KR20190020930A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light-emitting compound and an organic electroluminescent device comprising the same. The organic light-emitting compound is represented by chemical formula (I). When the organic light-emitting compound is applied in an electron blocking layer, a hole transport layer or a light-emitting layer, the organic electroluminescent device having excellent luminescent properties such as luminescent efficiency and quantum efficiency can be implemented.

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 electroluminescent compound, and more particularly, to an organic electroluminescent device employing an organic electroluminescent compound employed in an organic electroluminescent element in the organic electroluminescent device and a light emitting element such as quantum efficiency and luminous 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, an electron injecting material, an electron blocking material, The organic material layer for an organic electroluminescence device has not yet been developed sufficiently. Therefore, development of a new material capable of improving luminescence characteristics and development of an organic layer structure in a device are continuously required.

Therefore, 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 remarkably improve luminescent properties such as quantum efficiency and luminescent efficiency, Emitting 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 luminescent compound according to the present invention in the electron blocking layer, the hole transporting layer, or the luminescent layer has remarkably excellent luminescent properties such as luminescent efficiency as compared with the device employing the electron blocking layer, the hole transporting layer, Thereby being useful for various display devices.

1 is a schematic diagram showing the structure of an organic luminescent compound according to the present invention.

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

The present invention relates to an organic luminescent compound characterized by being represented by the following formula (I), wherein when it is employed in an organic layer such as a hole transporting layer, an electron blocking layer and a light emitting layer in an organic electroluminescence device, It is possible to realize an organic electroluminescent device in which light emission characteristics such as light emission efficiency are remarkably improved as compared with a device using a light emitting layer compound.

(I)

In the above formula (I)

Y is any one selected from O, S, CR _A R _B and SiR _A R _B , and R _A and R _B are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms.

R ₁ to R ₁₃ are the same or different and each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted C2 to 30 A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, and a substituted or unsubstituted aryl group having 2 to 30 carbon atoms, [Structural Formula 3].

R ₁ to R ₁₃ may be bonded to each other or may be connected with adjacent substituents to form a monocyclic or polycyclic ring of an alicyclic or aromatic group. The carbon atom of the monocyclic or aromatic monocyclic or polycyclic ring formed may be N, S And < RTI ID = 0.0 > O, < / RTI >

[Structural formula 1]

[Structural formula 2]

[Structural Formula 3]

In the above Structural Formulas 1 to 3,

X ₁ to X ₃ are the same or different and each independently CH or N,

L is a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 30 carbon atoms, A substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, A substituted or unsubstituted C2 to C50 heteroarylene group in which one or more substituted or unsubstituted C 6 to C 50 arylene groups and substituted or unsubstituted C 3 to C 30 cycloalkyls are fused together, (N is an integer of 1 to 3).

Ar ₁ to Ar ₃ are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted 6 to 30 carbon atom A substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group, a substituted or unsubstituted C3 to C30 cycloalkyl, And a substituted or unsubstituted C2 to C50 heteroaryl group in which one or more ring-opened cycloalkyl having 3 to 30 carbon atoms is fused.

The Ar ₁ to Ar ₃ may be bonded to each other or may be connected to adjacent substituents to form a single alicyclic or aromatic ring or polycyclic ring. The carbon atom of the alicyclic or aromatic monocyclic or polycyclic ring formed may be N , S and < RTI ID = 0.0 > O, < / RTI >

The organic luminescent compound according to the present invention is characterized in that any one of R ₁ to R ₁₃ is any one selected from the following Structural Formulas 1 to 3, Organic light emitting devices have excellent light emitting properties such as quantum efficiency and luminous efficiency.

On the other hand, the R ₁ to R _13, from the L, and the definition of Ar ₁ to Ar _3, substituted or non-substituted ring is the R ₁ to R _13, L and Ar ₁ to Ar ₃ heavy hydrogen, a cyano group, a halogen group, a hydroxyl 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, a heteroalkyl group having 1 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 aryl group having 1 to 24 carbon atoms An amino group, 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, Substituted with a substituent, or two or more of the substituents in the substituent are substituted with a connected group, 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 of each other an alkyl group having 1 to 10 carbon atoms and in this case an "alkylamino group"), an amidino 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, a heteroatom having 1 to 24 carbon atoms, An alkyl group having 6 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,

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.

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

The organic luminescent compound according to the present invention represented by the above-mentioned formula (I) can be used as an organic material layer of an organic light emitting device due to its structural specificity as described above. More specifically, A blocking layer, a hole transporting layer, or a host compound of a light emitting layer.

Specific preferred examples of the compound represented by the formula (I) according to the present invention include the following [compounds 1] to [296], but the scope of the present invention is not limited thereto.

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 the formula (I) according to the present invention is used as a host material of an electron blocking layer, a hole transporting layer or a light emitting layer, and particularly in an electron blocking layer, quantum efficiency and luminescence efficiency The luminescent characteristics 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 12

(One) Manufacturing example  1: Synthesis of Intermediate 12-1

Dibenzo [b, d] furan-3-ylboronic acid (6.70 g, 0.032 mol, Yurii), potassium carbonate (10.91 g, 0.079 mol, Sigma Aldrich), 1,8-diiodonaphthalene (10 g, _{, Pd (PPh 3) 4 (} 1.52 g, 0.0013 mol, sigma aldrich), Toluene 150 mL, Ethanol 40 mL, H 2 O 20 mL placed and reacted by stirring 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 8.7 g (yield: 78.7%) of Intermediate 12-1.

(2) Manufacturing example  2: Synthesis of intermediate 12-2

After stirring for 10 minutes at -78 ° C, n-BuLi (2.51 g, 0.039 mol, Sigma Aldrich) was slowly added dropwise to the mixture, and the mixture was stirred at -78 ° C For 1 hour and reacted with bubble CO ₂ at -78 ° C for 10 minutes at room temperature. After completion of the reaction, H ₂ O and 1M HCl were added and the mixture was oxidized to pH 1 and extracted with EtOAc to obtain 8.5 g (yield: 70.4%) of Intermediate 12-2.

(3) Manufacturing example  3: Synthesis of intermediate 12-3

Intermediate 12-2 (15 g, 0.044 mol) and methane sulfonic acid (400 mL) were added, and the mixture was reacted at 70 DEG C for 1 hour with stirring. After completion of the reaction, the reaction mixture was cooled to room temperature and slowly poured into ice water. The resulting solid was filtered, washed with water and dried to obtain 11.4 g (yield: 80%) of Intermediate 12-3.

(4) Manufacturing example  4: Synthesis of intermediate 12-4

Aluminum chloride (7.49 g, 0.056 mol, Sigma aldrich) was slowly added to 500 mL of diethyl ether and stirred for 15 minutes. The mixture was cooled to 0 ° C and lithium aluminum hydride (2.67 g, 0.070 mol, Sigma Aldrich) was slowly added thereto, followed by stirring for 1 hour. After completion of the reaction, the reaction mixture was warmed to room temperature, EA was slowly added dropwise, and 6M HCl was slowly added thereto. The reaction mixture was extracted with distilled water and EA, and then subjected to column purification (MC: EA) to obtain 12.3 g (yield: 85.7% .

(5) Manufacturing example  5: Synthesis of intermediate 12-5

Methyl iodide (55.6 g, 0.392 mol, Sigma aldrich) was added to the solution after stirring at 70 ° C for 20 minutes. Was slowly added dropwise and the mixture was reacted by stirring for 4 hours. After completion of the reaction, H ₂ O was added and stirred, and the resulting solid was filtered and recrystallized to obtain 11 g (yield 67%) of <Intermediate 12-5>.

(6) Manufacturing example  6: Synthesis of Intermediate 12-6

To a solution of Intermediate 12-5 (10 g, 0.030 mol) in chloroform (200 mL), cool to 0 ° C and slowly drop bromine (5.26 g, 0.033 mol, Sigma Aldrich) with stirring. The mixture was stirred at 0 ° C for 1 hour and reacted at room temperature for 12 hours. After completion of the reaction, an aqueous solution of sodium hydrogencarbonate was added thereto, the layers were separated and recrystallized to obtain 7.3 g (yield: 59%) of Intermediate 12-6.

(7) Manufacturing example  7: Synthesis of intermediate 12-7

Sodium tert-butoxide (11.67 g, 0.121 mol, Sigma aldrich), catalyst Pd (dba, 0.73 mol, _{) 2 (1.75 g, 0.003 mol} , sigma aldrich), tri-tert-Bu-phosphine (1.23 g, put on Toluene 250 mL 0.006 mol, sigma aldrich) was reacted under stirring at 100 ℃ 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: EA) to obtain 12.6 g (yield: 80%) of Intermediate 12-7.

(8) Manufacturing example  8: Synthesis of Compound 12

Sodium tert-butoxide (4.65 g, 0.050 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.70 g, 0.0012 mol) was added to a solution of intermediate 12-6 (10 g, 0.024 mol), intermediate 12-7 150 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: EA) to obtain 11 g (yield 76.8%) of Compound 12.

7.38 / m, 7.38 / m, 7.58 / m, 7.58 / m, 7.8 / d, 7.89 / d, 7.66 / d, 7.00 / d, 6.81 / m) 2H (7.64 / d, 7.43 / s, 7.42 / m, 7.20 /

LC / MS: m / z = 591 [(M + 1) ^&lt; ^{+ &}

Synthetic example  2: Compound 52 Synthesis

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

Sodium tert-butoxide (8.25 g, 0.086 mol, Sigma aldrich), 4-aminobiphenyl (8.71 g, 0.052 mol, sigma aldrich), catalyst Pd (dba) ₂ 200 mL of Toluene was added to 1.23 g, 0.002 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.87 g, 0.004 mol, Sigma aldrich) and reacted at 100 ° C for 2 hours. After the 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 11 g (yield 80%) of Intermediate 52-1.

(2) Production Example 2  : Synthesis of Compound 52

Sodium tert-butoxide (4.65 g, 0.048 mol, sigma aldrich), Catalyst Pd (dba) ₂ (10 g, 0.024 mol), Intermediate 52-1 (9.33 g, 0.029 mol) (0.70 g, 0.0012 mol, Sigma aldrich) and tri-tert-Bu-phosphine (0.70 g, 0.0012 mol, Sigma aldrich) were added 100 mL of toluene and reacted at 100 ° C for 8 hours with stirring. After completion of the reaction, the mixture was subjected to column separation with H ₂ O: EA, followed by column purification (N-HEXANE: EA) to obtain 12.4 g (yield 78%) of Compound 52.

D, 8.01 / d, 7.92 / d, 7.64 / d, 7.58 /, m 7.56 / s, 7.43 / s, 7.00 / d, 6.33 / d) (7.54 / d, 7.52 / d, 7.51 / m, 6.69 / d) 6H (1.85 / s)

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

Synthetic example  3: Compound 70 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 70-1

Sodium tert-butoxide (7.04 g, 0.073 mol, Sigma Aldrich), 4-aminobiphenyl (7.43 g, 0.044 mol, Sigma Aldrich), 2-bromo-9,9-dimethyl-9H- 150 mL of Toluene was added to the catalyst Pd (dba) ₂ (1.05 g, 0.0018 mol, sigma aldrich) and tri-tert-Bu-phosphine (0.74 g, 0.0037 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: EA) to obtain 10.5 g (yield 79%) of Intermediate 70-1.

(2) Manufacturing example  2: Synthesis of Compound 70

Sodium tert-butoxide (4.65 g, 0.048 mol, Sigma aldrich), Catalyst Pd (dba) ₂ (0.72 g, 0.0012 mol) was added to a solution of intermediate 12-6 (10 g, 0.024 mol), intermediate 70-1 150 mL of Toluene was added to tri-tert-Bu-phosphine (0.49 g, 0.0024 mol, Sigma aldrich) and reacted at 100 ° C for 1 hour. 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 13.3 g (yield: 79%) of Compound 70.

7.56 / s, 7.55 / d, 7.62 / d, 7.64 / d, 7.62 / d, 7.58 / 7.54 / d, 7.52 / d, 7.51 / m, 7.42 / m, 7.43 / s, 7.41 / m, 7.38 / m, 7.28 / m, 7.00 / d, 6.75 / s, 6.58 / d, 6.33 / 6.69 / d) 6H (1.85 / s, 1.72 / s)

LC / MS: m / z = 693 [(M + 1) ^&lt; ^{+ &}

Synthetic example  4: Compound 93 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 93-1

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 then subjected to column purification (N-HEXANE: MC) to obtain 14.3 g (yield: 72%) of Intermediate 93-1.

(2) Manufacturing example  2: Synthesis of intermediate 93-2

Potassium acetate (6.07 g, 0.062 mol, Sigma aldrich), PdCl ₂ (dppf) (0.68 g, 0.040 mol) was added to a solution of intermediate 93-1 (10 g, 0.031 mol), Bis (pinacolato) dibron 0.0009 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 8.2 g (yield: 72%) of Intermediate 93-2.

(3) Manufacturing example  3: Synthesis of intermediate 93-3

(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), 150 mL of THF and 40 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 93-3.

(4) Manufacturing example  4: Synthesis of intermediate 93-4

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 93-3 (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 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 10 g (yield: 82%) of Intermediate 93-4.

(5) Manufacturing example  5: Synthesis of compound 93

Sodium tert-butoxide (2.33 g, 0.024 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.35 g, 0.0006 mol), Intermediate 93-4 (7.08 g, 0.015 mol) 100 mL of toluene was added to tri-tert-Bu-phosphine (0.24 g, 0.0012 mol, Sigma aldrich) and the mixture was reacted at 100 ° C for 1 hour. 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 7.6 g (yield 76.6%) of Compound 93.

D, 8.01 / d, 7.92 / d, 7.64 / d, 7.58 / m, 7.56 / s, 7.43 / s, 7.00 / d, 6.33 / d) 7.55 / d, 7.81 / d, 7.42 / m, 7.41 / m, 7.38 /

LC / MS: m / z = 819 [(M + 1) ^&lt; ^{+ &}

Synthetic example  5: Compound 105 Synthesis

(One) Manufacturing example  1: Synthesis of Compound 105

Sodium tert-butoxide (4.65 g, 0.048 mol, sigma aldrich), Catalyst Pd (dba), and Pd (dba) were added to a solution of intermediate 12-6 (10 g, 0.024 mol), 4- (diphenylamino) phenylboronic acid (8.39 g, 0.029 mol, _{2 (0.70 g, 0.0012 mol,} sigma aldrich), tri-tert-Bu-phosphine into a 150 mL Toluene in (0.49 g, 0.0024 mol, sigma aldrich) was reacted under stirring at 100 ℃ 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: EA) to obtain 11.1 g (yield: 79.4%) of Compound 105.

D, 8.01 / d, 7.95 / d, 7.92 / d, 7.75 / d, 7.64 / s, 7.58 / m, 7.56 / s, 7.00 / d) 2H) (7.54 / d, 7.42 / m, 6.81 / m, 6.69 / d) 4H (7.20 /

LC / MS: m / z = 577 [(M + 1) ^&lt; ^{+ &}

Synthetic example  6: Compound 112 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 112-1

Sodium tert-butoxide (15.56 g, 0.16 mol, Sigma aldrich), Catalyst Pd (dba) ₂ (20 g, 0.081 mol, Yurii), 3-aminobiphenyl (16.44 g, 0.097 mol, Sigma aldrich) (1.33 g, 0.008 mol, Sigma aldrich) was added 250 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 and then subjected to column purification (N-HEXANE: EA) to obtain 19.2 g (yield: 70.7%) of Intermediate 112-1.

(2) Manufacturing example  2: Synthesis of intermediate 112-2

Sodium tert-butoxide (5.73 g, 0.060 mol, Sigma aldrich), Catalyst Pd (dba) ₂ (10 g, 0.030 mol), 4-bromophenylboronic acid (7.19 g, 0.036 mol, sigma aldrich) (0.86 g, 0.0015 mol, Sigma aldrich) and tri-tert-Bu-phosphine (0.60 g, 0.003 mol, Sigma aldrich) were added 150 mL of Toluene and 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 10.6 g (yield 78%) of Intermediate 112-2.

(3) Manufacturing example  3: Synthesis of Compound 112

Sodium tert-butoxide (4.65 g, 0.048 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.70 g, 0.029 mol), Intermediate 12-2 (13.22 g, 0.029 mol, sigma aldrich) 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 1 hour. After completion of the reaction, the mixture was separated into H ₂ O: MC and subjected to column purification (N-HEXANE: EA) to obtain 14 g (yield 77.8%) of Compound 112.

7.8 / d, 7.75 / d, 7.66 / d, 7.58 / m, 7.56 / s, 7.44 / d, 7.44 / d, 7.41 / m, 7.38 / m, 7.32 / m, 7.00 / d, 6.89 / d, 6.88 / d, 6.59 / d, 6.33 / 7.52 / d, 7.51 / m, 7.42 / m, 6.69 / d) 6H (1.85 / s)

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

Synthetic example  7: Synthesis of Compound 121

(One) Manufacturing example  1: Synthesis of intermediate 121-1

Dibenzo [b, d] thiophen-3-ylboronic acid (9.57 g, 0.042 mol, Yurii), potassium carbonate (14.50 g, 0.105 mol, Sigma Aldrich), 1,8-dibromonaphthalene (10 g, _{, Pd (PPh 3) 4 (} 2.02 g, 0.0017 mol, sigma aldrich), Toluene 150 mL, Ethanol 40 mL, H 2 O 20 mL placed and reacted by stirring 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 10.7 g (yield: 78.6%) of Intermediate 121-1.

(2) Manufacturing example  2: Synthesis of intermediate 121-2

BuLi (2.72 g, 0.0424 mol, Sigma Aldrich) was slowly added dropwise at -78 ° C after stirring for 15 minutes at -78 ° C, and then added dropwise at -78 ° C For 1 hour and bubble CO ₂ was reacted at -78 ° C for 10 minutes at room temperature. After completion of the reaction, H ₂ O and 1M HCl were added and the mixture was oxidized to pH 1 and extracted with EtOAc to obtain 10 g (yield: 73%) of Intermediate 121-2.

(3) Manufacturing example  3: Synthesis of intermediate 121-3

Intermediate 121-2 (15 g, 0.042 mol) and methane sulfonic acid (400 mL) were added, and the mixture was reacted at 70 DEG C for 1 hour with stirring. After the reaction was completed, the reaction mixture was cooled to room temperature and slowly poured into ice water. The resulting solid was filtered, washed with water and dried to obtain 11.6 g (yield: 81.5%) of Intermediate 121-3.

(4) Manufacturing example  4: Synthesis of intermediate 121-4

Aluminum chloride (7.13 g, 0.054 mol, Sigma aldrich) was slowly added to 500 ml of diethyl ether and stirred for 15 minutes. The mixture was cooled to 0 ° C and lithium aluminum hydride (2.54 g, 0.067 mol, Sigma aldrich) was added slowly and reacted for 1 hour with stirring. After completion of the reaction, the reaction mixture was warmed to room temperature, EA was slowly added dropwise, 6M HCl was slowly added thereto, and the mixture was extracted with distilled water and EA, followed by column purification (MC: EA) to obtain 12 g (yield: 83.5% .

(5) Manufacturing example  5: Synthesis of intermediate 121-5

Methyl iodide (52.83 g, 0.372 mol, Sigma aldrich) was added to the solution after stirring at 70 ° C for 20 minutes. Was slowly added dropwise and the mixture was reacted by stirring for 4 hours. After completion of the reaction, H ₂ O was added and stirred, and the resulting solid was filtered and recrystallized to obtain 11 g (yield 67%) of <Intermediate 121-5>.

(6) Manufacturing example  6: Synthesis of intermediate 121-6

Add bromine (5.02 g, 0.031 mol, Sigma Aldrich) dropwise with stirring to 0 ° C and stir with 200 mL of chloroform. The mixture was stirred at 0 ° C for 1 hour and reacted at room temperature for 12 hours. After completion of the reaction, an aqueous solution of sodium hydrogencarbonate was added thereto, the layers were separated, and recrystallization was conducted to obtain 7 g (yield: 57%) of <Intermediate 121-6>.

(7) Manufacturing example  7: Synthesis of intermediate 121-7

Sodium tert-butoxide (10.96 g, 0.114 mol, Sigma aldrich), Catalyst Pd (dba, 0.057 mol, Yurii), 3-bromodibenzo [b, d] thiophene _{) 2 (1.64 g, 0.003 mol} , sigma aldrich), tri-tert-Bu-phosphine (1.15 g, put on Toluene 250 mL 0.006 mol, 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 12.4 g (yield 79%) of Intermediate 121-7.

(2) Manufacturing example  8: Synthesis of Compound 121

Sodium tert-butoxide (4.49 g, 0.047 mol, sigma aldrich), Catalyst Pd (dba) ₂ (0.67 g, 0.0012 mol), Intermediate 121-7 (7.72 g, 0.028 mol) 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 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: EA) to obtain 11.2 g (yield: 76.8%) of Compound 121.

D, 8.01 / d, 8.00 / s, 7.98 / d, 7.92 / s, 7.74 / s, 7.58 / m, 7.52 / m, 7.50 / m, 7.42 / m, 7.00 / d, 6.81 / m) 2H (7.80 / d, 7.20 / m, 7.06 / s, 6.88 / d, 6.63 /

LC / MS: m / z = 623 [(M + 1) ^&lt; ^{+ &}

Synthetic example  8: Compound 145 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 145-1

Add bromine (10.51 g, 0.066 mol, Sigma Aldrich) slowly with stirring to 0 ° C, then stir with 200 ml of chloroform and add Intermediate 12-5 (10 g, 0.030 mol). The mixture was stirred at 0 ° C for 1 hour and reacted at room temperature for 12 hours. After completion of the reaction, an aqueous solution of sodium hydrogencarbonate was added thereto, followed by layer separation and recrystallization. 11.8 g (yield: 80%) of <Intermediate 145-1> was obtained.

(2) Manufacturing example  2: Synthesis of intermediate 145-2

Intermediate 145-1 (20 g, 0.041 mol) , phenylboronic acid (9.57 g, 0.042 mol, sigma aldrich), potassium carbonate (14.50 g, 0.105 mol, sigma aldrich), Pd (PPh 3) 4 (2.02 g, 0.0017 mol , sigma aldrich), 150 mL of Toluene, 40 mL of Ethanol, and 20 mL of H ₂ O were added and reacted by refluxing 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 10.7 g (yield: 78.6%) of Intermediate 121-2.

(3) Manufacturing example  3: Synthesis of intermediate 145-3

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 145-3.

(4) Manufacturing example  4: Synthesis of Compound 145

Sodium tert-butoxide (3.93 g, 0.041 mol, Sigma aldrich), Catalyst Pd (dba) ₂ (0.59 g, 0.0010 mol), Intermediate 145-2 (10 g, 0.020 mol) 150 mL of Toluene was added to tri-tert-Bu-phosphine (0.41 g, 0.0020 mol, Sigma aldrich) and reacted at 100 ° C for 6 hours with stirring. 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 12 g (yield 79%) of Compound 145.

D, 7.89 d, 7.82 d, 7.66 d, 7.64 d, 7.58 m, 7.56 s, 7.43 s, 7.42 d, d, 7.52 / d, 7.41 / m, 6.69 / d, 7.38 / d, 7.38 / / d) 4H (7.51 / m) 6H (1.85 / s)

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

Synthetic example  9: Compound 150 Synthesis

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

Add bromine (10.51 g, 0.066 mol, Sigma Aldrich) slowly with stirring to 0 ° C, then stir with 200 ml of chloroform and add Intermediate 12-5 (10 g, 0.030 mol). The mixture was stirred at 0 ° C for 1 hour and reacted at room temperature for 12 hours. After completion of the reaction, an aqueous solution of sodium hydrogencarbonate was added thereto and the layers were separated and recrystallized to obtain 3.2 g (yield: 26%) of Intermediate 150-1.

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

(7.99 g, 0.0315 mol, Sigma Aldrich), potassium acetate (4.75 g, 0.048 mol, Sigma Aldrich), PdCl ₂ (dppf) (0.53 g, 0.0007 mol, Sigma aldrich) and 1,4-dioxane (200 mL), and the mixture was stirred at 95 ° C for 12 hours. After completion of the reaction, the reaction mixture was poured into H ₂ O, the layers were separated, and the product was purified by column (N-HEXANE: MC) to obtain 8.5 g (yield 76%) of Intermediate 150-2.

(3) Manufacturing example  3: Synthesis of Compound 150

2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 0.037 mol, TCI), intermediate 150-2 (20.64 g, 0.045 mol), potassium carbonate (15.49 g, 0.112 mol, Sigma Aldrich ), Pd (PPh ₃ ) ₄ (2.16 g, 0.0019 mol, sigma aldrich), 150 mL of Toluene, 40 mL of ethanol and 20 mL of H ₂ O were added and reacted by refluxing for 8 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC, followed by column purification (N-HEXANE: MC) to obtain 17 g (yield 80%) of Compound 150.

D, 7.89 / d, 7.66 / d, 7.58 / d, 7.42 / m, 7.32 / m, 7.00 / d) 2H (7.41 / m, 7.38 / m) 4H (8.28 / d, 7.51 / m) 6H (1.85 / s)

LC / MS: m / z = 565 [(M + 1) ^&lt; ^{+ &}

Synthetic example  10: Compound 163 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 163-1

Dibenzo [b, d] furan-4-ylboronic acid (11.25 g, 0.053 mol, Yurui), 2-chloro-4,6-diphenyl-1,3,5-triazine (10 g, 0.044 mol, carbonate (18.34 g, 0.133 mol, sigma aldrich), Pd (PPh 3) 4 (2.56 g, 0.0022 mol, sigma aldrich), Toluene 150 mL, Ethanol 40 mL, H 2 O 20 mL into the mixture was stirred under reflux for 5 hours, the reaction . 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: 77%) of <Intermediate 163-1>.

(2) Manufacturing example  2: Synthesis of intermediate 163-2

(4.75 g, 0.0315 mol, Sigma Aldrich), potassium acetate (4.75 g, 0.048 mol, Sigma aldrich), PdCl ₂ (dppf) (0.53 g, 0.0007 mol, Sigma aldrich) and 1,4-dioxane (200 mL), and the mixture was stirred 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 column purification (N-HEXANE: MC) was conducted to obtain 8.5 g (yield 76%) of Intermediate 163-2.

(3) Manufacturing example  3: Synthesis of Compound 163

Intermediate 150-1 (10 g, 0.024 mol) , intermediate 163-2 (13.05 g, 0.029 mol) , potassium carbonate (10.03 g, 0.073 mol, sigma aldrich), Pd (PPh 3) 4 (1.40 g, 0.0012 mol, Sigma aldrich), 150 mL of Toluene, 40 mL of Ethanol, and 20 mL of H ₂ O were added and reacted by refluxing for 8 hours. After completion of the reaction, the reaction mixture was subjected to layer separation using H ₂ O: MC, followed by column purification (N-HEXANE: MC) to obtain 14 g (yield 79%) of Compound 163.

M, 7.41 / m, 7.00 / d) 2H (8.28 / d, 8.01 / d, 7.92 / d, 7.81 / d, 7.58 / d, 7.89 / d, 7.66 / d, 7.51 / m, 7.32 / m, 7.25 / d)

LC / MS: m / z = 565 [(M + 1) ^&lt; ^{+ &}

Synthetic example  11: Compound 257 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 257-1

4-biphenylboronic acid (10.51 g, 0.053 mol, Sigma aldrich), potassium carbonate (18.34 g, 0.133 mol) in 2-chloro-4,6-diphenyl-1,3,5-triazine , Sigma aldrich), Pd (PPh ₃ ) ₄ (2.56 g, 0.0022 mol, sigma aldrich), 150 mL of Toluene, 40 mL of ethanol and 20 mL of H ₂ O were added and reacted by refluxing for 8 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 g (yield 79%) of Intermediate 257-1.

(2) Manufacturing example  2: Synthesis of intermediate 257-2

(5.71 g, 0.058 mol, Sigma aldrich), PdCl ₂ (dppf) (0.64 g, 0.0009 mol, Sigma aldrich) and 1,4-dioxane (200 mL), and the mixture was stirred 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 9.8 g (yield 77%) of Intermediate 257-2.

(3) Manufacturing example  3: Synthesis of Compound 257

Intermediate 12-6 (10 g, 0.024 mol) , intermediate 257-2 (12.70 g, 0.029 mol) , potassium carbonate (10.03 g, 0.073 mol, sigma aldrich), Pd (PPh 3) 4 (1.40 g, 0.0012 mol, Sigma aldrich), 150 mL of Toluene, 40 mL of Ethanol, and 20 mL of H ₂ O were added and reacted by refluxing for 8 hours. After completion of the reaction, the mixture was subjected to layer separation using H ₂ O: MC and purified by column (N-HEXANE: MC) to obtain 12 g (yield 77%) of Compound 257.

D, 8.01 / d, 7.95 / d, 7.92 / d, 7.75 / d, 7.64 / s, 7.58 / m, 7.56 / s, 7.00 / d) M, 6H (1.85 / s) 2H (8.28 / d, 7.85 / d, 7.52 / d, 7.42 /

LC / MS: m / z = 641 [(M + 1) ^&lt; ^{+ &}

Synthetic example  12: Compound 277 Synthesis

(One) Manufacturing example  1: Synthesis of intermediate 277-1

(10.75 g, 0.0423 moles, Sigma Aldrich), potassium acetate (6.39 g, 0.065 moles, Sigma Aldrich), PdCl ₂ (dppf) (0.71 g, 0.033 mol), 2-bromotriphenylene (10 g, , 0.0010 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 9.5 g (yield: 82%) of Intermediate 277-1.

(2) Manufacturing example  2: Synthesis of intermediate 277-2

1-bromo-4-iodobenzene ( 10 g, 0.035 mol, sigma aldrich), Intermediate 277-1 (12.52 g, 0.0353 mol) , potassium carbonate (14.66 g, 0.106 mol, sigma aldrich), Pd (PPh 3) 4 ( 2.04 g, 0.0018 mol, sigma aldrich), 150 mL of Toluene, 40 mL of Ethanol, and 20 mL of H ₂ O were added, and the mixture was stirred under reflux for 8 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 10.7 g (yield 79%) of Intermediate 277-2.

(3) Manufacturing example  3: Synthesis of intermediate 277-3

To a solution of intermediate 277-2 (10 g, 0.026 mol), Bis (pinacolato) dibron (8.61 g, 0.034 mol, SigmaAldrich), potassium acetate (5.12 g, 0.052 mol, SigmaAldrich), PdCl ₂ (dppf) 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, H ₂ O was added, layer separation was performed, and column purification (N-HEXANE: MC) was performed to obtain 9 g (yield 80%) of <Intermediate 277-3>.

(4) Manufacturing example  4: Synthesis of Compound 277

Intermediate 12-6 (10 g, 0.024mol), intermediate 277-3 (12.49 g, 0.029 mol) , potassium carbonate (10.03 g, 0.073 mol, sigma aldrich), Pd (PPh 3) 4 (1.40 g, 0.0012 mol, Sigma aldrich), 150 mL of Toluene, 40 mL of Ethanol, and 20 mL of H ₂ O were added and reacted by refluxing for 8 hours. 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 12.4 g (yield: 80.5%) of Compound 277.

D, 8.01 / d, 7.95 / d, 7.92 / d, 7.75 / d, 7.64 / s, 7.58 / m, 7.56 / s, 7.00 / d) 2H (8.93 / d, 8.12 / d, 7.88 / m, 7.82 / m, 7.42 /

LC / MS: m / z = 636 [(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 manufactured by employing the compound implemented according to the present invention as an electron blocking layer compound, 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, a 5 nm thick layer was formed by vacuum thermal evaporation 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 by using the chemical vapor deposition (chemical vapor deposition) layers 12, 17, 44, 52, 58, 70, 93, 105, 112, 121, 142, 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

The organic electroluminescent device for Device Comparison Example 1 is the same as the first embodiment except that the conventionally used TCTA is used instead of the compound according to the present invention as the electron blocking layer material in the device structure of Example 1 Respectively.

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

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 12 4.18 8.20 6.89 0.143 0.154 2 Formula 17 4.20 8.10 6.80 0.145 0.155 3 44 4.22 8.20 6.83 0.145 0.154 4 Formula 52 4.15 8.25 6.96 0.144 0.155 5 58 4.09 8.33 7.06 0.144 0.154 6 70 4.16 8.12 6.81 0.145 0.155 7 Formula 93 4.21 8.18 6.82 0.144 0.154 8 105 4.17 8.15 6.84 0.144 0.154 9 Formula 112 4.19 8.20 6.88 0.145 0.154 10 Formula 121 4.25 8.09 6.70 0.145 0.155 11 Formula 142 4.23 8.06 6.75 0.145 0.155 12 145 4.20 8.13 6.82 0.144 0.154 Comparative Example TCTA 4.14 6.40 5.30 0.145 0.155

When the compounds of the present invention were applied to the electron blocking layer of the device, it was confirmed that the luminescent properties such as the luminous efficiency and the quantum efficiency were remarkably superior to those of the conventional device (comparative example) .

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

Claims (6)

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

In the above formula (I)
Y is any one selected from O, S, CR _A R _B, and SiR _A R _B , wherein R _A and R _B are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms,
R ₁ to R ₁₃ are the same or different and each independently represents hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted C2 to 30 A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, and a substituted or unsubstituted aryl group having 2 to 30 carbon atoms, Is selected from [formula 3]
R ₁ to R ₁₃ may be bonded to each other or may be connected with adjacent substituents to form a monocyclic or polycyclic ring of an alicyclic or aromatic group. The carbon atom of the monocyclic or aromatic monocyclic or polycyclic ring formed may be N, S And &lt; RTI ID = 0.0 &gt; O, &lt; / RTI &gt;
[Structural formula 1]

[Structural formula 2]

[Structural Formula 3]

In the above Structural Formulas 1 to 3,
X ₁ to X ₃ are the same or different and each independently CH or N,
L is a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 30 carbon atoms, A substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, A substituted or unsubstituted C2 to C50 heteroarylene group in which one or more substituted or unsubstituted C 6 to C 50 arylene groups and substituted or unsubstituted C 3 to C 30 cycloalkyls are fused together, (N is an integer of 1 to 3),
Ar ₁ to Ar ₃ are the same or different and each independently represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted 6 to 30 carbon atom A substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group, a substituted or unsubstituted C3 to C30 cycloalkyl, A substituted or unsubstituted C2 to C50 heteroaryl group in which one or more ring-opened cycloalkyls having 3 to 30 carbon atoms is fused,
Ar ₁ to Ar ₃ may be bonded to each other or may be connected with adjacent substituents to form a single alicyclic or aromatic ring or polycyclic ring. The carbon atom of the alicyclic or aromatic monocyclic or polycyclic ring may be N, S And &lt; RTI ID = 0.0 &gt; O, &lt; / RTI &gt; The method according to claim 1,
Any one of R ₁ to R ₁₃ is any one selected from the following Structural Formulas 1 to 3,
And the remainder are hydrogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, A substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms. 3. The method according to claim 1 or 2,
R ₁ to R ₁₃ , L and Ar ₁ to Ar ₃ each represent a hydrogen atom, 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, a heteroalkyl 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, Or a heteroarylalkyl group having 2 to 24 carbon atoms, an alkoxy group having 1 to 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, Group, an arylsilyl group having 1 to 24 carbon atoms, and an aryloxy group having 1 to 24 carbon atoms, which is substituted with one or more selected substituents or two or more The organic light emitting compound means that the substituent is substituted with a substituent is connected, or does not have any substituent. The method according to claim 1,
The organic luminescent compound according to claim 1, wherein the compound represented by Formula (I) is any one selected from the following Formulas (1) to (296)

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. The method according to claim 6,
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).

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