 0.1402 54 Formula 238 4.07 7.33 0.1304 0.1406 55 Formula 241 4.16 7.74 0.1313 0.1395 56 Formula 246 3.70 7.65 0.1316 0.1389 57 Formula 248 3.99 7.30 0.1347 0.1361 58 Formula 250 3.80 7.79 0.1316 0.1399 59 Formula 254 3.95 7.68 0.1304 0.1407 60 Formula 261 3.83 7.75 0.1303 0.1404 61 Formula 266 4.02 7.39 0.1340 0.1380 62 Formula 275 3.81 7.66 0.1304 0.1401 63 Formula 280 3.94 7.32 0.1307 0.1399 64 Formula 283 4.13 7.51 0.1304 0.1412 65 Formula 292 4.01 7.72 0.1301 0.1410 66 Chemical formula 301 3.89 7.86 0.1300 0.1410 67 Formula 310 3.76 7.57 0.1310 0.1399 68 Formula 338 3.70 7.74 0.1326 0.1380 69 Formula 357 3.88 7.67 0.1328 0.1379 70 Chemical formula 360 4.17 7.32 0.1329 0.1380 71 Formula 375 3.82 7.73 0.1313 0.1393 72 Formula 388 3.96 7.52 0.1303 0.1402 73 Formula 392 3.81 7.39 0.1318 0.1389 74 Formula 397 3.89 7.75 0.1312 0.1401 75 Formula 398 3.97 7.52 0.1332 0.1373 76 Chemical formula 401 3.71 7.50 0.1301 0.1408 77 Formula 406 3.84 7.63 0.1315 0.1392 78 Formula 413 4.10 7.82 0.1313 0.1385 79 Formula 419 3.78 7.30 0.1336 0.1371 80 Formula 420 3.85 7.64 0.1333 0.1382 Comparative Example 1 EB1 4.67 6.65 0.1353 0.1517 Comparative Example 2 EB2 4.71 6.52 0.1361 0.1337 Comparative Example 3 EB3 4.82 6.68 0.1366 0.1344 Comparative Example 4 EB4 4.65 6.54 0.1357 0.1359

Looking at the results shown in [Table 1], when the compound according to the present invention is employed in the electron blocking layer in an organic light-emitting device, the characteristic structure of the compound according to the present invention as a compound used as a conventional electron blocking layer material is compared to that of the compound according to the present invention. It can be seen that the luminous properties, such as low-voltage driving characteristics, luminous efficiency, and quantum efficiency, are significantly superior to those of devices employing the compound (Comparative Examples 1 to 4).

[HAT-CN] [HT1] [BH1] [BD1] [ET1]

[EB1] [EB2] [EB3] [EB4]

Claims (12)

Organic compounds represented by the following [Chemical Formula I]:
[Formula Ⅰ]

In the above [Chemical Formula I],
X is O or S,
R ₁ to R ₃ are the same or different from each other and are each independently hydrogen or deuterium,
Ar ₁ to Ar ₄ are the same or different from each other, and are each independently 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,
D is deuterium, n refers to the number of hydrogens in the formula (I) replaced with deuterium (D), and n is an integer from 0 to 60. According to paragraph 1,
An organic compound characterized in that at least one of Ar ₁ to Ar ₄ is selected from the following [Structural Formula 1] to [Structural Formula 6]:
[Structural Formula 1] [Structural Formula 2] [Structural Formula 3]

[Structural Formula 4] [Structural Formula 5] [Structural Formula 6]

In [Structural Formula 1] to [Structural Formula 6],
R and R' are each independently selected from hydrogen, deuterium, 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,
R ₄ to R ₆ are the same or different from each other, and each independently represents deuterium, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted 6 to 20 carbon atoms. Any one selected from an aryl group of 30 and a substituted or unsubstituted heteroaryl group of 3 to 30 carbon atoms,
R ₄ and R ₅ may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring,
The '*-' indicates a linking site, and in [Structural Formula 4], any one of R, R' and R ₆ is '*-'. According to paragraph 2,
An organic compound wherein Ar ₄ is any one selected from [Structural Formula 1] to [Structural Formula 6]. According to paragraph 1,
R ₁ to R ₃ and Ar ₁ to Ar ₄ in [Formula I] An organic compound characterized in that at least one of the substituents has a structure containing deuterium. According to claim 1 or 2,
In the definition of R, R', R ₁ to R ₆ and Ar ₁ to Ar ₄ , 'substituted or unsubstituted' means that R, R', R ₁ to R ₆ and Ar ₁ to Ar ₄ are deuterium. , cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, cycloalkyl group, heterocycloalkyl group, aryl group, fluorenyl group, heteroaryl group, silyl group and amine group. , an organic compound meaning that two or more of the above substituents are substituted with a linked substituent, or do not have any substituents. According to paragraph 1,
[Chemical formula I] is an organic compound characterized in that the hydrogen present in formula I is partially substituted with deuterium (D), and the deuterium (D) substitution rate is 10 to 90%. According to clause 6,
An organic compound characterized in that the deuterium (D) substitution rate is 20 to 80%. In clause 7,
An organic compound characterized in that the deuterium (D) substitution rate is 30 to 70%. According to paragraph 1,
[Formula I] is an organic compound selected from the following [Formula 1] to [Formula 420]:

































An organic light-emitting device comprising a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode,
An organic light-emitting device, wherein at least one of the organic layers includes at least one organic compound represented by [Chemical Formula I] according to claim 1. According to clause 10,
The organic layer includes one or more of an electron injection layer, an electron transport layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, and a light emitting layer,
An organic light-emitting device, wherein at least one of the layers includes an organic compound represented by the formula (I). According to clause 11,
An organic light-emitting device comprising an organic compound represented by [Chemical Formula I] in the electron blocking layer.