KR20190124620A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound represented by chemical formula 1, which is possible to drive the low voltage of a device when adopting a hole transporting material in an organic layer in an organic light emitting device, thereby having excellent power efficiency of the device, and is possible to implement an organic electroluminescent device having excellent luminous efficiency and service life properties at the same time.

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 as a hole injection material or a hole transporting material of an organic light emitting device and an organic light emitting device having a long life and light emission efficiency significantly improved by employing the same. It is about.

The organic light emitting diode can not only form a device on a transparent substrate, but also can drive a low voltage of 10 V or less, and consumes less power than a plasma display panel or an inorganic electroluminescent (EL) display. In addition, there is an advantage that the color is excellent, and three colors of green, blue, and red can be represented, which has recently attracted much attention as a next-generation display device.

However, in order for the organic electroluminescent device to exhibit such characteristics, a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., which constitute the organic layer in the device, are supported by a stable and efficient material. It should be preceded, but the development of a stable and efficient organic material layer for an organic light emitting device has not been made enough. Therefore, there is a continuing need for the development of new materials having low voltage driving, high efficiency and long life.

Particularly, conventional hole transport materials include copper phthalocyanine (CuPc), MTDATA, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB), N, N'-diphenyl- N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TPD) and the like are known, but when employed in a device, there is a problem in that efficiency and lifespan are reduced. In order to improve this, arylamine-based compounds having various substituents have been developed, but still have problems that are not sufficient to satisfy efficiency and long life.

Accordingly, the present invention provides an organic light emitting compound having excellent luminous efficiency and lifespan characteristics as compared to conventional hole transport materials.

In addition, by employing such an organic light emitting compound in the organic layer of the device to enable a lower voltage drive to provide an excellent organic light emitting device excellent in power efficiency and excellent luminous efficiency and lifetime characteristics.

The present invention, in order to solve the above problems, provides an organic light emitting compound represented by the following [Formula 1] and an organic electroluminescent device comprising the same.

[Formula 1]

Specific structures and substituents of the above [Formula 1] will be described later.

The organic light emitting compound according to the present invention is capable of realizing more improved luminous efficiency and longer life than the conventional hole transport compound, so that the organic light emitting device employing the organic light emitting compound can be usefully used in various display devices.

1 to 5 are cross-sectional views illustrating the structure of an organic light emitting display device according to an embodiment of the present invention.
6 is a representative view showing the structure of an organic light emitting compound according to the present invention.

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

The present invention is an organic light emitting compound represented by the following [Formula 1], when the organic layer in the organic light emitting device is employed as a hole transporting material when the low voltage drive of the device is capable of excellent power efficiency of the device, and at the same time luminous efficiency And it is possible to implement an organic light emitting device having excellent life characteristics.

[Formula 1]

In [Formula 1],

A is an arylene group having 6 to 20 carbon atoms, n is an integer of 1 to 2, when n is 2, two A may be the same or different from each other, according to a specific embodiment of the present invention, A may be a phenylene group or a naphthylene group, n may be 2, and two A's may be the same or different from each other.

R ₁ to R ₄ are the same as or different from each other, and each independently represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

Meanwhile, in the definition of R ₁ to R ₄ , substituted or unsubstituted means that R ₁ to R ₄ represent hydrogen, deuterium, cyano group, halogen group, nitro group, alkyl group having 1 to 10 carbon atoms, and cycloalkyl group having 3 to 20 carbon atoms. , An alkylsilyl group having 1 to 10 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an arylcycle having 6 to 30 carbon atoms Or an aryl group having 6 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms and a heteroaryl group having 2 to 30 carbon atoms, and is substituted with one or more selected substituents, or a substituent to which two or more substituents are connected. Substituted with, or having no substituent.

For example, a 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 tetrasenyl group, an anthracenyl group, etc. is substituted with another substituent. do.

Substituted heteroaryl groups include pyridyl groups, thiophenyl groups, triazine groups, quinoline groups, phenanthroline groups, imidazole groups, thiazole groups, oxazole groups, carbazole groups and their condensed heterocyclic groups such as benzquinoline groups and benz It means that the imidazole group, the benzoxazole group, the benzthiazole group, the benz carbazole group, the dibenzothiophenyl group, the dibenzofuran group, etc. are substituted by the other substituent.

In addition, when R ₁ to R ₄ are further substituted with one or more substituents, the one or more substituents may be bonded to each other or any one of adjacent substituents to form a saturated or unsaturated ring.

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

In the present invention, the alkyl group may be linear or branched chain, specific examples are 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 and the like, but are not limited thereto.

In the present invention, the aryl group may be monocyclic or polycyclic, and examples of the monocyclic aryl group include phenyl group, biphenyl group, terphenyl group, stilbene group, and the like, and examples of the polycyclic aryl group include naphthyl group and anthracenyl group. , Phenanthrenyl group, pyrenyl group, peryllenyl group, tetrasenyl group, chrysenyl group, fluorenyl group, acenaphthacenyl group, triphenylene group, fluoranthrene group, etc., but the scope of the present invention It is not limited only to these examples.

In the present invention, the heteroaryl group is a heterocyclic group containing O, N or S as a hetero atom, and examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group and oxa Diazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, acridil 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, isoxoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, etc. There is, but is not limited to these.

In the present invention, the aryl group in the aryloxy group, the arylthio group, and the arylamine group is the same as the examples of the aryl group described above.

In the present invention, the cycloalkyl group is not particularly limited, but specifically, cyclopropyl group cyclobutyl group cyclopentyl group 3-methylcyclopentyl group 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, etc., but are not limited thereto. Do not.

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

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, may be a polycyclic aryl group. The arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.

Specific examples of the arylamine group include phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 3-methyl-phenylamine group, 4-methyl-naphthylamine group, 2-methyl-biphenyl Amine groups, 9-methyl-anthracenylamine groups, diphenyl amine groups, phenyl naphthyl amine groups, ditolyl amine groups, phenyl tolyl amine groups, carbazole groups, and triphenyl amine groups, but are not limited thereto.

In the present invention, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group and the like. However, the present invention is not limited thereto.

The organic light emitting compound according to the present invention represented by the above [Formula 1] may be used as an organic material layer of the organic light emitting device due to its structural specificity, and more specifically may be used as a hole transport material in the organic material layer.

Preferred specific examples of the organic light emitting compound represented by [Formula 1] according to the present invention include the following compounds, but are not limited thereto.

By introducing various substituents into the core structure of the above structure, an organic light emitting compound having the intrinsic properties of the introduced substituents can be synthesized. For example, by introducing substituents used in the hole injection layer material, the hole transport layer material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic light emitting device, the material satisfying the conditions required for each organic material layer can be prepared. In particular, the compound of [Formula 1] according to the present invention can further improve the luminous efficiency and lifetime characteristics of the device when applied as a hole injection layer or a hole transport layer material.

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

An organic light emitting display device according to an embodiment of the present invention may have a structure including a first electrode and a second electrode, and an organic material layer disposed therebetween, and the organic light emitting compound according to the present invention is used for the organic material layer of the device. Can be manufactured using conventional methods and materials for the manufacture of devices.

The organic material layer of the organic light emitting device according to the present invention may be formed of a single layer structure, but may be formed of a multilayer structure in which two or more organic material 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. However, the present invention is not limited thereto, and may include fewer organic layers.

Therefore, in the organic light emitting device according to the present invention, the organic material layer may include at least one of a hole injection layer, a hole transport layer, and a layer for simultaneously injecting holes and transporting holes, wherein at least one of the layers is It may include a compound represented by [Formula 1].

For example, the structure of an organic electronic device according to the invention is illustrated in FIGS.

1 illustrates an organic light emitting diode in which an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and a cathode 7 are sequentially stacked on a substrate 1. The structure of is illustrated. In such a structure, the compound represented by [Formula 1] may be included in the hole injection layer 3, the hole transport layer 4, the light emitting layer 5 or the electron transport layer (6).

FIG. 2 illustrates a structure of an organic light emitting diode in which an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, and a cathode 7 are sequentially stacked on a substrate 1. . In such a structure, the compound represented by [Formula 1] may be included in the hole injection layer 3, the hole transport layer 4 or the electron transport layer (6).

3 illustrates a structure of an organic light emitting diode in which an anode 2, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and a cathode 7 are sequentially stacked on a substrate 1. In such a structure, the compound represented by [Formula 1] may be included in the hole transport layer 4, the light emitting layer 5 or the electron transport layer (6).

4 illustrates a structure of an organic light emitting display device in which an anode 2, a light emitting layer 5, an electron transport layer 6, and a cathode 7 are sequentially stacked on a substrate 1. In such a structure, the compound represented by [Formula 1] may be included in the light emitting layer 5 or the electron transport layer (6).

5 illustrates a structure of an organic light emitting diode in which an anode 2, a light emitting layer 5, and a cathode 7 are sequentially stacked on a substrate 1. In such a structure, the compound represented by [Formula 1] may be included in the light emitting layer (5).

According to a preferred embodiment of the present invention, the compound represented by [Formula 1] may be included in the hole injection layer 3 or the hole transport layer (4).

For example, the organic electroluminescent device according to the present invention is a metal oxide having a metal or conductivity on a substrate or a metal oxide on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation An alloy may be deposited to form an anode, and an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer may be formed thereon, and then deposited on the cathode.

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

As the cathode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material 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) 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 thereto.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof, and multilayers 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 the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

As a hole transporting material, a material capable of transporting holes from an anode or a hole injection layer to be transferred to a light emitting layer is a material having high mobility to holes. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is a material capable of emitting light in the visible 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 with respect to fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxyquinoline aluminum complex (Alq ₃ ), carbazole series compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazoles, benzthiazoles and Benzimidazole-based compounds, poly (p-phenylenevinylene) (PPV) -based polymers, spiro compounds, polyfluorenes, rubrene, and the like, but are not limited thereto.

As the electron transporting material, a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer is suitable. Specific examples include Al complexes of 8-hydroxyquinoline, complexes including Alq ₃ , organic radical compounds, hydroxyflavone-metal complexes, and the like, but are not limited thereto.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.

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

Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are intended to illustrate the invention, whereby the scope of the invention is not limited.

Synthesis Example  1: Synthesis of Compound 21

(One) Production Example  1: Synthesis of Intermediate 21-1

1-bromo-4-iodobenzene (10 g, 0.046 mol, sigma aldrich), naphthalen-1-ylboronic acid (7.3 g, 0.042 mol, sigma aldrich), potassium carbonate (14.66 g, 0.106 mol, sigma aldrich), Pd ( PPh ₃ ) ₄ (2.04 g, 0.0018 mol, sigma aldrich), THF 200 mL, H ₂ O 40 mL were added and reacted under reflux for 4 hours. After completion of the reaction, the layers were separated using H ₂ O: MC, and column purified (N-HEXANE: EA) to obtain 8 g (yield 80%) of <Intermediate 21-1>.

(2) Production Example  2: synthesis of intermediate 21-2

Intermediate 21-1 (10 g, 0.035 mol), 4-aminobiphenyl (6.57 g, 0.039 mol, sigma Aldrich), Sodium tert-butoxide (6.79 g, 0.071 mol, sigma aldrich), catalyst Pd (dba) ₂ (1.02 g , Toluene was added to 0.0017 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.71 g, 0.0035 mol, sigma aldrich) and stirred at 100 ° C. for 3 hours. After completion of the reaction, the mixture was separated into H ₂ O: MC and purified by column (N-HEXANE: EA) to obtain 10.2 g (yield 77.75%) of <intermediate 21-2>.

(3) Production Example  3: Synthesis of Intermediate 21-3

1,4-dibromonaphthalene (10 g, 0.035 mol, sigma aldrich), intermediate 21-2 (14.29 g, 0.039 mol), Sodium tert-butoxide (6.72 g, 0.070 mol, sigma aldrich), catalyst Pd (dba) ₂ ( 150 mL of Toluene was added to 1.01 g, 0.0017 mol, sigma aldrich), and tri-tert-Bu-phosphine (0.71 g, 0.0035 mol, sigma aldrich), followed by reaction at 100 ° C. for 3 hours. After completion of the reaction, the mixture was separated into H ₂ O: MC and purified by column (N-HEXANE: EA) to obtain 15.4 g (yield 76.4%) of <Intermediate 21-3>.

(4) Production Example  4: synthesis of intermediate 21-4

Intermediate 21-3 (10 g, 0.017 mol), Bis (pinacolato) dibron (5.73 g, 0.0225 mol, sigma aldrich), potassium acetate (3.40 g, 0.0347 mol, sigma aldrich), PdCl ₂ (dppf) (0.38 g, 0.0005 mol, sigma aldrich) and 200 mL of 1,4-Dioxane were added and reacted at 95 ° C. for 12 hours. After the completion of the reaction, H ₂ O was added and the layers were separated and column purified (N-HEXANE: MC) to obtain 8.3 g (yield 76.7%) of <Intermediate 21-4>.

(5) Production Example  5: Synthesis of Compound 21

Intermediate 21-3 (10 g, 0.017 mol), intermediate 21-4 (12.98 g, 0.021 mol), potassium carbonate (7.19 g, 0.052 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (1 g, 0.0009 mol, sigma aldrich), Tol 200 mL, EtOH, 40 mL, H ₂ O 20 mL was added and reacted by reflux stirring for 12 hours. After completion of the reaction, the mixture was purified by column separation using H ₂ O: MC, and purified by column to obtain 13.6 g (yield 78.9%) of compound 21.

H-NMR (200 MHz, CDCl 3): δ ppm, 2H (8.55 / d, 8.49 / d, 8.42 / d, 8.08 / d, 8.07 / d, 8.04 / d, 7.78 / d, 7.61 / m, 7.53 / m, 7.41 / m, 7.04 / d) 4H (7.55 / m, 7.52 / d, 7.51 / m) 8H (6.69 / d) 10H (7.54 / d)

LC / MS: m / z = 992 [(M + 1) ⁺ ]

Synthesis Example  2: Synthesis of Compound 31

(One) Production Example  1: Synthesis of Intermediate 31-1

2-bromonaphthalene (10 g, 0.048 mol, sigma aldrich), 4-aminobiphenyl (8.99 g, 0.053 mol, sigma aldrich), Sodium tert-butoxide (9.28 g, 0.0966 mol, sigma aldrich), catalyst Pd (dba) ₂ ( 150 mL of Toluene was added to 1.39 g, 0.0024 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.98 g, 0.0048 mol, sigma aldrich) and reacted at 100 ° C. for 3 hours. After completion of the reaction, the layer was separated into H ₂ O: MC and purified by column (N-HEXANE: EA) to obtain 11.2 g (yield 78.5%) of <intermediate 31-1>.

(2) Production Example  2: Synthesis of Intermediate 31-2

1,4-dibromonaphthalene (10 g, 0.035 mol, sigma aldrich), intermediate 31-2 (11.36 g, 0.039 mol), Sodium tert-butoxide (6.72 g, 0.070 mol, sigma aldrich), catalyst Pd (dba) ₂ ( 150 mL of Toluene was added to 1.01 g, 0.0017 mol, sigma aldrich), and tri-tert-Bu-phosphine (0.71 g, 0.0035 mol, sigma aldrich), followed by reaction at 100 ° C. for 3 hours. After completion of the reaction, the mixture was separated into H ₂ O: MC and purified by column (N-HEXANE: EA) to obtain 13.7 g (yield 78.3%) of <intermediate 31-2>.

(3) Production Example  3: Synthesis of Intermediate 31-3

Intermediate 31-2 (10 g, 0.020 mol), Bis (pinacolato) dibron (6.60 g, 0.026 mol, sigma aldrich), potassium acetate (3.92 g, 0.040 mol, sigma aldrich), PdCl ₂ (dppf) (0.44 g, 0.0006 mol, sigma aldrich) and 200 mL of 1,4-Dioxane were added and stirred at 95 ° C. for 12 hours. After completion of the reaction, H ₂ O was added and the layers were separated. Then, the column was purified (N-HEXANE: MC) to give 8.6 g (yield 78.6%) of <Intermediate 31-3>.

(4) Production Example  4: Synthesis of Compound 31

Intermediate 31-2 (10 g, 0.020 mol), intermediate 31-3 (13.13 g, 0.024 mol), potassium carbonate (8.29 g, 0.060 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (1.15 g, 0.0010 mol, sigma aldrich), Tol 200 mL, EtOH 40 mL, H ₂ O 20 mL was added and reacted under reflux for 12 hours. After completion of the reaction, layer separation was performed using H ₂ O: MC, and column purification to obtain 13.1 g (yield 78%) of compound 31.

H-NMR (200 MHz, CDCl 3): δ ppm, 2H (8.49 / d, 8.07 / d, 7.88 / d, 7.84 / d, 7.78 / d, 7.77 / d, 7.74 / d, 7.53 / m, 7.50 / m, 7.49 / d, 7.41 / m, 7.36 / m, 7.04 / d) 4H (7.52 / d, 7.51 / m, 6.69 / d) 6H (7.54 / m)

LC / MS: m / z = 840 [(M + 1) ⁺ ]

Synthesis Example  3: Synthesis of Compound 43

(One) Production Example  1: Synthesis of Intermediate 43-1

4-bromoaniline (10 g, 0.058 mol, sigma aldrich), 2-naphthylboronic acid (12 g, 0.070 mol, sigma aldrich), potassium carbonate (24.10 g, 0.174 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (3.36 g, 0.0029 mol, sigma aldrich), 200 mL of THF, and 40 mL of H ₂ O were added and reacted under reflux for 6 hours. After completion of the reaction, the layers were separated using H ₂ O: MC, and column purification (N-HEXANE: EA) gave 9.8 g (yield 76.9%) of <Intermediate 43-1>.

(2) Production Example  2: Synthesis of Intermediate 43-2

Intermediate 43-1 (10 g, 0.045 mol), 9-bromophenanthrene (11.73 g, 0.045 mol, sigma aldrich), Sodium tert-butoxide (8.77 g, 0.091 mol, sigma aldrich), catalyst Pd (dba) ₂ (1.31 g 150 mL of Toluene, 30 mL of EtOH and 15 mL of H ₂ O were added to 0.0023 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.92 g, 0.0046 mol, sigma aldrich), followed by stirring at 100 ° C. for 2 hours. I was. After completion of the reaction, the mixture was separated into H ₂ O: MC, and column purified (N-HEXANE: EA) to obtain 13.8 g (yield 76.5%) of <Intermediate 43-2>.

(3) Production Example  3: Synthesis of Intermediate 43-3

1,4-dibromonaphthalene (10 g, 0.035 mol, sigma aldrich), intermediate 43-2 (15.21 g, 0.039 mol), Sodium tert-butoxide (6.72 g, 0.070 mol, sigma aldrich), catalyst Pd (dba) ₂ ( 150 mL of Toluene was added to 1.01 g, 0.0017 mol, sigma aldrich), and tri-tert-Bu-phosphine (0.71 g, 0.0035 mol, sigma aldrich), followed by reaction at 100 ° C. for 3 hours. After completion of the reaction, the mixture was separated into H ₂ O: MC and purified by column (N-HEXANE: EA) to obtain 16.4 g (yield 78.1%) of <intermediate 43-3>.

(4) Production Example  4: Synthesis of Intermediate 43-4

Intermediate 43-3 (10 g, 0.0167 mol), Bis (pinacolato) dibron (5.50 g, 0.0216 mol, sigma aldrich), potassium acetate (3.27 g, 0.033 mol, sigma aldrich), PdCl ₂ (dppf) (0.37 g, 0.0005 mol, sigma aldrich) and 200 mL of 1,4-Dioxane were added and reacted at 95 ° C. for 12 hours. After completion of the reaction, H ₂ O was added and the layers were separated and column purified (N-HEXANE: MC) to obtain 8 g (yield 74.2%) of <Intermediate 43-4>.

(5) Production Example  5: Synthesis of Compound 43

Intermediate 43-3 (10 g, 0.015 mol), intermediate 43-4 (11.76 g, 0.018 mol), potassium carbonate (6.28 g, 0.045 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (0.87 g, 0.0008 mol, sigma aldrich), Tol 200 mL, EtOH 40 mL, H ₂ O 20 mL was added and reacted under reflux for 12 hours. After completion of the reaction, a layer was separated using H ₂ O: MC and column purified to obtain 12 g (yield 76.1%) of compound 43.

H-NMR (200 MHz, CDCl 3): δ ppm, 2H (8.49 / d, 8.07 / d, 7.92 / d, 7.78 / d, 7.73 / d, 7.58 / d, 7.53 / m, 7.04 / d, 6.91 / d) 4H (8.93 / d, 8.12 / d, 8.00 / d, 7.88 / m, 7.82 / m, 7.59 / m, 6.69 / d) 6H (7.54 / d)

LC / MS: m / z = 1040 [(M + 1) ⁺ ]

Synthesis Example  4: Synthesis of Compound 72

(One) Production Example  1: Synthesis of Intermediate 72-1

1,4-dibromonaphthalene (10 g, 0.035 mol, sigma aldrich), phenylboronic acid (5.12 g, 0.042 mol, sigma aldrich), potassium carbonate (14.5 g, 0.105 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (2.02 g, 0.0017 mol, sigma aldrich), 200 mL of THF, and 20 mL of H ₂ O were added and reacted under reflux for 4 hours. After completion of the reaction, H ₂ O: MC was subjected to layer separation and column purification to obtain 16.4 g of <Intermediate 72-1> (yield 78.1%).

(2) Preparation Example 2  Synthesis of Intermediate 72-2

Intermediate 72-1 (10 g, 0.035 mol), aniline (3.62 g, 0.039 mol, sigma aldrich), Sodium tert-butoxide (6.79 g, 0.071 mol, sigma aldrich), catalyst Pd (dba) ₂ (1.02 g, 0.0018 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.71 g, 0.0035 mol, sigma aldrich) were added 150 mL of Toluene and stirred at 100 ° C. for 2 hours. After completion of the reaction, H ₂ O: MC was separated into a layer and column purified to give 8.2 g (yield 78.9%) of <Intermediate 72-2>.

(3) Production Example  3: Synthesis of Intermediate 72-3

1,4-dibromonaphthalene (10 g, 0.035 mol, sigma aldrich), intermediate 72-2 (11.32 g, 0.038 mol), Sodium tert-butoxide (6.72 g, 0.07 mol, sigma aldrich), catalyst Pd (dba) 2 ( 150 mL of Toluene was added to 1.01 g, 0.0017 mol, sigma aldrich), and tri-tert-Bu-phosphine (0.71 g, 0.0035 mol, sigma aldrich), followed by reaction at 100 ° C. for 3 hours. After completion of the reaction, the mixture was separated into H ₂ O: MC, and column purified (N-HEXANE: EA) to obtain 13.8 g (yield 78.8%) of <Intermediate 72-3>.

(4) Production Example  4: synthesis of intermediate 72-4

1,4-dibromonaphthalene (10 g, 0.035 mol, sigma aldrich), diphenylamine (6.51 g, 0.039 mol, sigma aldrich), Sodium tert-butoxide (6.72 g, 0.070 mol, sigma aldrich), catalyst Pd (dba) ₂ ( Toluene 150 mL was added to 1.01 g, 0.0017 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.71 g, 0.0035 mol, sigma aldrich), and the mixture was stirred at 100 ° C. for 1 hour. After completion of the reaction, the mixture was separated into H ₂ O: MC, and column purified (N-HEXANE: EA) to obtain 10 g (yield 76.4%) of <Intermediate 72-4>.

(5) Production Example  5: synthesis of intermediate 72-5

Intermediate 72-4 (10 g, 0.0267 mol), Bis (pinacolato) dibron (8.82 g, 0.0347 mol, sigma aldrich), potassium acetate (5.24 g, 0.053 mol, sigma aldrich), PdCl ₂ (dppf) (0.59 g, 0.0008 mol, sigma aldrich) and 200 mL of 1,4-Dioxane were added and reacted at 95 ° C. for 12 hours. After completion of the reaction, H ₂ O was added and the layers were separated. Then, column purification (N-HEXANE: MC) was carried out to obtain 8.5 g (yield 75.5%) of <Intermediate 72-5>.

(6) Production Example  6: synthesis of compound 72

Intermediate 72-3 (10 g, 0.02 mol), intermediate 72-5 (10.10 g, 0.024 mol), potassium carbonate (8.29 g, 0.060 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (1.15 g, 0.001 mol, sigma aldrich), Tol 200 mL, EtOH 40 mL, H ₂ O 20 mL was added and reacted under reflux for 12 hours. After completion of the reaction, the layer was separated using H ₂ O: MC and purified by column to obtain 11 g (yield 77%) of compound 72.

H-NMR (200 MHz, CDCl 3): δ ppm, 1H (7.41 / m) 2H (7.79 / d, 7.51 / m) 3H (8.49 / d, 8.07 / d, 7.78 / d, 7.54 / m, 7.53 / m, 7.04 / d, 6.81 / m) 6H (7.20 / m, 6.63 /)

LC / MS: m / z = 1040 [(M + 1) ⁺ ]

Synthesis Example  5: Synthesis of Compound 137

(One) Production Example  1: Synthesis of Intermediate 137-1

4-bromobiphenyl (10 g, 0.043 mol, sigma aldrich), 4-aniline (4.49 g, 0.047 mol, sigma aldrich), Sodium tert-butoxide (8.25 g, 0.086 mol, sigma aldrich), catalyst Pd (dba) ₂ ( 150 mL of Toluene was added to 1.23 g, 0.0021 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.87 g, 0.0043 mol, sigma aldrich), followed by reaction at 100 ° C. for 1 hour. After completion of the reaction, the mixture was separated into H ₂ O: MC and purified by column (N-HEXANE: EA) to obtain 8.1 g (yield 77%) of <intermediate 137-1>.

(2) Production Example  2: Synthesis of Intermediate 137-2

1,4-dibromonaphthalene (10 g, 0.035 mol, sigma aldrich), intermediate 137-1 (9.44 g, 0.039 mol), Sodium tert-butoxide (6.72 g, 0.07 mol, sigma aldrich), catalyst Pd (dba) ₂ ( 150 mL of Toluene was added to 1.01 g, 0.0017 mol, sigma aldrich), and tri-tert-Bu-phosphine (0.71 g, 0.0035 mol, sigma aldrich), followed by reaction at 100 ° C. for 3 hours. After completion of the reaction, the mixture was separated into H ₂ O: MC, and column purified (N-HEXANE: EA) to obtain 12.1 g (Intermediate 137-2) (yield 76.8%).

(3) Production Example  3: Synthesis of Intermediate 137-3

Intermediate 137-2 (10 g, 0.022 mol), Bis (pinacolato) dibron (7.33 g, 0.029 mol, sigma aldrich), potassium acetate (4.36 g, 0.044 mol, sigma aldrich), PdCl ₂ (dppf) (0.49 g, 0.0007 mol, sigma aldrich) and 200 mL of 1,4-Dioxane were added and reacted at 95 ° C. for 12 hours. After completion of the reaction, H ₂ O was added and the layers were separated. Then, the column was purified (N-HEXANE: MC) to obtain 8 g (yield 72.4%) of <intermediate 137-3>.

(4) Production Example  4: Synthesis of Intermediate 137-4

1-bromodibenzofuran (10 g, 0.041 mol, Yurui), 4-bromobiphenyl (7.53 g, 0.045 mol, sigma aldrich), Sodium tert-butoxide (7.78 g, 0.081 mol, sigma aldrich), catalyst Pd (dba) ₂ (1.16 g, 0.002 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.82 g, 0.004 mol, sigma aldrich) were added 150 mL of Toluene and stirred at 100 ° C. for 3 hours. After completion of the reaction, the mixture was separated into H ₂ O: MC and purified by column (N-HEXANE: EA) to obtain 10.5 g (yield 77.6%) of <intermediate 137-3>.

(5) Production Example  5: Synthesis of Intermediate 137-5

1,4-dibromonaphthalene (10 g, 0.035 mol, sigma aldrich), intermediate 137-4 (12.86 g, 0.039 mol), Sodium tert-butoxide (6.72 g, 0.070 mol, sigma aldrich), catalyst Pd (dba) ₂ ( Toluene 150 mL was added to 1.01 g, 0.0017 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.71 g, 0.0035 mol, sigma aldrich), and the mixture was stirred at 100 ° C. for 1 hour. After completion of the reaction, the mixture was separated into H ₂ O: MC and purified by column (N-HEXANE: EA) to obtain 14.6 g (yield 77.2%) of <intermediate 137-5>.

(6) Production Example  6: Synthesis of Compound 137

Intermediate 137-5 (10 g, 0.019 mol), intermediate 137-3 (11.04 g, 0.022 mol), potassium carbonate (7.67 g, 0.056 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (1.07 g, 0.0009 mol, sigma aldrich), Tol 200 mL, EtOH 40 mL, H ₂ O 20 mL was added and reacted under reflux for 12 hours. After completion of the reaction, the layer was separated using H ₂ O: MC and purified by column to obtain 11.7 g (yield 76%) of compound 137.

H-NMR (200 MHz, CDCl 3): δ ppm, 1H (7.89 / d, 7.66 / d, 7.38 / m, 7.32 / m, 7.13 / m, 7.02 / d, 6.81 / m) 2H (8.49 / d, 8.07 / d , 7.78 / d, 7.53 / m, 7.41 / m, 7.20 / m, 7.04 / m) 3H (6.63 / d) 4H (7.52 / d, 7.51 / m, 6.69 / d) 6H (7.54 / m)

LC / MS: m / z = 830 [(M + 1) ⁺ ]

Synthesis Example  6: Synthesis of Compound 178

(One) Production Example  1: Synthesis of Intermediate 178-1

4-bromobiphenyl (10 g, 0.043 mol, sigma aldrich), 4-aminobiphenyl (8.71 g, 0.052 mol, sigma aldrich), Sodium tert-butoxide (8.25 g, 0.086 mol, sigma aldrich), catalyst Pd (dba) ₂ ( 150 mL of Toluene was added to 1.23 g, 0.0021 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.87 g, 0.0043 mol, sigma aldrich), followed by reaction at 100 ° C. for 1 hour. After completion of the reaction, the layer was separated into H ₂ O: MC and purified by column (N-HEXANE: EA) to obtain 11.1 g (yield 80.5%) of <intermediate 178-1>.

(2) Production Example  2: Synthesis of Intermediate 178-2

1,4-dibromonaphthalene (10 g, 0.035 mol, sigma aldrich), intermediate 178-1 (12.36 g, 0.039 mol), Sodium tert-butoxide (6.72 g, 0.070 mol, sigma aldrich), catalyst Pd (dba) ₂ ( Toluene 150 mL was added to 1.01 g, 0.0017 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.71 g, 0.0035 mol, sigma aldrich), and the mixture was stirred at 100 ° C. for 1 hour. After completion of the reaction, the mixture was H ₂ O: MC was separated and column purified to obtain 14 g (yield 76%) of <intermediate 178-2>.

(3) Production Example  3: Synthesis of Intermediate 178-3

Intermediate 178-2 (10 g, 0.022 mol), Bis (pinacolato) dibron (6.27 g, 0.025 mol, sigma aldrich), potassium acetate (3.73 g, 0.038 mol, sigma aldrich), PdCl ₂ (dppf) (0.42 g, 0.0006 mol, sigma aldrich) and 200 mL of 1,4-Dioxane were added and stirred at 95 ° C. for 12 hours. After completion of the reaction, H ₂ O was added and the layers were separated. Then, the column was purified (N-HEXANE: MC) to obtain 8 g (yield 73.8%) of <intermediate 178-3>.

(4) Production Example  4: Synthesis of Intermediate 178-4

9H-carbazole (10 g, 0.060 mol, sigma aldrich), 1-bromo-4-iodobenzene (20.3 g, 0.072 mol, sigma aldrich), potassium carbonate (20.66 g, 0.15 mol, sigma aldrich), Cu (7.60 g, Toluene 150 mL was added to 0.12 mol, sigma aldrich) and dibenzo-18-crwon-6 (2.16 g, 0.006 mol, sigma aldrich), and the mixture was stirred at 100 ° C. for 1 hour. After completion of the reaction, the mixture was H ₂ O: MC separated into layers and the column was purified to obtain 14.5 g (yield 75%) of <intermediate 178-4>.

(5) Production Example  5: synthesis of intermediate 178-5

Intermediate 178-4 (10 g, 0.031 mol), 4-aminobiphenyl (5.78 g, 0.034 mol, sigma aldrich), Sodium tert-butoxide (5.97 g, 0.062 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.89 g Toluene was added to 0.0016 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.63 g, 0.0031 mol, sigma aldrich) and stirred at 100 ° C. for 1 hour. After completion of the reaction, H ₂ O: MC was separated and the column was purified to obtain 10.2 g (yield 77%) of <Intermediate 178-5>.

(6) Production Example  6: synthesis of intermediate 178-6

1,4-dibromonaphthalene (10 g, 0.035 mol, sigma aldrich), intermediate 178-5 (16.41 g, 0.039 mol), Sodium tert-butoxide (6.72 g, 0.070 mol, sigma aldrich), catalyst Pd (dba) ₂ ( Toluene 150 mL was added to 1.01 g, 0.0017 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.71 g, 0.0035 mol, sigma aldrich), and the mixture was stirred at 100 ° C. for 1 hour. After completion of the reaction, H ₂ O: MC was separated and the column was purified to obtain 16.7 g (Intermediate 178-6) (yield 77.6%).

(7) Production Example  7: Synthesis of Compound 178

Intermediate 178-6 (10 g, 0.016 mol), intermediate 178-3 (11.18 g, 0.020 mol), potassium carbonate (6.74 g, 0.049 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (0.94 g, 0.0008 mol, sigma aldrich), Tol 200 mL, EtOH 40 mL, H ₂ O 20 mL was added and reacted under reflux for 12 hours. After completion of the reaction, the layer was separated using H ₂ O: MC and purified by column to obtain 12 g (yield 75.2%) of compound 178.

H-NMR (200 MHz, CDCl 3): δ ppm, 1H (8.55 / d, 8.12 / d, 7.94 / d, 7.63 / d, 7.50 / m, 7.33 / m, 7.29 / m, 7.25 / m) 2H (8.49 / d , 8.07 / d, 7.78 / d, 7.53 / m, 7.37 / d, 7.04 / d, 6.63 / d) 3H (7.41 / m) 6H (7.52 / d, 7.51 / m, 6.69 / d) 8H (7.54 / d )

LC / MS: m / z = 981 [(M + 1) ⁺ ]

Synthesis Example  7: Synthesis of Compound 227

(One) Production Example  1: Synthesis of Intermediate 227-1

1-bromo-4-methylbenzene (10 g, 0.059 mol, sigma aldrich), 4-aminobiphenyl (10.88 g, 0.064 mol, sigma aldrich), Sodium tert-butoxide (11.24 g, 0.117 mol, sigma aldrich), catalyst Pd ( dba) ₂ (1.68 g, 0.003 mol, sigma aldrich) and tri-tert-Bu-phosphine (1.18 g, 0.006 mol, sigma aldrich) were added 150 mL of Toluene and stirred at 100 ° C. for 3 hours. After the completion of the reaction, the mixture was extracted and purified by column to obtain 11.7 g (yield 77.1%) of <intermediate 227-1>.

(2) Production Example  2: Synthesis of Compound 227

4,4'-dibromobiphenyl (10 g, 0.032 mol, sigma aldrich), intermediate 227-1 (18.29 g, 0.071 mol), Sodium tert-butoxide (9.24 g, 0.096 mol, sigma aldrich), catalyst Pd (dba) ₂ 150 mL of Toluene was added to (0.92 g, 0.0016 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.65 g, 0.0032 mol, sigma aldrich), followed by reaction at 100 ° C. for 3 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 16.5 g (yield 76.9%) of compound 227.

H-NMR (200 MHz, CDCl 3): δ ppm, 2H (7.41 / m) 4H (7.52 / d, 7.51 / d, 6.98 / d, 6.51 / m) 6H (2.34 / s) 8H (7.54 / d, 6.69 / d )

LC / MS: m / z = 668 [(M + 1) ⁺ ]

Synthesis Example  8: compound 232 synthesis

(One) Production Example  1: Synthesis of Intermediate 232-1

4-bromoaniline (10 g, 0.058 mol, sigma aldrich), 2-naphthylboronic acid (12 g, 0.070 mol, sigma aldrich), potassium carbonate (24.10 g, 0.1740 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (3.36 g, 0.003 mol, sigma aldrich), Tol 200 mL, EtOH, 40 mL, H ₂ O 20 mL was added and reacted under reflux for 4 hours. After the completion of the reaction, the mixture was extracted and purified by column to obtain 9.8 g (yield 76.8%) of <intermediate 232-1>.

(2) Production Example  2: Synthesis of Intermediate 232-2

1-bromo-4-methylbenzene (10 g, 0.058 mol, sigma aldrich), intermediate 232-1 (14.1 g, 0.064 mol), Sodium tert-butoxide (16.86 g, 0.175 mol, sigma aldrich), catalyst Pd (dba) 150 mL of Toluene was added to ₂ (1.68 g, 0.0029 mol, sigma aldrich) and tri-tert-Bu-phosphine (1.18 g, 0.0058 mol, sigma aldrich) and reacted by stirring at 100 ° C. for 3 hours. After the completion of the reaction, the mixture was extracted and purified by column to obtain 14.2 g (yield 78.5%) of <intermediate 232-2>.

(3) Production Example  3: Synthesis of Compound 232

4,4'-dibromobiphenyl (10 g, 0.032 mol, sigma aldrich), intermediate 232-2 (21.82 g, 0.071 mol), Sodium tert-butoxide (9.24 g, 0.096 mol, sigma aldrich), catalyst Pd (dba) ₂ 150 mL of Toluene was added to (0.92 g, 0.0016 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.65 g, 0.0032 mol, sigma aldrich), followed by reaction at 100 ° C. for 5 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 19 g (yield 77.1%) of compound 232.

H-NMR (200 MHz, CDCl 3): δ ppm, 2H (7.92 / d, 7.73 / d, 7.58 / s) 4H (8.00 / d, 7.59 / m, 6.98 / d, 6.51 / d) 6H (2.32 / s) 8H (7.54 / d, 6.69 / d)

LC / MS: m / z = 768 [(M + 1) ⁺ ]

Synthesis Example  9: Synthesis of Compound 237

(One) Production Example  1: Synthesis of Intermediate 237-1

Bromobenzene (10 g, 0.064 mol, sigma aldrich), intermediate 232-1 (15.36 g, 0.070 mol), Sodium tert-butoxide (18.36 g, 0.019 mol, sigma aldrich), catalyst Pd (dba) ₂ (1.83 g, 0.0032 mol, sigma aldrich) and tri-tert-Bu-phosphine (1.29 g, 0.0064 mol, sigma aldrich) were added 150 mL of Toluene, 30 mL of EtOH, and 15 mL of H ₂ O, followed by stirring at 100 ° C. for 2 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 14.7 g (yield 78.1%) of <intermediate 237-1>.

(2) Production Example  2: Synthesis of Intermediate 237-2

2-bromobenzo [d] oxazole (10 g, 0.051 mol, Mascot.), 4-aminophenylboronic acid (8.30 g, 0.061 mol, Alfa.), Potassium carbonate (20.94 g, 0.152 mol, sigma aldrich), Pd (PPh ₃ ) ₄ (2.92 g, 0.003 mol, sigma aldrich), Tol 200 mL, EtOH 40 mL, H ₂ O 20 mL were added and reacted under reflux for 4 hours. After the completion of the reaction, the mixture was extracted and purified by column to obtain 8.2 g (yield 77.2%) of <intermediate 232-2>.

(3) Production Example  3: Synthesis of Intermediate 237-3

Bromobenzene (10 g, 0.064 mol, sigma aldrich), intermediate 237-2 (14.73 g, 0.070 mol), Sodium tert-butoxide (18.36 g, 0.191 mol, sigma aldrich), catalyst Pd (dba) ₂ (1.83 g, 0.003 150 mL of Toluene was added to mol, sigma aldrich) and tri-tert-Bu-phosphine (1.29 g, 0.006 mol, sigma aldrich) and reacted at 100 ° C. for 3 hours. After the completion of the reaction, the mixture was extracted and purified by column to obtain 14 g (yield 76.8%) of <intermediate 237-3>.

(4) Production Example  4: Synthesis of Intermediate 237-4

4,4'-dibromobiphenyl (10 g, 0.032 mol, sigma aldrich), intermediate 237-1 (10.41 g, 0.0356 mol), Sodium tert-butoxide (9.24 g, 0.096 mol, sigma aldrich), catalyst Pd (dba) ₂ 150 mL of Toluene was added to (0.92 g, 0.002 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.65 g, 0.003 mol, sigma aldrich) and reacted by stirring at 100 ° C. for 3 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 13 g (yield 77%) of <intermediate 237-3>.

(5) Production Example  5: Synthesis of Compound 237

Intermediate 237-4 (10 g, 0.019 mol), intermediate 237-3 (5.98 g, 0.021 mol), Sodium tert-butoxide (5.48 g, 0.057 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.55 g, 0.0009 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.38 g, 0.0019 mol, sigma aldrich) were added 150 mL of Toluene and stirred at 100 ° C. for 3 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 10.3 g (yield 74%) of compound 237.

H-NMR (200 MHz, CDCl 3): δ ppm, 1H (7.92 / d, 7.73 / d, 7.58 / s) 2H (8.00 / d, 7.74 / m, 7.59 / m, 7.39 / d, 6.81 / m) 4H (7.20 / m, 6.63 / d) 8H (7.54 / d, 6.69 / d)

LC / MS: m / z = 731 [(M + 1) ⁺ ]

Synthesis Example  10: compound 253 synthesis

(One) Production Example  1: Synthesis of Compound 253

1-bromo-4- (4-bromophenyl) naphthalene (10 g, 0.028 mol, TCI), intermediate 232-2 (18.8 g, 0.061 mol), Sodium tert-butoxide (10.62 g, 0.111 mol, sigma aldrich), catalyst 150 mL of Toluene was added to Pd (dba) ₂ (0.79 g, 0.0014 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.56 g, 0.0028 mol, sigma aldrich), followed by stirring at 100 ° C. for 3 hours. After completion of the reaction, the mixture was extracted and purified by column to obtain 16.5 g (yield 72.5%) of compound 253.

H-NMR (200 MHz, CDCl 3): δ ppm, 1H (8.49 / d, 8.07 / d, 7.78 / d, 7.53 / m, 7.04 / d) 2H (7.92 / d, 7.73 / d, 7.58 / s) 4H (8.00 / d, 7.59 / m, 6.98 / d, 6.51 / d) 6H (2.34 / s) 7H (7.54 / m)

LC / MS: m / z = 818 [(M + 1) ⁺ ]

Device Example

In an embodiment according to the present invention, the ITO transparent electrode is patterned on a glass substrate of 25 mm × 25 mm × 0.7 mm, using an ITO glass substrate with an ITO transparent electrode, so that the light emitting area is 2 mm × 2 mm in size. And then washed. The substrate was mounted in a vacuum chamber, and the base pressure was 1 × 10 ⁻⁶ torr. Then, the organic material and the metal were deposited on the ITO with the following structure.

Device Examples 1-16

Using the compound of Formula 1 according to the present invention as a compound of the hole transport layer, a blue light emitting organic light emitting device having a device structure as described below was manufactured, and light emission characteristics including light emission efficiency were measured.

ITO / hole injection layer (HAT_CN 5 nm) / hole transport layer (100 nm) / light emitting layer (20 nm) / electron transport layer (201: Liq 30 nm) / LiF (1 nm) / Al (100 nm)

In order to form a hole injection layer on an ITO transparent electrode, a HAT_CN compound was formed by a vacuum thermal deposition method at a thickness of 5 nm, and then the hole transport layer was formed by Chemical Formulas 1, 21, 31, 43, 54, 72, 96, 111, 137, 150, 164, 178, 227, 232, 237, and 253 were formed to a thickness of 100 nm. In the light emitting layer, [BH1] was used as the host compound, and [BD1] was used as the dopant compound, and the film was formed to have a thickness of about 20 nm. Further, an electron transport layer (doped 50% of the Liq [201] compound) was used. An organic light emitting device was manufactured by depositing 30 nm, 1 nm of LiF, and 100 nm of aluminum by vapor deposition.

Device comparison example 1

An organic light emitting display device according to Comparative Example 1 was manufactured in the same manner as in Example 1 to 12 except that α-NPB was used instead of the compound according to the present invention in the hole transport layer.

Experimental Example 1 Luminescence Characteristics of Device Examples 1 to 12

In the organic light emitting diode manufactured according to the above embodiment, voltage, current, and luminous efficiency were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research), and the current density was 10 mA / cm 2. The voltage to be defined as "drive voltage" was compared. The results are shown in the following [Table 1].

Example Hole transport material V cd / A QE (%) CIEx CIEy One One 4.18 7.26 6.84 0.145 0.155 2 21 4.09 7.38 6.95 0.144 0.155 3 31 4.20 7.32 6.88 0.145 0.154 4 43 4.19 7.18 6.73 0.143 0.154 5 54 4.22 7.09 6.65 0.144 0.155 6 72 4.17 6.97 6.53 0.145 0.155 7 96 4.12 7.30 6.85 0.145 0.155 8 111 4.10 7.12 6.68 0.144 0.155 9 137 4.13 7.04 6.64 0.145 0.154 10 150 4.23 6.88 6.49 0.146 0.155 11 164 4.21 7.17 6.73 0.145 0.154 12 178 4.17 7.20 6.76 0.145 0.155 13 227 4.15 7.24 6.83 0.144 0.154 14 232 4.12 7.31 6.88 0.144 0.154 15 237 4.19 7.20 6.76 0.144 0.154 16 253 4.16 7.26 6.84 0.145 0.155 Comparative Example 1 α-NPB 4.14 5.4 4.6 0.145 0.154

Looking at the results shown in [Table 1], first, in the case of the device employing the organic light emitting compound according to the present invention in the hole transport layer compared with the device (comparative example) employing the α-NPB compound widely employed in the hole transport layer It can be seen that the light emission characteristics such as light emission efficiency and quantum efficiency are remarkably excellent.

[HAT_CN]     [α-NPB] [BH1] [BD1] [201]

Claims (7)

An organic light emitting compound represented by the following [Formula 1]:
[Formula 1]

In [Formula 1],
A is an arylene group having 6 to 20 carbon atoms (n is an integer of 1 to 2, and when A is 2, two A's are the same or different from each other), and R ₁ to R ₄ are the same or different from each other, and each independently It is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms. The method of claim 1,
R ₁ to R ₄ may each be substituted with one or more substituents, and the one or more substituents may be hydrogen, deuterium, cyano group, halogen group, nitro group, alkyl group having 1 to 10 carbon atoms, or cycloalkyl group having 3 to 20 carbon atoms. , An alkylsilyl group having 1 to 10 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an arylcycle having 6 to 30 carbon atoms Organic light emitting compound, characterized in that it is selected from an aryl group having 6 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms and a heteroaryl group having 2 to 30 carbon atoms. The method of claim 2,
When the R ₁ to R ₄ is further substituted with one or more substituents, the one or more substituents are combined with any one of the adjacent or adjacent substituents to form a saturated or unsaturated ring. The method of claim 1,
Wherein A is a phenylene group or a naphthylene group, and n is 2 (wherein two A's are the same or different from each other). The method of claim 1,
[Formula 1] is an organic light emitting compound, characterized in that selected from Compound 1 to Compound 255:

An organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode.
At least one layer of the organic material layer is an organic light emitting device, characterized in that it comprises at least one organic light emitting compound implemented in [Formula 1] according to claim 1. The method of claim 6,
The organic material layer includes at least one layer of a hole injection layer, a hole transport layer and a layer for simultaneously injecting holes and transporting holes,
Organic light emitting device, characterized in that at least one of the layers comprises an organic light emitting compound represented by the above [Formula 1].

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