KR20180096458A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic electroluminescent compound represented by chemical formula I. When the organic electroluminescent compound is employed in a hole transporting layer, an electron blocking layer, a light emitting layer or the like, the compound exhibits excellent quantum efficiency and luminous efficiency, and can implement an organic electroluminescent device with remarkably superior lifetime characteristics.

Description

TECHNICAL FIELD The present invention relates to an organic electroluminescent compound and an electroluminescent device comprising the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic light emitting compound, and more particularly, to an organic light emitting compound which is employed in an organic compound layer in an organic electroluminescent device, and an organic electroluminescent compound having excellent luminous efficiency and quantum efficiency, .

The organic electroluminescent device can not only form an element on a transparent substrate but also can operate at a low voltage of 10 V or less as compared with a plasma display panel (Plasma Display Panel) or an inorganic electroluminescence (EL) display, It has the advantage of excellent color and has three colors of green, blue, and red. It has recently become a subject of interest as a next generation display device.

However, in order for such an organic electroluminescent device to exhibit such characteristics, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material, which are materials forming an organic layer in a device, However, until now, stable and efficient development of an organic material layer material for an organic electroluminescence device has not been sufficiently achieved. Therefore, development of a new material capable of improving luminescence characteristics and development of an organic layer structure in a device are continuously required.

Accordingly, the present invention relates to a novel organic luminescent compound which can be employed as a host compound of an electron blocking layer, a hole transporting layer or a luminescent layer in an organic electroluminescent device to improve luminescent efficiency and quantum efficiency, To provide an organic electroluminescent device.

In order to solve the above problems, the present invention provides an organic electroluminescent compound represented by the following formula (I) and an organic electroluminescent device comprising the same.

(I)

The specific structure and substituent of the above-mentioned formula (I) will be described later.

The organic electroluminescent device employing the organic electroluminescent compound according to the present invention in the electron blocking layer, the hole transporting layer, or the light emitting layer can realize excellent luminescent efficiency and significantly improved lifetime characteristics as compared with the conventional device, and thus can be usefully used in various display devices.

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

The present invention relates to an organic luminescent compound represented by the following formula (I), which is excellent in quantum efficiency and luminous efficiency when used in an organic layer such as a hole transport layer, an electron blocking layer and a luminescent layer in an organic electroluminescent device, It is possible to realize a significantly improved organic electroluminescent device.

(I)

In the above formula (I)

Ar ₁ is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and n and m are each an integer of 0 to 3 And when n is 2, a plurality of L ₁ and L ₂ may be the same or different from each other.

o is an integer of 1 to 3;

Ra and Rb are the same or different and each independently represents a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, or a cycloalkyl having 3 to 30 carbon atoms, A substituted or unsubstituted C2 to C50 heteroaryl group in which one or more substituted or unsubstituted aryl groups having 5 to 50 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms are fused together.

The Ra and Rb may be connected to each other or adjacent substituents to form a single ring or polycyclic ring of an alicyclic or aromatic group, and the carbon atom of the formed alicyclic or aromatic single ring or polycyclic ring may be N, S, Lt; / RTI > may be substituted with any one or more heteroatoms selected from < RTI ID = 0.0 >

According to a specific embodiment of the present invention, at least one of Ra and Rb may be a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms.

According to a specific embodiment of the present invention, at least one of Ra and Rb may be any one selected from the following Structural Formula (1).

[Structural formula 1]

In the above structural formula 1, X ₁ , X ₂ and Y are the same or different from each other and each independently represents a single bond or CR ₁₇ R ₁₈ , NR ₁₉ , O and S;

R ₁ to R ₁₉ each independently represent a hydrogen atom, a deuterium atom, an amino group, a cyano group, a hydroxy group, a nitro group, a halogen group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms , A substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having at least one heteroatom selected from O, N and S, and a substituted or unsubstituted silyl group, and at least one of R ₁ to R ₁₉ One of R ₁ to R ₁₉ and its substituent group together with the substituents adjacent to each other may form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero.

According to a specific embodiment of the present invention, X ₁ in the above formula [1] may be O.

In the definition of Ra, Rb, L ₁ , L ₂ , Ar ₁ and R ₁ to R ₁₉ , the substitution or unsubstitution means that Ra, Rb, L ₁ , L ₂ , Ar ₁ and R ₁ to R ₁₉ are deuterium , A halogen atom, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, An alkyl 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, an alkoxy group having 24 carbon atoms, An alkylamino group, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 1 to 24 carbon atoms, and an aryloxy group having 1 to 24 carbon atoms Selected 1 or 2, , Or two or more of the substituents in the substituents are substituted with a substituent to which they are linked, or have no substituent.

Specific examples of the substituted aryl group include a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group and an anthracenyl group 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 condensed heterocyclic groups thereof such as a benzquinoline group, An imidazole group, a benzoxazole group, a benzothiazole group, a benzoxazole group, a dibenzothiophenyl group, a dibenzofurane group and the like are substituted with other substituents.

In the present invention, examples of the substituents will be specifically described 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, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, Ethyl, propyl, isopropyl, n-butyl, isobutyl, isobutyl, isobutyl, A tert-butyl group, a tert-butyl group, a 2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl group, 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 are not limited thereto.

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 Can be further substituted.

Specific examples of the silyl group used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylpurylsilyl 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, , A chlorenyl group, a fluorenyl group, an acenaphthacenyl group, a triphenylene group, and a fluororanthrene group, but the scope of the present invention is not limited to these examples.

More specifically, at least one hydrogen atom of the aryl group may be substituted with at least one substituent selected from the group consisting of a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH (R), -N (R ') (R "), R' and R" are independently an alkyl group having 1 to 10 carbon atoms and in this case, an "alkylamino group" An alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, an alkyl group having 1 to 24 carbon atoms 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, and 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, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2-yl group, But are not limited to, - (naphthyl-1-yl) vinyl-1-yl group, 2,2-bis (diphenyl-1-yl) vinyl-1-yl group, stilbenyl group, styrenyl group and the like.

In the present invention, the heteroaryl group is a hetero ring group containing O, N or S as a heteroatom, and the number of carbon atoms is not particularly limited, but preferably 2 to 30 carbon atoms. Examples thereof include a thiophene group, a furan group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, , A pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyranyl group, a pyrazinopyranyl group, an isoquinoline group, , A carbazole group, a benzoxazole group, a benzoimidazole group, a benzothiazole group, a benzocarbazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a dibenzofuranyl group, a phenanthroline group, An oxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and the like, but are not limited thereto.

In the present invention, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically includes cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, Methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclo An octyl group, and the like, but are not limited thereto.

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

,

등이 있다.In the present invention, a fluorenyl group is a structure in which two cyclic organic compounds are connected via one atom,

,

.

,

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

,

.

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

The organic luminescent compound according to the present invention represented by the above formula (I) can be used as an organic material layer of an organic light emitting diode due to its structural specificity. More specifically, depending on the characteristics of various substituents to be introduced, Layer or a host compound of the light emitting layer.

Preferred examples of the compound represented by the formula (I) according to the present invention include, but are not limited to, the following compounds.

An organic luminescent compound having the intrinsic characteristics of the substituent introduced by introducing various substituents into the core structure having the above structure can be synthesized. For example, by introducing a substituent used in a hole injecting layer material, a hole transporting layer material, a light emitting layer material, an electron transporting layer material and an electron blocking layer material used in manufacturing an organic electroluminescent device into the above structure, In particular, when the compound of formula (I) according to the present invention is employed as a host material for a hole transport layer, an electron blocking layer and a light emitting layer, the luminous efficiency and quantum efficiency characteristics of the device can be further improved.

The organic luminescent compound according to the present invention can be applied to an organic electroluminescent device according to a conventional production method.

The organic electroluminescent device according to one embodiment of the present invention may have a structure including a first electrode, a second electrode and an organic material layer disposed therebetween, and the organic electroluminescent compound according to the present invention may be used for an organic material layer And can be manufactured using conventional device manufacturing methods and materials.

The organic material layer of the organic electroluminescent device according to the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and an electron blocking layer. However, it is not so limited and may include fewer or greater numbers of organic layers.

Therefore, in the organic electroluminescent device according to the present invention, the organic material layer may include at least one of a hole transporting layer, an electron blocking layer and a light emitting layer, and at least one of the layers may be an organic light emitting ≪ / RTI > compounds.

The organic light emitting device according to the present invention may be formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation A hole transporting layer, an electron blocking layer, a light emitting layer, and an electron transporting layer on the anode, and then depositing a material usable as a cathode thereon.

In addition to such a method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate. The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, and an electron transport layer, but may have a single layer structure. In addition, the organic material layer may be formed using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.

As the anode material, a material having a large work function is preferably used so as to smoothly inject holes into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof, zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO) metal oxides, ZnO: Al or SnO _2: a combination of a metal and an oxide such as 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.

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

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline and a polythiophene-based conductive polymer, but are not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high mobility to holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having a high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazol-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole, benzthiazole and A benzimidazole-based compound, a poly (p-phenylene vinylene) (PPV) -based polymer, a spiro compound, polyfluorene, rubrene, and the like.

As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is highly mobile, is suitable. Specific examples thereof include, but are not limited to, an Al complex of 8-hydroxyquinoline, a complex containing Alq ₃ , an organic radical compound, and a hydroxyflavone-metal complex.

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

Also, the organic luminescent compound according to the present invention can act on a principle similar to that applied to an organic luminescent device in an organic electronic device including an organic solar cell, an organophotoreceptor, an organic transistor and the like.

Hereinafter, synthesis examples and device embodiments of preferred compounds are shown to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

Synthetic example  1: Synthesis of compound 1

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

2-bromophenylboronic acid (59.6 g, 0.297 mol, Sigma aldrich), potassium carbonate (90.4 g, 0.94 mol, Sigma aldrich), catalyst Pd (PPh ₃ ) ₄ (17.16 g, 0.015 mol, Sigma aldrich) were added 400 mL of THF and 80 mL of water, and the mixture was reacted at 60 ° C for 12 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC and then subjected to column purification (N-HEXANE: EA) to obtain 66.7 g (yield: 96%) of Intermediate 1-1.

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

200 mg of intermediate 1-1 (28 g, 0.1 mol), triphenylphosphine (79.2 g, 0.302 mol, sigma aldrich) and 1,2-dichlorobenzene were added and reacted at 180 ° C for 12 hours with stirring. After completion of the reaction, the reaction mixture was subjected to column separation with H ₂ O: MC and then subjected to column purification (N-HEXANE) to obtain 20 g (yield 80%) of Intermediate 1-2.

(3) Manufacturing example  3: Synthesis of intermediate 1-3

Iodobenzene (41.4 g, 0.203 mol, Sigma Aldrich), potassium carbonate (33.69 g, 0.244 mol, SigmaAldrich), Cu (10.33 g, 0.162 mol, Sigma Aldrich), dibenzo -18-crown-6 (2.93 g, 0.008 mol, Sigma Aldrich) and 150 mL of dimethylformamide, and the mixture was reacted at 150 ° C for 12 hours. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC and then subjected to column purification (N-HEXANE) to obtain 24 g (yield 93%) of <Intermediate 1-3>.

(4) Manufacturing example  4: Synthesis of intermediate 1-4

(34.86 g, 0.137 mol, Sigma Aldrich), potassium acetate (33.68 g, 0.343 mol, Sigma Aldrich), PdCl ₂ (dppf) (2.488 g, 0.0034 mol, Sigma aldrich) and 1,4-dioxane (400 mL), and the mixture was reacted at 95 ° C for 12 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: toluene and then subjected to column purification (N-HEXANE: MC) to obtain 19 g (yield: 40%) of <Intermediate 1-4>.

(5) Manufacturing example  5: Synthesis of intermediate 1-5

Intermediate 1-4 (17 g, 0.046 mol) , 1-boromo-4-iodobenzene (15.68 g, 0.055 mol, sigma aldrich), sodium hydroxide (5.54 g, 0.138 mol, sigma aldrich), Pd (PPh 3) 4 ( 3.26 g, 0.0028 mol, sigma aldrich), 200 mL of THF and 60 mL of water, and the mixture was reacted at 60 DEG C for 12 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and purified by column (N-HEXANE: MC) to obtain 16.9 g (yield 92%) of Intermediate 1-5.

(6) Manufacturing example  6: Synthesis of intermediate 1-6

4,6-dibromodibenzofuran (20 g, 0.061 mol, Yurui), phenylboronic acid (8.98 g, 0.074 mol, sigma aldrich), potassium carbonate (16.96 g, 0.123 mol, sigma aldrich), Pd (PPh 3) 4 (3.54 g , 0.0031 mol, Sigma aldrich), 250 mL of THF and 50 mL of H ₂ O were added, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 14.3 g (yield 72%) of Intermediate 1-6.

(7) Manufacturing example  7: Synthesis of intermediate 1-7

(14.8 g, 0.087 mol, Sigma Aldrich), PdCl ₂ (dppf) (0.95 g, 0.043 mol), bis (pinacolato) dibron (14.3 g, 0.0013 mol, sigma aldrich) and 1,4-dioxane (200 mL), and the mixture was reacted at 95 ° C for 12 hours with stirring. After completion of the reaction, the reaction mixture was poured into H ₂ O, layer separation was performed, and column purification (N-HEXANE: MC) was conducted to obtain 11.3 g (yield 70.5%) of <Intermediate 1-7>.

(8) Manufacturing example  8: Synthesis of intermediate 1-8

(15.71 g, 0.042 mol, Sigma aldrich), potassium carbonate (9.77 g, 0.071 mol, Sigma aldrich), Pd (PPh ₃ ), 1-bromo-4-iodobenzene ) ₄ (2.04 g, 0.0018 mol, sigma aldrich), 250 mL of THF and 50 mL of H ₂ O were added, and the mixture was stirred under reflux for 12 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 11.6 g (yield 82%) of Intermediate 1-8.

(9) Manufacturing example  9: Synthesis of intermediate 1-9

Sodium tert-butoxide (4.81 g, 0.050 mol, Sigma aldrich), Catalyst Pd (dba) ₂ (0.72 g, 0.03 mol) were added to a solution of intermediate 1-8 (10 g, 0.025 mol), 2-aminobiphenyl , 0.0013 mol, Sigma aldrich) and tri-tert-Bu-phosphine (0.51 g, 0.0025 mol, Sigma aldrich) were added and reacted at 100 ° C for 8 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC and purified by column (N-HEXANE: MC) to obtain 9.8 g (yield 80%) of Intermediate 1-9.

(10) Manufacturing example  10: Synthesis of compound 1

Intermediate 1-5 (5 g, 0.0126 mol), intermediate 1-9 (7.35 g, 0.015 mol), sodium tert-butoxide (2.41 g, 0.025 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.36 g, 0.0006 100 mL of Toluene was added to tri-tert-Bu-phosphine (0.25 g, 0.0013 mol, Sigma aldrich) and reacted at 100 ° C for 8 hours. After completion of the reaction, the mixture was subjected to column separation with H ₂ O: MC and then subjected to column purification (N-HEXANE: EA) to obtain 13.2 g (yield 74.4%) of Compound 1.

M, 7.36 / m, 7.25 / m, 7.16 / m, 7.75 / d, 7.95 / 7.58 / d, 7.58 / d, 7.50 / d, 7.41 / m, 7.38 / m, 7.08 / d) 6.69 / d)

LC / MS: m / z = 804 [(M + 1) ^&lt; ^{+ &}

Synthetic example  2: Synthesis of Compound 3

(One) Manufacturing example  1: Synthesis of intermediate 3-1

Sodium tert-butoxide (4.81 g, 0.050 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.72 g, 0.03 mol) was added to a solution of intermediate 1-8 (10 g, 0.025 mol), 4-aminobiphenyl , 0.0013 mol, Sigma aldrich) and tri-tert-Bu-phosphine (0.51 g, 0.0025 mol, Sigma aldrich) were added and reacted at 100 ° C for 8 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC, followed by column purification (N-HEXANE: MC) to obtain 9.8 g (yield 80%) of Intermediate 3-1.

(2) Manufacturing example  2: Synthesis of Compound 3

Intermediate 1-5 (5 g, 0.0126 mol), Intermediate 3-1 (7.35 g, 0.015 mol), Sodium tert-butoxide (2.41 g, 0.025 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.36 g, 100 mL of Toluene was added to tri-tert-Bu-phosphine (0.25 g, 0.0013 mol, Sigma aldrich) and reacted at 100 ° C for 8 hours. After completion of the reaction, the mixture was subjected to column separation with H ₂ O: MC and then subjected to column purification (N-HEXANE: EA) to obtain 13.2 g (yield: 74.4%) of Compound 3.

7.85 / d, 7.49 / d, 7.45 / m, 7.43 / m, 7.33 / m, 7.25 / m) 2H (7.85 / d, 7.81 / d, 7.58 / m, 7.50 / d, 7.41 / m, 7.38 /

LC / MS: m / z = 804 [(M + 1) ^&lt; ^{+ &}

Synthetic example  3: Synthesis of Compound 6

(One) Manufacturing example  1: Synthesis of intermediate 6-1

4-bromoaniline (10 g, 0.058 mol, sigma aldrich), 2-Biphenylboronic acid (13.81 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), 250 mL of THF and 50 mL of H ₂ O, and the mixture was stirred under reflux for 12 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 11.4 g (yield 80%) of Intermediate 16-1.

(2) Manufacturing example  2: Synthesis of intermediate 6-2

Intermediate 1-8 (10 g, 0.025 mol) , intermediate 6-1 (7.37 g, 0.03 mol) , Sodium tert-butoxide (4.81 g, 0.050 mol, sigma aldrich), catalyst _{Pd (dba) 2 (0.72 g} , 0.0013 150 mL of toluene was added to tri-tert-Bu-phosphine (0.51 g, 0.0025 mol, Sigma aldrich) and stirred at 100 ° C for 8 hours. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC, and column purification (N-HEXANE: MC) was conducted to obtain 11 g (yield 78%) of <Intermediate 6-2>.

(3) Manufacturing example  3: Synthesis of Compound 6

Intermediate 1-5 (5 g, 0.0126 mol), intermediate 6-2 (8.49 g, 0.015 mol), sodium tert-butoxide (2.41 g, 0.025 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.36 g, 0.0006 100 mL of Toluene was added to tri-tert-Bu-phosphine (0.25 g, 0.0013 mol, Sigma aldrich) and reacted at 100 ° C for 8 hours. After completion of the reaction, the reaction mixture was subjected to column separation with H ₂ O: MC, followed by column purification (N-HEXANE: EA) to obtain 8.6 g (yield: 77.8%) of Compound 6.

D, 7.58 / d, 7.45 / m, 7.43 / m, 7.33 / m, 7.25 / m) 2H (7.81 / d, 7.58 / m, 7.52 / d, 7.50 / d, 7.47 / m, 7.41 / m, 7.38 / m) 3H 7.85 / d, 7.51 /

LC / MS: m / z = 880 [(M + 1) ^&lt; ^{+ &}

Synthetic example  4: Synthesis of compound 18

(One) Manufacturing example  1: Synthesis of intermediate 18-1

Phenylboronic acid (4.28 g, 0.035 mol, Sigma Aldrich), potassium carbonate (12.12 g, 0.088 mol, Sigma Aldrich), Pd (PPh 3), 4,6-dibromodibenzo [b, d] thiophene ₃ ) ₄ (1.69 g, 0.0015 mol, sigma aldrich), 150 mL of THF and 30 mL of H ₂ O were added and reacted by refluxing for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 7 g (yield 70.6%) of <Intermediate 18-1>.

(2) Manufacturing example  2: Synthesis of intermediate 18-2

PdCl ₂ (dppf) (0.65 g, 0.038 mol, Sigma Aldrich), potassium acetate (5.79 g, 0.059 mol, Sigma Aldrich), Bis (pinacolato) dibron (6.59 g, 0.0009 mol, Sigma aldrich) and 1,4-dioxane (200 ml), and the mixture was reacted at 95 DEG C for 12 hours with stirring. After completion of the reaction, the reaction mixture was poured into H ₂ O and the mixture was subjected to column separation (N-HEXANE: MC) to obtain 7.6 g (yield: 66.74%) of Intermediate 18-2.

(3) Manufacturing example  3: Synthesis of intermediate 18-3

(16.39 g, 0.042 mol), Sodium tert-butoxide (9.37 g, 0.098 mol, sigma aldrich), Catalyst Pd (dba), 1-bromo-4-iodobenzene (10 g, 0.035 mol, _{2 (1.40 g, 0.0024 mol,} sigma aldrich), tri-tert-Bu-phosphine into a 150 mL Toluene in (0.99 g, 0.0049 mol, sigma aldrich) was reacted under stirring at 100 ℃ for 6 hours. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC, followed by column purification (N-HEXANE: MC) to obtain 15.8 g (yield: 82%) of Intermediate 18-3.

(4) Manufacturing example  4: Synthesis of Intermediate 18-4

Sodium tert-butoxide (4.98 g, 0.052 mol, Sigma aldrich), Catalyst Pd (dba) ₂ (0.74 g, 0.031 mol) was added to a solution of intermediate 1-8 (10 g, 0.026 mol), 3-aminobiphenyl , 0.0013 mol, Sigma aldrich) and tri-tert-Bu-phosphine (0.52 g, 0.0026 mol, Sigma aldrich) were added and reacted at 100 ° C for 8 hours. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC, followed by column purification (N-HEXANE: MC) to obtain 9.3 g (yield: 71%) of Intermediate 18-4.

(5) Manufacturing example  5: Synthesis of compound 18

Intermediate 1-5 (5 g, 0.0126 mol), intermediate 18-4 (7.59 g, 0.015 mol), sodium tert-butoxide (2.41 g, 0.025 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.36 g, 0.0006 100 mL of Toluene was added to tri-tert-Bu-phosphine (0.25 g, 0.0013 mol, Sigma aldrich) and reacted at 100 ° C for 8 hours. After completion of the reaction, the mixture was subjected to column separation with H ₂ O: MC, followed by column purification (N-HEXANE: EA) to obtain 7.4 g (yield: 71.8%) of Compound 18.

M, 7.43 / m, 7.35 / m, 7.45 / m, 7.49 / d, 7.49 / 7.58 / d, 6.59 / d) 2H (8.41 / d, 8.20 / d, 7.50 / d, 7.41 / d)

LC / MS: m / z = 820 [(M + 1) ^&lt; ^{+ &}

Synthetic example  5: Synthesis of Compound 72

(One) Manufacturing example  1: Synthesis of intermediate 72-1

1-bromo-3-iodobenzene ( 10 g, 0.035 mol, sigma aldrich), intermediate 1-7 (15.71 g, 0.042 mol) , potassium carbonate (14.66 g, 0.106 mol, sigma aldrich), Pd (PPh 3) 4 ( 2.04 g, 0.0018 mol, sigma aldrich), 200 mL of Toluene and 40 mL of ethanol were added, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 11 g (yield 78%) of Intermediate 72-1.

(2) Manufacturing example  2: Synthesis of intermediate 72-2

Sodium tert-butoxide (4.81 g, 0.050 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.72 g, 0.030 mol) were added to a solution of intermediate 72-1 (10 g, 0.025 mol), 3-aminobiphenyl , 0.0013 mol, Sigma aldrich) and tri-tert-Bu-phosphine (0.51 g, 0.0025 mol, Sigma aldrich) were added and reacted at 100 ° C for 8 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC, followed by column purification (N-HEXANE: MC) to obtain 8.8 g (yield 72%) of Intermediate 72-2.

(3) Manufacturing example  3: Synthesis of Compound 72

Intermediate 1-5 (5 g, 0.0126 mol), Intermediate 72-2 (7.35 g, 0.015 mol), Sodium tert-butoxide (2.41 g, 0.0251 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.36 g, 100 mL of Toluene was added to tri-tert-Bu-phosphine (0.25 g, 0.0013 mol, Sigma aldrich) and reacted at 100 ° C for 8 hours. After completion of the reaction, the mixture was subjected to column separation with H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 7.8 g (yield 77%) of Compound 72.

7.85 / d, 7.49 / d, 7.45 / m, 7.43 / m, 7.33 / m, 7.25 / m) 2H (7.85 / d, 7.81 / d, 7.58 / m, 7.54 / d, 7.50 / d, 7.44 / m, 7.41 / m, 7.38 / m, 6.89 / s, 6.88 / d, 6.69 / d, 6.59 / d, 7.51 / m)

LC / MS: m / z = 804 [(M + 1) ^&lt; ^{+ &}

Synthetic example  5: Synthesis of Compound 94

(One) Manufacturing example  1: Synthesis of intermediate 94-1

(7.46 g, 0.076 moles, Sigma Aldrich), PdCl (0.08 mol, Sigma Aldrich), Bis (pinacolato) dibron (8.50 g, 0.050 mol, Sigma Aldrich), 4-bromodibenzo [b, d] thiophene ₂ (dppf) (0.83 g, 0.0011 mol, Sigma aldrich) and 1,4-dioxane (200 mL) were added and reacted at 95 ° C for 12 hours. After completion of the reaction, the reaction mixture was poured into H ₂ O and the mixture was subjected to column separation (N-HEXANE: MC) to obtain 8.1 g (yield: 68.7%) of Intermediate 94-1.

(2) Manufacturing example  2: Synthesis of intermediate 94-2

(14.66 g, 0.106 mol, Sigma aldrich), Pd (PPh ₃ ) ₄ (0.1 g, 0.042 mol), 1-bromo-4-iodobenzene (10 g, 0.035 mol, 2.04 g, 0.0018 mol, sigma aldrich), 150 mL of THF and 30 mL of H ₂ O were added, and the mixture was stirred under reflux for 6 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and purified by column (N-HEXANE: MC) to obtain 9.2 g (yield: 76.7%) of Intermediate 94-2.

(3) Manufacturing example  3: Synthesis of intermediate 94-3

Sodium tert-butoxide (5.67 g, 0.059 mol, Sigma aldrich), Catalyst Pd (dba) ₂ (0.85 g, 0.035 mol) were added to a solution of intermediate 94-2 (10 g, 0.030 mol), 3-aminobiphenyl , 0.0015 mol, Sigma aldrich) and tri-tert-Bu-phosphine (0.60 g, 0.0029 mol, Sigma aldrich) were added and reacted at 100 ° C for 6 hours. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC, followed by column purification (N-HEXANE: MC) to obtain 9.7 g (yield: 77%) of Intermediate 94-3.

(4) Manufacturing example  4: Synthesis of Compound 94

Intermediate 1-5 (5 g, 0.013 mol), intermediate 94-3 (6.44 g, 0.015 mol), sodium tert-butoxide (2.41 g, 0.025 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.36 g, 0.0006 100 mL of Toluene was added to tri-tert-Bu-phosphine (0.25 g, 0.0013 mol, Sigma aldrich) and reacted at 100 ° C for 12 hours. After completion of the reaction, the mixture was subjected to column separation with H ₂ O: MC, followed by column purification (N-HEXANE: MC) to obtain 7 g (yield: 4.8%) of Compound 94.

D, 7.49 / d, 7.9 / d, 7.9 / d, 7.59 / d, 7.45 / d, 8.41 / d, 8.20 / d, 7.98 / d, M, 7.50 / m, 7.43 / m, 7.41 / m, 7.33 / m, 7.25 / m, 6.89 / s, 6.88 / d, 6.59 / m) 4H (7.54 / d, 6.69 / d)

LC / MS: m / z = 744 [(M + 1) ^&lt; ^{+ &}

Synthetic example  7: Synthesis of Compound 101

(One) Manufacturing example  1: Synthesis of intermediate 101-1

Sodium tert-butoxide (15.56 g, 0.16 mol, Sigma aldrich), catalyst Pd (dba) ₂ (2.33 g, 0.097 mol, Sigma aldrich), 4-bromodibenzofuran (20 g, 200 mL of toluene was added to tri-tert-Bu-phosphine (1.64 g, 0.008 mol, Sigma aldrich) and reacted at 100 ° C for 1 hour. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC and then subjected to column purification (N-HEXANE: EA) to obtain 19.2 g (yield 70.7%) of Intermediate 101-1.

(2) Manufacturing example  2: Synthesis of compound 101

Intermediate 1-5 (5 g, 0.0126 mol), Intermediate 101-1 (5.05 g, 0.0151 mol), Sodium tert-butoxide (2.41 g, 0.025 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.36 g, 0.0006 150 mL of Toluene was added to tri-tert-Bu-phosphine (0.25 g, 0.0013 mol, Sigma aldrich) and reacted at 100 ° C for 8 hours. After completion of the reaction, the mixture was separated into H ₂ O: MC and purified by column (N-HEXANE: MC) to obtain 6.5 g (yield: 79%) of Compound 101.

7.43 / d, 7.89 / d, 7.79 / d, 7.66 / d, 7.59 / d, 7.45 / m, 7.43 / m, 7.41 / m, (7.58 / m, 7.52 / d, 7.51 / m, 7.50 / d, 7.25 / m) 4H (7.54 / d, 6.69 / d, 7.38 / m, 7.33 / m, 7.32 / d)

LC / MS: m / z = 652 [(M + 1) ^&lt; ^{+ &}

Synthetic example  8: Synthesis of Compound 154

(One) Manufacturing example  1: Synthesis of intermediate 154-1

4,6-dibromodibenzofuran (20 g, 0.061 mol, Yurui), phenylboronic acid (8.98 g, 0.074 mol, sigma aldrich), potassium carbonate (16.96 g, 0.123 mol, sigma aldrich), Pd (PPh 3) 4 (3.54 g , 0.0031 mol, Sigma aldrich), 250 mL of THF and 50 mL of H ₂ O were added, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and purified by column (N-HEXANE: MC) to obtain 14.3 g (yield: 72%) of Intermediate 154-1.

(2) Manufacturing example  2: Synthesis of intermediate 154-2

Sodium tert-butoxide (5.95 g, 0.62 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.40 g, 0.032 mol), 3-aminodibenzofuran (6.80 g, 0.037 mol, Sigma aldrich) (0.63 g, 0.0031 mol, Sigma aldrich) was charged with 150 mL of Toluene, and the mixture was reacted at 100 ° C. for 1 hour with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC, followed by column purification (N-HEXANE: EA) to obtain 10 g (yield 76%) of Intermediate 154-2.

(3) Manufacturing example  3: Synthesis of Compound 154

Intermediate 1-5 (5 g, 0.0126 mol), intermediate 154-2 (6.41 g, 0.015 mol), sodium tert-butoxide (2.41 g, 0.0251 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.36 g, 0.0006 100 mL of Toluene was added to tri-tert-Bu-phosphine (0.25 g, 0.0013 mol, Sigma aldrich) and reacted at 100 ° C for 8 hours. After completion of the reaction, the mixture was subjected to column separation with H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 7 g (yield 75%) of Compound 154.

D, 7.89 / d, 7.85 / d, 7.81 / d, 7.79 / d, 7.66 / d, 7.64 / d, 7.59 / d, 7.54 / d, 7.52 / d, 7.51 / m, 7.50 / d, 7.34 / d, 7.47 / m, 7.41 / m, 7.33 / 7.43 / m, 7.38 / m, 7.25 / m, 6.69 / d)

LC / MS: m / z = 742 [(M + 1) ^&lt; ^{+ &}

Synthetic example  9: Synthesis of Compound 177

(One) Manufacturing example  1: Synthesis of intermediate 177-1

Sodium tert-butoxide (6.22 g, 0.065 mol, Sigma aldrich), Catalyst Pd (dba, 0.039 mol, Sigma Aldrich), 4-Bromo-p-terphenyl (10 g, 0.03 mol, _{) 2 (0.93 g, 0.0016 mol} , sigma aldrich), tri-tert-Bu-phosphine (0.65 g, 0.0032 mol, 150 mL Toluene put on sigma aldrich) was reacted under stirring at 100 ℃ for 1 hour. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC, followed by column purification (N-HEXANE: EA) to obtain 9.4 g (yield: 73%) of Intermediate 177-1.

(2) Manufacturing example  2: Synthesis of Compound 177

Intermediate 1-5 (5 g, 0.0126 mol), Intermediate 177-1 (5.99 g, 0.015 mol), Sodium tert-butoxide (2.41 g, 0.0251 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.36 g, 100 mL of Toluene was added to tri-tert-Bu-phosphine (0.25 g, 0.0013 mol, Sigma aldrich) and reacted at 100 ° C for 8 hours. After completion of the reaction, the mixture was subjected to column separation with H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 6.7 g (yield: 74.7%) of Compound 177.

(7.58 / m, 7.50 / d, 7.75 / d, 7.59 / d, 7.45 / m, 7.43 / m, 7.33 / m) d, 7.41 / m) 4H (7.52 / d, 7.51 / m) 5H (7.25 /

LC / MS: m / z = 742 [(M + 1) ^&lt; ^{+ &}

Synthetic example  10: Synthesis of Compound 187

(One) Manufacturing example  1: Synthesis of intermediate 187-1

1,3-dibromo-5-iodobenzene ( 10 g, 0.028 mol, TCI), intermediate 1-4 (12.25 g, 0.033 mol) , potassium carbonate (11.46 g, 0.83 mol, sigma aldrich), Pd (PPh 3) 4 (1.60 g, 0.0014 mol, Sigma aldrich), 150 mL of THF and 40 mL of H ₂ O, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 10.3 g (yield 78%) of Intermediate 187-1.

(2) Manufacturing example  2: Synthesis of intermediate 187-2

Intermediate 187-1 (10 g, 0.021 mol) , phenylboronic acid (3.07 g, 0.025 mol, sigma aldrich), potassium carbonate (8.69 g, 0.63 mol, sigma aldrich), Pd (PPh 3) 4 (1.21 g, 0.001 mol , sigma aldrich), 150 mL of THF, 40 mL of H ₂ O, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 7.8 g (yield 78.5%) of Intermediate 187-2.

(3) Manufacturing example  3: Synthesis of Compound 187

(8.48 g, 0.025 mol), Sodium tert-butoxide (4.05 g, 0.0422 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.61 g, 0.0011 200 mL of Toluene was added to tri-tert-Bu-phosphine (0.43 g, 0.0021 mol, Sigma aldrich) and reacted at 100 ° C for 8 hours. After completion of the reaction, the mixture was subjected to column separation with H ₂ O: MC, followed by column purification (N-HEXANE: MC) to obtain 11.8 g (yield: 76.8%) of Compound 187.

7.9 / d, 7.79 / d, 7.66 / d, 7.59 / d, 7.45 / m, 7.43 / m, 7.38 / m, 7.58 / m, 7.54 / d, 7.50 / d, 7.41 / m, 7.25 / m, 6.85 / s, 6.69 / d) 4H (7.52 / d, 7.51 / m)

LC / MS: m / z = 728 [(M + 1) ^&lt; ^{+ &}

Synthetic example  11: Synthesis of Compound 228

(One) Manufacturing example  1: Synthesis of intermediate 228-1

2-chlorophenylboronic acid (5.72 g, 0.037 mol, SigmaAldrich), potassium carbonate (12.65 g, 0.092 mol, SigmaAldrich), Pd (PPh ₃ ) ₄ (1.76 g, 0.0014 mol, sigma aldrich), 150 mL of THF and 40 mL of H ₂ O were added, and the mixture was stirred under refluxing for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 7.7 g (yield 80.8%) of Intermediate 228-1.

(2) Manufacturing example  2: Synthesis of intermediate 228-2

150 mL of the intermediate 1-1 (10 g, 0.032 mol), triphenylphosphine (25.18 g, 0.096 mol, sigma aldrich) and 1,2-dichlorobenzene were added and reacted at 180 ° C for 12 hours. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC and then subjected to column purification (N-HEXANE) to obtain 7.2 g (yield 80%) of Intermediate 228-2.

(3) Manufacturing example  3: Synthesis of intermediate 228-3

Intermediate 228-2 (10 g, 0.036 mol) , phenylboronic acid (5.22 g, 0.043 mol, sigma aldrich), potassium carbonate (14.78 g, 0.107 mol, sigma aldrich), Pd (PPh 3) 4 (2.06 g, 0.0018 mol , sigma aldrich), 150 mL of THF, 40 mL of H ₂ O, and the mixture was stirred under reflux for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 7.4 g (yield: 74.8%) of Intermediate 228-3.

(4) Manufacturing example  4: Synthesis of intermediate 228-4

Iodobenzene (11 g, 0.054 mol, Sigma Aldrich), potassium carbonate (12.44 g, 0.090 mol, Sigma Aldrich), Cu (4.58 g, 0.072 mol, Sigma Aldrich), dibenzo -18-crown-6 (1.3 g, 0.004 mol, Sigma Aldrich) and 150 mL of dimethylformamide, and the mixture was reacted at 150 ° C for 12 hours. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC and then subjected to column purification (N-HEXANE) to obtain 9.7 g (yield 76%) of Intermediate 228-4.

(5) Manufacturing example  5: Synthesis of intermediate 228-5

PdCl ₂ (dppf) (0.62 g, 0.037 mol, Sigma Aldrich), potassium acetate (5.55 g, 0.057 mol, Sigma Aldrich), Intermediate 228-4 (10 g, 0.028 mol) 0.0008 mol, Sigma aldrich) and 1,4-dioxane (200 mL), and the mixture was reacted at 95 ° C for 12 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: toluene and then subjected to column purification (N-HEXANE: MC) to obtain 8.6 g (yield 68%) of Intermediate 228-5.

(6) Manufacturing example  6: Synthesis of intermediate 228-6

Intermediate 228-5 (10 g, 0.023 mol) , 1-boromo-4-iodobenzene (7.62 g, 0.027 mol, sigma aldrich), potassium carbonate (9.31 g, 0.067 mol, sigma aldrich), Pd (PPh 3) 4 ( 1.30 g, 0.0011 mol, sigma aldrich), 200 mL of THF and 60 mL of water, and the mixture was reacted at 60 DEG C for 12 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC and purified by column (N-HEXANE: MC) to obtain 16.9 g (yield 92%) of Intermediate 228-6.

(7) Manufacturing example  7: Synthesis of intermediate 228-7

Sodium tert-butoxide (27.55 g, 0.28 mol, Sigma Aldrich) was added to a solution of 9,9-dimethyl-9H-fluoren-2-amine (20 g, 0.096 mol, Yurii), 4-bromobiphenyl (22.28 g, 0.096 mol, SigmaAldrich) 200 mL of toluene was added to the catalyst Pd (dba) ₂ (2.75 g, 0.005 mol, sigma aldrich) and tri-tert-Bu-phosphine (1.93 g, 0.01 mol, Sigma aldrich) Lt; / RTI &gt; After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: MC, followed by column purification (N-HEXANE: MC) to obtain 28 g (yield: 81%) of Intermediate 228-7.

(8) Manufacturing example  8: Synthesis of Compound 228

Sodium tert-butoxide (4.05 g, 0.042 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.61 g, 0.025 mol, Sigma aldrich), Intermediate 228-6 (10 g, 0.021 mol), Intermediate 228-7 200 mL of toluene was added to tri-tert-Bu-phosphine (0.43 g, 0.0021 mol, Sigma aldrich) and reacted at 100 ° C for 1 hour. After completion of the reaction, the reaction mixture was subjected to column separation with H ₂ O: MC, followed by column purification (N-HEXANE: MC) to obtain 12.4 g (yield 78%) of Compound 228.

M, 7.38 / m, 7.8 / d, 7.87 / d, 7.79 / d, 7.55 / d, 7.45 / (7.54 / d, 7.52 / d, 7.51 / m, 6.69 / d) 6H (7.28 / m, 6.75 / s, 6.58 / 1.72 / s)

LC / MS: m / z = 754 [(M + 1) ^&lt; ^{+ &}

Device Example

In the embodiment according to the present invention, the ITO transparent electrode is formed by patterning an ITO glass substrate having an ITO transparent electrode on a glass substrate of 25 mm x 25 mm x 0.7 mm so as to have a light emitting area of 2 mm x 2 mm And then washed. After the substrate was mounted in a vacuum chamber and the base pressure was adjusted to 1 × 10 ^-6 torr, organic matter and metal were deposited on the ITO by the following structure.

Device Embodiments 1 through 12

A blue light emitting organic electroluminescent device having the following device structure was prepared by using the compound represented by Formula (I) according to the present invention as a compound of the electron blocking layer, and the luminescent characteristics including the luminescent efficiency were measured.

Electron transport layer (201 nm Liq 30 nm) / LiF (1 nm) / ITO / hole injection layer (HAT_CN 5 nm) / hole transport layer (α-NPB 100 nm) / electron blocking layer (10 nm) / Al (100 nm)

In order to form a hole injection layer on the ITO transparent electrode, the hole injection layer was formed to a thickness of 5 nm by vacuum thermal deposition method using [HAT_CN], and then the hole transport layer was formed by using α-NPB. The electron blocking layer was formed to have a thickness of 10 nm using Formulas 1, 3, 6, 18, 36, 54, 72, 94, 101, 126, 154 and 177 of the present invention. Further, an electron transport layer (doped with Liq 50% of the following compound [201]) was further formed in the light emitting layer so as to have a thickness of about 20 nm by using [BH1] as a host compound and [BD1] 30 nm, LiF 1 nm and aluminum 100 nm were deposited by vapor deposition to produce an organic electroluminescent device.

Device Comparative Example 1

An organic electroluminescent device for Device Comparison Example 1 was fabricated in the same manner except that the electron blocking layer was not used in the device structure of Example 1 above.

EXPERIMENTAL EXAMPLE 1: Luminescent characteristics of element embodiments 1 to 12

The 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 10 mA / cm &lt; 2 &gt; was defined as &quot; driving voltage &quot; The results are shown in Table 1 below.

Example Electronic stop layer V cd / A QE (%) life span One Formula 1 3.92 9.22 8.68 146 2 (3) 4.06 9.00 8.47 121 3 6 4.13 8.95 8.39 132 4 18 4.10 8.64 8.10 122 5 Formula 36 4.16 8.72 8.18 128 6 54 4.10 8.56 8.02 132 7 (72) 4.02 9.07 8.51 136 8 94 4.04 8.91 8.36 121 9 Formula 101 4.10 8.89 8.38 126 10 126 4.18 8.77 8.26 117 11 154 4.12 8.83 8.28 118 12 177 4.09 8.90 8.35 115 Comparative Example 1 not used 4.14 5.4 4.6 2

When the electron blocking layer according to the present invention is applied to a compound device, the light emitting properties such as light emitting efficiency, quantum efficiency and lifetime are remarkably superior to those of the conventional device (Comparative Example 1) Can be confirmed.

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

Device Embodiments 13 to 24

A blue light emitting organic electroluminescent device having the following device structure was prepared by using the compound represented by formula (I) according to the present invention as a compound of the hole transport layer, and the luminescent characteristics including the luminescent efficiency were measured.

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

In order to form a hole injection layer on the ITO transparent electrode, the thickness of the hole injection layer was set to 5 nm by a vacuum thermal evaporation method using [HAT_CN], and then the hole transport layer was formed using the general formulas 1, 3, 6, 18, 36, 54, 72, 94, 101, 126, 154, and 177, respectively. Further, an electron transport layer (doped with Liq 50% of the following compound [201]) was further formed in the light emitting layer so as to have a thickness of about 20 nm by using [BH1] as a host compound and [BD1] 30 nm, LiF 1 nm and aluminum 100 nm were deposited by vapor deposition to produce an organic electroluminescent device.

Device Comparative Example 2

An organic electroluminescent device for Device Comparison Example 2 was fabricated in the same manner except that α-NPB was used instead of the compound according to the present invention in the hole transport layer in the device structure of Example 1.

Experimental Example 2: Luminescent characteristics of the device examples 13 to 24

The 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 / cm2 was defined as the "driving voltage" and the lifetime was measured by comparing T95% based on 1000 nit. The results are shown in Table 2 below.

Example Hole transport layer V cd / A QE (%) Life span (h) 13 Formula 1 4.09 7.38 6.95 75 14 (3) 4.18 7.26 6.84 62 15 6 4.20 7.34 6.88 68 16 18 4.19 7.18 6.73 63 17 Formula 36 4.22 7.09 6.65 66 18 54 4.19 6.97 6.53 68 19 (72) 4.13 7.30 6.85 70 20 94 4.10 7.12 6.68 62 21 Formula 101 4.13 7.04 6.64 65 22 126 4.23 6.88 6.49 60 23 154 4.21 7.17 6.73 61 24 177 4.17 7.20 6.76 59 Comparative Example 2 α-NPB 4.14 5.4 4.6 2

The results shown in the above Table 2 show that the luminous efficiency such as luminous efficiency, quantum efficiency and lifetime is remarkably superior to the conventional device (Comparative Example 2) when the hole transport layer according to the present invention is applied to a compound device .

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

Claims (11)

An organic light-emitting compound represented by the following formula (I):
(I)

In the above formula (I)
Ar ₁ is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms,
L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and n and m are each an integer of 0 to 3 And when n is 2, a plurality of L ₁ and L ₂ are the same or different from each other,
o is an integer from 1 to 3,
Ra and Rb are the same or different and each independently represents a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, or a cycloalkyl having 3 to 30 carbon atoms, A substituted or unsubstituted C2 to C50 heteroaryl group in which one or more substituted or unsubstituted aryl groups having 5 to 50 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms are fused,
The Ra and Rb may be connected to each other or adjacent substituents to form a single ring or polycyclic ring of an alicyclic or aromatic group. The carbon atoms of the formed alicyclic or aromatic single ring or polycyclic ring may be either N, S, or O And may be substituted with any one or more heteroatoms selected. The method according to claim 1,
Wherein at least one of Ra and Rb is a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms. The method according to claim 1,
Wherein at least one of Ra and Rb is any one selected from the following Structural Formula 1:
[Structural formula 1]

In the above formula 1,
X ₁ , X ₂ and Y are the same or different and are each independently a single bond or any one of CR ₁₇ R ₁₈ , NR ₁₉ , O and S,
R ₁ to R ₁₉ each independently represent a hydrogen atom, a deuterium atom, an amino group, a cyano group, a hydroxy group, a nitro group, a halogen group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms , A substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having at least one heteroatom selected from O, N and S, and a substituted or unsubstituted silyl group, and at least one of R ₁ to R ₁₉ One is a single coupling connector forming a connection,
The R ₁ to R ₁₉ and substituents thereof may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero together with substituents adjacent to each other. The method of claim 3,
The [formula 1] wherein X ₁ is an organic luminescent compound, characterized in that O at. The method according to claim 1, 2, or 3,
Wherein _{Ra, Rb, L 1, L} 2, L 3, Ar 1 and R ₁ to a substituted or unsubstituted ring in the definition of R ₁₉ is wherein _{Ra, Rb, L 1, L} 2, L 3, Ar 1 and R ₁ to R ₁₉ is a group selected from the group consisting of deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, 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, an alkoxy group having 24 carbon atoms, An alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, an arylsilyl group having 1 to 24 carbon atoms, and an aryloxy group having 1 to 24 carbon atoms Selected from the group consisting of 1 or 2 selected Or an organic luminescent compound in which at least two of the substituents in the substituent group are substituted with a substituted or unsubstituted substituent. The organic luminescent compound according to claim 1, wherein the compound represented by Formula (I) is any one selected from the following [compounds 1] to [246]:

1. 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,
Wherein at least one of the organic material layers comprises at least one organic light emitting compound represented by Formula (I) according to Claim 1. 8. The method of claim 7,
Wherein the organic material 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,
Wherein at least one of the layers comprises an organic light emitting compound represented by the formula (I). 8. The method of claim 7,
Wherein the hole transport layer comprises an organic luminescent compound represented by the formula (I). 8. The method of claim 7,
Wherein the electron blocking layer comprises an organic luminescent compound represented by the formula (I). 8. The method of claim 7,
Wherein the light emitting layer comprises an organic light emitting compound represented by Formula (I).