KR20180063707A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound employed in an organic light emitting device, and specifically, to an organic light emitting compound, which is represented by chemical formula I, and can realize an organic light emitting device, which has remarkably excellent light emitting properties such as light emitting efficiency, quantum efficiency and the like by being employed in an electron blocking layer.

Description

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

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device employing the organic electroluminescent compound in an organic material layer of the device, and capable of realizing a device having remarkably excellent light emitting properties such as luminous efficiency and quantum efficiency.

An organic light emitting phenomenon is a phenomenon that converts electric energy into light energy by using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer has a multi-layer structure composed of different materials. For example, the organic material layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, Layer, and the like. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material, a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, a hole blocking material, . In addition, the luminescent material can be classified into blue, green and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color depending on the luminescent color.

In order for the organic light emitting device to fully exhibit the above-described excellent characteristics, it is necessary that various materials constituting the organic material layer in the device are supported by stable and efficient materials. However, development of stable and efficient organic material layer materials for organic light emitting devices It is not done. Therefore, the development of new materials is continuously required, and the necessity of developing such materials is the same in other organic electronic devices.

The present invention provides a novel organic electroluminescent compound which is employed in an organic layer of an organic electroluminescent device and can realize excellent luminescent properties such as luminous efficiency and quantum efficiency, and an organic light emitting device comprising the same.

In order to solve the above problems, the present invention provides an organic light emitting device represented by the following formula (I).

(I)

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

The present invention also provides an organic light emitting device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers comprises the organic light emitting compound And an organic electroluminescent device.

The device employing the organic luminescent compound according to the present invention in the electron blocking layer is superior to the conventional device in light emission characteristics such as luminous efficiency and quantum efficiency, and thus can be applied to various display devices.

Hereinafter, the present invention will be described more specifically.

One aspect of the present invention relates to an organic light-emitting compound which is employed in an organic material layer of an organic light-emitting device, preferably an electron-blocking layer, to realize excellent light-emitting properties such as luminous efficiency and quantum efficiency. .

(I)

In the above formula (I)

X is CR ₁ R ₂ , O or S, R ₁ to R ₂ are the same or different and each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, And R ₁ to R ₂ may be connected to each other or adjacent substituents to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring.

L ₁ to L ₂ are the same or different and are each independently a single bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted Or a substituted or unsubstituted heteroarylene group containing at least one of N, O and S atoms.

Ar ₁ to Ar ₃ are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, or a substituted or unsubstituted C3 to C20 cycloalkyl having 3 to 20 carbon atoms, A substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted carbazole group.

The substituted or unsubstituted alkyl group may have 1 or 2 substituents selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, silyl, alkyl, cycloalkyl, alkoxy, alkenyl, Substituted with at least two of the above substituents, or at least two of the substituents are substituted with a substituted or unsubstituted substituent.

Specific examples of the substituted arylene group include a phenyl group, a biphenyl group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group and a tetracenyl group. Anthracenyl group and the like are substituted with other substituents.

The substituted heteroarylene 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, A benzimidazole group, a benzimidazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzzcarbazole 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, and specific examples thereof include a methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, Butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylpentyl group, Methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, Dimethylhexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, and the like. It is not limited.

In the present invention, the alkoxy group may be linear or branched. The number of carbon atoms of the alkoxy group is not particularly limited and is preferably within a range that does not cause steric hindrance. Specifically, a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, Isobutoxy group, sec-butoxy group, n-pentyloxy group, neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3,3-dimethylbutyloxy group, N-hexyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, benzyloxy group, p-methylbenzyloxy group 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. Specific examples thereof include a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, Butenyl group, an allyl group, a 1-phenylvinyl-1-yl group, a 2-phenylpropyl group, a 2-phenylpropyl group, Vinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl- 2- (naphthyl- A vinyl-1-yl group, a stilbenyl group, a styryl group, 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.

In the present invention, the heterocyclic 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 3 to 30 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane 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 pyrazinopyrazinyl group, an isoquinoline group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, , An indole 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 dibenzofurancyl group, a phenanthroline group, An isothiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group and the like, but is not limited thereto.

In the present invention, the cycloalkyl group is not particularly limited, but preferably has 3 to 20 carbon atoms. Specifically, the cycloalkyl group is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 3-methylcyclopentyl group, a 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 the present invention, the silyl group is specifically exemplified by trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, But are not limited thereto.

The organic electroluminescent 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 device due to its structural specificity, and more specifically, as an electron blocking layer material of an organic material 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.

By introducing various substituents to the core structure having the above structure, it is possible to synthesize an organic luminescent compound having the intrinsic characteristics of the substituent introduced thereto, thereby manufacturing a material satisfying the requirements of various organic layers of the organic luminescent device have. The compound of the present invention can be applied to a device according to a conventional manufacturing method of an organic light emitting device.

The organic light emitting 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 interposed therebetween, and the organic light emitting compound according to the present invention may be used for an organic material layer And can be produced using ordinary device manufacturing methods and materials.

The organic material layer of the organic light emitting 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, an electron blocking layer, a hole blocking layer, a light emitting layer, an electron transporting layer, and an electron injecting layer as well as a layer having various functions. However, it is not limited to this and may include a smaller number of organic layers.

Accordingly, in the organic light emitting device according to the present invention, at least one of the layers may include a compound represented by the above formula (I).

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, preferred embodiments of the present invention will be described in order 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 29

(1) Synthesis of intermediate 29-1

Phenylboronic acid (13.30 g, 0.109 mol, Sigma Aldrich), potassium carbonate (25.13 g, 0.182 mol, Sigma Aldrich), Pd ( PPh ₃ ) ₄ (3.15 g, 0.0027 mol, sigma aldrich), 220 mL of Toluene and 40 mL of ethanol were placed and reacted by refluxing for 5 hours with stirring. After completion of the reaction, the mixture was subjected to layer separation using H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 17.6 g (yield 89%) of Intermediate 29-1.

(2) Synthesis of intermediate 29-2

200 mL of dimethylformamide was added to intermediate 29-1 (15 g, 0.069 mol, Sigma aldrich), 2-bromophenol (11.95 g, 0.069 mol, Sigma aldrich) and potassium carbonate (19.09 g, 0.138 mol, after stirring an additional hour the catalyst _{Pd (OAc) 2 (0.78 g} , 0.0035 mol, sigma aldrich), triphenylphosphin e (1.81 g, 0.007mol, sigma Aldrich) was added and the reaction mixture was stirred at 90 ℃ for 2.5 hours. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 15.8 g (yield 79%) of <Intermediate 29-2>.

(3) Synthesis of intermediate 29-3

Iron powder (14.48 g, 0.26 mol, Sigma Aldrich) and hydrochloric acid were added to the flask, and the mixture was stirred under reflux for 2 hours to react the intermediate 29-2 (15 g, 0.052 mol) in ethanol: H ₂ O . After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: EA, followed by column purification (N-HEXANE: EA) to obtain 10 g (yield: 74%) of Intermediate 29-3.

(4) Synthesis of intermediate 29-4

2-bromo-4-iodophenol ( 20 g, 0.067 mol, yurui), phenylboronic acid (9.79 g, 0.080 mol, sigma aldrich), potassium carbonate (18.50 g, 0.134 mol, sigma aldrich), Pd (PPh 3) 4 ( 3.87 g, 0.0033 mol, sigma aldrich), 220 mL of Toluene and 40 mL of Ethanol, 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 14.1 g (yield: 84.6%) of Intermediate 29-4.

(5) Synthesis of intermediate 29-5

Intermediate 29-4 (14 g, 0.056 mol) , 2-fluorophenylboronic acid (9.44 g, 0.067 mol, sigma aldrich), potassium carbonate (15.54 g, 0.112 mol, sigma aldrich), Pd (PPh 3) 4 (3.25 g, 0.0028 mol, sigma aldrich), 200 mL of Toluene, and 40 mL of ethanol, 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 13.2 g (yield: 88.9%) of Intermediate 29-5.

(6) Synthesis of intermediate 29-6

Intermediate 29-5 (13 g, 0.050 mol), N-bromosuccinimide (8.76 g, 0.050 mol, sigma aldrich) and 150 mL of dimethylformamide were added and reacted at 60 ° C for 12 hours. After completion of the reaction, 1M aqueous NaOH solution was added, stirred, filtered and dried to obtain 10.2 g (yield: 60%) of <Intermediate 29-6>.

(7) Synthesis of intermediate 29-7

Intermediate 29-6 (10 g, 0.030 mol), NaH (1.4 g, 0.058 mol, sigma aldrich) and 100 mL of dimethyl sulfoxide were added and reacted at 140 ° C for 5 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 3 g (yield: 31.9%) of Intermediate 29-7.

(8) Synthesis of intermediate 29-8

Sodium tert-butoxide (7.41 g, 0.077 mol, sigma aldrich), catalyst Pd (dba) ₂ (1.11 g, 0.042 mol) were added to a solution of intermediate 29-3 (10 g, 0.039 mol), 4-bromobiphenyl , 0.0019 mol, Sigma aldrich) and tri-tert-Bu-phosphine (0.78 g, 0.004 mol, Sigma aldrich) were added and reacted at 100 ° C for 4 hours. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 12.4 g (yield 78%) of Intermediate 29-8.

(9) Synthesis of Compound 29

(9.42 g, 0.029 mol), Sodium tert-butoxide (4.67 g, 0.049 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.70 g, 0.0012 150 mL of Toluene was added to tri-tert-Bu-phosphine (0.49 g, 0.0024 mol, Sigma aldrich) and reacted at 100 ° C for 4 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 11.7 g (yield: 73.6%) of Compound 29.

7.38 / m, 7.07 / s, 6.69 / d) 3H (7.41 / d, 7.57 / m) 6H (7.52 / d, 7.51 / m)

LC / MS: m / z = 653 [(M + 1) ^&lt; ^{+ &}

Synthetic example  2: Synthesis of Compound 38

(1) Synthesis of intermediate 38-1

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 the 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 38-1.

(2) Synthesis of intermediate 38-2

(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 38-2.

(3) Synthesis of intermediate 38-3

(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 purified by column (N-HEXANE: MC) to obtain 11.6 g (yield: 82%) of Intermediate 38-3.

(4) Synthesis of Compound 38

Sodium tert-butoxide (4.67 g, 0.049 mol, Sigma aldrich), Catalyst Pd (dba) ₂ (0.70 g, 0.03 mol, Sigma Aldrich), Intermediate 29-8 (10 g, 0.024 mol) 150 mL of Toluene was added to tri-tert-Bu-phosphine (0.49 g, 0.0024 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 13.2 g (yield: 74.4%) of Compound 38.

(7.85 / d, 7.81 / d) 3H (7.41 / m, 7.07 / s) 7.38 / m) 4H (7.54 / d, 6.69 / d) 6H (7.52 / d, 7.51 / m)

LC / MS: m / z = 729 [(M + 1) ^&lt; ^{+ &}

Synthetic example  3: Compound 48 Synthesis

(1) Synthesis of intermediate 48-1

200 mL of dimethylformamide was added to 200 mL of 2-bromo-4-chlorobenzoic acid (20 g, 0.085 mol, Sigma Aldrich), iodomethane (18.08 g, 0.127 mol, Sigma aldrich) and sodium bicarbonate (14.27 g, 0.0 &gt; C &lt; / RTI &gt; for 24 hours. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 12.4 g (yield 79%) of Intermediate 48-1.

(2) Synthesis of intermediate 48-2

150 mg of THF was added to the intermediate 48-1 (12 g, 0.048 mol), and phenyl magnesium bromide (13.08 g, 0.072 mol, Sigma aldrich) was slowly added thereto while stirring at 0 ° C and stirred at room temperature for 12 hours. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 11.2 g (yield 78.8%) of Intermediate 48-2.

(3) Synthesis of intermediate 48-3

Intermediate 48-2 (20 g, 0.068 mol) , silver oxide (23.52 g, 0.102 mol, sigma aldrich), potassium carbonate (23.38 g, 0.169 mol, sigma aldrich), catalyst _{Pd (OAc) 2 (0.61 g} , 0.0011 mol , Sigma aldrich) was added with trifluoroacetic acid (TFA) and reacted at 140 ° C for 24 hours with stirring. After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 12.6 g (yield: 77%) of Intermediate 48-3.

(4) Synthesis of intermediate 48-4

(3.87 g, 0.102 mol, Sigma aldrich) and 300 mL of tetrahydrofuran were placed, and the mixture was refluxed with stirring for 2 hours to obtain an intermediate 48-3 (20 g, 0.068 mol), sodium borohydride (149.07 g, 0.341 mol, sigma aldrich) Lt; / RTI &gt; After completion of the reaction, the reaction mixture was subjected to layer separation with H ₂ O: EA and then subjected to column purification (N-HEXANE: EA) to obtain 13 g (yield: 68%) of Intermediate 48-3.

(5) Synthesis of intermediate 48-5

Iodomethane (22.85 g, 0.161 mol, Sigma aldrich) was added to 200 mL of tetrahydrofuran, followed by stirring at 0 ° C for 10 minutes. And the mixture was reacted at room temperature for 12 hours with stirring. After completion of the reaction, hexane was added thereto, followed by stirring and filtration. Column purification (N-HEXANE: EA) yielded 11 g (yield 66.7%) of Intermediate 48-5.

(6) Synthesis of intermediate 48-6

Sodium tert-butoxide (9.37 g, 0.098 mol, Sigma aldrich), Catalyst Pd (dba) ₂ (1.40 g, 0.09 mol) was added to a solution of intermediate 48-5 (15 g, 0.049 mol), 4-aminobiphenyl , 0.9924, 0.0024 mol, Sigma aldrich), tri-tert-Bu-phosphine (0.99 g, 0.0049 mol, Sigma aldrich) and reacted at 100 ° C for 6 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 15.8 g (yield: 82%) of Intermediate 48-6.

(7) Synthesis of intermediate 48-7

Intermediate 48-6 (15 g, 0.038 mol) , phenylboronic acid (5.54 g, 0.046 mol, sigma aldrich), potassium carbonate (10.47 g, 0.076 mol, sigma aldrich), Pd (PPh 3) 4 (2.19 g, 0.0019 mol , sigma aldrich), 200 mL of Toluene and 40 mL of ethanol, 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 13.3 g (yield 80%) of Intermediate 48-7.

(8) Synthesis of Compound 48

(10.69 g, 0.027 mol), Sodium tert-butoxide (4.39 g, 0.046 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.66 g, 0.0011 150 mL of Toluene was added to tri-tert-Bu-phosphine (0.46 g, 0.0023 mol, Sigma aldrich) and reacted at 100 ° C for 6 hours with stirring. 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 13.2 g (yield 76%) of Compound 48.

(7.87 / d, 7.51 / d, 7.42 / s, 7.28 / m, 6.70 / s) 7.38 / m) 4H (7.54 / d, 6.69 / d) 6H (7.52 / d, 7.51 /

LC / MS: m / z = 755 [(M + 1) ^&lt; ^{+ &}

Synthetic example  4: Synthesis of Compound 58

(1) Synthesis of intermediate 58-1

Phenylboronic acid (6.99 g, 0.057 mol, Sigma Aldrich), potassium carbonate (13.21 g, 0.096 mol, Sigma Aldrich), Pd (PPh ₃ ) ₄ (0.015 mol), 2-bromo-4-iodobenzenethiol 2.76 g, 0.0024 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 10 g (yield 79%) of Intermediate 58-1.

(2) Synthesis of intermediate 58-2

Intermediate 58-1 (15 g, 0.057 mol) , 2-fluorophenylboronic acid (9.50 g, 0.068 mol, sigma aldrich), potassium carbonate (15.64 g, 0.113 mol, sigma aldrich), Pd (PPh 3) 4 (3.27 g, 0.0028 mol, sigma aldrich), 200 mL of Toluene, and 40 mL of ethanol, 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 12.7 g (yield 80%) of Intermediate 58-2.

(3) Synthesis of intermediate 58-3

Intermediate 58-2 (10 g, 0.0360 mol), N-Bromosuccinimide (6.35 g, 0.036 mol, sigma aldrich) and 150 mL of dimethylformamide were added and reacted at 60 ° C for 12 hours. After completion of the reaction, a 1M aqueous NaOH solution was added, stirred, filtered and dried to obtain 9.7 g (yield 75.7%) of Intermediate 58-3.

(4) Synthesis of intermediate 58-4

Intermediate 29-6 (10 g, 0.028 mol), NaH (1.0 g, 0.042 mol, sigma aldrich) and 100 mL of dimethyl sulfoxide were added and reacted at 140 ° C for 5 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: MC) to obtain 3.3 g (yield: 35%) of Intermediate 58-4.

(5) Synthesis of intermediate 58-5

Sodium tert-butoxide (5.65 g, 0.059 mol, Sigma aldrich), Catalyst Pd (dba) ₂ (0.85 g, 0.035 mol) were added to a solution of intermediate 58-4 (10 g, 0.029 mol), 4-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 10 g (yield: 79.5%) of Intermediate 58-5.

(6) Synthesis of compound 58

Sodium tert-butoxide (4.5 g, 0.047 mol, Sigma aldrich), Catalyst Pd (dba) ₂ (0.67 g, 0.0012 mol) was added to a solution of intermediate 58-5 (10 g, 0.023 mol), intermediate 38-3 150 mL of Toluene was added to tri-tert-Bu-phosphine (0.47 g, 0.0023 mol, Sigma aldrich) and reacted at 100 ° C for 6 hours with stirring. After completion of the reaction, the mixture was separated into H ₂ O: MC and purified by column (N-HEXANE: MC) to obtain 13.9 g (yield: 79.7%) of Compound 58.

7.85 / d, 7.81 / d, 7.38 / m) &lt; 3 &gt; H (CDCl3): ppm, 1H (8.45 / d, 7.98 / d, 7.50 / 7.41 / m) 4H (7.54 / d, 6.69 / d) 6H (7.51 / m) 7H (7.52 /

LC / MS: m / z = 745 [(M + 1) ^&lt; ^{+ &}

Synthetic example  5: Synthesis of Compound 69

(1) Synthesis of intermediate 69-1

(11.92 g, 0.121 mol, Sigma Aldrich), PdCl ₂ (dppf) (1.33 g, 0.079 mol, Sigma Aldrich), 2-bromodibenzofuran (15 g, 0.061 mol, Sigma Aldrich) g, 0.0018 mol, sigma aldrich) and 1,4-dioxane (200 mL), and the mixture was reacted at 95 ° C for 12 hours. After completion of the reaction, the reaction mixture was poured into H ₂ O, layer separation was performed, and 12.5 g (yield 70%) of <Intermediate 69-1> was obtained by column purification (N-HEXANE: MC).

(2) Synthesis of intermediate 69-2

(13.72 g, 0.046 mol), potassium carbonate (9.77 g, 0.071 mol, Sigma aldrich), Pd (PPh ₃ ) ₄ (0.1 g, 0.035 mol), 1-bromo-4-iodobenzene 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 purified by column (N-HEXANE: MC) to obtain 9.6 g (yield: 84%) of Intermediate 69-2.

(3) Synthesis of intermediate 69-3

(14.16 g, 0.046 mol), Sodium tert-butoxide (7.41 g, 0.077 mol, sigma aldrich), catalyst Pd (dba) ₂ (1.11 g, 0.0019 150 mL of Toluene was added to tri-tert-Bu-phosphine (0.78 g, 0.0039 mol, Sigma aldrich) and reacted at 100 ° C for 6 hours. After completion of the reaction, the reaction mixture was separated into H ₂ O: MC and purified by column (N-HEXANE: MC) to obtain <Intermediate 69-3> (15.3 g, yield 79%).

(4) Synthesis of Compound 69

(7.73 g, 0.024 mol), Sodium tert-butoxide (3.83 g, 0.040 mol, sigma aldrich), catalyst Pd (dba) ₂ (0.57 g, 0.0010 150 mL of Toluene was added to tri-tert-Bu-phosphine (0.40 g, 0.0020 mol, Sigma aldrich) and reacted at 100 ° C for 12 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: MC) to obtain 11.7 g (yield 78.9%) of Compound 69.

(7.89 / d, 7.81 / d) 2H (7.57 / s, 7.54 / d, 7.41 / m, 7.07 / s, 6.69 / d) 7.66 / d, 7.32 / m) 4H (7.52 / d, 7.51 / m, 7.38 / m)

LC / MS: m / z = 743 [(M + 1) ^&lt; ^{+ &}

Synthetic example  6: Synthesis of Compound 75

(1) Synthesis of Intermediate 75-1

Intermediate 29-7 (15 g, 0.046 mol), Bis (pinacolato) dibron (10.38 g, 0.060 mol, Sigma aldrich), potassium acetate (9.11 g, 0.093 mol, Sigma aldrich), PdCl ₂ (dppf) 0.0014 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 and the mixture was subjected to column separation (N-HEXANE: MC) to obtain 12.6 g (yield: 73%) of Intermediate 75-1.

(2) Synthesis of intermediate 75-2

(15.71 g, 0.042 mol), potassium carbonate (9.77 g, 0.071 mol, Sigma aldrich), Pd (PPh ₃ ) ₄ (0.07 mol), 1-bromo-4-iodobenzene 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 then subjected to column purification (N-HEXANE: MC) to obtain 11.7 g (yield: 83%) of Intermediate 75-2.

(3) Synthesis of intermediate 75-3

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 75-3.

(4) Synthesis of Compound 75

Intermediate 75-2 (10.86 g, 0.030 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 mixture was subjected to column separation with H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 13.7 g (yield 75%) of Compound 75.

M, 7.28 / m, &lt; RTI ID = 0.0 &gt; 7. &lt; / RTI &gt; 6.75 / s, 6.58 / d) 2H (7.41 / m, 7.38 / m) 4H (7.54 / d, 7.52 / d, 7.51 /

LC / MS: m / z = 679 [(M + 1) ^&lt; ^{+ &}

Synthetic example  7: Synthesis of Compound 86

(1) Synthesis of intermediate 86-1

Sodium tert-butoxide (4.81 g, 0.050 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.72 g, 0.030 mol) was added to a solution of Intermediate 75-2 (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 150 mL of Toluene and reacted at 100 ° C for 6 hours with stirring. After completion of the reaction, the reaction mixture was separated into H ₂ O: MC and purified by column (N-HEXANE: MC) to obtain 9.6 g (yield: 78.6%) of Intermediate 86-1.

(2) Synthesis of Compound 86

(14.65 g, 0.030 mol), Sodium tert-butoxide (4.81 g, 0.051 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 mixture was subjected to column separation with H ₂ O: MC, followed by column purification (N-HEXANE: MC) to obtain 16.5 g (yield 81.7%) of 86.

(7.85 / d, 7.81 / d) 3H (7.41 / m, 7.63 / s) 7.38 / m) 6H (7.54 / d, 7.52 / d, 7.51 / m, 6.69 / d)

LC / MS: m / z = 805 [(M + 1) ^&lt; ^{+ &}

Synthetic example  8: Synthesis of Compound 96

Sodium tert-butoxide (4.86 g, 0.051 mol, Sigma aldrich), Catalyst Pd (dba, 0.025 mol), 2-amino-9,9-dimethylfluorene _{) 2 (0.73 g, 0.0013 mol} , sigma aldrich), tri-tert-Bu-phosphine (0.51 g, put Toluene 150 mL to 0.0025 mol, sigma aldrich) was reacted under stirring at 100 ℃ 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 16.4 g (yield: 81%) of Compound 96.

M, 7.28 / m, &lt; RTI ID = 0.0 &gt; 7. &lt; / RTI &gt; D, 7.51 / m, 6.69 / d, 7.58 / d) 2H (7.75 / d, 7.41 / m, 7.38 / m, 7.35 / d, 7.19 / d)

LC / MS: m / z = 801 [(M + 1) ^&lt; ^{+ &}

Synthetic example  9: Synthesis of Compound 111

(1) Synthesis of intermediate 111-1

Sodium tert-butoxide (4.81 g, 0.050 mol, Sigma aldrich), Catalyst Pd (dba, 0.030 mol, _{) 2 (0.72 g, 0.0013 mol} , sigma aldrich), tri-tert-Bu-phosphine (0.51 g, put Toluene 150 mL to 0.0025 mol, sigma aldrich) was reacted under stirring at 100 ℃ for 4 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 <Intermediate 111-1> (10.6 g, yield 80%).

(2) Synthesis of Compound 111

Sodium tert-butoxide (3.64 g, 0.038 mol, Sigma aldrich), Catalyst Pd (0.013 mol), Sodium tert-butoxide (10 g, 0.019 mol), 2-bromo-9,9-dimethylfluorene _{dba) 2 (0.54 g, 0.0009} mol, sigma aldrich), tri-tert-Bu-phosphine (0.38 g, put Toluene 150 mL to 0.0019 mol, sigma aldrich) was reacted under stirring at 100 ℃ 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 Compound 111 (10.8 g, yield 79%).

7.87 / d, 7.62 / d, 7.62 / d, 7.63 / s, 7.41 / m, 7.32 / m) d, 7.54 / d, 7.52 / d, 7.51 / m, 7.28 / m, 6.75 / s, 6.69 / d, 6.58 / d) 3H (7.38 /

LC / MS: m / z = 719 [(M + 1) ^&lt; ^{+ &}

Synthetic example  10: Synthesis of Compound 126

(1) Synthesis of intermediate 126-1

(10.78 g, 0.110 moles, Sigma Aldrich), PdCl 2 (0.15 g, 0.071 mol, Sigma Aldrich), Bis (pinacolato) dibron ₂ (dppf) (1.21 g, 0.0016 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, layer separation was carried out, and 12.3 g (yield 70%) of <Intermediate 126-1> was obtained by column purification (N-HEXANE: MC).

(2) Synthesis of intermediate 126-2

2-bromo-4-iodophenol ( 10 g, 0.034 mol, yurui), Intermediate 126-1 (12.86 g, 0.040 mol) , potassium carbonate (9.25 g, 0.067 mol, sigma aldrich), Pd (PPh 3) 4 (1.93 g, 0.0017 mol, sigma aldrich), 150 mL of THF and 30 mL of H ₂ O, and the mixture was stirred under reflux for 5 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 g (yield: 82%) of Intermediate 126-2.

(3) Synthesis of intermediate 126-3

Intermediate 126-2 (15 g, 0.041 mol) , 2-fluorophenylboronic acid (6.90 g, 0.049 mol, sigma aldrich), potassium carbonate (11.35 g, 0.082 mol, sigma aldrich), Pd (PPh 3) 4 (2.37 g, 0.0021 mol, sigma aldrich), 200 mL of Toluene and 40 mL of ethanol, 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 12.2 g (yield 78%) of Intermediate 126-3.

(4) Synthesis of intermediate 126-4

Intermediate 126-4 (15 g, 0.050 mol), N-bromosuccinimide (7.72 g, 0.043 mol, sigma aldrich) and 200 mL of dimethylformamide were added and reacted at 60 ° C for 12 hours with stirring. After completion of the reaction, 1M aqueous NaOH solution was added, stirred, filtered and dried to obtain 13 g (yield: 71.8%) of Intermediate 126-4.

(5) Synthesis of intermediate 126-5

Intermediate 126-4 (15 g, 0.033 mol), NaH (1.18 g, 0.049 mol, sigma aldrich) and 200 mL of dimethyl sulfoxide were added and reacted at 140 ° C for 5 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 5.6 g (yield 39%) of Intermediate 126-5.

(6) Synthesis of intermediate 126-6

Sodium tert-butoxide (6.56 g, 0.068 mol, Sigma aldrich), Catalyst Pd (dba) ₂ (0.98 g, 0.041 mol) were added to a solution of intermediate 126-5 (15 g, 0.034 mol), 4-aminobiphenyl , 0.0017 mol, Sigma aldrich) and tri-tert-Bu-phosphine (0.68 g, 0.0034 mol, Sigma aldrich) were added 200 mL of Toluene and reacted at 100 ° C for 6 hours with stirring. 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 14.5 g (yield: 80.5%) of Intermediate 126-6.

(7) Synthesis of intermediate 126-7

Iodobenzene (41.4 g, 0.203 moles, Sigma Aldrich), potassium carbonate (33.69 g, 0.244 mol, Sigma Aldrich), Cu (10.33 g, 0.162 mol), 3-bromo-9H-carbazole (20 g, 0.081 mol, SigmaAldrich) , sigma aldrich), dibenzo-18-crown-6 (2.93 g, 0.008 mol, Sigma Aldrich) and 150 mL of dimethylformamide were added and 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 126-7.

(8) Synthesis of intermediate 126-8

Intermediate 126-7 (36.86 g, 0.114 mol), Bis (pinacolato) dibron (34.86 g, 0.137 mol, Sigma Aldrich), potassium acetate (33.68 g, 0.343 mol, Sigma Aldrich), PdCl ₂ (dppf) 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 126-8.

(9) Synthesis of intermediate 126-9

Intermediate 126-8 (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 126-9.

(10) Synthesis of Compound 126

Intermediate 126-9 (10 g, 0.025 mol), Intermediate 126-6 (15.9 g, 0.030 mol), Sodium tert-butoxide (4.83 g, 0.050 mol, sigma aldrich), Catalyst Pd (dba) ₂ 150 mL of Toluene was added to tri-tert-Bu-phosphine (0.51 g, 0.0025 mol, Sigma aldrich) and reacted at 100 ° C for 6 hours with stirring. 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 17 g (yield 80%) of Compound 126.

D, 7.69 / d, 7.69 / d, 7.66 / d, 7.63 / d, 7.57 / s, 7.55 / d, 7.7 / d, 7.77 / d, 7.58 / m, 7.52 / d, 7.51 / m, 7.48 / m, 7.41 / m, 7.33 / m, 7.32 / m, 7.28 / 7.50 / d, 7.38 / m) 4H (7.54 / d, 6.69 / d) 6H (1.72 / s)

LC / MS: m / z = 844 [(M + 1) ^&lt; ^{+ &}

Synthetic example  11: Synthesis of compound 133

Sodium tert-butoxide (3.65 g, 0.038 mol, Sigma aldrich), Catalyst Pd (dba (2-amino-9,9-dimethylfluorene) _{) 2 (0.54 g, 0.0009 mol} , sigma aldrich), tri-tert-Bu-phosphine (0.38 g, put Toluene 150 mL to 0.0019 mol, sigma aldrich) was reacted under stirring at 100 ℃ 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 13 g (yield 81%) of 133.

M, 7.32 / m, &lt; RTI ID = 0.0 &gt; 7. &lt; / RTI &gt; 7.58 / d, 7.58 / d, 7.51 / m, 7.28 / m, 7.26 / m, 6.69 / m) 4H (7.33 / m, 7.11 / d) 6H (1.72 / s)

LC / MS: m / z = 844 [(M + 1) ^&lt; ^{+ &}

Synthetic example  12: Synthesis of Compound 134

Sodium tert-butoxide (3.64 g, 0.038 mol, Sigma aldrich), Catalyst Pd (dba, 0.023 mol) _{) 2 (0.54 g, 0.0009 mol} , sigma aldrich), tri-tert-Bu-phosphine (0.38 g, put Toluene 150 mL to 0.0019 mol, sigma aldrich) was reacted under stirring at 100 ℃ 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: MC) to obtain 11.3 g (yield: 82.8%) of 134.

M, 7.32 / m, &lt; RTI ID = 0.0 &gt; 7. &lt; / RTI &gt; 7.57 / d, 7.58 / d, 7.51 / m, 7.28 / m, 6.69 / d) 3H (7.38 / 1.72 / s)

LC / MS: m / z = 719 [(M + 1) ^&lt; ^{+ &}

Synthetic example  13: Synthesis of Compound 146

(1) Synthesis of intermediate 146-1

2-bromo-4-iodophenol ( 20 g, 0.067 mol, yurui), 4-biphenylboronic acid (15.90 g, 0.080 mol, sigma aldrich), potassium carbonate (18.50 g, 0.134 mol, sigma aldrich), Pd (PPh 3) ₄ (3.87 g, 0.0033 mol, sigma aldrich), 250 mL of Toluene and 50 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 17.4 g (yield: 80%) of Intermediate 146-1.

(2) Synthesis of intermediate 146-2

Intermediate 146-1 (20 g, 0.062 mol) , 2-fluorophenylboronic acid (10.33 g, 0.074 mol, sigma aldrich), potassium carbonate (17.00 g, 0.123 mol, sigma aldrich), Pd (PPh 3) 4 (3.55 g, 0.0031 mol, sigma aldrich), 250 mL of Toluene and 40 mL of ethanol, 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 17 g (yield: 81%) of Intermediate 146-2.

(3) Synthesis of intermediate 146-3

N-Bromosuccinimide (8.63 g, 0.049 mol, Sigma aldrich) and 200 mL of dimethylformamide were added and the mixture was reacted at 60 ° C for 12 hours with stirring. After completion of the reaction, 1M aqueous NaOH solution was added, stirred, filtered and dried to obtain 13.5 g (yield: 73%) of Intermediate 146-3.

(4) Synthesis of intermediate 146-4

Intermediate 146-4 (15 g, 0.036 mol), NaH (1.03 g, 0.043 mol, sigma aldrich) and 200 mL of dimethyl sulfoxide were added and reacted at 140 ° C for 5 hours with stirring. After completion of the reaction, the mixture was subjected to layer separation with H ₂ O: MC and then subjected to column purification (N-HEXANE: MC) to obtain 5.7 g (yield: 40%) of Intermediate 146-4.

(5) Synthesis of Compound 146

(10.81 g, 0.042 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 reacted at 100 ° C for 4 hours. After completion of the reaction, the reaction mixture was subjected to column separation with H ₂ O: EA, followed by column purification (N-HEXANE: EA) to obtain 13.9 g (yield 81.6%) of Compound 146.

7.7 / d, 7.62 / d, 7.57 / s, 7.55 / d, 7.32 / m, 7.28 / m, 7.07 / s, 6.75 / s, 6.58 / d) 2H (7.54 / d, 7.41 / m, 7.38 / m, 6.69 / d) 4H (7.52 / d, 7.51 /

LC / MS: m / z = 679 [(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 to 15

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: Liq 30 nm) / LiF (1 nm) / electron transport layer (20 nm) / ITO / hole injection layer (HAT_CN 5 nm) / hole transport layer / 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 a thickness of 10 nm by using the chemical formulas 29, 38, 48, 58, 69, 75, 86, 96, 111, 126, 133, 134, 146, 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 15

The voltage, current and luminous efficiency of the organic EL device were measured using a source meter (Model 237, Keithley) and a luminance meter (PR-650, Photo Research). The current density was 10 mA / Is defined as " driving voltage " The results are shown in Table 1 below.

Example Electronic stop layer V cd / A QE (%) CIEx CIEy One Formula 29 4.18 8.13 7.62 0.145 0.154 2 Formula 38 4.20 8.07 7.60 0.145 0.155 3 48 4.22 8.19 7.70 0.144 0.154 4 58 4.20 8.18 7.65 0.144 0.155 5 Formula 69 4.16 8.12 7.64 0.145 0.155 6 75 4.08 8.20 7.72 0.145 0.155 7 86 4.13 8.15 7.65 0.146 0.154 8 96 4.10 8.16 7.60 0.144 0.155 9 Formula 111 4.15 8.04 7.68 0.146 0.156 10 126 4.23 8.03 7.64 0.145 0.154 11 (133) 4.21 8.14 7.68 0.145 0.155 12 (134) 4.17 8.20 7.71 0.144 0.154 13 146 4.07 8.12 7.67 0.145 0.154 14 Formula 155 4.14 8.10 7.65 0.145 0.155 15 176 4.16 8.13 7.62 0.144 0.155 Comparative Example not used 4.14 5.4 4.6 0.147 0.156

In the case of a device using a compound represented by the formula (I) according to the present invention as an electron blocking layer compound, the emission efficiency, the quantum efficiency It can be confirmed that the light-emitting property is remarkably excellent.

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

Claims (6)

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

In the above formula (I)
X is CR &lt; ₁ &_gt; R &lt; ₂ &gt;, O or S,
Wherein R ₁ to R ₂ are the same or different and are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,
The R ₁ to R ₂ may form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle by being connected to each other or adjacent substituents,
L ₁ to L ₂ are the same or different and are each independently a single bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted Or a substituted or unsubstituted heteroarylene group containing at least one of N, O and S atoms,
Ar ₁ to Ar ₃ are the same or different from each other and each independently represents hydrogen, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, or a substituted or unsubstituted C3 to C20 cycloalkyl having 3 to 20 carbon atoms, A substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted carbazole group,
Wherein said substituted or unsubstituted heterocyclic group is one or two or more substituents selected from the group consisting of hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, silyl, alkyl, cycloalkyl, alkoxy, alkenyl, , Or two or more of the substituents of the substituents are substituted with a substituted or unsubstituted substituent. The method according to claim 1,
Wherein the compound represented by the formula (I) is any one selected from the group consisting of the following compounds 1 to 183:

1. An organic light emitting device comprising a first electrode, a second electrode, and at least one organic compound layer disposed between the first electrode and the second electrode,
Wherein at least one of the organic material layers comprises an organic light emitting compound represented by the general formula (I) of claim 1. The method of claim 3,
Wherein the organic material layer includes at least one of a hole injecting layer, a hole transporting layer, an electron blocking layer, a light emitting layer, an electron transporting layer, and an electron injecting layer,
Wherein at least one of the layers comprises an organic luminescent compound represented by the formula (I). 5. The method of claim 4,
Wherein the electron blocking layer comprises an organic luminescent compound represented by the formula (I). The method of claim 3,
Wherein at least one of the organic light emitting layers emitting red, green or blue light is further included in the organic material layer to emit white light.