KR20220089623A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention is an organic light emitting compound represented by the following [Formula I], and when it is employed in an electron blocking layer, a hole transport layer, etc., it is possible to realize an organic light emitting device having very excellent light emitting properties such as luminous efficiency and quantum efficiency.
[Formula Ⅰ]

Description

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 employed in an organic layer in an organic light emitting device and an organic light emitting device having significantly improved light emitting characteristics such as long lifespan and luminous efficiency by employing the same.

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, the development of a new material capable of improving light emitting characteristics and development of an organic layer structure in a device are continuously required.

Accordingly, the present invention provides a novel organic light emitting compound capable of remarkably improving light emitting characteristics such as long lifespan and luminous efficiency by being employed as an organic layer material such as an electron blocking layer and a hole transport layer in an organic light emitting device, and an organic light emitting device including the same want to

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

[Formula Ⅰ]

The specific structure of the [Formula I] and specific compounds implemented thereby and R, X, L ₁ to L ₃ , Ar ₁ and Ar ₂ etc. will be described later.

The organic light emitting device employing the organic light emitting compound according to the present invention in an organic layer such as an electron blocking layer and a hole transport layer has significantly superior light emitting characteristics such as long lifespan and luminous efficiency compared to conventional devices, so it can be usefully used in various display devices.

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

The present invention relates to an organic light emitting compound represented by the following [Formula I], and when employed in various organic layers in an organic light emitting device, preferably a hole transport layer, an electron blocking layer, etc. It is possible to implement an improved organic light emitting device.

The organic light emitting compound represented by the following [Formula I] according to the present invention is structurally characterized in that an amine derivative is linked to any one of 4-7 carbon positions of benzoxazole or a benzothiazole derivative through a linking group as follows do it with

[Formula Ⅰ]

In the [Formula I],

L ₁ to L ₃ are the same as or different from each other, and each independently is a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted carbazolylene group , a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms, a substituted or unsubstituted arylene group having 6 to 50 carbon atoms in which one or more substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms is fused, and a substituted or unsubstituted It is selected from a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms in which at least one cycloalkyl having 3 to 30 carbon atoms is fused.

n, m, and o are each an integer of 0 to 3, and when n, m, and o are 2 or more, a plurality of L ₁ to L ₃ are the same as or different from each other, respectively.

Ar ₁ To Ar ₂ are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 6 to C 30 An aryl group, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms in which one or more substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms is fused, and a substituted or unsubstituted It is selected from a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms in which at least one cyclic cycloalkyl having 3 to 30 carbon atoms is fused.

X is O or S.

R is selected from a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, and a substituted or unsubstituted C 2 to C 50 heteroaryl group.

As described above, the organic light emitting compound according to the present invention has a long lifespan and light emitting properties such as luminous efficiency of the organic light emitting device employing it in an organic layer such as a hole transport layer and an electron blocking layer by the characteristics of the introduced substituent and the framework structure as described above. Very good.

Meanwhile, in the definition of R, Ar ₁ to Ar ₂ and L ₁ to L ₃ , 'substituted or unsubstituted' means that R, Ar ₁ to Ar ₂ and L ₁ to L ₃ are deuterium, a cyano group, a halogen group, respectively. , hydroxy group, nitro group, alkyl group, halogenated alkyl group, deuterated alkyl group, alkenyl group, alkynyl group, heteroalkyl group, aryl group, arylalkyl group, heteroaryl group, heteroarylalkyl group, cycloalkyl group, heterocycloalkyl group, alkoxy group, It is selected from the group consisting of a halogenated alkoxy group, a deuterated alkoxy group, an alkylamino group, an arylamino group, a heteroarylamino group, an alkylsilyl group, an arylsilyl group, and an aryloxy group, and is substituted with one or two or more selected substituents, or the substituents It means that two or more of the substituents are substituted with a connected substituent, or do 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.

The substituted heteroaryl group includes 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 benz It means that an imidazole group, a benzoxazole group, a benzthiazole group, a benzcarbazole group, a dibenzothiophenyl group, a dibenzofuran group, etc. 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. 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, the alkyl group or the alkoxy group may be a deuterated alkyl group or an alkoxy group, a halogenated alkyl group or an alkoxy group by being substituted with deuterium or a halogen group.

Specific examples of the aryloxy group used in the present invention include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, indenyloxy, and the like, and at least one hydrogen atom contained in the aryloxy group. is further substitutable.

Specific examples of the silyl group used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylfurylsilyl and the like.

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 only 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 addition, the aryl group may also be further substituted with one or more substituents, and more specifically, at least one hydrogen atom of the aryl group is a deuterium atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH(R), -N(R')(R"), R' and R" are each independently an alkyl group having 1 to 10 carbon atoms, in this case referred to as an "alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, C1-C24 alkenyl group, C1-C24 alkynyl group, C1-C24 hetero It may be substituted with an alkyl group, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, a heteroarylalkyl group having 2 to 24 carbon atoms, or the like.

In the present invention, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 20. Specific examples include a vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1 -Butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, styrenyl group, etc., but are not limited thereto.

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 it is preferably from 2 to 30 carbon atoms. Examples include 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, 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, iso An oxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and the like, are not limited thereto.

In the present invention, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, specifically cyclopropyl group cyclobutyl group cyclopentyl group 3-methylcyclopentyl group 2,3-dimethylcyclopentyl group, cyclohexyl group Sil group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclo Octyl group, spirodecyl, spirodecyl, adamantyl, and the like, but is not limited thereto.

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, or the like.

In the present invention, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group including two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

Specific examples of the arylamine group include a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 3-methyl-phenylamine group, a 4-methyl-naphthylamine group, and a 2-methyl-biphenyl group. an amine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a phenyl naphthylamine group, a ditolylamine group, a phenyltolylamine group, a carbazole group, and a triphenylamine group, but is not limited thereto.

In the present invention, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heterocyclic group described above.

In the present invention, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In addition, various specific examples of the substituent according to the present invention can be clearly identified in the specific compounds described below.

The organic light emitting compound according to the present invention represented by the above [Formula I] can be used as an organic layer of an organic light emitting device due to its structural specificity as described above, and more specifically, depending on the characteristics of various substituents introduced, the electrons of the organic layer It can be used as a material such as a blocking layer and a hole transport layer.

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

An organic light emitting compound having a unique characteristic of a substituent can be synthesized through the above-described characteristic structure and substituent, for example, organic light emitting that satisfies the conditions required for each organic layer such as a hole transport layer and an electron blocking layer when manufacturing an organic light emitting device. A compound material can be prepared, and in particular, when the compound of [Formula I] according to the present invention is employed in the electron blocking layer and the hole transport layer, it is possible to further improve the luminescent properties such as long lifespan and luminous efficiency of the device.

The organic light emitting 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 and a second electrode and an organic layer disposed therebetween. Except that, it may 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, but may have a multi-layered 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, and the like. However, the present invention is not limited thereto and may include a smaller number or a larger number of organic layers.

Accordingly, in the organic light emitting device according to the present invention, the organic layer may include a hole transport layer or an electron blocking layer, and at least one of the layers may include an organic light emitting compound represented by the [Formula I].

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, an electron blocking 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, an electron blocking 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, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer using various polymer materials. 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, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

The light emitting material is a material capable of emitting light in the visible ray region by transporting 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 Benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, rubrene, and the like, but are 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, synthesis examples and device examples of preferred compounds are provided to help the understanding of the present invention. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereby.

Synthesis example 1: Synthesis of compound 2

(One) production example 1: Synthesis of compound 2

6-Bromo-2-phenyl-benzooxazole (10.0 g, 0.037 mol), Bis(4-biphenylyl)amine (17.6 g, 0.055 mol), NaOtBu (7.0 g, 0.073 mol), Pd(dba) ₂ (1.1 g, 0.002 mol), t-Bu ₃ P (0.7 g, 0.004 mol) was added with 120 mL of Toluene, and stirred at 70 °C for 4 hours to react. After completion of the reaction, 13.4 g (yield 71.4%) of <Compound 2> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=514 [(M) ⁺ ]

Synthesis example 2: Synthesis of compound 5

(One) production example 1: Synthesis of compound 5

6-Bromo-2-phenyl-benzooxazole (10.0 g, 0.037 mol), 2-(4-Biphenylyl)amino-9,9-dimethylfluorene (19.8 g, 0.056 mol), NaOtBu (10.5 g, 0.112 mol), Pd ( Toluene 120 mL was added to dba) ₂ (0.8 g, 1.48 mmol) and t-Bu ₃ P (0.6 g, 2.96 mmol), and the reaction was stirred at 70° C. for 4 hours. After completion of the reaction, 15.4 g (yield 76.1%) of <Compound 5> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=554 [(M) ⁺ ]

Synthesis example 3: Synthesis of compound 16

(One) production example 1: Synthesis of Intermediate 16-1

2-Bromo-9,9'-spirobi[9H-fluorene] (10.0 g, 0.025 mol), 2-Amino-9,9-dimethylfluorene (7.9 g, 0.038 mol), NaOtBu (4.9 g, 0.051 mol), Pd (dba) ₂ (0.7 g, 0.001 mol), t-Bu ₃ P (0.5 g, 0.003 mol) was added to 120 mL of Toluene, stirred at 80 ℃ for 4 hours to react. After completion of the reaction, 8.4 g (yield 63.4%) of <Intermediate 16-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 16-2

1-Bromo-2-iodobenzene (10.0 g, 0.035 mol), Intermediate 16-1 (27.8 g, 0.053 mol), NaOtBu (6.8 g, 0.071 mol), Pd(dba) ₂ (1.0 g, 0.002 mol), t 120 mL of Toluene was added to -Bu ₃ P (0.7 g, 0.004 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 14.2 g (yield 59.2%) of <Intermediate 16-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) production example 3: Synthesis of compound 16

(2-Phenylbenzo[d]oxazol-6-yl)boronic acid (10.0 g, 0.042 mol), Intermediate 16-2 (34.1 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), Pd(PPh) ₃ ) Toluene 200 mL, Ethanol 50 mL, and H ₂ O 50 mL were added to ₄ (1.0 g, 0.001 mol) and stirred at 80 °C for 6 hours to react. After completion of the reaction, 19.4 g (yield 58.5%) of <Compound 16> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=792 [(M) ⁺ ]

Synthesis example 4: Synthesis of compound 32

(One) production example 1: Synthesis of Intermediate 32-1

1-Bromo-4-iodobenzene (10.0 g, 0.035 mol), 2-(4-Biphenylyl)amino-9,9-dimethylfluorene (19.2 g, 0.053 mol), NaOtBu (10.2 g, 0.106 mol), Pd(dba) ₂ (0.8 g, 1.4 mmol), t-Bu ₃ P (0.6 g, 2.8 mmol) was added with 120 mL of Toluene, and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 12.7 g (yield 69.6%) of <Intermediate 32-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 32

(2-Phenylbenzo[d]oxazol-6-yl)boronic acid (10.0 g, 0.042 mol), Intermediate 32-1 (25.9 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), Pd(PPh) ₃ ) 200 mL of Toluene, 50 mL of Ethanol, and 50 mL of H ₂ O were added to ₄ (1.0 g, 0.84 mmol), and the reaction was stirred at 80 °C for 6 hours. After completion of the reaction, 19.2 g (yield 72.8%) of <Compound 32> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=630 [(M) ⁺ ]

Synthesis example 5: Synthesis of compound 44

(One) production example 1: Synthesis of intermediate 44-1

2'-Bromo-2-iodobiphenyl (10.0 g, 0.028 mol), Dinaphthylamine (11.3 g, 0.042 mol), NaOtBu (5.4 g, 0.056 mol), Pd(dba) ₂ (0.8 g, 0.001 mol), t-Bu Toluene 120 mL was added to ₃ P (0.6 g, 0.003 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 9.2 g (yield 66.0%) of <Intermediate 44-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 44

(2-Phenyl-1,3-benzoxazol-5-yl)boronic acid (10.0 g, 0.042 mol), Intermediate 44-1 (25.1 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), Pd 200 mL of Toluene, 50 mL of Ethanol, and 50 mL of H ₂ O were added to (PPh ₃ ) ₄ (1.0 g, 0.001 mol), and the reaction was stirred at 80 °C for 6 hours. After completion of the reaction, 16.4 g (yield 63.8%) of <Compound 44> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=614 [(M) ⁺ ]

Synthesis example 6: Synthesis of compound 82

(One) production example 1: Synthesis of Intermediate 82-1

1-Bromo-4-iodobenzene (10.0 g, 0.035 mol), N-[1,1'-Biphenyl]-2-yl-[1,1'-biphenyl]-2-amine (17.0 g, 0.053 mol), Toluene 120 mL was added to NaOtBu (6.8 g, 0.071 mol), Pd(dba) ₂ (1.0 g, 0.002 mol), and t-Bu ₃ P (0.7 g, 0.004 mol), and the reaction was stirred at 70 °C for 4 hours. . After completion of the reaction, 10.0 g (yield 59.4%) of <Intermediate 82-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 82-2

Intermediate 82-1 (10.0 g, 0.021 mol), Bis(pinacolato)diboron (6.4 g, 0.025 mol), KOAc (4.1 g, 0.042 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, 8.6 g (yield 78.3%) of <Intermediate 82-2> was obtained by extraction, concentration, and column.

(3) production example 3: Synthesis of intermediate 82-3

2-Bromo-1-chloronaphthalene (10.0 g, 0.041 mol), Intermediate 82-2 (26.0 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 stirred at 80 °C for 6 hours to react. After completion of the reaction, 17.2 g (yield 74.4%) of <Intermediate 82-3> was obtained by extraction and concentration, followed by column and recrystallization.

(4) production example 4: Synthesis of compound 82

(2-Phenylbenzo[d]oxazol-6-yl)boronic acid (10.0 g, 0.042 mol), Intermediate 82-3 (28.0 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), X-phos (2.0 g, 0.004 mol), Pd(OAc) ₂ (2.4 g, 0.002 mol) was added with 180 mL of THF and 45 mL of H ₂ O, followed by stirring at 80 °C for 6 hours. After completion of the reaction, 20.3 g (yield 67.7%) of <Compound 82> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=716 [(M) ⁺ ]

Synthesis example 7: Synthesis of compound 117

(One) production example 1: Synthesis of intermediate 117-1

1-Bromo-4-iodobenzene (10.0 g, 0.035 mol), N-[4-(4-Dibenzothienyl)phenyl]-4-aminebiphenyl (22.7 g, 0.053 mol), NaOtBu (6.8 g, 0.071 mol), Pd ( Toluene 120 mL was added to dba) ₂ (1.0 g, 0.002 mol), t-Bu ₃ P (0.7 g, 0.004 mol), and the reaction was stirred at 70° C. for 4 hours. After completion of the reaction, 13.1 g (yield 63.6%) of <Intermediate 117-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 117-2

Dioxane 200 in Intermediate 117-1 (10.0 g, 0.017 mol), Bis(pinacolato)diboron (5.2 g, 0.021 mol), KOAc (3.4 g, 0.034 mol), Pd(dppf)Cl ₂ (0.4 g, 0.001 mol) mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, 7.8 g (yield 72.2%) of <Intermediate 117-2> was obtained by extraction, concentration, and column.

(3) production example 3: Synthesis of intermediate 117-3

1-Bromo-3-chloronaphthalene (10.0 g, 0.041 mol), Intermediate 117-2 (31.3 g, 0.050 mol), K ₂ CO ₃ (17.2 g, 0.124 mol), Pd(PPh ₃ ) ₄ (1.0 g, 0.001) mol) was added 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, 20.8 g (yield 75.6%) of <Intermediate 117-3> was obtained by extraction and concentration, followed by column and recrystallization.

(4) production example 4: Synthesis of compound 117

(2-Phenyl-1,3-benzoxazol-5-yl)boronic acid (10.0 g, 0.042 mol), Intermediate 117-3 (33.4 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), X -phos (2.0 g, 0.004 mol), Pd(OAc) ₂ (2.4 g, 0.002 mol) was added with 180 mL of THF and 45 mL of H ₂ O, followed by stirring at 80 °C for 6 hours to react. After completion of the reaction, 22.8 g (yield 66.2%) of <Compound 117> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=822 [(M) ⁺ ]

Synthesis example 8: Synthesis of compound 132

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

1-Bromo-4-iodobenzene (10.0 g, 0.035 mol), Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)amine (25.8 g, 0.053 mol), NaOtBu (6.8 g, 0.071) mol), Pd(dba) ₂ (1.0 g, 0.002 mol), and t-Bu ₃ P (0.7 g, 0.004 mol) were added with 120 mL of Toluene and stirred at 70 °C for 4 hours to react. After completion of the reaction, 13.9 g (yield 61.4%) of <Intermediate 132-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 132-2

Intermediate 132-1 (10.0 g, 0.016 mol), Bis(pinacolato)diboron (4.8 g, 0.019 mol), KOAc (3.1 g, 0.031 mol), Pd(dppf)Cl ₂ (0.3 g, 0.001 mol) in Dioxane 200 mL and stirred at 100 °C for 12 hours to react. After completion of the reaction, 8.2 g (yield 76.4%) of <Intermediate 132-2> was obtained by extraction and concentration by column.

(3) production example 3: Synthesis of intermediate 132-3

1-Bromo-4-chloronaphthalene (10.0 g, 0.041 mol), intermediate 132-2 (34.2 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 stirred at 80 °C for 6 hours to react. After completion of the reaction, 22.3 g (yield 74.6%) of <Intermediate 132-3> was obtained by extraction and concentration, followed by column and recrystallization.

(4) production example 4: Synthesis of compound 132

(2-Phenylbenzo[d]oxazol-6-yl)boronic acid (10.0 g, 0.042 mol), Intermediate 132-3 (36.3 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), X-phos (2.0 g, 0.004 mol), Pd(OAc) ₂ (2.4 g, 0.002 mol) was added with 180 mL of THF and 45 mL of H ₂ O, followed by stirring at 80 °C for 6 hours. After completion of the reaction, 25.2 g (yield 68.4%) of <Compound 132> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=880 [(M) ⁺ ]

Synthesis example 9: Synthesis of compound 150

(One) production example 1: Synthesis of intermediate 150-1

1-Bromo-4-iodobenzene (10.0 g, 0.035 mol), 4-(2-Naphthyl)-N-[4-(2-naphthyl)phenyl]aniline (22.4 g, 0.053 mol), NaOtBu (6.8 g, 0.071) mol), Pd(dba) ₂ (1.0 g, 0.002 mol), and t-Bu ₃ P (0.7 g, 0.004 mol) were added with 120 mL of Toluene and stirred at 70 °C for 4 hours to react. After completion of the reaction, 11.7 g (yield 57.4%) of <Intermediate 150-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 150-2

Intermediate 150-1 (10.0 g, 0.017 mol), Bis(pinacolato)diboron (5.3 g, 0.021 mol), KOAc (3.4 g, 0.035 mol), Dioxane 200 in Pd(dppf)Cl ₂ (0.4 g, 0.001 mol) mL was added, and the reaction was stirred at 100 °C for 12 hours. After completion of the reaction, 7.8 g (yield 72.1%) of <Intermediate 150-2> was obtained by extraction, concentration, and column.

(3) production example 3: Synthesis of intermediate 150-3

9-Chlor-10-brom-phenanthren (10.0 g, 0.034 mol), intermediate 150-2 (25.7 g, 0.041 mol), K ₂ CO ₃ (14.2 g, 0.103 mol), Pd(PPh ₃ ) ₄ (0.8 g , 0.001 mol) was added 200 mL of Toluene, 50 mL of Ethanol, and 50 mL of H ₂ O, and stirred at 80 °C for 6 hours to react. After completion of the reaction, 18.9 g (yield 77.8%) of <Intermediate 150-3> was obtained by extraction and concentration, followed by column and recrystallization.

(4) production example 4: Synthesis of compound 150

(2-Phenylbenzo[d]oxazol-6-yl)boronic acid (10.0 g, 0.042 mol), Intermediate 150-3 (35.6 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), X-phos (2.0 g, 0.004 mol), Pd(OAc) ₂ (2.4 g, 0.002 mol) was added with 180 mL of THF and 45 mL of H ₂ O, followed by stirring at 80 °C for 6 hours. After completion of the reaction, 17.6 g (yield 48.5%) of <Compound 150> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=866[(M) ⁺ ]

Synthesis example 10: Synthesis of compound 173

(One) production example 1: Synthesis of intermediate 173-1

5-Bromo-7,7-dimethyl-7H-benzo[c]fluorene (10.0 g, 0.031 mol), 4-Aminobiphenyl (7.9 g, 0.046 mol), NaOtBu (6.0 g, 0.062 mol), Pd(dba) ₂ (0.9 g, 0.002 mol), 120 mL of Toluene was added to t-Bu ₃ P (0.6 g, 0.003 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 9.2 g (yield 72.3%) of <Intermediate 173-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 173-2

1-Bromo-3-iodobenzene (10.0 g, 0.035 mol), Intermediate 173-1 (21.8 g, 0.053 mol), NaOtBu (6.8 g, 0.071 mol), Pd(dba) ₂ (1.0 g, 0.002 mol), t 120 mL of Toluene was added to -Bu ₃ P (0.7 g, 0.004 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 12.7 g (yield 63.4%) of <Intermediate 173-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) production example 3: Synthesis of compound 173

(2-Phenyl-1,3-benzothiazol-6-yl)boronic acid (10.0 g, 0.039 mol), Intermediate 173-2 (26.7 g, 0.047 mol), K ₂ CO ₃ (16.3 g, 0.118 mol), Pd 200 mL of Toluene, 50 mL of Ethanol, and 50 mL of H ₂ O were added to (PPh ₃ ) ₄ (0.9 g, 0.001 mol), and the reaction was stirred at 80 °C for 6 hours. After completion of the reaction, extraction and concentration were performed, followed by column and recrystallization to obtain 20.3 g (yield 74.3%) of <Compound 173>.

LC/MS: m/z=696 [(M) ⁺ ]

Synthesis example 11: Synthesis of compound 211

(One) production example 1: Synthesis of intermediate 211-1

4-Bromodibenzofuran (10.0 g, 0.041 mol), 2-Amino-9,9-dimethylfluorene (12.7 g, 0.061 mol), NaOtBu (7.8 g, 0.081 mol), Pd(dba) ₂ (1.2 g, 0.002 mol), Toluene 120 mL was added to t-Bu ₃ P (0.8 g, 0.004 mol), and the reaction was stirred at 70° C. for 4 hours. After completion of the reaction, 11.0 g (yield 72.4%) of <Intermediate 211-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 211-2

Dibromo-p-terphenyl (10.0 g, 0.026 mol), intermediate 211-1 (14.5 g, 0.039 mol), NaOtBu (5.0 g, 0.052 mol), Pd(dba) ₂ (0.7 g, 0.001 mol), t-Bu Toluene 120 mL was added to ₃ P (0.5 g, 0.003 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 6.4 g (yield 36.4%) of <Intermediate 211-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) production example 3: Synthesis of compound 211

(2-Phenyl-1,3-benzothiazol-6-yl)boronic acid (10.0 g, 0.039 mol), Intermediate 211-2 (32.1 g, 0.047 mol), K ₂ CO ₃ (16.3 g, 0.118 mol), Pd 200 mL of Toluene, 50 mL of Ethanol, and 50 mL of H ₂ O were added to (PPh ₃ ) ₄ (0.9 g, 0.001 mol), and the reaction was stirred at 80 °C for 6 hours. After completion of the reaction, 25.7 g (yield 80.6%) of <Compound 211> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=812 [(M) ⁺ ]

Synthesis example 12: Synthesis of compound 226

(One) production example 1: Synthesis of Intermediate 226-1

4-Bromo-1-naphthonitrile (10.0 g, 0.043 mol), 4-Amino-1-naphthalenecarbonitrile (10.9 g, 0.065 mol), NaOtBu (8.3 g, 0.086 mol), Pd(dba) ₂ (1.2 g, 0.002 mol) ), t-Bu ₃ P (0.9 g, 0.004 mol) was added with 120 mL of toluene and stirred at 70 ° C for 4 hours to react. After completion of the reaction, 10.1 g (yield 73.4%) of <Intermediate 226-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 226-2

1-Bromo-4-iodobenzene (10.0 g, 0.035 mol), Intermediate 226-1 (16.9 g, 0.053 mol), NaO ^t Bu (6.8 g, 0.071 mol), Pd(dba) ₂ (1.0 g, 0.002 mol) , 120 mL of Toluene was added to t-Bu ₃ P (0.7 g, 0.004 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 10.7 g (yield 63.8%) of <Intermediate 226-2> was obtained by extraction, concentration, and column.

(3) production example 3: Synthesis of intermediate 226-3

Intermediate 226-2 (10.0 g, 0.021 mol), Bis(pinacolato)diboron (6.4 g, 0.025 mol), KOAc (4.1 g, 0.042 mol), Pd(dppf)Cl ₂ (0.5 g, 0.001 mol) in Dioxane 200 mL was added, and the reaction was stirred at 100 °C for 12 hours. After completion of the reaction, 8.1 g (yield 73.7%) of <Intermediate 226-3> was obtained by extraction, concentration, and column.

(4) production example 4: Synthesis of intermediate 226-4

2-Bromo-1-chloronaphthalene (10.0 g, 0.041 mol), Intermediate 226-3 (25.9 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 stirred at 80 °C for 6 hours to react. After completion of the reaction, 17.5 g (yield 76.0%) of <Intermediate 226-4> was obtained by extraction and concentration, followed by column and recrystallization.

(5) production example 5: Synthesis of compound 226

(2-Phenyl-1,3-benzothiazol-6-yl)boronic acid (10.0 g, 0.039 mol), Intermediate 226-4 (26.2 g, 0.047 mol), K ₂ CO ₃ (16.3 g, 0.118 mol), X -phos (1.9 g, 0.004 mol), Pd(OAc) ₂ (2.3 g, 0.002 mol), 180 mL of THF, 45 mL of H ₂ O were added, and the reaction was stirred at 80 °C for 6 hours. After completion of the reaction, 18.2 g (yield 63.5%) of <Compound 226> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=730 [(M) ⁺ ]

Synthesis example 13: Synthesis of compound 294

(One) production example 1: Synthesis of intermediate 294-1

1-Bromo-4-iodobenzene (10.0 g, 0.035 mol), N-[1,1'-Biphenyl]-4-yl-4-dibenzofuranamine (17.8 g, 0.053 mol), NaOtBu (6.8 g, 0.071 mol), Toluene 120 mL was added to Pd(dba) ₂ (1.0 g, 0.002 mol), t-Bu ₃ P (0.7 g, 0.004 mol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 10.5 g (yield 60.6%) of <Intermediate 294-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 294-2

Intermediate 294-1 (10.0 g, 0.020 mol), Bis(pinacolato)diboron (6.2 g, 0.025 mol), KOAc (4.0 g, 0.041 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, 8.2 g (yield 74.8%) of <Intermediate 294-2> was obtained by extraction, concentration, and column.

(3) production example 3: Synthesis of intermediate 294-3

9-Chlor-10-brom-phenanthren (10.0 g, 0.034 mol), Intermediate 294-2 (22.1 g, 0.041 mol), K ₂ CO ₃ (14.2 g, 0.103 mol), Pd(PPh ₃ ) ₄ (0.8 g , 0.001 mol) was added 200 mL of Toluene, 50 mL of Ethanol, and 50 mL of H ₂ O, and stirred at 80 °C for 6 hours to react. After completion of the reaction, 15.2 g (yield 71.2%) of <Intermediate 294-3> was obtained by extraction and concentration, followed by column and recrystallization.

(4) production example 4: Synthesis of compound 294

(2-Phenyl-1,3-benzothiazol-5-yl)boronic acid (10.0 g, 0.039 mol), Intermediate 294-3 (29.2 g, 0.047 mol), K ₂ CO ₃ (16.3 g, 0.118 mol), X -phos (1.9 g, 0.004 mol), Pd(OAc) ₂ (2.3 g, 0.002 mol), 180 mL of THF, 45 mL of H ₂ O were added, and the reaction was stirred at 80 °C for 6 hours. After completion of the reaction, 20.1 g (yield 64.3%) of <Compound 294> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=796 [(M) ⁺ ]

Synthesis example 14: Synthesis of compound 316

(One) production example 1: Synthesis of intermediate 316-1

1-Bromo-4-iodobenzene (10.0 g, 0.035 mol), Bis(9,9-dimethyl-9H-fluoren-2-yl)amine (21.3 g, 0.053 mol), NaOtBu (10.2 g, 0.106 mol), Pd (dba) ₂ (0.8 g, 1.4 mmol), t-Bu ₃ P (0.6 g, 2.8 mmol) was added with 120 mL of Toluene, and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 13.5 g (yield 68.6%) of <Intermediate 316-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 316

B-(2-Phenyl-7-benzoxazolyl)boronic acid (10.0 g, 0.042 mol), Intermediate 316-1 (27.9 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), Pd(PPh ₃ ) ₄ (1.0 g, 0.84 mmol) was added to 200 mL of Toluene, 50 mL of Ethanol, and 50 mL of H ₂ O, followed by stirring at 80 °C for 6 hours to react. After completion of the reaction, 20.5 g (yield 73.1%) of <Compound 316> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=670[(M) ⁺ ]

Synthesis example 15: Synthesis of compound 322

(One) production example 1: Synthesis of Intermediate 322-1

4-Bromo-2-phenylbenzo[d]oxazole (10.0 g, 0.037 mol), Bis(pinacolato)diboron (11.1 g, 0.044 mol), KOAc (10.7 g, 0.111 mol), Pd(dppf)Cl ₂ (1.3 g , 1.85 mmol) was added with 200 mL of Dioxane, and the reaction was stirred at 100 °C for 12 hours. After completion of the reaction, 8.8 g (yield 75.1%) of <Intermediate 322-1> was obtained by extraction, concentration, and column.

(2) production example 2: Synthesis of intermediate 322-2

1-Bromo-4-iodobenzene (10.0 g, 0.035 mol), N-Biphenyl-4-yl-3-dibenzofuranamine (17.8 g, 0.053 mol), NaOtBu (10.2 g, 0.106 mol), Pd(dba) ₂ (0.8 g, 1.4 mmol), t-Bu ₃ P (0.6 g, 2.8 mmol) was added with 120 mL of Toluene, and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 11.7 g (yield 67.5%) of <Intermediate 322-2> was obtained by extraction and concentration, followed by column and recrystallization.

(3) production example 3: Synthesis of compound 322

Intermediate 322-1 (10.0 g, 0.031 mol), Intermediate 322-2 (18.3 g, 0.037 mol), K ₂ CO ₃ (12.9 g, 0.093 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.62 mmol) Toluene 200 mL, Ethanol 50 mL, H ₂ O 50 mL were added, and the reaction was stirred at 80 °C for 6 hours. After completion of the reaction, 13.9 g (yield 73.8%) of <Compound 322> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=604 [(M) ⁺ ]

Synthesis example 16: Synthesis of compound 366

(One) production example 1: Synthesis of Intermediate 366-1

2-Bromo-6-iodonaphthalene (10.0 g, 0.030 mol), Bis(9,9-dimethyl-9H-fluoren-2-yl)amine (18.1 g, 0.045 mol), NaOtBu (8.7 g, 0.090 mol), Pd (dba) ₂ (0.7 g, 1.2 mmol), t-Bu ₃ P (0.5 g, 2.4 mmol) was added to 120 mL of Toluene, and stirred at 70 °C for 4 hours to react. After completion of the reaction, 12.6 g (yield 69.2%) of <Intermediate 366-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 366

B-(2-Phenyl-7-benzoxazolyl)boronic acid (10.0 g, 0.042 mol), Intermediate 366-1 (30.5 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), Pd(PPh ₃ ) ₄ (1.0 g, 0.84 mmol) was added to 200 mL of Toluene, 50 mL of Ethanol, and 50 mL of H ₂ O, followed by stirring at 80 °C for 6 hours to react. After completion of the reaction, 23.4 g (yield 77.6%) of <Compound 366> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=720[(M) ⁺ ]

Synthesis example 18: Synthesis of compound 351

(One) production example 1: Synthesis of intermediate 351-1

2-Bromo-6-iodonaphthalene (10.0 g, 0.030 mol), N-[1,1'-Biphenyl]-4yl-dibenzothiophene-3-amine (15.8 g, 0.045 mol), NaOtBu (8.7 g, 0.090 mol), Toluene 120 mL was added to Pd(dba) ₂ (0.7 g, 1.2 mmol) and t-Bu ₃ P (0.5 g, 2.4 mmol), and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 10.7 g (yield 64.0%) of <Intermediate 351-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 351

Intermediate 322-1 (10.0 g, 0.031 mol), Intermediate 351-1 (20.8 g, 0.037 mol), K ₂ CO ₃ (12.9 g, 0.093 mol), Pd(PPh ₃ ) ₄ (0.7 g, 0.62 mmol) Toluene 200 mL, Ethanol 50 mL, H ₂ O 50 mL were added, and the reaction was stirred at 80 °C for 6 hours. After completion of the reaction, 14.9 g (yield 71.3%) of <Compound 351> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=670[(M) ⁺ ]

Synthesis example 18: synthesis of compound 361

(One) production example 1: Synthesis of intermediate 361-1

4-Bromo-4'-iodobiphenyl (10.0 g, 0.028 mol), 2-(2-Biphenylyl)amino-9,9-dimethylfluorene (15.1 g, 0.042 mol), NaOtBu (8.0 g, 0.084 mol), Pd(dba ) ₂ (0.6 g, 1.12 mmol), t-Bu ₃ P (0.5 g, 2.24 mmol) was added with 120 mL of Toluene, and the reaction was stirred at 70 °C for 4 hours. After completion of the reaction, 11.0 g (yield 66.6%) of <Intermediate 361-1> was obtained by extraction and concentration, followed by column and recrystallization.

(2) production example 2: Synthesis of compound 361

B-(2-Phenyl-7-benzoxazolyl)boronic acid (10.0 g, 0.042 mol), Intermediate 361-1 (29.8 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), Pd(PPh ₃ ) ₄ (1.0 g, 0.84 mmol) was added to 200 mL of Toluene, 50 mL of Ethanol, and 50 mL of H ₂ O, followed by stirring at 80 °C for 6 hours to react. After completion of the reaction, 21.9 g (yield 74.1%) of <Compound 361> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=706 [(M) ⁺ ]

Synthesis example 20: Synthesis of compound 389

(One) production example 1: Synthesis of compound 389

(2-Phenylbenzo[d]oxazol-6-yl)boronic acid (10.0 g, 0.042 mol), Intermediate 366-1 (30.5 g, 0.050 mol), K ₂ CO ₃ (17.4 g, 0.126 mol), Pd(PPh) ₃ ) 200 mL of Toluene, 50 mL of Ethanol, and 50 mL of H ₂ O were added to ₄ (1.0 g, 0.84 mmol), and the reaction was stirred at 80 °C for 6 hours. After completion of the reaction, 23.5 g (yield 77.9%) of <Compound 389> was obtained by extraction and concentration, followed by column and recrystallization.

LC/MS: m/z=720[(M) ⁺ ]

device Example ( HTL )

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, the base pressure was set to 1 × 10 -6 torr, and the organic material and the metal were deposited on the ITO in the following structure.

device Example 1 to 60

The compound implemented according to the present invention was employed in the hole transport layer to fabricate an organic light emitting device having the following device structure, and then, 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 (100 nm) / electron blocking layer (EB1, 10 nm) / light emitting layer (20 nm) / electron transport layer (ET1:Liq, 30 nm) / LiF (1 nm) / Al (100 nm)

[HAT-CN] was formed on top of the ITO transparent electrode to a thickness of 5 nm to form a hole injection layer, and then the compound according to the present invention described in [Table 1] was formed at 100 nm to form a hole transport layer, [ EB1] to a thickness of 10 nm to form an electron blocking layer. Then, a light emitting layer was formed by co-deposition at 20 nm using [BH1] as a host compound and [BD1] as a dopant compound. After depositing an electron transport layer (50% doping of [ET1] compound Liq below) at 30 nm, LiF was added to 1 An electron injection layer was formed by forming a film to a thickness of nm. Then, Al was formed into a film to a thickness of 100 nm to manufacture an organic light emitting device.

device comparative example One

The organic light emitting device for Device Comparative Example 1 was manufactured in the same manner except that α-NPB was used as a hole hydrogen material in the device structure of Example 1.

Experimental example 1: element Example 1 to 60 luminescent properties

The driving voltage, current efficiency and color coordinates were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research) for the organic light emitting device manufactured according to the Examples and Comparative Examples, and 1,000 nits The standard result values are shown in [Table 1] below.

Example hole transport layer V cd/A CIEx CIEy One Formula 2 4.3 7.5 0.130 0.147 2 Formula 3 4.5 7.5 0.132 0.148 3 Formula 5 4.1 7.0 0.133 0.150 4 Formula 6 4.0 7.2 0.132 0.149 5 Formula 13 4.4 7.3 0.131 0.152 6 Formula 16 4.3 7.4 0.130 0.149 7 Formula 24 4.3 7.5 0.130 0.150 8 Formula 27 4.4 7.1 0.131 0.147 9 Formula 31 4.3 7.0 0.130 0.149 10 compound 32 4.2 7.3 0.132 0.141 11 Formula 33 4.1 7.3 0.133 0.150 12 Formula 41 4.2 7.2 0.134 0.149 13 Formula 44 4.3 7.0 0.131 0.150 14 Formula 55 4.5 7.4 0.133 0.150 15 chemical formula 57 4.2 7.2 0.130 0.151 16 Formula 61 4.5 7.1 0.131 0.149 17 Formula 70 4.3 7.1 0.133 0.151 18 Formula 78 4.2 7.6 0.133 0.147 19 Formula 79 4.4 7.5 0.133 0.148 20 Formula 82 4.4 7.3 0.132 0.151 21 Formula 84 4.1 7.5 0.134 0.150 22 Formula 86 4.4 7.1 0.131 0.147 23 Formula 90 4.3 7.6 0.133 0.148 24 Formula 91 4.3 7.2 0.134 0.153 25 Formula 95 4.0 7.4 0.132 0.147 26 Formula 100 4.3 7.3 0.132 0.148 27 Formula 117 4.1 7.6 0.132 0.148 28 Formula 127 4.2 7.1 0.132 0.154 29 Formula 132 4.0 7.2 0.131 0.150 30 Formula 140 4.2 7.4 0.132 0.146 31 Formula 150 4.1 7.7 0.134 0.145 32 Formula 173 4.0 7.2 0.134 0.147 33 Formula 181 4.0 7.1 0.133 0.148 34 Formula 196 4.4 7.3 0.132 0.150 35 Formula 206 4.1 7.7 0.132 0.152 36 Formula 211 4.4 7.4 0.132 0.147 37 Formula 216 4.3 7.3 0.133 0.148 38 Formula 226 4.3 7.1 0.134 0.150 39 Formula 227 4.2 7.8 0.131 0.147 40 Formula 243 4.2 7.2 0.132 0.148 41 Formula 256 4.4 7.2 0.132 0.150 42 Formula 262 4.3 7.4 0.133 0.150 43 Formula 294 4.3 7.2 0.132 0.149 44 Formula 302 4.1 7.1 0.132 0.149 45 compound 306 4.0 7.2 0.136 0.148 46 compound 307 4.2 7.1 0.136 0.147 47 compound 308 4.4 7.2 0.140 0.149 48 compound 316 4.1 7.5 0.138 0.150 49 compound 321 4.4 7.2 0.140 0.143 50 compound 326 4.1 7.4 0.134 0.144 51 compound 330 4.0 7.1 0.136 0.148 52 compound 334 4.3 7.8 0.134 0.150 53 compound 336 4.1 7.3 0.132 0.143 54 compound 339 4.1 7.2 0.137 0.141 55 compound 348 4.4 7.2 0.136 0.149 56 compound 370 4.2 7.1 0.132 0.145 57 compound 371 4.2 7.5 0.133 0.147 58 compound 376 4.2 7.1 0.136 0.142 59 compound 387 4.3 7.7 0.135 0.148 60 compound 389 4.1 7.7 0.132 0.149 Comparative Example 1 α-NPB 4.7 6.6 0.135 0.151

Looking at the results shown in [Table 1], in the case of the device employed in the hole transport layer of the compound organic light emitting device according to the present invention, low voltage driving compared to the device employing a compound widely used as a conventional hole transport material (Comparative Example 1) It can be seen that the luminous properties such as characteristics and luminous efficiency are remarkably excellent.

[HAT_CN] [α-NPB] [BH1] [BD1] [201]

[EBL1]

Claims (7)

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

In the [Formula I],
L ₁ To L ₃ Are the same as or different from each other, and each independently is a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted carbazolylene group , a substituted or unsubstituted C2 to C50 heteroarylene group, a substituted or unsubstituted C6 to C50 arylene group in which one or more substituted or unsubstituted C3 to C30 cycloalkyl is fused, and a substituted or unsubstituted It is selected from a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms in which at least one cycloalkyl having 3 to 30 carbon atoms is fused,
n, m and o are each an integer of 0 to 3, and when n, m and o are 2 or more, a plurality of L ₁ to L ₃ are the same or different from each other,
Ar ₁ to Ar ₂ are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 6 to C 30 An aryl group, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms in which one or more substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms is fused, and a substituted or unsubstituted It is selected from a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms in which one or more cyclic cycloalkyl having 3 to 30 carbon atoms is fused,
X is O or S;
R is selected from a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, and a substituted or unsubstituted C 2 to C 50 heteroaryl group. The method of claim 1,
In the definition of R, Ar ₁ to Ar ₂ and L ₁ to L ₃ , substituted or unsubstituted means that R, Ar ₁ to Ar ₂ and L ₁ to L ₃ are deuterium, cyano group, halogen group, hydroxyl group, nitro group, alkyl group, halogenated alkyl group, deuterated alkyl group, alkenyl group, alkynyl group, heteroalkyl group, aryl group, arylalkyl group, heteroaryl group, heteroarylalkyl group, cycloalkyl group, heterocycloalkyl group, alkoxy group, halogenated alkoxy group , is selected from the group consisting of a deuterated alkoxy group, an alkylamino group, an arylamino group, a heteroarylamino group, an alkylsilyl group, an arylsilyl group and an aryloxy group, and is substituted with one or more selected substituents, or two or more substituents among the substituents is substituted with a linked substituent, or an organic light emitting compound which means that it 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 [Formula 1] to [Formula 389]:

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,
At least one of the organic layers is an organic light emitting device comprising at least one organic light emitting compound implemented by [Formula I] according to claim 1. 5. The method of claim 4,
The organic layer includes at least one 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,
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 [Formula I] in the hole transport layer. 6. The method of claim 5,
An organic light emitting device comprising an organic light emitting compound represented by the [Formula I] in the electron blocking layer.