KR101904297B1 - Compound for organic optoelectronic device, organic light emitting diode including the same and display including the organic light emitting diode - Google Patents

Abstract

The present invention relates to a compound for an organic optoelectronic device, an organic light emitting device including the same, and a display device including the organic light emitting device.
(3)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device,

A compound for an organic optoelectronic device, an organic light emitting device including the same, and a display device including the organic light emitting device.

An organic optoelectronic device refers to a device that requires charge exchange between an electrode and an organic material using holes or electrons.

Organic optoelectronic devices can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Type electronic device.

The second type is an electronic device in which holes or electrons are injected into an organic semiconductor forming an interface with an electrode by applying a voltage or current to two or more electrodes and operated by injected electrons and holes.

Examples of organic optoelectronic devices include organic optoelectronic devices, organic light-emitting devices, organic solar cells, organic photo conductor drums, and organic transistors, all of which are used for the injection or transport of holes, An injection or transport material, or a luminescent material.

In particular, organic light emitting diodes (OLEDs) have been attracting attention in recent years as the demand for flat panel displays increases. In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

Such an organic light emitting device is a device that converts electric energy into light by applying an electric current to an organic light emitting material, and is usually composed of a structure in which a functional organic layer is interposed between an anode and a cathode. Here, in order to enhance the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layered structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected into the anode and electrons are injected into the organic layer from the cathode. The injected holes and electrons meet and recombine Energy excitons are formed. At this time, the exciton formed again moves to the ground state, and light having a specific wavelength is generated.

In recent years, it is known that not only a fluorescent light emitting material but also a phosphorescent emitting material can be used as a light emitting material of an organic light emitting device. Such phosphorescent emitting is a phenomenon in which electrons transition from a ground state to an excited state, cross-linking of the triplet exciton to the triplet exciton, and then the triplet exciton transitions to the ground state.

As described above, 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 such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system can be used as a light emitting material in order to increase the light emitting efficiency and stability through the light emitting layer.

In order for the organic luminescent device to fully exhibit the above-described excellent characteristics, a host material and / or a dopant such as a hole injecting material, a hole transporting material, a luminescent material, an electron transporting material, an electron injecting material, The organic material layer for organic light emitting devices has not been sufficiently developed yet. Therefore, development of new materials has been continuously required. The necessity of developing such a material is the same in other organic optoelectronic devices described above.

In addition, the low-molecular organic light-emitting device has good efficiency and long life performance because it is manufactured in the form of a thin film by a vacuum deposition method. The polymer organic light-emitting device uses an inkjet or spin coating method, There is an advantage that the large area is advantageous.

Low molecular organic light emitting devices and polymer organic light emitting devices are attracting attention as next generation displays because they have advantages such as self-emission, fast response, wide viewing angle, ultra-thin, high image quality, durability and wide driving temperature range. Compared to conventional liquid crystal displays (LCDs), it is self-luminous and has good visibility even when dark or external light enters. It can reduce thickness and weight to 1/3 of that of LCD without backlight.

In addition, the response speed is 1000 times faster than that of LCD, so it is possible to realize perfect video without residual image. Therefore, it is anticipated that it will be seen as an optimal display for the full-scale multimedia age in the recent era. Based on these advantages, after the first development in the late 1980s, the efficiency has been rapidly increased to 80 times and 100 times or more. And organic light-emitting device panels have been announced, and the size of the organic light-emitting device panel is rapidly increasing.

In order to increase the size, it is necessary to increase the luminous efficiency and the lifetime of the device. Therefore, it is necessary to develop a stable and efficient organic material layer material for an organic light emitting device.

And which can provide an organic optoelectronic device having characteristics such as high efficiency, long life, and the like.

An organic light emitting device including the compound for an organic optoelectronic device, and a display device including the organic light emitting device.

In one embodiment of the present invention, there is provided a compound for an organic optoelectronic device represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, Ar ¹ and Ar ² are, independently of each other, a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group, and L ¹ to L ³ independently of one another are substituted Or a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof , n1 to n3 are each independently any one of 0 to 3, X ¹ is -NR'-, -O-, -S- or -CR'R "- and R ¹ , R ² , R 'And R''are each independently of the other hydrogen, deuterium, halogen, cyano, hydroxyl, amino, substituted or unsubstituted C1 to C20 amine groups, nitro, A C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C Substituted or unsubstituted C1 to C20 alkoxy groups, substituted or unsubstituted C6 to C20 aryloxy groups, substituted or unsubstituted C3 to C40 silyloxy groups, substituted or unsubstituted C1 to C20 acyl groups , A substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, A substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, A substituted or unsubstituted C1 to C20 heterocyclic thiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl Or a combination thereof.

X ¹ may be -NR'-.

At least one of Ar ¹ and Ar ² may be represented by the following formula (S-1) or (S-2).

[Formula S-1] [Formula S-2]

X ² is -NR'-, -O-, -S- or -CR'R "-, X ³ is -NR'-, -O- or -S- and, R ^5, R ^6, R 'and R "are independently, hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group, a carboxyl group with each other, A substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, A substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 A substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted acyloxy group, Or a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, An unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or combinations thereof .

In another embodiment of the present invention, there is provided a compound for an organic optoelectronic device represented by the following formula (2).

(2)

Wherein Ar ¹ and Ar ² independently represent a substituted or unsubstituted C6 to C30 aryl group, a group represented by the following formula: S-1 or S-2, and at least one of Ar ¹ and Ar ² is a group represented by the following formula S-1 or S-2, L ¹ to L ³ independently represent a substituted or unsubstituted C 2 to C 6 alkenylene group, a substituted or unsubstituted C 2 to C 6 alkynylene group, a substituted or unsubstituted C6- C30 arylene group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof, n1 to n3 are independently 0 to 3 any integer of one another, R ¹ to R ⁴ represent, independently of each other, hydrogen , A substituted or unsubstituted C1 to C20 amine group, a nitro group, a carboxyl group, a ferrocenyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1-C20 alkyl group, A C6 to C30 aryl group, a substituted or unsubstituted C2 A substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted C1 to C20 acyl group, Substituted or unsubstituted C2 to C20 alkoxycarbonyl groups, substituted or unsubstituted C2 to C20 acyloxy groups, substituted or unsubstituted C2 to C20 acylamino groups, substituted or unsubstituted C2 to C20 alkoxycarbonylamino groups, substituted Or a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, A substituted or unsubstituted C1 to C20 heterocyclic thiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 A group or a combination thereof.

[Formula S-1] [Formula S-2]

X ² is -NR'-, -O-, -S- or -CR'R "-, X ³ is -NR'-, -O- or -S- and, R ^5, R ^6, R 'and R "are independently, hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group, a carboxyl group with each other, A substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, A substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 A substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted acyloxy group, Or a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, An unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or combinations thereof .

In another embodiment of the present invention, there is provided a compound for organic optoelectronic devices represented by the following formula (3).

(3)

In Formula 3, Ar ¹ and Ar ² are independently from each other, a substituted or unsubstituted C6 to C30 aryl group, to the formula and S-1 or S-2, at least one of the Ar ¹ and Ar ² have the formula and S-1 or S-2, Ar ³ and Ar ⁴ are independently, a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group unsubstituted one another, L ¹ to L ³ are each Independently, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, And n1 to n3 are each independently any one of 0 to 3.

[Formula S-1] [Formula S-2]

X ² is -NR'-, -O-, -S- or -CR'R "-, X ³ is -NR'-, -O- or -S- and, R ^5, R ^6, R 'and R "are independently, hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group, a carboxyl group with each other, A substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, A substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 A substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted acyloxy group, Or a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, An unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or combinations thereof .

Ar ¹ and Ar ² may be independently of each other the above-described formula (S-1).

Ar ¹ and Ar ² may be independently of each other the above formula (S-2).

Ar ¹ and Ar ² may be any one of the following substituents independently of each other.

In this substituent, X is -O- or -S- and Ar ⁵ to Ar ⁷ are each independently selected from the group consisting of hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine A substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group , A substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C20 aryloxycarbonylamino , A substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, a substituted or unsubstituted C6 to C20 arylthiol group, An unsubstituted C1 to C20 heterocyclythiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof.

The L ¹ to L ³ may independently be any one of the following substituents.

In this substituent, X is -O- or -S-.

Ar ¹ and Ar ² may be, independently of each other, a substituted or unsubstituted C 14 to C 30 aryl group having a fused ring having a plurality of rings.

Ar ¹ and Ar ² may be, independently of each other, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, or a substituted or unsubstituted phenanthrenyl group.

The organic optoelectronic device may be any one selected from the group consisting of organic optoelectronic devices, organic light emitting devices, organic solar cells, organic transistors, organic photoconductor drums, and organic memory devices.

In still another embodiment of the present invention, at least one organic thin film layer interposed between an anode and a cathode and between the anode and the cathode is provided, wherein at least one of the organic thin film layers is formed of the above- And a compound for an organic optoelectronic device according to an embodiment of the present invention.

The organic thin film layer may be any one selected from the group consisting of a light emitting layer, a hole transporting layer, a hole injecting layer, an electron transporting layer, an electron injecting layer, a hole blocking layer, and combinations thereof.

The compound for an organic optoelectronic device may be included in a hole injection layer or a hole transport layer.

According to another embodiment of the present invention, there is provided a display device including the organic light emitting device according to an embodiment of the present invention.

The organic optoelectronic device including the compound for an organic optoelectronic device has excellent electrochemical and thermal stability, has excellent lifetime characteristics, and can have a high luminous efficiency even at a low driving voltage.

1 to 5 are cross-sectional views illustrating various embodiments of an organic light emitting device that can be manufactured using a compound for an organic optoelectronic device according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, unless otherwise defined, at least one of the substituents or at least one hydrogen in the compound is substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, C1 to C10 alkyl groups such as a C3 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a fluoro group, A trifluoroalkyl group or a cyano group.

A substituted or unsubstituted C1 to C20 amine group, a nitro group, a substituted or unsubstituted C3 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C10 alkylsulfinyl group, A C1 to C10 trifluoroalkyl group such as a C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a fluoro group or a trifluoromethyl group, or a cyano group may be fused together to form a ring .

Means one to three heteroatoms selected from the group consisting of N, O, S and P in one functional group, and the remainder is carbon, unless otherwise defined.

In the present specification, the term " combination thereof " means that two or more substituents are bonded to each other via a linking group or two or more substituents are condensed and bonded.

As used herein, the term "alkyl group" means an aliphatic hydrocarbon group, unless otherwise defined. The alkyl group may be a " saturated alkyl group " which does not contain any double or triple bonds.

The alkyl group may be an alkyl group of C1 to C20. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, C1 to C4 alkyl groups mean that from 1 to 4 carbon atoms are included in the alkyl chain and include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec- Indicating that they are selected from the group.

Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, And the like.

The term " aryl group " means a substituent in which all the elements of the cyclic substituent have p-orbital and the p-orbital forms a conjugation, and monocyclic or fused-ring polycyclic That is, rings that divide adjacent pairs of carbon atoms) functional groups.

&Quot; Heteroaryl group " means that the aryl group contains 1 to 3 heteroatoms selected from the group consisting of N, O, S and P, and the remainder is carbon. When the heteroaryl group is a fused ring, it may contain 1 to 3 heteroatoms in each ring.

In the present specification, the hole property means a property of facilitating the injection into the light emitting layer and the movement in the light emitting layer of the hole formed in the anode due to conduction characteristics along the HOMO level. More specifically, it may be similar to the characteristic of pushing electrons.

Further, the electron characteristic means a property of facilitating the injection of electrons formed in the anode into the luminescent layer and the movement in the luminescent layer due to conduction characteristics along the LUMO level. More specifically, it may be similar to the characteristic of attracting electrons.

In one embodiment of the present invention, a compound for an organic optoelectronic device represented by the following Formula 1 can be provided.

[Chemical Formula 1]

In Formula 1, Ar ¹ and Ar ² are, independently of each other, a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group, and L ¹ to L ³ independently of one another are substituted Or a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof , n1 to n3 are each independently any one of 0 to 3, X ¹ is -NR'-, -O-, -S- or -CR'R "- and R ¹ , R ² , R 'And R''are each independently of the other hydrogen, deuterium, halogen, cyano, hydroxyl, amino, substituted or unsubstituted C1 to C20 amine groups, nitro, A C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C Substituted or unsubstituted C1 to C20 alkoxy groups, substituted or unsubstituted C6 to C20 aryloxy groups, substituted or unsubstituted C3 to C40 silyloxy groups, substituted or unsubstituted C1 to C20 acyl groups , A substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, A substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, A substituted or unsubstituted C1 to C20 heterocyclic thiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl Or a combination thereof.

The compound represented by Formula 1 may have a core structure including a substituted phenyl group bonded to a carbazole-based substituent.

More specifically, when a carbazole-based substituent and a phenyl group are connected to each other as in the compound according to an embodiment of the present invention, a compound having a low HOMO level can be obtained. Compounds having such a low HOMO level are required for the implementation of phosphorescent blue organic optoelectronic devices.

Further, the carbazole-based substituent and the phenyl group are connected without breaking the pi bond, so that the flow of holes or electrons can occur more organically. In addition, the compound can be improved in electrochemical and thermal stability.

The compound for organic optoelectronic devices represented by Formula 1 may be a compound having various energy bandgaps by introducing various substituents to the substituents of the core portion and the core portion.

By using a compound having an appropriate energy level according to the substituent of the compound in an organic optoelectronic device, the hole transporting ability or the electron transporting ability is enhanced to have an excellent effect in terms of efficiency and driving voltage, and excellent electrochemical and thermal stability. The lifetime characteristics can be improved when the device is driven.

More specifically, in one embodiment of the present invention, the substituted or unsubstituted C6 to C30 aryl group and / or the substituted or unsubstituted C2 to C30 heteroaryl group may be substituted or unsubstituted phenyl group, substituted or unsubstituted naphtha A substituted or unsubstituted phenanthryl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, Substituted or unsubstituted m-terphenyl groups, substituted or unsubstituted chrysenyl groups, substituted or unsubstituted triphenylenyl groups, substituted or unsubstituted perylenyl groups, substituted or unsubstituted A substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, A substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted thiazolyl group, A substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, Substituted or unsubstituted quinazolinyl groups, substituted or unsubstituted quinazolinyl groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted quinolinyl groups, A substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazine group, a substituted or unsubstituted benzothiazine group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazine Group, it may be a substituted or unsubstituted phenothiazine group, a substituted or unsubstituted phenoxazine group, or a combination thereof, are not limited.

In addition, the conjugation length of the entire compound can be determined by selectively controlling the L ¹ and L ² , and the triplet energy band gap can be controlled therefrom. This makes it possible to realize the characteristics of the materials required in organic optoelectronic devices. Further, the triplet energy bandgap can be controlled by changing the bonding position of the ortho, para, and meta.

Specific examples of L ¹ to L ³ include a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted A substituted or unsubstituted phenanthryl group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-tert A phenyl group, a substituted or unsubstituted perylenyl group and the like.

More specifically, each of L ¹ to L ³ independently of each other may be any one of the following substituents. However, the present invention is not limited thereto.

In this substituent, X is -O- or -S-.

More specifically, L ¹ to L ³ may be, independently of one another, a phenylene group. In the case where L ¹ to L ³ are phenylene groups, both side core portions may be bonded to ortho, meta or para to the phenylene group.

At least one of Ar ¹ and Ar ² may be represented by the following formula (S-1) or (S-2). The above-mentioned formulas S-1 and S-2 are commonly compounds having a non-covalent electron pair and have a higher electron mobility or electron mobility than general ring compounds. This enables high-efficiency and low-voltage organic optoelectronic devices to be realized.

[Formula S-1] [Formula S-2]

X ² is -NR'-, -O-, -S- or -CR'R "-, X ³ is -NR'-, -O- or -S- and, R ^5, R ^6, R 'and R "are independently, hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group, a carboxyl group with each other, A substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, A substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 A substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted acyloxy group, Or a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, An unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or combinations thereof .

More specifically, Ar ¹ and Ar ² may be any one of the following substituents independently of each other. However, the present invention is not limited thereto.

In this substituent, X is -O- or -S- and Ar ⁵ to Ar ⁷ are each independently selected from the group consisting of hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine A substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group , A substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C20 aryloxycarbonylamino , A substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, a substituted or unsubstituted C6 to C20 arylthiol group, An unsubstituted C1 to C20 heterocyclythiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof.

More specifically, Ar ¹ and Ar ² may be, independently of each other, a substituted or unsubstituted C 14 to C 30 aryl group.

More specifically, when Ar ¹ and Ar ² have no substituent or have a substituent that is too small, the transfer of holes or electrons to the carbazole-based substituent is crowded and the compound becomes unstable.

This may adversely affect the lifetime of the organic optoelectronic device using the compound.

In addition, when Ar ¹ and Ar ² are substituted with a substituent having a too large molecular weight or a large substituent, a thermal stability problem occurs as a deposition material. In general, a compound having a high molecular weight has a high melting point, and therefore, the deposition temperature also increases together with the compound. Therefore, the compound may be exposed to high heat for a long time during the deposition of the compound.

The substituted or unsubstituted C14 to C30 aryl group is of a suitable substituent size, which permits uniform distribution of electrons in the compound and can improve the lifetime of the organic optoelectronic device with a low molecular weight.

More specifically, Ar ¹ and Ar ² may be, independently of each other, a substituted or unsubstituted C 14 to C 30 aryl group having a fused ring having a plurality of rings.

The plurality of fused rings has a withdrawing group due to the resonance structure, which can prevent the concentration of too much electrons or holes in the carbazole in the compound.

In general, a carbazole-based substituent is known as a substituent having good flow of holes or electrons. However, when the flow of holes or electrons is limited, excessive load may be applied to break the compound. If a plurality of fused rings are substituted with Ar ¹ and Ar ² and complemented, the fused rings can be transported by holes or electrons, and a high-efficiency, low-voltage, high-precision device can be expected.

More specifically, for example, Ar ¹ and Ar ² may be, independently of each other, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, or a substituted or unsubstituted phenanthrenyl group. However, the present invention is not limited thereto.

X ¹ may be -NR'-. When X ¹ is -NR'-, a compound having a HOMO level lower than that of the phosphorescent blue element can be prepared.

In another embodiment of the present invention, there is provided a compound for an organic optoelectronic device represented by the following formula (2). When a phenyl group is bound in the N-direction of the carbazole as shown in Formula 2 below, a compound having a low HOMO level can be prepared. In addition, since the compound represented by the following formula (2) has a low molecular weight, it is easy to introduce a substituent having excellent hole or electron transporting ability into another substituent.

(2)

Wherein Ar ¹ and Ar ² independently represent a substituted or unsubstituted C6 to C30 aryl group, a group represented by the following formula: S-1 or S-2, and at least one of Ar ¹ and Ar ² is a group represented by the following formula S-1 or S-2, L ¹ to L ³ independently represent a substituted or unsubstituted C 2 to C 6 alkenylene group, a substituted or unsubstituted C 2 to C 6 alkynylene group, a substituted or unsubstituted C6- C30 arylene group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof, n1 to n3 are independently 0 to 3 any integer of one another, R ¹ to R ⁴ represent, independently of each other, hydrogen , A substituted or unsubstituted C1 to C20 amine group, a nitro group, a carboxyl group, a ferrocenyl group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1-C20 alkyl group, A C6 to C30 aryl group, a substituted or unsubstituted C2 A substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted C1 to C20 acyl group, Substituted or unsubstituted C2 to C20 alkoxycarbonyl groups, substituted or unsubstituted C2 to C20 acyloxy groups, substituted or unsubstituted C2 to C20 acylamino groups, substituted or unsubstituted C2 to C20 alkoxycarbonylamino groups, substituted Or a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, A substituted or unsubstituted C1 to C20 heterocyclic thiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 A group or a combination thereof.

[Formula S-1] [Formula S-2]

X ² is -NR'-, -O-, -S- or -CR'R "-, X ³ is -NR'-, -O- or -S- and, R ^5, R ^6, R 'and R "are independently, hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group, a carboxyl group with each other, A substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, A substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 A substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted acyloxy group, Or a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, An unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or combinations thereof .

In the above formula (2), Ar ¹ , Ar ² and L ¹ to L ³ are the same as in the above formula (1) within the scope of no inconsistency.

In another embodiment of the present invention, there is provided a compound for organic optoelectronic devices represented by the following formula (3). A compound having a structure represented by the following formula (3) can prevent the driving voltage of the device from rising when applied to the device.

(3)

In Formula 3, Ar ¹ and Ar ² are independently from each other, a substituted or unsubstituted C6 to C30 aryl group, to the formula and S-1 or S-2, at least one of the Ar ¹ and Ar ² have the formula and S-1 or S-2, Ar ³ and Ar ⁴ are independently, a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group unsubstituted one another, L ¹ to L ³ are each Independently, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, And n1 to n3 are each independently any one of 0 to 3.

[Formula S-1] [Formula S-2]

X ² is -NR'-, -O-, -S- or -CR'R "-, X ³ is -NR'-, -O- or -S- and, R ^5, R ^6, R 'and R "are independently, hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group, a carboxyl group with each other, A substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, a substituted or unsubstituted C 1 to C 20 alkoxy group, A substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 A substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted acyloxy group, Or a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group, An unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or combinations thereof .

In the above formula (3), Ar ¹ , Ar ^2, and L ¹ to L ³ are the same as in the above formula (1) within the range not inconsistent.

In Formula 3, Ar ¹ and Ar ² may be independently of each other the formula S-1, or Ar ¹ and Ar ² may independently be S-2. In each case, S-1 and S-2 are compounds having unshared electron pairs in common, and have higher electron mobility or electron mobility than general ring compounds. This enables high-efficiency and low-voltage organic optoelectronic devices to be realized.

More specifically, for example, the compound for an organic optoelectronic device according to an embodiment of the present invention is as follows. However, this is only an example.

According to another embodiment of the present invention, there is provided an organic electroluminescent device comprising a cathode, a cathode, and at least one organic thin film layer sandwiched between the anode and the cathode, wherein at least one of the organic thin film layers includes the above- Thereby providing an organic optoelectronic device.

The compound for an organic optoelectronic device is used in an organic thin film layer to improve lifetime characteristics, efficiency characteristics, electrochemical stability and thermal stability of an organic optoelectronic device, and can lower a driving voltage.

The organic thin film layer may specifically be an electron injection layer or an electron transport layer.

The organic optoelectronic device may be an organic light emitting device, an organic photoelectric device, an organic solar cell, an organic transistor, an organic photoconductor drum, or an organic memory device.

More specifically, the organic optoelectronic device may be an organic light emitting device. 1 to 5 are sectional views of an organic light emitting device including a compound for an organic optoelectronic device according to an embodiment of the present invention.

1 to 5, organic light emitting devices 100, 200, 300, 400, and 500 according to an embodiment of the present invention include a cathode 120, a cathode 110, And a structure including at least one organic thin film layer (105).

The anode 120 includes a cathode material. As the anode material, a material having a large work function is preferably used to facilitate injection of holes into the organic thin film layer. Specific examples of the positive electrode material include metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold or alloys thereof and zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide ), And combinations of metals and oxides such as ZnO and Al or SnO ₂ and Sb, and poly (3-methylthiophene), poly (3,4- (ethylene- 2-dioxythiophene (PEDT), polypyrrole, and polyaniline, but the present invention is not limited thereto. More specifically, a transparent electrode including ITO (indium tin oxide) may be used as the anode.

The cathode 110 includes a cathode material, and the anode material is preferably a material having a small work function to facilitate electron injection into the organic thin film layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium and the like, , LiO ₂ / Al, LiF / Ca, LiF / Al, and BaF ₂ / Ca. However, the present invention is not limited thereto. More specifically, a metal electrode such as aluminum can be used for the cathode.

1 illustrates an organic light emitting device 100 in which only a light emitting layer 130 is present as an organic thin film layer 105. The organic thin film layer 105 may exist only in the light emitting layer 130. FIG.

2 illustrates a two-layer organic light emitting device 200 having a light emitting layer 230 including an electron transporting layer and a hole transporting layer 140 as an organic thin film layer 105. As shown in FIG. 2, Similarly, the organic thin film layer 105 may be of a two-layer type including a light emitting layer 230 and a hole transporting layer 140. In this case, the light emitting layer 130 functions as an electron transporting layer, and the hole transporting layer 140 functions to improve the bonding property with a transparent electrode such as ITO and the hole transporting property.

3 is a three-layer organic light emitting device 300 in which an electron transport layer 150, a light emitting layer 130 and a hole transport layer 140 are present as an organic thin film layer 105. The organic thin film layer 105, The emissive layer 130 is in the form of an independent layer and has a form in which a film having excellent electron transportability and hole transportability (the electron transport layer 150 and the hole transport layer 140) is stacked as a separate layer.

4, a four-layer organic light emitting device 400 having an electron injection layer 160, a light emitting layer 130, a hole transport layer 140, and a hole injection layer 170 as organic thin film layers 105, And the hole injection layer 170 can improve the bonding property with ITO used as the anode.

5, the organic thin film layer 105 has different functions such as an electron injection layer 160, an electron transport layer 150, a light emitting layer 130, a hole transport layer 140, and a hole injection layer 170 Layer organic light emitting device 500. The organic light emitting device 500 is effective for lowering the voltage by forming the electron injection layer 160 separately.

1 to 5, the electron transport layer 150, the electron injection layer 160, the light emitting layers 130 and 230, the hole transport layer 140, the hole injection layer 170, and the organic thin film layer 105, And combinations thereof, includes a material for the organic optoelectronic device.

The organic light emitting device described above may be formed by a dry film forming method such as evaporation, sputtering, plasma plating, and ion plating after an anode is formed on a substrate; Or a wet film formation method such as spin coating, dipping or flow coating, and then forming a cathode on the organic thin film layer.

In another embodiment of the present invention, there is provided a display device including the organic optoelectronic device.

Example

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

( For organic optoelectronic devices  Preparation of compounds <

Synthetic example  1: Preparation of intermediate I-1

Naphthalen-1-ylboronic acid (50 g, 290.7 mmol) was dissolved in 0.8 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 1,3-dibromo-5-chlorobenzene (117.9 g, 436.1 mmol) and tetrakis (triphenylphosphine) palladium (3.36 g, 2.91 mmol) were added and stirred. Saturated potassium permanganate (85.6 g, 581.4 mmol) was added to the reaction mixture, and the mixture was refluxed by heating at 80 ° C for 9 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound I-1 (42.5 g, 46%).

Synthetic example  2: Preparation of intermediate I-2

(30 g, 94.5 mmol) was dissolved in 0.2 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then phenylboronic acid (12.7 g, 103.9 mmol) and tetrakis (triphenylphosphine) palladium (3.28 g, 2.84 mmol) And stirred. Saturated water-saturated potassium carbonate (27.8 g, 189 mmol) was added and the mixture was refluxed by heating at 80 ° C for 16 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The obtained residue was purified by flash column chromatography to obtain intermediate I-2 (29.7 g, 53%).

Synthetic example  3: Preparation of intermediate I-3

Bis (pinacolato) diboron (24.2 g, 95.3 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 0.2 L of dimethylformamide (DMF) ferrocene dichloropalladium (II) (0.52 g, 0.64 mmol) and potassium acetate (12.5 g, 127 mmol) were added and the mixture was refluxed by heating at 150 ° C for 21 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The obtained residue was purified by flash column chromatography to obtain intermediate I-3 (25.8 g, 55%).

Synthetic example  4: Preparation of intermediate I-4

1-bromo-4-chlorobenzene (9.42 g, 49.2 mmol) and tetrakis (triphenylphosphine) palladium (1.71 g, 49.2 mmol) were dissolved in 0.15 L of tetrahydrofuran , 1.48 mmol) were added and stirred. Potassium carbonate (14.5 g, 98.4 mmol) saturated with water was added and the mixture was refluxed by heating at 80 ° C for 20 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain intermediate I-4 (16.5 g, 86%).

Synthetic example  5: Preparation of intermediate I-5

3,5-phenylbenzyl-1-boronic acid (50 g, 182.4 mmol) was dissolved in 0.8 L of tetrahydrofuran (THF) in a nitrogen atmosphere and 2,7-dibromo-9,9-dimethyl-9H-fluorene 95.8 g, 273.6 mmol) and tetrakis (triphenylphosphine) palladium (2.11 g, 1.82 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (53.7 g, 364.8 mmol) was added and the mixture was refluxed by heating at 80 ° C for 8 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain Intermediate I-5 (17.8 g, 25%).

Synthetic example  6: Preparation of intermediate I-6

Dibenzofuran-4ylboronic acid (26.1 g, 123.3 mmol) was dissolved in 0.4 L of tetrahydrofuran (THF) in a nitrogen atmosphere and 1,3-dibromo-5-chlorobenzene (50 g, 185 mmol) and tetrakis (triphenylphosphine) palladium 1.42 g, 1.23 mmol) were added and stirred. Saturated water-saturated potassium carbonate (36.3 g, 246.6 mmol) was added and heated at 80 ° C for 10 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was purified by flash column chromatography to obtain intermediate I-6 (19.3 g, 44%).

Synthetic example  7: Preparation of Intermediate I-7

(7.24 g, 59.4 mmol) and tetrakis (triphenylphosphine) palladium (1.87 g, 1.62 mmol) were dissolved in 0.15 L of tetrahydrofuran (THF) And stirred. Potassium carbonate (15.9 g, 108 mmol) saturated with water was added and the mixture was refluxed by heating at 80 ° C for 17 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain intermediate I-7 (19.1 g, 56%).

Synthetic example  8: Preparation of intermediate I-8

Bis (pinacolato) diboron (20.4 g, 80.3 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 0.2 L of dimethylformamide (DMF) ferrocene dichloropalladium (II) (0.44 g, 0.54 mmol) and potassium acetate (10.5 g, 107 mmol) were added and heated at 150 ° C for 18 hours to reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The thus-obtained residue was purified by flash column chromatography to obtain intermediate I-8 (12.2 g, 51%).

Synthetic example  9: Preparation of intermediate I-9

Intermediate I-8 (12 g, 26.9 mmol) was dissolved in 0.1 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 1-bromo-4-chlorobenzene (5.15 g, 26.9 mmol) and tetrakis (triphenylphosphine) palladium , 0.81 mmol) were added and stirred. Saturated water-saturated potassium carbonate (7.92 g, 53.8 mmol) was added and heated at 80 ° C for 18 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain Intermediate I-9 (9.73 g, 84%).

Synthetic example  10: Preparation of intermediate I-10

Dibenzofuran-4-ylboronic acid (100 g, 369.89 mmol) was dissolved in 1.5 L of tetrahydrofuran (THF), and then dibenzofuran-4ylboronic acid (196.1 g, 924.7 mmol) and tetrakis triphenylphosphine) palladium (21.4 g, 18.5 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (108.9 g, 739.8 mmol) was added and the mixture was refluxed by heating at 100 ° C for 23 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The thus obtained residue was purified by flash column chromatography to obtain intermediate I-10 (148.4 g, 90%).

Synthetic example  11: Preparation of intermediate I-11

Bis (pinacolato) diboron (147.5 g, 580.8 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 1.5 L of dimethylformamide (DMF) ferrocene) dichloropalladium (II) (9.49 g, 11.6 mmol) and potassium acetate (76.0 g, 774.4 mmol) were added and heated at 150 ° C for 16 hours to reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was purified by flash column chromatography to obtain Intermediate I-11 (121.3 g, 58%).

Synthetic example  12: Preparation of Intermediate I-12

Intermediate I-11 (50 g, 93.2 mmol) was dissolved in 0.1 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 1-bromo-4-chlorobenzene (17.8 g, 93.2 mmol) and tetrakis (triphenylphosphine) palladium , 2.80 mmol) were added and stirred. Saturated water-saturated potassium carbonate (27.4 g, 186.4 mmol) was added and heated at 80 ° C for 21 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain Intermediate I-12 (44.2 g, 91%).

Synthesis Example 13: Preparation of Intermediate I-13

Benzofuran-2-ylboronic acid (100 g, 617.5 mmol) was dissolved in 1.8 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 1,3-dibromo-5-chlorobenzene (250.4 g, 926.2 mmol) and tetrakis (triphenylphosphine) palladium (7.14 g, 6.18 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (181.9 g, 1,235 mmol) was added and heated at 80 ° C for 8 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The obtained residue was purified by flash column chromatography to obtain intermediate I-13 (104.5 g, 55%).

Synthesis Example 14: Preparation of Intermediate I-14

Intermediate I-13 (100 g, 325.1 mmol) was dissolved in 0.7 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then phenylboronic acid (43.6 g, 357.6 mmol) and tetrakis (triphenylphosphine) palladium (11.3 g, 9.75 mmol) And stirred. Saturated potassium salt of potassium carbonate (95.7 g, 650.2 mmol) was added and the mixture was refluxed by heating at 80 ° C for 20 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was purified by flash column chromatography to obtain intermediate I-14 (46.6 g, 47%).

Synthesis Example 15: Preparation of Intermediate I-15

Bis (pinacolato) diboron (57.5 g, 226.4 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 0.5 L of dimethylformamide (DMF) ferrocene dichloropalladium (II) (1.23 g, 1.51 mmol) and potassium acetate (29.6 g, 301.8 mmol) were added and heated at 150 ° C for 15 hours to reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was purified by flash column chromatography to obtain intermediate I-15 (25.7 g, 43%).

Synthesis Example 16: Preparation of Intermediate I-16

(25 g, 63.1 mmol) was dissolved in 0.2 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 1-bromo-4-chlorobenzene (12.1 g, 63.1 mmol) and tetrakis (triphenylphosphine) palladium , 1.89 mmol) were added and stirred. Saturated water-saturated potassium carbonate (18.6 g, 126.2 mmol) was added and the mixture was refluxed by heating at 80 ° C for 24 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was purified by flash column chromatography to obtain intermediate I-16 (21.4 g, 89%).

Synthesis Example 17: Preparation of Intermediate I-17

Benzofuran-2-ylboronic acid (149.8 g, 924.7 mmol) was dissolved in 1.3 L of tetrahydrofuran (THF) in a nitrogen atmosphere, and 1,3-dibromo-5-chlorobenzene dibenzofuran-4ylboronic acid (100 g, 369.89 mmol) tetrakis (triphenylphosphine) palladium (21.4 g, 18.5 mmol) was added thereto and stirred. Saturated water-saturated potassuim carbonate (108.9 g, 739.8 mmol) was added and heated at 100 ° C for 22 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was purified by flash column chromatography to obtain Intermediate I-17 (103.3 g, 81%).

Synthesis Example 18: Preparation of Intermediate I-18

Bis (pinacolato) diboron (110.5 g, 435.0 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 1.5 L of dimethylformamide (DMF) ferrocene dichloropalladium (II) (2.37 g, 2.9 mmol) and potassium acetate (56.9 g, 580 mmol) were added and heated at 150 ° C for 28 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The obtained residue was purified by flash column chromatography to obtain Intermediate I-18 (62.0 g, 49%).

Synthesis Example 19: Preparation of Intermediate I-19

Intermediate I-18 (62 g, 142.1 mmol) was dissolved in 0.5 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 1-bromo-4-chlorobenzene (27.2 g, 142.1 mmol) and tetrakis (triphenylphosphine) palladium , 4.26 mmol) were added and stirred. Potassium carbonate (41.9 g, 284.2 mmol) saturated with water was added and the mixture was refluxed by heating at 80 ° C for 27 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain intermediate I-19 (58.0 g, 97%).

Synthesis Example 20: Preparation of Intermediate I-20

Bis (pinacolato) diboron (44.2 g, 174.0 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 0.5 L of dimethylformamide (DMF) ferrocene dichloropalladium (II) (0.95 g, 1.16 mmol) and potassium acetate (22.8 g, 232 mmol) were added and the mixture was refluxed by heating at 150 ° C for 42 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was purified by flash column chromatography to obtain intermediate I-20 (33.9 g, 56%).

Synthesis Example 21: Preparation of Intermediate I-21

Bis (pinacolato) diboron (36.6 g, 144 mmol) and (1,1'-bis (diphenylphosphine) diphenylphosphine) were dissolved in 0.4 L of dimethylformamide (DMF) ferrocene) dichloropalladium (II) (0.78 g, 0.96 mmol) and potassium acetate (18.8 g, 192 mmol) were added and the mixture was refluxed by heating at 150 ° C. for 46 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was purified by flash column chromatography to obtain Intermediate I-21 (27.6 g, 47%).

Synthesis Example 22: Preparation of Intermediate I-22

Bis (pinacolato) diboron (50.0 g, 196.9 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 0.5 L of dimethylformamide (DMF) ferrocene dichloropalladium (II) (1.07 g, 1.31 mmol) and potassium acetate (25.8 g, 262.6 mmol) were added and the mixture was refluxed by heating at 150 ° C for 49 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was purified by flash column chromatography to obtain intermediate I-22 (31.0 g, 50%).

Synthesis Example 23: Preparation of Intermediate I-23

Bis (pinacolato) diboron (45.3 g, 178.2 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 0.5 L of dimethylformamide (DMF) ferrocene dichloropalladium (II) (0.97 g, 1.19 mmol) and potassium acetate (23.3 g, 237.6 mmol) were added and heated at 150 ° C. for 41 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was purified by flash column chromatography to obtain intermediate I-23 (28.6 g, 47%).

Synthesis Example 24: Preparation of Intermediate I-24

Intermediate I-18 (30 g, 68.8 mmol) was dissolved in 0.3 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 1-bromo-4-iodobenzene (29.2 g, 103.1 mmol) and tetrakis (triphenylphosphine) palladium , 0.69 mmol) were added and stirred. Saturated water-saturated potassium carbonate (20.3 g, 137.6 mmol) was added and the mixture was refluxed by heating at 80 ° C for 8 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain intermediate I-24 (13.1 g, 41%).

Synthesis Example 25: Preparation of Intermediate I-25

4-boronic acid (183.1 g, 924.7 mmol) was dissolved in 1.5 L of tetrahydrofuran (THF) in a nitrogen atmosphere, tetrakis (triphenylphosphine) palladium (21.4 g, 18.5 mmol) was added thereto and stirred. Saturated water-saturated potassuim carbonate (108.9 g, 739.8 mmol) was added and heated at 100 ° C for 22 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain intermediate I-25 (134.2 g, 87%).

Synthesis Example 26: Preparation of Intermediate I-26

Bis (pinacolato) diboron (91.4 g, 359.8 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 1.0 L of dimethylformamide (DMF) ferrocene) dichloropalladium (II) (1.96 g, 1.19 mmol) and potassium acetate (47.1 g, 479.6 mmol) were added and the mixture was refluxed by heating at 150 ° C for 48 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was purified by flash column chromatography to obtain intermediate I-26 (53.7 g, 44%).

Synthesis Example 27: Preparation of Intermediate I-27

Intermediate I-26 (50 g, 98.3 mmol) was dissolved in 0.5 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 1-bromo-4-chlorobenzene (18.8 g, 98.3 mmol) and tetrakis (triphenylphosphine) palladium , 2.95 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (29.0 g, 196.6 mmol) was added and heated at 80 ° C for 16 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The obtained residue was purified by flash column chromatography to obtain Intermediate I-27 (42.7 g, 88%).

Synthesis Example 28: Preparation of Intermediate I-28

Bis (pinacolato) diboron (23.2 g, 91.3 mmol) and (1,1'-bis (diphenylphosphine)) were dissolved in 0.3 L of dimethylformamide (DMF) ferrocene dichloropalladium (II) (0.50 g, 0.61 mmol) and potassium acetate (11.9 g, 121.6 mmol) were added and heated at 150 ° C for 50 hours to reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was purified by flash column chromatography to obtain intermediate I-28 (18.5 g, 52%).

Example 1: Preparation of compound 1-7

The intermediate dibiphenyl-4-ylamine (10 g, 31.1 mmol) was dissolved in 0.1 L of toluene in a nitrogen atmosphere and the intermediate I-4 (12.2 g, 31.1 mmol) and tris (diphenylideneacetone) dipalladium 0.31 mmol), tris-tert butylphosphine (0.19 g, 0.93 mmol) and sodium tert-butoxide (3.14 g, 32.7 mmol) were successively added thereto and heated at 100 ° C for 45 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 1-7 (14.8 g, 71%).

Example 2: Preparation of Compound 1-20

The intermediate dibiphenyl-4-ylamine (10 g, 31.1 mmol) was dissolved in 0.15 L of toluene in a nitrogen atmosphere and the intermediate I-5 (15.6 g, 31.1 mmol) and tris (diphenylideneacetone) dipalladium 0.31 mmol), tris-tert butylphosphine (0.19 g, 0.93 mmol) and sodium tert-butoxide (3.14 g, 32.7 mmol) were successively added thereto and refluxed by heating at 100 ° C for 40 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 1-20 (18.9 g, 82%).

Example 3: Preparation of Compound 2-1

The intermediate dibiphenyl-4-ylamine (10 g, 31.1 mmol) was dissolved in 0.1 L of toluene in a nitrogen atmosphere and the intermediate I-9 (13.4 g, 31.1 mmol) and tris (diphenylideneacetone) dipalladium 0.31 mmol), tris-tert butylphosphine (0.19 g, 0.93 mmol) and sodium tert-butoxide (3.14 g, 32.7 mmol) were successively added thereto and heated at 100 ° C for 45 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 2-1 (20.0 g, 90%).

Example 4: Preparation of Compound 3-1

The intermediate dibiphenyl-4-ylamine (10 g, 31.1 mmol) was dissolved in 0.15 L of toluene in a nitrogen atmosphere and the intermediate I-12 (16.2 g, 31.1 mmol) and tris (diphenylideneacetone) dipalladium 0.31 mmol), tris-tert butylphosphine (0.19 g, 0.93 mmol) and sodium tert-butoxide (3.14 g, 32.7 mmol) were successively added thereto and heated at 100 ° C for 38 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 3-1 (20.3 g, 81%).

Example 5: Preparation of compound 4-1

(11.8 g, 31.1 mmol) and tris (diphenylideneacetone) dipalladium (o) (0.28 g, 31.1 mmol) were dissolved in 0.1 L of toluene in a nitrogen atmosphere, and then the intermediate dibiphenyl-4-ylamine 0.31 mmol), tris-tert butylphosphine (0.19 g, 0.93 mmol) and sodium tert-butoxide (3.14 g, 32.7 mmol) were successively added and refluxed by heating at 100 ° C for 46 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain compound 4-1 (15.5 g, 75%).

Example 6: Preparation of compound 5-1

Intermediate I-19 (13.1 g, 31.1 mmol) and tris (diphenylideneacetone) dipalladium (0) (0.28 g, 31.1 mmol) were dissolved in 0.1 L of toluene in a nitrogen atmosphere, followed by dissolving the intermediate dibiphenyl- 0.31 mmol), tris-tert-butylphosphine (0.19 g, 0.93 mmol) and sodium tert-butoxide (3.14 g, 32.7 mmol) were successively added and refluxed by heating at 100 ° C for 50 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 5-1 (18.2 g, 83%).

Example 7: Preparation of Compound 6-1

Intermediate I-9 (25.8 g, 59.8 mmol) and tris (diphenylideneacetone) dipalladium (o) (1.64 g, 1.79 mmol) were dissolved in 0.1 L of toluene in a nitrogen atmosphere and the intermediate cabazole (10 g, 59.8 mmol) tris-tert butylphosphine (1.45 g, 7.16 mmol) and sodium tert-butoxide (6.9 g, 71.8 mmol) were successively added thereto, followed by heating at 130 ° C for 47 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 6-1 (28.9 g, 86%).

Example 8: Preparation of Compound 7-1

The intermediate compound I-12 (31.2 g, 59.8 mmol) and tris (diphenylideneacetone) dipalladium (o) (1.64 g, 1.79 mmol) were dissolved in 0.1 L of toluene in a nitrogen atmosphere, tris-tert butylphosphine (1.45 g, 7.16 mmol) and sodium tert-butoxide (6.9 g, 71.8 mmol) were successively added thereto, and the mixture was refluxed by heating at 130 ° C for 45 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 7-1 (34.3 g, 88%).

Example 9: Preparation of compound 8-1

The intermediate compound I-16 (22.8 g, 59.8 mmol) and tris (diphenylideneacetone) dipalladium (o) (1.64 g, 1.79 mmol) were dissolved in 0.1 L of toluene in a nitrogen atmosphere, tris-tert butylphosphine (1.45 g, 7.16 mmol) and sodium tert-butoxide (6.9 g, 71.8 mmol) were successively added thereto, and the mixture was refluxed by heating at 130 ° C for 68 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain Compound 8-1 (22.9 g, 75%).

Example 10: Preparation of compound 9-3

Intermediate I-19 (25.2 g, 59.8 mmol) and tris (diphenylideneacetone) dipalladium (o) (1.64 g, 1.79 mmol) were dissolved in 0.1 L of toluene in a nitrogen atmosphere and the intermediate cabazole (10 g, 59.8 mmol) tris-tert butylphosphine (1.45 g, 7.16 mmol) and sodium tert-butoxide (6.9 g, 71.8 mmol) were successively added thereto, and the mixture was refluxed by heating at 130 ° C for 70 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 9-3 (25.7 g, 78%).

Example 11: Preparation of compound 10-1

(16.2 g, 31.0 mmol) and tetrakis (triphenylphosphine) were dissolved in 0.15 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 3-bromo-9-phenyl-9H- palladium (1.07 g, 0.93 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (9.13 g, 62.0 mmol) was added and the mixture was refluxed by heating at 80 ° C for 23 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 10-1 (18.0 g, 91%).

Example 12: Preparation of compounds 10-24

(21.1 g, 40.5 mmol) and tetrakis (triphenylphosphine) palladium (1.40 g, 1.22 mmol) were dissolved in 0.15 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 4-bromodibenzofuran And the mixture was stirred. Potassium hydroxide (11.9 g, 81 mmol) saturated with water was added and the mixture was refluxed by heating at 80 ° C for 18 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The thus-obtained residue was purified by flash column chromatography to obtain Compound 10-24 (20.3 g, 89%).

Example 13: Preparation of compound 11-1

(19.0 g, 31.0 mmol) and tetrakis (triphenylphosphine) were dissolved in 0.1 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 3-bromo-9-phenyl-9H- palladium (1.07 g, 0.93 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (9.13 g, 62.0 mmol) was added and the mixture was refluxed by heating at 80 ° C for 21 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 11-1 (21.0 g, 93%).

Example 14: Preparation of compound 12-1

After dissolving 3-bromo-9-phenyl-9H-carbazole (10 g, 31.0 mmol) in 0.1 L of tetrahydrofuran (THF) in a nitrogen atmosphere, 14.6 g (31.0 mmol) of intermediate I- and tetrakis (triphenylphosphine) palladium (1.07 g, 0.93 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (9.13 g, 62.0 mmol) was added and the mixture was refluxed by heating at 80 ° C for 26 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 12-1 (17.0 g, 93%).

Example 15: Preparation of compound 13-1

23 (15.9 g, 31.0 mmol) and tetrakis (triphenylphosphine) were dissolved in 0.1 L of tetrahydrofuran (THF) in a nitrogen atmosphere and then 3-bromo-9-phenyl-9H- palladium (1.07 g, 0.93 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (9.13 g, 62.0 mmol) was added and heated at 80 ° C for 24 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 13-1 (17.5 g, 90%).

Example 16: Preparation of compound 14-1

2-ylboronic acid (3.83 g, 23.6 mmol) and tetrakis (triphenylphosphine) palladium (0.75 g, 21.6 mmol) were dissolved in 0.1 L of tetrahydrofuran (THF) , 0.65 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (6.33 g, 43 mmol) was added and heated at 80 ° C for 16 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 14-1 (9.9 g, 92%).

Example 17: Preparation of compound 15-1

(10.1 g, 31.0 mmol) was dissolved in 0.15 L of tetrahydrofuran (THF), and then the intermediate I-28 (18.1 g, 31.0 mmol) and tetrakis (triphenylphosphine) palladium (1.07 g, 0.93 mmol) were added and stirred. Saturated water-saturated potassuim carbonate (9.13 g, 62.0 mmol) was added and heated at 80 ° C for 24 hours to reflux. After completion of the reaction, water was added to the reaction mixture, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO ₄ , followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound 15-1 (20.6 g, 91%).

(Energy level system using Gaussian tool)

The energy level of each material was calculated by the Gaussian 09 method using a supercomputer GAIA (IBM power 6). The results are shown in Table 1 below.

material HOMO LUMO 1-7 5.34 2.49 1-20 5.39 2.27 2-1 5.34 2.19 3-1 5.37 2.33 4-1 5.47 2.36 5-1 5.38 2.39 6-1 5.53 2.06 7-1 5.55 2.44 8-1 5.54 2.29 9-3 5.65 2.38 10-1 5.53 2.13 10-24 5.70 2.19 11-1 5.50 2.32 12-1 5.51 2.29 13-1 5.52 2.38 14-1 5.68 2.25 15-1 5.73 2.32 NPHBH2
(NPB) 5.19 2.12 HT1 5.24 2.10 HT2 5.38 2.26

The comparative example structure used for the calculation is as follows.

According to the calculation results, it can be seen that all of the HOMO levels are deeper than those of the comparative example. It is presumed that the substituent is connected to the benzene group. It is also found that the carbazole has a deeper HOMO level than the arylamine, and, in particular, the benzene substituent is connected to the carbazole N position, the HOMO level is deeper.

(Production of organic light emitting device)

Example 18: Preparation of organic light emitting device (blue auxiliary layer)

Glass substrate coated with ITO (Indium tinoxide) thin film with thickness of 1500 Å was washed with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and transferred to a plasma cleaner. Then, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transferred to a vacuum evaporator. The prepared ITO transparent electrode was used as an anode to form a 4,4'-bis [N- [4- {N, N-bis (3-methylphenyl) amino} -phenyl] -N-phenylamino] biphenyl ) Was vacuum deposited thereon to form a hole injection layer having a thickness of 600 Å. Then HT1 was used to form a 250 Å thick hole transport layer by vacuum deposition. As an auxiliary layer, Compound 1-7 prepared in Example 1 was used to form an auxiliary layer of a 50 Å thick hole transporting layer by vacuum evaporation. (2-naphthyl) anthracene (AND) was used as a host on top of the hole transport layer and 3, 5 wt% of 2,5,8,11-tetra (tert-butyl) perylene And a 250 Å thick light emitting layer was formed by vacuum deposition. Thereafter, Alq ₃ was vacuum deposited on the light emitting layer to form an electron transporting layer 250 Å thick. LiF 10 Å and Al 1000 Å were sequentially vacuum deposited on the electron transport layer to form a cathode, thereby preparing an organic light emitting device.

The organic light emitting device has five layers of organic thin film layers. Specifically, the organic light emitting device has a structure of Al (1000 Å) / LiF (10 Å) / Alq3 (250 Å) / EML [AND: TBPe = 97: 3] ) / Auxiliary layer (50 Å) / HT1 (250 Å) / DNTPD (600 Å) / ITO (1500 Å).

Example 19

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 2 was used instead of Example 1.

Example 20

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 3 was used instead of Example 1.

Example 21

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 4 was used instead of Example 1.

Example 22

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 5 was used instead of Example 1.

Example 23

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 6 was used instead of Example 1.

Example 24

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 7 was used instead of Example 1.

Example 25

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 8 was used instead of Example 1.

Example 26

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 9 was used instead of Example 1.

Example 27

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 10 was used instead of Example 1.

Example 28

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 11 was used instead of Example 1.

Example 29

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 12 was used instead of Example 1.

Example 30

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 13 was used instead of Example 1.

Example 31

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 14 was used instead of Example 1.

Example 32

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 15 was used instead of Example 1.

Example 33

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 16 was used instead of Example 1.

Example 34

An organic light emitting device was prepared in the same manner as in Example 18, except that Example 17 was used instead of Example 1.

Comparative Example 1

In Example 18, an organic light emitting device was manufactured in the same manner except that NPB was used in place of Example 1. The structure of the NPB is described below.

Comparative Example 2

In Example 18, an organic light emitting device was manufactured in the same manner except that HT1 was used instead of Example 1. The structure of HT1 is described below.

Comparative Example 3

In Example 18, an organic light emitting device was manufactured in the same manner except that HT3 was used in place of Example 1. The structure of HT3 is described below

The structures of DNTPD, AND, TBPe, NPB, HT1 and HT3 used for the organic light emitting device are as follows.

(Performance Measurement of Organic Light Emitting Device)

For each of the organic light emitting devices manufactured in Examples 18 to 34 and Comparative Examples 1 to 3, the current density change, the luminance change, and the light emitting efficiency were measured according to the voltage. Specific measurement methods are as follows, and the results are shown in Table 2 below

(1) Measurement of change in current density with voltage change

For the organic light emitting device manufactured, the current flowing through the unit device was measured using a current-voltage meter (Keithley 2400) while raising the voltage from 0 V to 10 V, and the measured current value was divided by the area to obtain the result.

(2) Measurement of luminance change according to voltage change

For the organic light-emitting device manufactured, luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0 V to 10 V, and the result was obtained.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) at the same current density (10 mA / cm 2) was calculated using the luminance, current density and voltage measured from the above (1) and (2).

device Compound used in hole transport layer Voltage (V) Color (EL color) Efficiency (cd / A) Half life (h)
At 1000 cd / m ² Example 18 1-7 4.1 Blue 6.5 1,400 Example 19 1-20 3.9 Blue 6.7 1,350 Example 20 2-1 3.8 Blue 7.0 1,200 Example 21 3-1 3.8 Blue 6.8 1,850 Example 22 4-1 4.0 Blue 6.5 1,300 Example 23 5-1 3.9 Blue 6.1 1,400 Example 24 6-1 4.7 Blue 7.8 1,650 Example 25 7-1 4.5 Blue 7.6 1,800 Example 26 8-1 4.6 Blue 6.8 1,350 Example 27 9-3 4.7 Blue 6.5 1,500 Example 28 10-1 5.0 Blue 6.3 1,700 Example 29 10-24 5.3 Blue 6.0 1,400 Example 30 11-1 5.1 Blue 6.5 1,950 Example 31 12-1 5.5 Blue 5.9 1,200 Example 32 13-1 5.6 Blue 5.8 1,450 Example 33 14-1 5.8 Blue 6.2 1,350 Example 34 15-1 6.5 Blue 5.5 1,300 Comparative Example 1 NPB 7.1 Blue 3.9 760 Comparative Example 2 HT1 6.6 Blue 5.7 1,340 Comparative Example 3 HT2 5.9 Blue 6.1 1,450

According to the results shown in Table 2, the driving voltage of the material used as the auxiliary layer of the hole transport layer in Examples 18 to 34 was much lower than that of Comparative Examples 1 to 3. It can be seen that this is the role of the auxiliary layer suitable for the deep HOMO level of the blue host. In addition, it is possible to manufacture a device with high efficiency and long life when it is used well (Examples 21, 25, 28 and 30). Based on this, a low voltage, high efficiency, high brightness, long life organic light emitting device having excellent hole injection and hole transporting ability could be manufactured.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

100: organic light emitting device 110: cathode
120: anode 105: organic thin film layer
130: luminescent layer 140: hole transport layer
150: electron transport layer 160: electron injection layer
170: Hole injection layer 230: Emission layer + Electron transport layer

Claims (12)

A compound for an organic optoelectronic device represented by the following Formula 3:
(3)

In Formula 3,
Ar ¹ and Ar ² are, independently of each other, a substituted or unsubstituted C6 to C30 aryl group or a group represented by the following formula (S-2)
At least one of the Ar ¹ and Ar ² is the formula S-2,
Ar ³ and Ar ⁴ are, independently of each other, a substituted or unsubstituted C6 to C30 aryl group,
L ¹ to L ³ independently represent a substituted or unsubstituted C6 to C30 arylene group,
n1 to n3 are independently of each other an integer of 0 or 1;
[Formula S-2]

In the above formula (S-2)
X ³ is -NR'-, -O-, or -S-,
R ⁵ , R ⁶ and R 'are independently of each other hydrogen, deuterium, cyano, C 1 to C 20 alkyl, C 6 to C 30 aryl, or combinations thereof. The method according to claim 1,
Wherein Ar ¹ and Ar ² are, independently of each other, the above-described formula (S-2). The method according to claim 1,
Wherein Ar ¹ and Ar ² are each independently any one of the following substituents:

In this substituent,
Ar ⁵ to Ar ⁷ are independently of each other hydrogen, deuterium, cyano group, C1 to C20 alkyl group, C6 to C30 aryl group, or combinations thereof. The method according to claim 1,
Wherein L &^lt; ¹ > to L &^lt; ^{3 & gt} ; are each independently any one of the following substituents:

. The method according to claim 1,
Wherein Ar ¹ and Ar ² are independently of each other a substituted or unsubstituted C 14 to C 30 aryl group having a fused ring having a plurality of rings. The method according to claim 1,
Wherein Ar ¹ and Ar ² are, independently of each other, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, or a substituted or unsubstituted phenanthrenyl group. A compound selected from the group consisting of the following chemical formulas:

The method according to claim 1,
Wherein the organic optoelectronic device is any one selected from the group consisting of an organic photoelectric device, an organic light emitting device, an organic solar cell, an organic transistor, an organic photoreceptor drum, and an organic memory device. An organic light emitting device comprising an anode, a cathode, and at least one organic thin film layer interposed between the anode and the cathode,
Wherein at least one of the organic thin film layers comprises the compound for an organic optoelectronic device according to any one of claims 1 to 8. 10. The method of claim 9,
Wherein the organic thin film layer is any one selected from the group consisting of a light emitting layer, a hole transporting layer, a hole injecting layer, an electron transporting layer, an electron injecting layer, a hole blocking layer, and combinations thereof. 11. The method of claim 10,
Wherein the compound for an organic optoelectronic device is contained in a hole injection layer or a hole transport layer. 10. A display device comprising the organic light emitting element according to claim 9.

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