KR102193068B1 - Hole transfer material for organic electroluminescent device and organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to a compound for an organic electroluminescent device represented by the following structural formula 1. Accordingly, the purpose of improving the characteristics of the organic EL device is to introduce a heteroaromatic derivative compound for an organic EL device having excellent hole transport properties into the hole transport layer or the light emitting layer.
[Structural Formula 1]

Description

Hole transport material for organic electroluminescent device and organic electroluminescent device including the same {HOLE TRANSFER MATERIAL FOR ORGANIC ELECTROLUMINESCENT DEVICE AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME}

The present invention relates to a hole transport material for an organic electroluminescent device and an organic electroluminescent device including the same, and more particularly, a heteroaromatic derivative compound for an organic electroluminescent device having hole transport ability, and a light emitting layer, a hole injection layer, and a hole transport layer It relates to an organic electroluminescent device introduced in.

In the organic light emitting diode, an anode and a cathode, and a device structure therebetween have a shape including an organic material layer. Each organic material layer forms a multi-layer composed of different materials, and is largely composed of a hole injection and transport layer, an emission layer, and an electron transport and injection layer. In this structure, when a voltage is applied to the anode, holes in the anode and electrons in the cathode are injected and moved through each layer, and excitons are formed in the emission layer and fall back to the ground state, and light is generated while changing to light energy.

The organic layers form different energy levels according to color implementation, efficiency, and role, and embody red, green, and blue light according to the energy level in the emission layer. In terms of the manufacturing process, it can be largely classified into low-molecular and high-molecular materials. Devices using low-molecular materials form a thin film through vacuum evaporation and have the advantage of being able to easily implement color pixels due to easy purification and high purity. There are problems to be solved, such as preventing crystallization and improving color purity.

In the case of a light emitting device using a polymer, a thin film is simply formed by a method such as spin coating or printing, so that the device manufacturing process is simple, the cost is low, and it has high thermal stability, so that a thin film having excellent mechanical properties can be provided. In addition, polymer-based OLEDs can compensate for the shortcomings of low-molecular-based OLEDs that are vulnerable to heat, and there are economic advantages such as reduction in material usage, manufacturing cost, and simple production processes by forming a layer through a solution process. do. Therefore, from a commercial perspective, it is expected that polymer devices will have greater competitiveness than small molecules in the long term.

Through the present invention, it is intended to improve the characteristics of a device by introducing a monomer having hole transport properties from a blue polymer material among red, green, and blue polymer materials to perform polymerization.

Korean Patent Publication No. 10-2007-0086613

An object of the present invention is to provide a new heteroaromatic derivative compound for an organic electroluminescent device having excellent hole transport properties.

Another object of the present invention is to improve the characteristics of the organic EL device by introducing a heteroaromatic derivative compound for an organic EL device having excellent hole transport properties into the hole transport layer or the light emitting layer.

According to one aspect of the invention,

A compound for an organic electroluminescent device represented by the following structural formula 1 is provided.

[Structural Formula 1]

In structural formula 1,

이고,X ¹ is an oxygen atom, a sulfur atom, or

ego,

, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴기이고,R ³ is

, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted Is a C1 to C30 heteroaryl group,

n ¹ is a repetition number that is an integer selected from 0 to 10,

R ⁴ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,

, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴기이고,Ar ¹ is

, A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

n ² is a repetition number that is any one integer selected from 0 to 10,

R ⁵ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,

Ar ² and Ar ³ are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

이고,R ¹ and R ² are the same as or different from each other, and each independently a halogen group, or

ego,

R ⁶ and R ⁷ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 hetero A cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, or R ⁵ and R ⁶ are bonded to each other to form a fused ring with three atoms therebetween Thereby forming a substituted or unsubstituted C2 to C30 heterocycloalkyl group.

According to another aspect of the present invention,

A compound for an organic electroluminescent device represented by the following Structural Formula 2 is provided.

[Structural Formula 2]

In formula 2,

k, l, and m are repetitions,

The ratio of k, l, and m is k: l+m = 0.01~1: 0~0.99,

이고, X ² is an oxygen atom, a sulfur atom, or

ego,

, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴기이고,R ⁸ is

, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted Is a C1 to C30 heteroaryl group,

n ³ is a repeating number that is an integer selected from 0 to 10,

R ⁹ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,

, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴기이고,Ar ⁴ is

, A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

n ⁴ is a repeating number that is any one integer selected from 0 to 10,

R ¹⁰ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,

Ar ⁵ and Ar ⁶ are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

Ar ⁷ and Ar ⁸ are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group.

,

,

,

,

,

, 또는

이고,Preferably, Ar ¹ and Ar ⁴ are the same as or different from each other, and each independently a C1 to C10 alkoxy group, a C1 to C10 alkyl group,

,

,

,

,

,

, or

ego,

X ³ and X ⁴ are the same as or different from each other, and each independently an oxygen atom or a sulfur atom,

이고, Y ¹ to Y ⁴ are the same as or different from each other, and each independently a nitrogen atom, or

ego,

R ²³ is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

n ⁵ is a repetition number that is an integer selected from 0 to 10,

R ¹¹ to R ²² are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cyclo It may be an alkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

Preferably, Ar ² , Ar ³ , Ar ⁵ , and Ar ⁶ are the same as or different from each other, and each independently may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted biphenyl group. have.

,

,

,

, 또는

이고,More preferably, Ar ² , Ar ³ , Ar ⁵ , and Ar ⁶ are the same as or different from each other, and each independently

,

,

,

, or

ego,

R ²⁴ to R ³⁶ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cyclo It may be an alkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

,

,

,

, 또는

이고,Preferably, Ar ⁷ and Ar ⁸ are the same as or different from each other, and each independently,

,

,

,

, or

ego,

또는

이고, X ⁵ oxygen atom, sulfur atom,

or

ego,

R ⁵³ to R ⁵⁵ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 hetero A cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

R ³⁷ to R ⁵² are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cyclo It may be an alkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

The compound for an organic electroluminescent device may be any one selected from compounds 1 to 42 represented by the following formula.

According to another aspect of the present invention,

An organic electroluminescent device including the compound for an organic electroluminescent device is provided.

The organic light emitting device includes a first electrode, a second electrode facing the first electrode, and an organic layer between the first electrode and the second electrode,

The organic layer may include the compound for an organic electroluminescent device.

The organic layer may include at least one selected from a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, and an electron injection layer.

The compound for an organic light emitting device may be included in at least one selected from the emission layer, the hole injection layer, and the hole transport layer.

Since the heteroaromatic derivative compound for an organic electroluminescent device of the present invention has excellent hole transport properties, it is introduced into at least one of a hole injection layer, a hole transport layer, and a light emitting layer to an organic electroluminescent device to improve hole transport and light emission characteristics. It is possible to improve the characteristics of a blue organic electroluminescent device.

The present invention is intended to illustrate specific embodiments and to be described in detail in the detailed description, since various transformations may be applied and various embodiments may be provided. However, this is not intended to limit the present invention to a specific embodiment, it is to be understood to include all conversions, equivalents, and substitutes included in the spirit and scope of the present invention. In describing the present invention, when it is determined that a detailed description of a related known technology may obscure the subject matter of the present invention, a detailed description thereof will be omitted.

In addition, terms including ordinal numbers such as first and second to be used hereinafter may be used to describe various elements, but the elements are not limited by the terms. These terms are used only for the purpose of distinguishing one component from another component. For example, without departing from the scope of the present invention, a first element may be referred to as a second element, and similarly, a second element may be referred to as a first element.

In addition, when a component is referred to as being "formed" or "stacked" on another component, it may be formed or stacked by being directly attached to the front surface or one surface on the surface of the other component. It should be understood that there may be more other components in the.

Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance.

In the present specification, "atomic bond" means a single bond, a double bond, or a triple bond unless otherwise defined.

The "substituted" means that at least one hydrogen atom is deuterium, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, a C1 to C30 halogenated alkyl group, a C6 to C30 aryl group, a C1 to C30 heteroaryl group, C1 to C30 alkoxy group, C2 to C30 alkenyl group, C2 to C30 alkynyl group, C6 to C30 aryloxy group, silyloxy group (-OSiH ₃ ), -OSiR ¹ H ₂ (R ¹ is a C1 to C30 alkyl group or C6 to C30 aryl group), -OSiR ¹ R ² H (R ¹ and R ² are each independently a C1 to C30 alkyl group or a C6 to C30 aryl group), -OSiR ¹ R ² R ³ , (R ¹ , R ² , and R ³ is each independently a C1 to C30 alkyl group or a C6 to C30 aryl group), a C1 to C30 acyl group, a C2 to C30 acyloxy group, a C2 to C30 heteroaryloxy group, a C1 to C30 sulfonyl group, a C1 to C30 alkylthiol group , C6 to C30 arylthiol group, C1 to C30 heterocyclothiol group, C1 to C30 phosphate amide group, silyl group (SiR ¹ R ² R ³ ₎ (R ¹ , R ² , and R ³ are each independently a hydrogen atom, C1 to C30 alkyl group or C6 to C30 aryl group), amine group (-NRR') (wherein R and R'are each independently selected from the group consisting of a hydrogen atom, a C1 to C30 alkyl group, and a C6 to C30 aryl group Is a substituent), a carboxyl group, a halogen group, a cyano group, a nitro group, an azo group, and a substituent selected from the group consisting of a hydroxy group.

In addition, two adjacent substituents among the substituents may be fused to form a saturated or unsaturated ring.

In addition, the range of carbon number of the alkyl group or aryl group in the "substituted or unsubstituted C1 to C30 alkyl group" or "substituted or unsubstituted C6 to C30 aryl group" etc. is unsubstituted without considering the portion where the substituent is substituted It refers to the total number of carbon atoms constituting the alkyl moiety or the aryl moiety when viewed as being made For example, a phenyl group in which a butyl group is substituted in the para position corresponds to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

In addition, the range of carbon number of the fused aryl group in the "substituted or unsubstituted C6 to C30 fused aryl group", etc., is fused and additionally formed when viewed as unsubstituted without considering the substituted portion of the substituent. It means the total number of carbon atoms constituting the aryl moiety.

In the present specification, unless otherwise defined, "hetero" means that one functional group contains 1 to 4 heteroatoms selected from the group consisting of N, O, S and P, and the rest are carbon.

In the present specification, unless otherwise defined, "a combination thereof" means that two or more substituents are bonded with a linking group or two or more substituents are condensed and bonded.

In the present specification, "hydrogen" refers to singlet hydrogen, dihydrogen, or tritium unless otherwise defined.

In the present specification, "alkyl (alkyl) group" refers to an aliphatic hydrocarbon group unless otherwise defined.

The alkyl group may be a "saturated alkyl group" that does not contain any double bonds or triple bonds.

The alkyl group may be an "unsaturated alkyl group" including at least one double bond or triple bond.

“Alkenylene group” refers to a functional group in which at least two carbon atoms are formed of at least one carbon-carbon double bond, and “alkynylene group” refers to at least two carbon atoms at least one carbon-carbon triple It means a functional group consisting of a bond. Alkyl groups, whether saturated or unsaturated, can be branched, straight-chain or cyclic.

The alkyl group may be a C1 to C30 alkyl group. More specifically, it may be a C1 to C20 alkyl group, a C1 to C10 alkyl group, or a C1 to C6 alkyl group.

For example, a C1 to C4 alkyl group has 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl. It indicates that it is selected from the group consisting of.

For specific examples, the alkyl group is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, ethenyl group, propenyl group, butenyl group, cyclopropyl group, cyclo It means a butyl group, a cyclopentyl group, a cyclohexyl group, etc.

“Amine group” includes an amino group, an arylamine group, an alkylamine group, an arylalkylamine group, or an alkylarylamine group, and may be represented by -NRR', wherein R and R'are each independently a hydrogen atom , A C1 to C30 alkyl group, and a C6 to C30 aryl group.

“Cycloalkyl groups” include monocyclic or fused ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

"Heterocycloalkyl group" means that the cycloalkyl group contains 1 to 4 heteroatoms selected from the group consisting of N, O, S, and P, and the remainder is carbon. When the heterocycloalkyl group is a fused ring, at least one ring among the fused rings may contain 1 to 4 hetero atoms.

"Aromatic group" refers to a functional group in which all elements of a functional group in the form of a ring have a p-orbital, and these p-orbitals form a conjugation. Specific examples include an aryl group and a heteroaryl group.

“Aryl groups” include monocyclic or fused ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) functional groups.

"Heteroaryl group" means that the aryl group contains 1 to 4 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, at least one ring among the fused rings may contain 1 to 4 hetero atoms.

In the aryl group and the heteroaryl group, the number of ring atoms is the sum of the number of carbon atoms and the number of non-carbon atoms.

When used in combination such as "alkylaryl group" or "arylalkyl group", the terms of each of the alkyl and aryl mentioned above have the meanings and contents indicated above.

The term "arylalkyl group" refers to an aryl substituted alkyl radical such as benzyl and is included in the alkyl group.

The term "alkylaryl group" refers to an alkyl substituted aryl radical and is included in an aryl group.

Hereinafter, the heteroaromatic derivative compound for an organic electroluminescent device of the present invention will be described. The heteroaromatic derivative compound for an organic electroluminescent device of the present invention may be represented by the following structural formula 1.

[Structural Formula 1]

In structural formula 1,

이고,X ¹ is an oxygen atom, a sulfur atom, or

ego,

, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴기이고,R ³ is

, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted Is a C1 to C30 heteroaryl group,

n ¹ is a repetition number that is an integer selected from 0 to 10,

R ⁴ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,

, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴기이고,Ar ¹ is

, A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

n ² is a repetition number that is any one integer selected from 0 to 10,

R ⁵ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,

Ar ² and Ar ³ are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

이고,R ¹ and R ² are the same as or different from each other, and each independently a halogen group, or

ego,

R ⁶ and R ⁷ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 hetero A cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, or R ⁵ and R ⁶ are bonded to each other to form a fused ring with three atoms therebetween Thereby forming a substituted or unsubstituted C2 to C30 heterocycloalkyl group.

In addition, the heteroaromatic derivative compound for an organic electroluminescent device of the present invention may be represented by the following structural formula 2.

[Structural Formula 2]

In formula 2,

k, l, and m are repetitions,

The ratio of k, l, and m is k: l+m = 0.01~1: 0~0.99,

이고, X ² is an oxygen atom, a sulfur atom, or

ego,

, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴기이고,R ⁸ is

, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted Is a C1 to C30 heteroaryl group,

n ³ is a repeating number that is an integer selected from 0 to 10,

R ⁹ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,

, 치환 또는 비치환된 C1 내지 C30 알콕시기, 치환 또는 비치환된 C1 내지 C30 알킬기, 치환 또는 비치환된 C3 내지 C30 시클로알킬기, 치환 또는 비치환된 C1 내지 C30 헤테로시클로알킬기, 치환 또는 비치환된 C6 내지 C30 아릴기, 또는 치환 또는 비치환된 C1 내지 C30 헤테로아릴기이고,Ar ⁴ is

, A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

n ⁴ is a repeating number that is any one integer selected from 0 to 10,

R ¹⁰ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,

Ar ⁵ and Ar ⁶ are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

Ar ⁷ and Ar ⁸ are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group.

,

,

,

,

,

, 또는

이고,Preferably, Ar ¹ and Ar ⁴ are the same as or different from each other, and each independently a C1 to C10 alkoxy group, a C1 to C10 alkyl group,

,

,

,

,

,

, or

ego,

X ³ and X ⁴ are the same as or different from each other, and each independently an oxygen atom or a sulfur atom,

이고, Y ¹ to Y ⁴ are the same as or different from each other, and each independently a nitrogen atom, or

ego,

R ²³ is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

n ⁵ is a repetition number that is an integer selected from 0 to 10,

R ¹¹ to R ²² are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cyclo It may be an alkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

Preferably, Ar ² , Ar ³ , Ar ⁵ , and Ar ⁶ are the same as or different from each other, and each independently may be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted biphenyl group. have.

,

,

,

, 또는

이고,More preferably, Ar ² , Ar ³ , Ar ⁵ , and Ar ⁶ are the same as or different from each other, and each independently

,

,

,

, or

ego,

R ²⁴ to R ³⁶ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cyclo It may be an alkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

,

,

,

, 또는

이고,Preferably, Ar ⁷ and Ar ⁸ are the same as or different from each other, and each independently,

,

,

,

, or

ego,

또는

이고, X ⁵ oxygen atom, sulfur atom,

or

ego,

R ⁵³ to R ⁵⁵ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 hetero A cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,

R ³⁷ to R ⁵² are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cyclo It may be an alkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group.

Examples of the substituted or unsubstituted C2 to C30 heteroaryl group include a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted thiophenyl group , A substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted imidazo[1,2-a]pyridinyl group, a substituted or unsubstituted Benziimidazolyl group, substituted or unsubstituted indazolyl group, substituted or unsubstituted phenothiazinyl group, substituted or unsubstituted phenazinyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted dibenzo Thiophenyl group, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted tetrazolyl group, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted oxatriazolyl Group, a substituted or unsubstituted thitriazolyl group, a substituted or unsubstituted benzotriazolyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted purinyl group, A substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted phthalazinyl group, a substituted or unsubstituted naphpyridinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or Unsubstituted quinazolinyl group, substituted or unsubstituted acridinyl group, or substituted or unsubstituted phenanthrolinyl group, preferably substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted A substituted triazinyl group, a substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted imidazo[1 ,2-a]pyridinyl group, substituted or unsubstituted benziimidazolyl group, substituted or unsubstituted indazolyl group, substituted or unsubstituted phenothiazinyl group, substituted or unsubstituted phenazinyl group, substituted or It may be an unsubstituted carbazolyl group, or a substituted or unsubstituted dibenzothiophenyl group.

The compound for an organic EL device may be any one selected from compounds 1 to 42 represented by the above formula, but is not limited thereto.

Hereinafter, the organic electroluminescent device of the present invention will be described.

The organic electroluminescent device of the present invention may include the above-described heteroaromatic derivative compound and polymer compound for an organic electroluminescent device of the present invention in an organic material layer.

The organic light-emitting device of the present invention includes a first electrode, a second electrode facing the first electrode, and an organic layer between the first electrode and the second electrode, and the organic light-emitting device of the present invention in the organic layer It may contain a solvent compound.

The organic layer may include at least one of a hole injection layer, a hole transport layer, a hole blocking layer, an emission layer, an electron blocking layer, an electron transport layer, and an electron injection layer, and the organic electroluminescence is applied to a double emission layer, a hole injection layer, or a hole transport layer. The device compound may be included by copolymerization with a light emitting material.

In the organic electroluminescent device of the present invention, a hole injection layer and a hole transport layer are stacked on the first electrode, and an emission layer including a heteroaromatic derivative containing a hetero atom represented by Formula 1 is stacked. In addition, an electron transport layer (ETL) and an electron injection layer (EIL) are stacked on the emission layer, and a second electrode is formed on the emission layer. In the organic light emitting diode, a hole injection layer (HIL) and a hole transport layer (HTL) may be formed between the first electrode and the emission layer, and in some cases, an electron transport layer (ETL) except for the hole suppression layer (HBL) on the emission layer. ) And an electron injection layer (EIL) may be formed. The organic electroluminescent device having the above-described stacked structure can be formed by a conventional manufacturing method, and the manufacturing method is not particularly limited.

Hereinafter, a method of manufacturing an organic light emitting diode according to an embodiment of the present invention will be described in detail, but the present invention is not limited thereto.

First, a patterned first electrode is formed on the substrate. Here, the substrate is not limited as long as it is a substrate used in a typical organic electroluminescent device, but specific examples include a glass substrate, a transparent plastic substrate, a polyethylene terephthalate substrate, a polycarbonate substrate, a polyimide substrate, etc., preferably A glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproofness is preferable. In this case, the thickness of the substrate is preferably 0.3 to 1.1 mm, but is not limited.

The material for forming the first electrode is not particularly limited, but if the first electrode is a cathode, the cathode is made of a conductive metal or oxide that facilitates hole injection, and a specific example thereof is ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), nickel (Ni), platinum (Pt), gold (Au), iridium (Ir), graphene, or PEDOT: may be an electrode such as a graphene hybrid, Preferably, it may be a material capable of injecting holes well depending on the structure of the substrate.

After cleaning the substrate on which the first electrode is formed, UV-ozone treatment is performed. At this time, it is preferable to use an organic solvent such as isopropanol (IPA) or acetone for washing.

A hole injection layer may be formed on the first electrode of the substrate, and a light emitting layer may be formed on the hole injection layer.

The hole injection layer (HIL) can be formed by a method such as a vacuum evaporation method, a spin coating method, a cast method, a Langmuir Blodgett (LB) method, etc., but it is preferably formed by a vacuum evaporation method in which it is easy to obtain a uniform film quality. In the case of forming the hole injection layer by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the desired hole injection layer structure and thermal characteristics, but generally, a deposition temperature of 50 to 500 °C, The vacuum degree of 10 ^-8 to 10 ^-3 torr, a deposition rate of 0.01 to 100 Å/sec, and a layer thickness of 10 Å to 5 μm are preferably adjusted appropriately. The compound used for the hole injection layer is not particularly limited, and TCTA(4,4',4''-tri(N-), which is a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429, or starburst-type amine derivatives. Carbazolyl)triphenylamine), m-MTDATA(4,4',4''-tris(3-methylphenylamino)triphenylamine), m-MTDAPB(4,4',4''-tris(3- Methylphenylamino)phenoxybenzene) or HI-406(N ¹ ,N ¹ '-(biphenyl-4,4'-diyl) bis(N1-(naphthalen-1-yl)-N ⁴ ,N ⁴ -diphenyl Benzene-1,4-diamine) and the like can be used.

Next, a hole transport layer (HTL) may be formed on the hole injection layer by a vacuum deposition method, a spin coating method, a cast method, or an LB method, but preferably, a vacuum deposition method is used. It is preferable to select the hole transport layer in the range of conditions substantially the same as for formation by the vacuum deposition method. In addition, the hole transport layer compound is not particularly limited, and may be arbitrarily selected from common known materials used in the hole transport layer, and specific examples include carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine (TPD) or N.N'-di(naphthalene-1- 1)-N,N'-diphenyl benzidine (α-NPD) may be used, such as a conventional amine derivative, but is not limited thereto.

Next, it is preferable to form a light emitting layer (EML) on the hole transport layer using the vacuum deposition method. In addition, when the light emitting layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound to be used, but in general, it is preferable to select within the same range of conditions as the hole injection layer formation.

The light-emitting layer includes the compound for an organic light-emitting device of the present invention copolymerized with a blue light-emitting material.

The light emitting host may further include a dopant compound, and the dopant compound may be used as a phosphorescent dopant, a fluorescent dopant, or a mixture thereof to form a light emitting layer. At this time, as the fluorescent dopant compound, IDE102 or IDE105, BD142 (N6,N12-bis(3,4-dimethylphenyl)-N6,N12-dimethylchrysene-6,12 available from Idemitsu) -Diamine) and BD02 (N1,N1,N6,N6-tetraphenylpyrene-1,6-diamine), BD04 (N1,N1,N6,N6-tetrakis(4-tertiary-butylphenyl)pyrene A pyrene compound substituted with a diarylamine having a smaller band gap than the host compound, such as -1,6-diamine), can be used. As the phosphorescent dopant, a green phosphorescent dopant Ir(ppy)3 (tris(2-phenyl) Pyridine) iridium), blue phosphorescent dopant F2Irpic (iridium(?) bis[4,6-difluorophenyl)-pyridinato-N,C2'] picolinate), UDC's red phosphorescent dopant RD61, etc. It can be used, but is not limited thereto. In addition, the dopant compound is preferably doped by a vacuum deposition method, but is not limited thereto.

The doping concentration of the dopant compound is not particularly limited, but it is preferable that the dopant compound is doped in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the host compound. If the content of the dopant compound is less than 0.01 parts by weight, there is a problem that the amount of the dopant compound is insufficient and color development is not performed properly, and if it exceeds 15 parts by weight, there is a problem that the efficiency is rapidly reduced due to concentration quenching.

In addition, in the case of using with a phosphorescent dopant compound in the light emitting layer, a hole blocking layer (HBL) is selectively added to the vacuum deposition method or spin coating method to prevent diffusion of triplet excitons or holes into the electron transport layer (HTL). It is preferable to laminate by. The material of the hole blocking layer that can be used at this time is not particularly limited, but any one of known materials used as a hole suppressing material can be selected and used, and specific examples include oxadiazole derivatives, triazole derivatives, and phenanthroline derivatives. Alternatively, a phenanthrolines-based compound (eg, UDC's BCP (basocuproin)) may be used.

A hole suppression layer and an electron transport layer may be formed on the emission layer by using a vacuum deposition or spin coating method. Here, the hole suppression layer serves to prevent excitons formed in the light-emitting material from being transferred to the electron transport layer or to prevent holes from being transferred to the electron transport layer. Compounds usable in the hole suppression layer are TAZ(3-phenyl-4-(1'-naphthyl)-5-phenyl-1,2,4-triazole), BCP(2,9-dimethyl-4,7-diphenyl) -1,10-phenanthroline), LiF, MgF ₂ , phenanthrolines compounds (e.g. UDC, BCP), imidazole compounds, triazoles compounds, oxadiazoles A compound (eg, PBD) or an aluminum complex (UDC) may be used, but the present invention is not limited thereto. In addition, the deposition conditions of the electron transport layer (ETL) vary depending on the compound to be used, but in general, it is preferable to select the electron transport layer (ETL) within the same range of conditions as the formation of the hole injection layer.

An electron injection layer (EIL) may be formed on the electron transport layer, wherein the electron transport layer is formed by a vacuum deposition method, a spin coating method, or a cast method using a conventional electron injection layer compound. It is desirable to form.

Finally, a metal for forming a cathode is formed on the electron injection layer by a method such as vacuum deposition or sputtering, and is used as a cathode. Here, as the metal for forming the cathode, a metal, an alloy, an electrically conductive compound, or a mixture thereof having a low work function may be used, and specific examples include lithium (Li), magnesium (Mg), aluminum (Al), and aluminum-lithium ( Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like may be used. In addition, a transmissive cathode using ITO or IZO may be used to obtain a top light emitting device, but is not limited thereto.

In the present invention, the heteroaromatic derivative compound may be used as a material for forming a light emitting layer by copolymerizing with a light emitting material when manufacturing the organic electroluminescent device, and as a material having hole transport capability, it may be used as a material for forming a hole injection layer or a hole transport layer.

Hereinafter, the compound for an organic electroluminescent device according to the present invention and a method of manufacturing an organic electroluminescent device including the same will be described in more detail through examples.

The heteroaromatic hole transport material represented by Structural Formula 1 of the present invention can be obtained through halogen substitution reaction and C-N coupling as shown in Scheme 1 below, but the scope of the present invention is not limited thereto.

[Scheme 1]

In addition, as shown in Scheme 2 below, the polymer material incorporating a heteroaromatic-based hole transport monomer represented by Structural Formula 2 of the present invention is a hole transport material prepared through Scheme 1 above, as shown in Scheme 2 below. As shown in Fig. 3, polymerization may be performed through a Suzuki coupling, but the scope of the present invention is not limited thereto.

[Scheme 2]

[Scheme 3]

[ Example ]

Comparative example 1: Synthesis of Comparative Compound 1

Step 1.

10H-phenothiazine (15 g, 75.3 mmol), 1-bromo-4 tert butyl) benzene (17.65 g, 82.8 mmol) and potassium tert butoxide (21 g, 225.8 mmol) in anhydrous toluene (526.92 mL) After dissolving, tris (dibenzylidene acetone) di palladium (0) (2.01 g, 2.3 mmol), tritert butylphosphine (0.91 g, 4.5 mmol) was stirred at 110° C. for 1 hour under a nitrogen stream, followed by column chromatography. The product is obtained (yield: 75%).

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.62-7.56 (d, 2H), 7.32-7.27 (d, 2H), 7.00 (dd, J = 7.4, 1.7 Hz, 2H), 6.84 (td, J = 7.7 , 1.8 Hz, 2H), 6.79 (td, J = 7.4, 1.4 Hz, 2H), 6.20 (dd, J = 8.0, 1.4 Hz, 2H), 1.40 (s, 9H).

Step 2.

After dissolving 10- (4- (tert butyl) phenyl) -10H- phenothiazine (10 g, 30.2 mmol) prepared in step 1 in dichloromethane (1993. 08 mL), N-bromo Add succinimide (11.81 g, 66.4 mmol). After stirring at room temperature for 4 hours, the product is obtained through column chromatography. (Yield: 92%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.64-7.56 (d, 2H), 7.25-7.21 (d, 2H), 7.08 (d, J = 2.3 Hz, 2H), 6.90 (dd, J = 8.8, 2.3 Hz, 2H), 6.00 (d, J = 8.8 Hz, 2H), 1.40 (s, 9H).

Example 1: compound 1 synthesis

Step 1.

4-Butyl aniline (15 g, 100.5 mmol), 1-bromo-4-iodobenzene (28.44, 100.5 mmol) and sodium tert butoxide (19.32 g, 201 mmol) were dissolved in anhydrous toluene (201 ml). After adding 1,1-ferrocene diyl-bis (diphenyl phosphine) (1.11 g, 2 mmol), tris (dibenzylidene acetone) di palladium (0) (0.920 g, 1 mmol) to the solution, under a nitrogen stream It stirs at 100 degreeC for 12 hours. After that, a product is obtained through column chromatography. (Yield: 62%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.39-7.33 (d, 2H), 7.14 (d, J = 8.0, 5.8 Hz, 2H), 7.06-7.01 (d, 2H), 6.95-6.88 (d, 2H ), 5.64 (s, 1H), 2.67-2.54 (m, 2H), 1.71-1.58 (m, 2H), 1.50-1.36 (m, 2H), 1.00 (td, J = 7.3, 2.8 Hz, 3H).

Step 2.

It was carried out in the same manner as in Comparative Example 1.

Step 3.

It was carried out in the same manner as in Comparative Example 1.

Step 4.

3,7- Dibromo -10- (4- (tert-butyl) phenyl) -10H-phenothiazine (5 g, 10.2 mmol) prepared in step 3 was added to anhydrous tetrahydrofuran (113.55 mL) under a nitrogen stream. ), and then slowly add normal butyllithium solution (2.5 M) (8.99 ml, 22.5 mmol) at -78°C. Thereafter, a solution obtained by dissolving iodine (10.38 g, 40.9 mmol) in anhydrous tetrahydrofuran (68.13 mL) was slowly added. Then, the temperature was slowly raised to room temperature, stirred for 2 hours, and then the product was obtained through column chromatography. (Yield: 71%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.65-7.51 (d, 2H), 7.22 (dd, J = 8.3, 1.9 Hz, 4H), 7.08 (dd, J = 8.7, 2.0 Hz, 2H), 5.86 ( d, J = 8.7 Hz, 2H), 1.39 (s, J = 6.0 Hz, 9H).

Step 5.

4-bromo-N- (4-butyl phenyl) aniline (3.44 g, 11.3 mmol) prepared in step 1, 10- (4- (tert butyl) phenyl) prepared in step 4 -3,7- Diiodo-10H- phenothiazine (3 g, 5.1 mmol), potassium tert butoxide (2.97 g, 30.9 mmol) was dissolved in anhydrous toluene (54.86 mL) and then tris (dibenzylidene acetone) dipalladium (0). ) (0.09 g, 0.1 mmol), tritert butylphosphine (0.03 g, 0.2 mmol) was added, stirred at 100° C. for 4 hours under a nitrogen stream, and the product was obtained through column chromatography. (Yield: 62%)

¹ H NMR (400 MHz, DMSO) δ 7.43 (d, J = 7.4 Hz, 4H), 7.27 (d, J = 7.7 Hz, 2H), 7.20 (d, J = 1.4 Hz, 2H), 7.17 (d, J = 7.4 Hz, 4H), 7.08 (dd, J = 11.2, 7.5 Hz, 4H), 7.05-6.97 (m, 10H), 2.48 (t, J = 7.9 Hz, 4H), 1.67 (p, J = 7.8 Hz, 4H), 1.43 (dt, J = 14.4, 7.1 Hz, 4H), 1.37 (s, 9H), 1.00 (t, J = 6.6 Hz, 6H).

Example 2: Synthesis of compound 8

Step 1.

After dissolving 4-aminophenol (15 g, 137.5 mmol), 1-bromohexane (24.96 g, 151.2 mmol) and potassium carbonate (151.04 g, 164.9 mmol) in acetone (288.65 mL), the mixture was stirred at room temperature for 24 hours. The product is obtained through column chromatography. (Yield: 73%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 6.67 (d, J = 7.7 Hz, 2H), 6.53 (d, J = 7.4 Hz, 2H), 3.96 (t, J = 7.7 Hz, 2H), 3.39 (s , 2H), 1.75 (p, J = 7.8 Hz, 2H), 1.49-1.24 (m, 6H), 1.14-0.89 (m, 3H).

Step 2.

4- (hexyloxy) aniline (15 g, 77.6 mmol) prepared in step 1 and 1-bromo-4-iodobenzene (24.15 g, 85.4 mmol), cuprous iodide (0.15 g, 0.8 mmol) , 1,10-phenanthroline (0.28 g, 1.6 mmol) and potassium hydroxide (4.35 g, 77.6 mmol) were dissolved in toluene 108.65 ml) and then 100? After stirring for 5 hours, the product is obtained through column chromatography. (Yield: 64%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.39 (d, J = 7.4 Hz, 2H), 7.01 (d, J = 7.4 Hz, 2H), 6.92 (d, J = 7.4 Hz, 2H), 6.83 (d , J = 7.7 Hz, 2H), 3.97 (t, J = 7.7 Hz, 2H), 3.44 (s, 1H), 1.76 (p, J = 7.8 Hz, 2H), 1.45-1.24 (m, 6H), 1.04 -0.92 (m, 3H).

Step 3.

10H-phenothiazine (15 g, 75.3 mmol), 4-bromoanisole (15.49 g, 82.8 mmol), potassium tert butoxide (21 g, 225.8 mmol) were dissolved in anhydrous toluene (526.92 mL) and then tris (Dibenzylidene acetone) di palladium (0) (2.01 g, 2.3 mmol), tritert butylphosphine (0.91 g, 4.5 mmol) was stirred at 110° C. for 1 hour under a nitrogen stream, and the product was obtained through column chromatography. (Yield: 85%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.18 (dd, J = 7.5, 1.6 Hz, 2H), 7.03 (ddd, J = 7.5, 5.0, 1.2 Hz, 4H), 6.94-6.85 (m, 4H), 6.64 (dd, J = 7.4, 1.5 Hz, 2H), 3.82 (s, 3H).

Step 4.

After dissolving 10-(4-methoxyphenyl)-10H-phenothiazine (10 g, 32.7 mmol) prepared in step 3 in dichloromethane (209.57 mL), N-bromosuccinimide ( 12.82 g, 72 mmol) was added. After stirring at room temperature for 4 hours, the product is obtained through column chromatography. (Yield rate: 90%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.47 (d, J = 1.6 Hz, 2H), 7.28 (dd, J = 7.5, 1.4 Hz, 2H), 6.93 (d, J = 7.4 Hz, 2H), 6.82 (dd, J = 9.3, 7.5 Hz, 4H), 3.80 (s, 3H).

Step 5.

3,7-di bromo -10- (4-methoxyphenyl) -10H- phenothiazine (5 g, 10.8 mmol) prepared in step 4 was dissolved in anhydrous tetrahydrofuran (119.94 mL) under a nitrogen stream. After that, normal butyllithium solution (2.5 M) (9.50 ㎖, 23.7 mmol) was slowly added at -78°C. Then, a solution obtained by dissolving iodine (10.96 g, 43.2 mmol) in anhydrous tetrahydrofuran (71.97 mL) was slowly added. Thereafter, the temperature was slowly raised to room temperature, stirred for 2 hours, and then the product was obtained through column chromatography. (Yield: 71%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.62 (d, J = 1.4 Hz, 2H), 7.39 (dd, J = 7.5, 1.4 Hz, 2H), 7.01 (d, J = 7.4 Hz, 2H), 6.88 (d, J = 7.4 Hz, 2H), 6.35 (d, J = 7.5 Hz, 2H), 3.82 (s, 3H).

Step 6.

4-bromo-N- (4-butyl phenyl) aniline (4.13 g, 11.8 mmol) prepared in step 2, 3,7-diiodo-10- (4-methoxyphenyl) prepared in step 5 ) -10H-phenothiazine (3 g, 5.4 mmol), potassium tert butoxide (3.11 g, 32.3 mol) was dissolved in anhydrous toluene (57.43 ml) and then tris (dibenzylidene acetone) dipalladium (0) ( 0.1 g, 0.1 mmol) and tritert butylphosphine (0.03 g, 0.2 mmol) were added, and the mixture was stirred at 100°C for 4 hours under a nitrogen stream, and the product was obtained through column chromatography. (Yield Rate: 60%)

¹ H NMR (400 MHz, DMSO) δ 7.45-7.39 (m, 4H), 7.22-7.20 (m, 2H), 7.15-7.11 (m, 2H), 7.09-7.04 (m, 4H), 7.00-6.96 ( m, 4H), 6.96-6.92 (m, 2H), 6.91-6.84 (m, 6H), 6.77-6.73 (m, 2H), 3.98-3.89 (m, 4H), 3.83-3.80 (m, 3H), 1.78-1.66 (m, 4H), 1.40-1.27 (m, 12H), 1.02-0.94 (m, 6H).

Example 3: Synthesis of compound 10

Step 1.

Naphthalene-2-amine (10 g, 69.8 mmol), 1-bromo-4-iodobenzene (19.76, 69.8 mmol) and sodium tert butoxide (13.42 g, 139.7 mmol) were dissolved in anhydrous toluene (139.68 mL). 1,1-ferrocene diyl-bis (diphenyl phosphine) (0.80 g, 1.4 mmol), tris (dibenzylidene acetone) dipalladium (0) (0.77 g, 0.7 mmol) was added to the solution, and nitrogen flow And stirred at 100° C. for 12 hours. After that, a product is obtained through column chromatography. (Yield: 68%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.73-7.61 (m, 2H), 7.50 (dd, J = 7.5, 1.4 Hz, 1H), 7.39 (dd, J = 11.5, 4.4 Hz, 3H), 7.33- 7.20 (m, 2H), 6.99-6.83 (m, 3H), 3.83 (s, 1H).

Step 2.

10H- Phenothiazine (15 g, 75.3 mmol), 1-bromooctane (26.17 g, 135.5 mmol) and potassium tert-butoxide (9.29 g, 82.8 mmol) were dissolved in anhydrous tetrahydrofuran (149.13 mL). After that, the mixture was stirred at 66° C. for 4 hours, and the product was obtained through column chromatography. (Yield rate: 95%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.22 (dd, J = 7.4, 1.4 Hz, 2H), 7.11 (td, J = 7.4, 1.4 Hz, 2H), 6.94 (td, J = 7.5, 1.5 Hz, 2H), 6.81 (dd, J = 7.4, 1.5 Hz, 2H), 4.91 (t, J = 5.4 Hz, 2H), 1.63 (tt, J = 7.9, 5.4 Hz, 2H), 1.40-1.26 (m, 10H ), 0.98 (t, J = 6.3 Hz, 3H).

Step 3.

After dissolving 10-octyl-10H-phenothiazine (10 g, 32.1 mmol) prepared in step 2 in dichloromethane (205.47 mL), N-bromosuccinimide (12.57 g, 70.6 mmol) at 0°C. Put in. After stirring at room temperature for 4 hours, the product is obtained through column chromatography. (Yield: 94%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.52 (d, J = 1.4 Hz, 2H), 7.27 (dd, J = 7.5, 1.4 Hz, 2H), 6.70 (d, J = 7.5 Hz, 2H), 4.88 (t, J = 5.4 Hz, 2H), 1.62 (tt, J = 7.9, 5.4 Hz, 2H), 1.40-1.24 (m, 10H), 0.98 (t, J = 6.3 Hz, 3H).

Step 4.

The 3,7-dibromo-10-octyl-10H-phenothiazine (5 g, 10.7 mmol) prepared in step 3 was dissolved in anhydrous tetrahydrofuran (118.38 ml) under a nitrogen stream and then at -78°C. Normal butyllithium solution (2.5 M) (9.38 ml, 23.4 mmol) was slowly added. Thereafter, a solution obtained by dissolving iodine (10.82 g, 42.6 mmol) in anhydrous tetrahydrofuran (71.03 ml) was slowly added. Thereafter, the temperature was slowly raised to room temperature, stirred for 2 hours, and then the product was obtained through column chromatography. (Yield: 65%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.73 (d, J = 1.6 Hz, 2H), 7.48 (dd, J = 7.6, 1.5 Hz, 2H), 6.57 (d, J = 7.7 Hz, 2H), 4.76 (t, J = 7.4 Hz, 2H), 1.57-1.45 (m, 2H), 1.47-1.19 (m, 10H), 1.03-0.93 (m, 3H).

Step 5.

N- (4-bromophenyl) naphthalene-2-amine (3.49 g, 11.7 mmol) prepared in step 1, 3,7-diiodo -10-octyl -10H-phenothi prepared in step 4 Azine (3 g, 5.3 mmol), potassium tert butoxide (3.07 g, 32.0 mmol) was dissolved in anhydrous toluene (56.81 mL) and then tris (dibenzylidene acetone) dipalladium (0) (0.10 g, 0.1 mmol) , Tritert butylphosphine (0.03 g, 0.2 mmol) was added, stirred at 100° C. for 4 hours under a nitrogen stream, and the product was obtained through column chromatography. (Yield: 59%)

¹ H NMR (400 MHz, DMSO) δ 7.77-7.68 (m, 4H), 7.47 (ddd, J = 17.0, 11.7, 4.4 Hz, 8H), 7.39-7.30 (m, 4H), 7.26 (t, J = 1.3 Hz, 2H), 7.13 (d, J = 1.4 Hz, 2H), 7.02 (d, J = 7.4 Hz, 4H), 6.92 (dd, J = 7.5, 1.6 Hz, 2H), 6.68 (d, J = 7.5 Hz, 2H), 4.90 (t, J = 7.6 Hz, 2H), 1.59 (p, J = 7.7 Hz, 2H), 1.40-1.27 (m, 10H), 0.98 (t, J = 6.3 Hz, 3H) .

Example 4: Synthesis of compound 21

Step 1.

[1,1'-biphenyl] -4-amine (10 g, 59.1 mmol) and 1-bromo-4-iodobenzene (16.72, 59.1 mmol) and sodium tert butoxide (11.36 g, 118.2 mmol) were added. 1,1-ferrocene diyl-bis (diphenylphosphine) (0.66 g, 1.2 mmol), tris (dibenzylidene acetone) dipalladium (0) (0.54 g, in a solution after dissolving in anhydrous toluene (118.19 ml) 0.6 mmol) was added and stirred at 100°C for 12 hours under a nitrogen stream. After that, a product is obtained through column chromatography. (Yield: 61%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.64 (dd, J = 7.4, 1.3 Hz, 2H), 7.60 (d, J = 7.7 Hz, 2H), 7.45 (t, J = 7.4 Hz, 2H), 7.40 (d, J = 7.4 Hz, 2H), 7.38-7.32 (m, 1H), 7.22 (d, J = 7.4 Hz, 2H), 6.94 (d, J = 7.4 Hz, 2H), 3.81 (s, 1H) .

Step 2.

10H-phenoxazine (15 g, 81.9 mmol), 1-bromohexane (24.33 g, 147.4 mmol) and potassium tert-butoxide (10.11 g, 90.1 mmol) were dissolved in anhydrous tetrahydrofuran (162.20 mL). Then, the mixture was stirred at 66° C. for 4 hours, and the product was obtained through column chromatography. (Yield: 93%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.17-7.13 (m, 2H), 7.11-7.01 (m, 6H), 4.88 (t, J = 7.4 Hz, 2H), 1.72-1.53 (m, 2H), 1.53-1.25 (m, 6H), 1.07-0.91 (m, 3H).

Step 3.

The 10-hexyl-10H-phenoxy picture (10 g, 37.4 mmol) prepared in step 2 was dissolved in dichloromethane (239.37 mL), and then N-bromosuccinimide (14.65 g, 82.3 mmol) was prepared at 0°C. Put it in. After stirring at room temperature for 4 hours, the product is obtained through column chromatography. (Yield: 92%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.43 (d, J = 1.4 Hz, 2H), 7.23 (dd, J = 7.5, 1.4 Hz, 2H), 6.92 (d, J = 7.5 Hz, 2H), 4.84 (t, J = 7.4 Hz, 2H), 1.72-1.55 (m, 2H), 1.54-1.25 (m, 6H), 1.06-0.90 (m, 3H).

Step 4.

After dissolving the 3,7-dibromo-10-hexyl-10H-phenoxy photo (5 g, 11.8 mmol) prepared in step 3 in anhydrous tetrahydrofuran (130.67 ml) under a nitrogen stream, normal at -78°C Add butyllithium solution (2.5 M) (10.35 mL, 25.9 mmol) slowly. Thereafter, a solution obtained by dissolving iodine (11.94 g, 47.0 mmol) in anhydrous tetrahydrofuran (78.40 ml) was slowly added thereto. Thereafter, the temperature was slowly raised to room temperature, stirred for 2 hours, and then the product was obtained through column chromatography. (Yield rate: 70%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.63 (d, J = 1.4 Hz, 2H), 7.44 (dd, J = 7.5, 1.4 Hz, 2H), 6.78 (d, J = 7.5 Hz, 2H), 4.82 (t, J = 7.4 Hz, 2H), 1.70-1.56 (m, 2H), 1.50-1.26 (m, 6H), 1.03-0.93 (m, 3H).

Step 5.

N- (4-bromophenyl)-[1,1'-biphenyl] -4-amine (4.12 g, 12.7 mmol) prepared in step 1, 3,7- diiodo prepared in step 4 -10- Hexyl -10H-phenoxyphoto (3 g, 5.8 mmol), potassium tert butoxide (3.33 g, 34.7 mmol) was dissolved in anhydrous toluene (61.64 mL) and then tris (dibenzylidene acetone) dipalladium (0 ) (0.11 g, 0.1 mmol), tritert butylphosphine (0.04 g, 0.2 mmol) was added, stirred at 100° C. for 4 hours under a nitrogen stream, and the product was obtained through column chromatography. (Yield: 63%)

¹ H NMR (400 MHz, DMSO) δ 7.64 (dd, J = 7.4, 1.2 Hz, 4H), 7.60 (d, J = 7.4 Hz, 4H), 7.49-7.41 (m, 8H), 7.41-7.35 (m , 2H), 7.26 (d, J = 7.4 Hz, 4H), 7.16 (d, J = 1.4 Hz, 2H), 7.12 (d, J = 7.5 Hz, 2H), 6.99 (d, J = 7.4 Hz, 4H ), 6.91 (dd, J = 7.5, 1.4 Hz, 2H), 5.10 (t, J = 5.2 Hz, 2H), 1.61 (tt, J = 7.8, 5.2 Hz, 2H), 1.39-1.25 (m, 6H) , 1.03-0.92 (m, 3H).

Example 5: Synthesis of compound 23

Step 1.

1-iodo-4-methyl naphthalene (10 g, 37.3 mmol), 4-bromoaniline (6.42 g, 37.3 mmol) and sodium tert butoxide (7.17 g, 74.6 mmol) are dissolved in anhydrous toluene (74.60 ml) 1,1-ferrocene diyl-bis (diphenylphosphine) (0.41 g, 0.7 mmol), tris (dibenzylidene acetone) dipalladium (0) (0.34 g, 0.4 mmol) was added to the solution, and nitrogen flow At 100° C. for 12 hours. After that, a product is obtained through column chromatography. (Yield: 57%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.88 (dd, J = 7.2, 1.8 Hz, 2H), 7.45-7.38 (m, 2H), 7.36 (t, J = 4.6 Hz, 2H), 7.19 (d, J = 7.5 Hz, 1H), 7.07 (d, J = 7.5 Hz, 1H), 6.85 (d, J = 7.4 Hz, 2H), 2.70 (s, 1H), 2.56 (s, 3H).

Step 2.

10H-phenoxy photo (15 g, 81.9 mmol), 2-bromo naphthalene (18.65 g, 90.1 mmol), potassium tert butoxide (23.60 g, 245.6 mmol) was dissolved in anhydrous toluene (573.11 ml) and then tris (dis(di) Benzylidene acetone) dipalladium (0) (2.25 g, 2.5 mmol) and tritert butylphosphine (0.99 g, 4.9 mmol) were stirred at 110° C. for 1 hour under a nitrogen stream, and the product was obtained through column chromatography. (Yield: 74%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.70 (dt, J = 7.4, 1.5 Hz, 2H), 7.63 (dt, J = 7.5, 1.4 Hz, 2H), 7.42 (dd, J = 7.5, 1.3 Hz, 2H), 7.38 (dd, J = 7.5, 1.4 Hz, 2H), 7.32 (td, J = 7.4, 1.6 Hz, 2H), 7.28-7.22 (m, 4H), 7.12-7.07 (m, 4H), 7.02 -6.93 (m, 12H).

Step 3.

The 10-(naphthalen-2-yl)-10H-phenoxy picture (10 g, 32.3 mmol) prepared in step 2 was dissolved in dichloromethane (206.88 mL) and then N-bromosuccinimide (12.66 mL) at 0°C. g, 71.1 mmol). After stirring at room temperature for 4 hours, the product is obtained through column chromatography. (Yield: 85%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.70 (dt, J = 7.4, 1.5 Hz, 1H), 7.64 (d, J = 7.4 Hz, 1H), 7.42 (d, J = 8.0 Hz, 2H), 7.32 (td, J = 7.5, 1.6 Hz, 1H), 7.25 (td, J = 7.4, 1.5 Hz, 1H), 7.21-7.16 (m, 3H), 7.12 (dd, J = 7.5, 1.4 Hz, 2H), 6.84 (d, J = 7.5 Hz, 2H).

Step 4.

3,7- Dibromo -10- (naphthalen-2-yl) -10H-phenoxy picture (5 g, 10.7 mmol) prepared in step 3 was dissolved in anhydrous tetrahydrofuran (118.92 mL) under a nitrogen stream. Then, normal butyllithium solution (2.5 M) (9.42 ml, 23.5 mmol) was slowly added at -78°C. Thereafter, a solution obtained by dissolving iodine (10.87 g, 42.8 mmol) in anhydrous tetrahydrofuran (71.36 mL) was slowly added. Thereafter, the temperature was slowly raised to room temperature, stirred for 2 hours, and then the product was obtained through column chromatography. (Yield: 63%)

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.70 (dt, J = 7.4, 1.5 Hz, 1H), 7.64 (dt, J = 7.5, 1.3 Hz, 1H), 7.47-7.41 (m, 2H), 7.39 ( d, J = 1.6 Hz, 2H), 7.36-7.29 (m, 3H), 7.25 (td, J = 7.4, 1.5 Hz, 1H), 7.20 (t, J = 1.2 Hz, 1H), 6.71 (d, J = 7.5 Hz, 2H).

Step 5.

N- (4-bromophenyl) -4- methyl naphthalene -1-amine (3.67 g, 11.8 mmol) prepared in step 1, 3,7-diiodo -10- (naphthalene) prepared in step 4 -2-yl) -10H-phenoxazine (3 g, 5.3 mmol), potassium tert butoxide (3.08 g, 32.1 mmol) was dissolved in anhydrous toluene (57.03 mL) and then tris (dibenzylidene acetone) dipalladium ( 0) (0.10 g, 0.1 mmol), tritert butylphosphine (0.03 g, 0.2 mmol) was added, stirred at 100° C. for 4 hours under a nitrogen stream, and the product was obtained through column chromatography. (Yield: 57%)

¹ H NMR (400 MHz, DMSO) δ 8.14 (dt, J = 7.5, 1.4 Hz, 1H), 8.06 (dt, J = 7.5, 1.3 Hz, 1H), 7.90-7.86 (m, 4H), 7.83 (td , J = 7.5, 1.4 Hz, 1H), 7.75 (dd, J = 7.0, 1.9 Hz, 2H), 7.63 (ddd, J = 15.3, 7.7, 1.5 Hz, 2H), 7.46-7.34 (m, 8H), 7.21 (d, J = 7.5 Hz, 2H), 7.16 (d, J = 7.5 Hz, 2H), 6.97 (dd, J = 7.4, 5.9 Hz, 6H), 6.70 (d, J = 1.4 Hz, 2H), 6.66 (dd, J = 7.5, 1.4 Hz, 2H), 2.37 (s, 6H).

Example 6: Synthesis of compound 28

Step 1.

After dissolving 4-aminophenol (15 g, 137.5 mmol), 1-bromo-4-methylpentane (24.96 g, 151.2 mmol) and potassium carbonate (151.04 g, 164.9 mmol) in acetone (288.65 mL) at room temperature, After stirring for 24 hours, the product is obtained through column chromatography. (Yield: 69%)

¹ H NMR (400 MHz, Chloroform) δ 6.68 (d, J = 7.4 Hz, 2H), 6.54 (d, J = 7.4 Hz, 2H), 3.95 (t, J = 7.6 Hz, 2H), 3.42 (s, 2H), 1.83-1.68 (m, 2H), 1.64 (td, J = 13.3, 6.6 Hz, 1H), 1.26 (q, J = 7.8 Hz, 2H), 1.02 (d, J = 6.3 Hz, 6H).

Step 2.

4-((4-methylpentyl) oxy) aniline (15 g, 77.6 mmol) and 1-bromo-4-iodobenzene (24.15 g, 85.4 mmol) prepared in step 1, cuprous iodide (0.15 g) , 0.8 mmol), 1,10-phenanthroline (0.28 g, 1.6 mmol), potassium hydroxide (4.35 g, 77.6 mmol) were dissolved in toluene 108.65 mL), stirred at 100° C. for 5 hours, and then through column chromatography. To obtain the product. (Yield: 77%)

¹ H NMR (400 MHz, Chloroform) δ 7.21 (t, J = 7.5 Hz, 2H), 7.03 (dd, J = 11.3, 4.4 Hz, 4H), 6.90 (ddd, J = 8.8, 2.7, 1.3 Hz, 1H ), 6.83 (d, J = 7.4 Hz, 2H), 4.01 (t, J = 4.7 Hz, 2H), 3.47 (s, 1H), 1.75 (pd, J = 8.2, 4.2 Hz, 2H), 1.73-1.58 (m, 1H), 1.28 (q, J = 7.9 Hz, 2H), 1.03 (d, J = 6.3 Hz, 6H).

Step 3.

5,10-Dimethyl-5,10-dihydrophenazine (10 g, 47.6 mmol) was dissolved in dichloromethane (304.37 mL) and then N-bromosuccinimide (18.62 g, 104.6 mmol) was added at 0°C. Put it in. After stirring at room temperature for 4 hours, the product is obtained through column chromatography. (Yield: 72%)

¹ H NMR (400 MHz, Chloroform) δ 7.22 (dd, J = 7.5, 1.4 Hz, 2H), 7.17 (d, J = 1.5 Hz, 2H), 6.92 (d, J = 7.5 Hz, 2H), 3.19 ( s, 3H), 3.16 (s, 3H).

Step 4.

2,8-dibromo-5,10-dimethyl-5,10-dihydrophenazine (5 g, 13.6 mmol) prepared in step 3 was dissolved in anhydrous tetrahydrofuran (150.94 ml) under a nitrogen stream. Then, normal butyllithium solution (2.5 M) (11.95 ml, 29.9 mmol) was slowly added at -78°C. Thereafter, a solution obtained by dissolving iodine (13.79 g, 54.3 mmol) in anhydrous tetrahydrofuran (71.97 mL) was slowly added. Thereafter, the temperature was slowly raised to room temperature, stirred for 2 hours, and then the product was obtained through column chromatography. (Yield: 55%)

¹ H NMR (400 MHz, Chloroform) δ 7.36 (dd, J = 7.5, 1.4 Hz, 2H), 7.28 (d, J = 1.4 Hz, 2H), 6.78 (d, J = 7.5 Hz, 2H), 3.17 ( s, 6H).

Step 5.

4-((4-methyl pentyl) oxy) -N-phenylaniline (3.85 g, 14.3 mmol) prepared in step 2, 2,8-diiodo -5,10- dimethyl prepared in step 4- 5,10-dihydrophenazine (3 g, 6.5 mmol) and potassium tert butoxide (3.74 g, 39.0 mol) were dissolved in anhydrous toluene (69.25 ml) and then tris (dibenzylidene acetone) dipalladium (0) (0.12 g, 0.1 mmol) and tritert butylphosphine (0.04 g, 0.2 mmol) were added, stirred at 100° C. for 4 hours under a nitrogen stream, and the product was obtained through column chromatography. (Yield: 56%)

1H NMR (400 MHz, DMSO) δ 7.43 (d, J = 7.4 Hz, 4H), 7.12 (d, J = 7.5 Hz, 2H), 7.06 (d, J = 7.4 Hz, 4H), 6.98 (d, J = 7.4 Hz, 4H), 6.94 (d, J = 1.4 Hz, 2H), 6.90-6.82 (m, 6H), 3.93 (t, J = 7.4 Hz, 4H), 3.17 (d, J = 15.1 Hz, 6H ), 1.83-1.62 (m, 6H), 1.31-1.20 (m, 4H), 1.01 (d, J = 6.3 Hz, 12H).

Example 7: Synthesis of compound 30

Step 1.

It was carried out in the same manner as in Comparative Example 1.

Step 2.

It was carried out in the same manner as in Comparative Example 1.

Step 3.

It was carried out in the same manner as in Step 4 of Example 1.

Step 4.

10- (4- (tert-butyl) phenyl) -3,7- diiodo -10H- phenothiazine (3 g, 5.1 mmol) prepared in step 3, 4-bromo-N-phenylaniline ( 2.8 g, 11.3 mmol), potassium tert butoxide (2.97 g, 30.9 mmol) was dissolved in anhydrous toluene (54.86 mL) and then tris (dibenzylidene acetone) dipalladium (0) (0.09 g, 0.1 mmol), tri Tert butylphosphine (0.03 g, 0.2 mmol) was added, stirred at 100° C. for 4 hours under a nitrogen stream, and the product was obtained through column chromatography. (Yield: 68%)

¹ H NMR (400 MHz, DMSO) δ 7.43 (d, J = 7.4 Hz, 4H), 7.29-7.21 (m, 8H), 7.06 (m, J = 8.5, 7.5, 4.4 Hz, 8H), 7.01-6.93 (m, 8H), 1.37 (s, 9H).

Step 5.

N7, N7-bis (4-bromophenyl) -10- (4- (tert butyl) phenyl) -N3, N7-diphenyl -10H- phenothiazine -3,7-diamine prepared in step 4 above ( 3 g, 3.6 mmol) was dissolved in anhydrous tetrahydrofuran (36.42 ml) under a nitrogen stream, and then a normal butyllithium solution (2.5 M) (5.8 ml, 14.6 mmol) was slowly added at -78°C. Then, triisopropyl borate (4.1 g, 21.9 mmol) was slowly added. Thereafter, the temperature was slowly raised to room temperature, stirred for 12 hours, 1M HCl was added, extracted with dichloromethane, and the product was obtained through column chromatography. (Yield: 79%)

Example 8: compound 32 synthesis

Step 1.

It was carried out in the same manner as in Step 1 of Example 1.

Step 2.

5,10-dihydrophenazine (15 g, 82.3 mmol), 1-bromo-4 tert butyl) benzene (38.59 g, 181.1 mmol) and potassium tert butoxide (21 g, 225.8 mmol) anhydrous toluene (878.06) Ml), then tris (dibenzylidene acetone) dipalladium (0) (3.77 g, 4.1 mmol), tritert butylphosphine (1.67 g, 8.2 mmol) stirred at 110° C. for 2 hours under a nitrogen stream, followed by column chromatography The product is obtained through photography. (Yield rate: 90%)

1H NMR (400 MHz, Chloroform) δ 7.27 (d, J = 7.4 Hz, 4H), 6.98 (td, J = 6.6, 4.1 Hz, 8H), 6.93-6.88 (m, 4H), 1.41 (s, 18H) .

Step 3.

After dissolving 5,10- bis (4- (tert butyl) phenyl) -5,10- dihydrophenazine (10 g, 22.4 mmol) prepared in step 2 in dichloromethane (143. 26 mL), 0 N-bromosuccinimide (8.86 g, 49.3 mmol) was added at °C. After stirring at room temperature for 4 hours, the product is obtained through column chromatography. (Yield: 88%)

1H NMR (400 MHz, Chloroform) δ 7.27 (dd, J = 7.4, 3.5 Hz, 4H), 7.14 (dd, J = 7.5, 1.4 Hz, 2H), 7.01-6.94 (m, 6H), 6.79 (d, J = 7.5 Hz, 2H), 1.41 (s, 18H).

Step 4.

2,8-dibromo-5,10-bis (4- (tert butyl) phenyl) -5,10-dihydrophenazine (5 g, 8.3 mmol) prepared in step 3 was mixed with anhydrous tetra After dissolving in hydrofuran (91.92 ml), normal butyllithium solution (2.5 M) (7.28 ml, 18.2 mmol) is slowly added at -78°C. Thereafter, a solution obtained by dissolving iodine (8.40 g, 33.1 mmol) in anhydrous tetrahydrofuran (55.15 mL) was slowly added. Thereafter, the temperature was slowly raised to room temperature, stirred for 2 hours, and then the product was obtained through column chromatography. (Yield: 71%)

¹ H NMR (400 MHz, Chloroform) δ 7.35 (dd, J = 7.5, 1.4 Hz, 2H), 7.30-7.22 (m, 6H), 6.98 (dd, J = 7.5, 2.3 Hz, 4H), 6.68 (d , J = 7.5 Hz, 2H), 1.41 (s, 18H).

Step 5.

5,10-bis (4- (tert butyl) phenyl) -2,8-diiodine -5,10-dihydrophenazine (3 g, 4.3 mmol) prepared in step 4, 4 prepared in step 1 -Bromo-N- (4-butylphenyl) aniline (2.86 g, 9.4 mmol), potassium tert butoxide (2.48 g, 25.8 mmol) was dissolved in anhydrous toluene (45.82 mL) and then tris (dibenzylidene acetone) Dipalladium (0) (0.08 g, 0.1 mmol) and tritert butylphosphine (0.02 g, 0.1 mmol) were added, and the mixture was stirred at 100° C. for 4 hours under a nitrogen stream, and the product was obtained through column chromatography. (Yield: 68%)

¹ H NMR (400 MHz, DMSO) δ 7.42 (d, J = 7.4 Hz, 4H), 7.34 (d, J = 7.4 Hz, 2H), 7.29 (d, J = 7.5 Hz, 2H), 7.15 (d, J = 7.4 Hz, 4H), 7.13-7.01 (m, 10H), 6.97 (d, J = 7.4 Hz, 4H), 6.83 (td, J = 3.9, 1.5 Hz, 4H), 2.47 (t, J = 7.9 Hz, 4H), 1.65 (p, J = 7.8 Hz, 4H), 1.47-1.34 (m, 22H), 1.00 (t, J = 6.6 Hz, 6H).

Step 6.

5,10-bis (4- (tert butyl) phenyl) -2,8-diiodine -5,10-dihydrophenazine (3 g, 2.9 mmol), bis (pina colato) prepared in step 5 above Diborone (1.74 g, 6.9 mmol), potassium acetate (1.68 g, 17.1 mmol), [1,1'-bis (diphenyl phosphino) ferrocene] dichloro palladium (II) (0.04 g, 0.1 mmol), tritert After dissolving butylphosphine (0.04 g, 0.2 mmol) in dimethyl sulfoxide (19.41 ml), the mixture was stirred at 80° C. for 24 hours under a nitrogen stream, and the product was obtained through column chromatography. (Yield: 84%)

Comparative example 2: Synthesis of Comparative Compound 2

3,7- dibromo -10- (4- (tert butyl) phenyl) -10H- phenothiazine (1.4 g, 2.86 mmol) prepared in Comparative Example 1 under nitrogen stream anhydrous tetrahydrofuran (71 ml) After dissolving in, nitrogen bubbling was performed for 10 minutes. After raising the temperature to 40°C, 2,2'-bipyridyl (0.89 g, 5.72 mmol) was added, and the temperature was raised to 60°C again, and then bis (1,5-cyclooctadiene) nickel (0) (1.97 g, 7.15 mmol) was added and stirred for 2 hours, then bromobenzene (1 ml) was added and stirred for 12 hours. After completion of the reaction, the mixture was precipitated in a solvent in a ratio of methanol and acetone 3: 1, and then an aqueous hydrochloric acid solution and an aqueous ammonia solution were added in order, washed with distilled water and methanol, and then filtered. The filtered mixture was purified by Soxhlet extraction to obtain a compound. (Yield: 77%)

Example 9: Synthesis of compound 34

N7, N7- bis (4-bromophenyl) -10- (4- (tert butyl) phenyl) -N3, N7- bis (4-butyl phenyl) -10H- phenothi prepared in Example 1 under a nitrogen stream After dissolving azine-3,7-diamine (1.2 g, 1.28 mmol) in anhydrous tetrahydrofuran (32 mL), nitrogen bubbling was performed for 10 minutes. Thereafter, the temperature was raised to 40℃, 2,2'-bipyridyl (0.40 g, 2.56 mmol) was added, and the temperature was raised to 60℃ again, and bis (1,5-cyclooctadiene) nickel (0) (0.88 g , 3.21 mmol) was added and stirred for 2 hours, then bromobenzene (1 ml) was added and stirred for 12 hours. After completion of the reaction, the mixture was precipitated in a solvent in a ratio of methanol and acetone 3: 1, and then an aqueous hydrochloric acid solution and an aqueous ammonia solution were added in order, washed with distilled water and methanol, and then filtered. The filtered mixture was purified by Soxhlet extraction to obtain a compound. (Yield: 74%)

Comparative example 3: Synthesis of Comparative Compound 3

2,7-dibromo -9,9-dioctyl -9H-fluorene (1.01 g, 1.8 mmol) under nitrogen stream, 3,7-dibromo -10- (4- ( Tert butyl) phenyl) -10H-phenothiazine (0.1 g, 0.2 mmol) was dissolved in anhydrous tetrahydrofuran (50 mL), followed by nitrogen bubbling for 10 minutes. Thereafter, the temperature was raised to 40℃, 2,2'-bipyridyl (0.64 g, 4.09 mmol) was added, and the temperature was raised to 60℃ again, and bis (1,5-cyclooctadiene) nickel (0) (1.41 g , 5.11 mmol) and stirred for 2 hours, bromobenzene (1 ㎖) was added and stirred for 12 cases. After completion of the reaction, the mixture was precipitated in a solvent in a ratio of methanol and acetone 3: 1, and then an aqueous hydrochloric acid solution and an aqueous ammonia solution were added in order, washed with distilled water and methanol, and then filtered. The filtered mixture was purified by Soxhlet extraction to obtain a compound. (Yield: 72%)

Example 10: compound 35 synthesis

2,7-dibromo -9,9-dioctyl -9H-fluorene (1.05 g, 1.89 mmol) under nitrogen stream, N7, N7-bis (4-bromophenyl) -10 prepared in Example 1 -(4- (tert-butyl) phenyl) -N3, N7- bis (4-butyl phenyl) -10H- phenothiazine -3,7- diamine (0.2 g, 0.21 mmol) in anhydrous tetrahydrofuran (50 ml) ), followed by nitrogen bubbling for 10 minutes. Thereafter, the temperature was raised to 40°C, 2,2'-bipyridyl (0.67 g, 4.27 mmol) was added, and the temperature was raised to 60°C again, and then bis (1,5-cyclooctadiene) nickel (0) (1.47 g) , 5.34 mmol) was added and stirred for 2 hours, then bromobenzene (1 ml) was added and stirred for 12 hours. After completion of the reaction, the mixture was precipitated in a solvent in a ratio of methanol and acetone 3: 1, and then an aqueous hydrochloric acid solution and an aqueous ammonia solution were added in order, washed with distilled water and methanol, and then filtered. The filtered mixture was purified by Soxhlet extraction to obtain a compound. (Yield: 71%)

Example 11: Synthesis of compound 36

2', 7'-dibromo-2,3,6,7-tetrakis (octyloxy) -9,9'-spirobi [fluorene] (0.98 g, 1 mmol) under a nitrogen stream, Example 3 N7, N7- bis (4-bromophenyl) -N3, N7- di(naphthalen-2-yl) -10- octyl -10H- phenothiazine -3,7-diamine (0.1 g, 0.11 mmol ) Was dissolved in anhydrous tetrahydrofuran (30 ml), followed by nitrogen bubbling for 10 minutes. Thereafter, the temperature was raised to 40°C, 2,2'-bipyridyl (0.35 g, 2.2 mmol) was added, and the temperature was raised to 60°C again, and bis (1,5-cyclooctadiene) nickel (0) (0.76 g , 2.77 mmol) was added and stirred for 2 hours, then bromobenzene (1 ml) was added and stirred for 12 hours. After completion of the reaction, the mixture was precipitated in a solvent in a ratio of methanol and acetone 3: 1, and then an aqueous hydrochloric acid solution and an aqueous ammonia solution were added in order, washed with distilled water and methanol, and then filtered. The filtered mixture was purified by Soxhlet extraction to obtain a compound. (Yield: 68%)

Example 12: Synthesis of compound 37

1,6-dibromo-3,8-dioctyl pyrene (1.04 g, 1.8 mmol) under nitrogen stream, N7, N7-di ([1,1'-biphenyl] -4- prepared in Example 4) 1) -N3, N7-bis (4-bromophenyl) -10- hexyl -10H-phenoxazine -3,7-diamine (0.18 g, 0.2 mmol) was dissolved in anhydrous tetrahydrofuran (50 ml) Nitrogen bubbling was performed for 10 minutes. Thereafter, the temperature was raised to 40°C, 2,2'-bipyridyl (0.62 g, 3.95 mmol) was added, and the temperature was raised to 60°C again, and then bis (1,5-cyclooctadiene) nickel (0) (1.36 g) , 4.94 mmol) and stirred for 2 hours, bromobenzene (1 ㎖) was added and stirred for 12 hours. After completion of the reaction, the mixture was precipitated in a solvent in a ratio of methanol and acetone 3: 1, and then an aqueous hydrochloric acid solution and an aqueous ammonia solution were added in order, washed with distilled water and methanol, and then filtered. The filtered mixture was purified by Soxhlet extraction to obtain a compound. (Yield: 63%)

Example 13: Synthesis of compound 38

9,10-dibromo-2,6-dihexyl anthracene (1.17 g, 2.34 mmol) under a nitrogen stream, N7, N7-bis (4-bromophenyl) -N3, N7-bis prepared in Example 5 (4-methylnaphthalen-1-yl) -10- (naphthalen-2-yl) -10H-phenoxazine-3,7-diamine (0.24 g, 0.26 mmol) was dissolved in anhydrous tetrahydrofuran (65 mL) After 10 minutes, nitrogen bubbling was performed. After that, the temperature was raised to 40°C, 2,2'-bipyridyl (0.81 g, 5.16 mmol) was added, and the temperature was raised to 60°C again, and then bis (1,5-cyclooctadiene) nickel (0) (1.78 g) , 6.45 mmol) was added and stirred for 2 hours, then bromobenzene (1 ml) was added and stirred for 12 hours. After completion of the reaction, the mixture was precipitated in a solvent in a ratio of methanol and acetone 3: 1, and then an aqueous hydrochloric acid solution and an aqueous ammonia solution were added in order, washed with distilled water and methanol, and then filtered. The filtered mixture was purified by Soxhlet extraction to obtain a compound. (Yield: 61%)

Example 14: compound 39 synthesis

2,7- dibromo -9,9- bis (4- (octyloxy) phenyl) -9H- fluorene (1.24 g, 1.71 mmol) under a nitrogen stream, N8- bis (4- Methylpentyl) oxy) phenyl) -5,10-dihydrophenazine -2,8-diamine (0.17 g, 0.19 mmol) was dissolved in anhydrous tetrahydrofuran (48 ml), followed by nitrogen bubbling for 10 minutes. . Thereafter, the temperature was raised to 40℃, 2,2'-bipyridyl (0.59 g, 3.77 mmol) was added, and the temperature was raised to 60℃ again, and then bis (1,5-cyclooctadiene) nickel (0) (1.29 g) , 4.71 mmol) and stirred for 2 hours, bromobenzene (1 ml) was added, and stirred for 12 hours. After completion of the reaction, the mixture was precipitated in a solvent in a ratio of methanol and acetone 3: 1, and then an aqueous hydrochloric acid solution and an aqueous ammonia solution were added in order, washed with distilled water and methanol, and then filtered. The filtered mixture was purified by Soxhlet extraction to obtain a compound. (Yield: 58%)

Example 15: compound 40 synthesis

N7, N7- bis (4-bromophenyl) -N3, N7- bis (4- (hexyloxy) phenyl) -10- (4- methoxyphenyl) -10H- prepared in Example 2 under a nitrogen stream Phenothiazine-3,7-diamine (0.5 g, 0.5 mmol), (9,9-dioctyl-9H-fluorene-2,7-diyl) diboronic acid (0.96 g, 2.0 mmol), 2,7- After dissolving dibromo-9,9-dioctyl-9H-fluorene (1.37 g, 2.5 mmol) in anhydrous toluene (50.10 mL), tetrakis (triphenyl phosphine) palladium (0) (0.03 g, 0.1 mmol) and potassium carbonate (0.29 g, 3.0 mmol) were dissolved in distilled water (12.53 ml) and reacted at 80°C for 72 hours. After completion of the reaction, the mixture was precipitated in methanol, filtered, and purified by Soxhlet extraction to obtain a compound. (Yield: 66%)

Example 16: Synthesis of compound 41

N7, N7-bis (4-bromophenyl) -10- (4- (tert-butyl) phenyl) -N3, N7-diphenyl -10H- phenothiazine -3 prepared in Example 7 under a nitrogen stream 7-diamine (0.5 g, 0.7 mmol), (2', 3', 6', 7'- tetrakis (octyloxy) -9,9'- spirobi [fluorene] -2,7- diyl) dibo After dissolving the acid (2.43 g, 2.7 mmol), 2,7-dibromo -9,9-dioctyl-9H-fluorene (1.8 g, 3.4 mmol) in anhydrous toluene (66.36 ml), tetrakis (trikis) Phenylphosphine) palladium (0) (0.04 g, 0.1 mmol) and potassium carbonate (0.38 g, 4.0 mmol) dissolved in distilled water (16.59 mL) was added and reacted at 80° C. for 72 hours After the reaction was completed, it was added to methanol. After precipitated, the mixture was filtered and purified by Soxhlet extraction to obtain a compound (yield: 55%).

Example 17: compound 42 synthesis

N2, N8- bis (4-bromophenyl) -5,10- bis (4- (tert-butyl) phenyl) -N2, N8- bis (4- butyl phenyl) prepared in Example 8 under a nitrogen stream- 5,10-dihydrophenazine-2,8-diamine (0.5 g, 0.4 mmol), 2,2'- (9,9-dioctyl-9H-fluorene-2,7-diyl) bis (4, 4,5,5-tetramethyl-1,3,2-dioxaborolane) (1.12 g, 1.7 mmol), 9,10-dibromo-2,6-dihexyl anthracene (1.1 g, 2.1 mmol) Was dissolved in anhydrous toluene (43.66 ml), tetrakis (triphenyl phosphine) palladium (0) (0.03 g, 0.1 mmol) and potassium carbonate (0.25 g, 2.6 mmol) were dissolved in distilled water (10.92 ml). Put the solution and react at 80℃ for 72 hours. After completion of the reaction, the mixture was precipitated in methanol, filtered, and purified by Soxhlet extraction to obtain a compound. (Yield: 51%)

Device Example 1 to 8: Organic light emitting device Produce

PEDOT (poly(styrene sulfonate)-doped poly(3,4-ethylenedioxy thiophene) on a transparent electrode substrate patterned with indium-tin oxide (ITO) after washing with acetone and isopropanol for 30 minutes each, and then treated with UV/ozone. : Bayer's Batron P4083) was coated to a thickness of 600 Å, and then baked at 180° C. for about 1 hour to form a hole injection layer. The light-emitting polymer prepared on the hole injection layer was dissolved in chlorobenzene and After spin coating and baking treatment, a thin film was formed by completely removing the solvent in a vacuum oven, the thickness of the thin film was formed by controlling the concentration of the solution and the spin speed to form a thin film of 300 Å. Then, while maintaining the degree of vacuum below 4×10 ^-6 torr, TPBi (300Å), LiF (5 Å), and Al (1000 Å) were sequentially deposited to form a cathode and encapsulated it to complete an organic electroluminescent device. During the deposition of LiF and Al, the film thickness and the growth rate of the film were controlled using a crystal sensor The structure of the organic electroluminescent device thus fabricated was ITO/PEDOT:PSS (600 Å)/emission layer compound (300 Å)/TPBi (300 Å)/LiF (5 Å)/Al (1500 Å), and the emission area was 6 mm ^2. The emission layer compound was prepared from compounds 35 to 42 as shown in Table 2 below. The light-emitting layer included in the device was prepared by polymerization of the example compound and the light-emitting monomer.

Element comparison example One: Organic light emitting device Produce

An organic light emitting diode was manufactured in the same manner as in Device Examples 1 to 8, except that Comparative Compound 3 of Comparative Example 3 was used instead of the compound of Example as the emission layer compound.

[ Experimental example ]

Experimental example 1: Optical data comparison analysis

Various copolymers were prepared in a ratio of 10 to 100 mol% of a heteroaromatic monomer according to an embodiment of the present invention and 0 to 90 mol% of a light-emitting monomer illustrated below. The polymerization method proceeded largely to the following method 1) or method 2).

Method 1. Yamamoto coupling polymerization

In a nitrogen stream, the above-mentioned light emitting monomer and the newly synthesized hole transport monomer were dissolved in anhydrous tetrahydrofuran, followed by nitrogen bubbling for 10 minutes. After that, the temperature was raised to 40℃, 2,2'-bipyridyl was added, the temperature was raised to 60℃, bis (1,5-cyclooctadiene) nickel (0) was added, and the mixture was stirred for 2 hours. Benzene (1 ml) was added and stirred for 12 hours. After completion of the reaction, the mixture was precipitated in a solvent in a ratio of methanol and acetone 3: 1, and then an aqueous hydrochloric acid solution and an aqueous ammonia solution were added in order, washed with distilled water and methanol, and then filtered. The filtered mixture was purified by Soxhlet extraction to obtain a compound.

Method 2. Suzuki coupling polymerization

After dissolving the light-emitting monomer and hole transport monomer listed above in anhydrous toluene under a nitrogen stream, a solution in which tetrakis (triphenyl phosphine) palladium (0) potassium carbonate was dissolved in distilled water was added and reacted at 80° C. for 72 hours. After completion of the reaction, the mixture was precipitated in methanol, filtered, and purified by Soxhlet extraction to obtain a compound.

The polymer material thus prepared was dissolved in toluene at a concentration of 2.0 x 10 ^-5 [M], and the emission wavelength was measured through a PL equipment, and the results are shown in Table 1 below.

According to Table 1, in the random copolymer prepared by the above method, the light emission wavelength by blocking the conjugation system by introducing an amine group into the structure of a new hole transport material of phenothiazine, phenoxazine, phenoxazine, and phenazine series. It showed the effect of moving the region to a short wavelength. In particular, Compound 34 of Example 9 is a structure in which an amine group is introduced into the structure of Comparative Compound 2, and it can be seen that the value of the emission wavelength shifts to a short wavelength of 27 nm. As a result of the above, it was found that the color purity was improved in the fabrication of the organic electroluminescent device.

Experimental example 2: Organic light emitting device Characterization

The characteristics of the organic light emitting devices manufactured according to Device Examples 1 to 8 were analyzed, and the results of luminous efficiency and driving voltage are shown in Table 2 below.

Accordingly, it was confirmed that the luminous efficiency measured at 1000 cd/m ² was increased by more than 2 times in Device Examples 1 to 8 compared to Device Comparative Example 3, and the driving voltage was also significantly lowered by about 4 V or more. The life of the product was greatly improved.

Therefore, the random copolymer compound obtained by copolymerizing the compound for an organic electroluminescent device of the present invention and a light emitting material is an electro-development advertising molecule capable of improving the color purity of the material, and the introduction of heteroaromatic monomers with high thermal safety and excellent hole transport capability. It can be seen that silver improves the basic device characteristics and lifespan of the organic electroluminescent polymer.

Claims (11)

A compound for an organic electroluminescent device represented by the following structural formula 1;
[Structural Formula 1]

In structural formula 1,
X ¹ is an oxygen atom, a sulfur atom, or

ego,
R ³ is

, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted Is a C1 to C30 heteroaryl group,
n ¹ is a repetition number that is an integer selected from 0 to 10,
R ⁴ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,
Ar ¹ is

,

,

,

,

,

, or

ego,
X ³ and X ⁴ are the same as or different from each other, and each independently an oxygen atom or a sulfur atom,
Y ¹ to Y ⁴ are the same as or different from each other, and each independently a nitrogen atom, or

ego,
R ²³ is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,
n ⁵ is a repeating number that is an integer selected from 1 to 10,
R ¹¹ to R ²² are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cyclo An alkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,
Ar ² and Ar ³ are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,
R ¹ and R ² are the same as or different from each other, and each independently a halogen group, or

ego,
R ⁶ and R ⁷ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 hetero A cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group, or R ⁶ and R ⁷ are bonded to each other to form a fused ring with three atoms therebetween Thereby forming a substituted or unsubstituted C2 to C30 heterocycloalkyl group. A compound for an organic electroluminescent device represented by the following structural formula 2;
[Structural Formula 2]

In formula 2,
k, l, and m are repetitions,
The ratio of k, l, and m is k: l+m = 0.01~1: 0~0.99,
X ² is an oxygen atom, a sulfur atom, or

ego,
R ⁸ is

, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted Is a C1 to C30 heteroaryl group,
n ³ is a repeating number that is an integer selected from 0 to 10,
R ⁹ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,
Ar ⁴ is

, A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,
n ⁴ is a repeating number that is any one integer selected from 0 to 10,
R ¹⁰ is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or It is an unsubstituted C1 to C30 heteroaryl group,
Ar ⁵ and Ar ⁶ are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,
Ar ⁷ and Ar ⁸ are the same as or different from each other, and each independently a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C1 to C30 heteroarylene group. The method of claim 2,
Ar ⁴ is a C1 to C10 alkoxy group, a C1 to C10 alkyl group,

,

,

,

,

,

, or

ego,
X ³ and X ⁴ are the same as or different from each other, and each independently an oxygen atom or a sulfur atom,
Y ¹ to Y ⁴ are the same as or different from each other, and each independently a nitrogen atom, or

ego,
R ²³ is a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,
n ⁵ is a repetition number that is an integer selected from 0 to 10,
R ¹¹ to R ²² are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cyclo A compound for an organic electroluminescent device, characterized in that it is an alkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group. The method according to claim 1 or 2,
Ar ² , Ar ³ , Ar ⁵ , and Ar ⁶ are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted biphenyl group. Compounds for electroluminescent devices. The method of claim 4,
Ar ² , Ar ³ , Ar ⁵ , and Ar ⁶ are the same as or different from each other, and each independently

,

,

,

, or

ego,
R ²⁴ to R ³⁶ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cyclo A compound for an organic electroluminescent device, characterized in that it is an alkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group. The method of claim 2,
Ar ⁷ and Ar ⁸ are the same as or different from each other, and each independently,

,

,

,

, or

ego,
X ⁵ oxygen atom, sulfur atom,

or

ego,
R ⁵³ to R ⁵⁵ are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, or a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C1 to C30 hetero A cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group,
R ³⁷ to R ⁵² are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cyclo A compound for an organic electroluminescent device, characterized in that it is an alkyl group, a substituted or unsubstituted C1 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C1 to C30 heteroaryl group. A compound for an organic electroluminescent device which is any one compound selected from the following compounds 1 to 42.

An organic electroluminescent device comprising the compound for an organic electroluminescent device according to any one of claims 1, 2 and 7. The method of claim 8,
The organic light emitting device includes a first electrode, a second electrode facing the first electrode, and an organic layer between the first electrode and the second electrode,
The organic layer is an organic electroluminescent device, characterized in that comprising the compound for an organic electroluminescent device. The method of claim 9,
The organic layer is an organic light emitting device comprising at least one selected from a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, and an electron injection layer. The method of claim 10,
An organic electroluminescent device comprising the compound for an organic light emitting device in at least one selected from the emission layer, the hole injection layer and the hole transport layer.