KR20230149689A - Compound, Composition for Organic EL Device, Organic EL Device and Display Device - Google Patents

Abstract

According to the present invention, a compound applicable to the electron transport layer, hole blocking layer, charge generation layer, etc. of an organic electroluminescent device, a composition for an organic electroluminescent device containing such a compound, an organic electroluminescent device using such a compound, and A display device including such an organic electroluminescent device is provided.

Description

Compound, Composition for Organic EL Device, Organic EL Device and Display Device {Compound, Composition for Organic EL Device, Organic EL Device and Display Device}

The present invention relates to a novel organic compound that can be used as a material for an organic electroluminescent device, a composition for an organic electroluminescent device containing the same, and an organic electroluminescent device and display device containing the same.

Recently, displays using organic electroluminescent elements have been attracting attention as full-color flat displays, and are being used in display devices such as smartphones, TVs, automobiles, and VR (Virtual Reality) head-mounted devices.

An organic electroluminescent element has a structure including a pair of electrodes consisting of an anode and a cathode, and an organic material layer portion disposed between the pair of electrodes and having one or more organic compound layers. The organic material layer includes a light-emitting layer and a charge transport/injection layer that transports or injects charges such as holes and electrons, and various organic materials suitable for these layers are being developed.

In order to further expand the application fields of displays using organic electroluminescent devices, there is a need to reduce device power consumption (lower voltage and improve external quantum efficiency) and extend lifespan. In particular, there is a demand for lower power consumption and longer lifespan of blue light-emitting devices, and to this end, various materials for electron transport/injection layers are being examined.

For example, as materials for the electron transport/injection layer, pyridine derivatives or bipyridine derivatives (Patent Document 1), benzimidazole or benzothiazole derivatives (Patent Documents 2 to 4), pyrimidine derivatives, or triazine derivatives (Patent Document 1). 5) Organic electroluminescent devices using are known.

However, in the case of these conventional electron transport/injection layer materials, further improvements are required in terms of luminous efficiency, driving voltage, and lifespan.

In particular, in conventional organic electroluminescent devices, excitons and/or holes generated in the light-emitting layer diffuse into the electron transport layer and emit light at the interface with the electron transport layer, resulting in reduced luminous efficiency and reduced lifespan.

On the other hand, an organic electroluminescent device having a plurality of light-emitting stacked parts between a pair of electrodes (so-called tandem structure) includes a charge generation layer formed between the light-emitting stacked parts. Due to this structure, the driving voltage is high and the efficiency is low. , there was a problem of reduced lifespan.

Japanese Patent Publication No. 2003-123983 US Patent Publication 2003/215667 International Publication 2003/060956 International Publication 2008/117976 Registered Patent Publication No. 2084906

The present invention provides a novel compound that has high stability for electrons and high electron mobility, can suppress diffusion of excitons and/or holes into the electron transport layer, and is suitable as an n-type charge generation layer in a tandem structure, such compound. The purpose of the present invention is to provide a composition for an organic electroluminescent device containing a composition, an organic electroluminescent device having high efficiency, low driving voltage, and long lifespan, and a display device using the same.

In order to achieve the above object, the present invention provides a compound containing the structure represented by the following formula (1).

In Formula 1,

X ₁ and X ₂ are the same or different from each other, and are each independently CR ₁ or N, and at least one of X ₁ and X ₂ is N,

Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents deuterium, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted alkyl group of C ₁ -C ₂₀ , substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group, substituted or an unsubstituted aralkyl group of C ₃ -C ₂₀ , a substituted or unsubstituted aryl group of C ₆ -C ₃₀ , a substituted or unsubstituted heteroaryl group of C ₃ -C ₃₀ , or a substituted or unsubstituted C ₃ - C ₂₀ heteroaralkyl group, substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, substituted or unsubstituted C ₆ -C ₃₀ arylsilyl group and substituted or unsubstituted C ₃ -C ₃₀ heteroaryl It is selected from the group consisting of silyl groups.

In addition, the present invention provides a composition for an organic electroluminescent device in which a compound containing the structure represented by the above formula (1) is mixed with an organometallic compound containing an alkali metal or an alkaline earth metal, and an organic electroluminescent device comprising such a compound in an organic material layer. A display device including a light emitting device and an organic electroluminescent device is provided.

When the novel compound containing the structure represented by Formula 1 of the present invention is used as a material for the electron transport layer and/or the hole blocking layer (electron transport auxiliary layer), it has excellent luminescence performance, low driving voltage, and superior luminescence performance compared to conventional materials. Organic electroluminescent devices with high efficiency and long lifespan can be manufactured, and furthermore, full-color display panels with greatly improved performance and lifespan can be manufactured.

In addition, when a new compound containing the structure represented by Formula 1 is used as a material for the n-type charge generation layer of a tandem structure organic electroluminescent device, a white organic electroluminescent device with low driving voltage, high efficiency, and long lifespan can be realized. You can.

Figure 1 is a schematic cross-sectional view of an organic electroluminescent device having one light-emitting stacked portion according to an embodiment of the present invention.
2 and 3 are schematic cross-sectional views of an organic electroluminescent device having a plurality of light-emitting stacked parts according to another embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. In describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted.

<Description of the compounds of the present invention>

The compound according to the present invention includes a structure represented by the following formula (1).

In Formula 1,

X ₁ and X ₂ are the same or different from each other, and are each independently CR ₁ or N, and at least one of X ₁ and X ₂ is N,

Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents deuterium, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted alkyl group of C ₁ -C ₂₀ , substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group, substituted or an unsubstituted aralkyl group of C ₃ -C ₂₀ , a substituted or unsubstituted aryl group of C ₆ -C ₃₀ , a substituted or unsubstituted heteroaryl group of C ₃ -C ₃₀ , or a substituted or unsubstituted C ₃ - C ₂₀ heteroaralkyl group, substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, substituted or unsubstituted C ₆ -C ₃₀ arylsilyl group and substituted or unsubstituted C ₃ -C ₃₀ heteroaryl It is selected from the group consisting of silyl groups.

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

The position where a substituent is not bonded to the compound described herein may be hydrogen or deuterium may be bonded thereto.

In this specification, the term “substitution” means changing the hydrogen atom bonded to the carbon atom of the compound to another substituent, and the position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, the position where the substituent can be substituted, 2 In the case of more than one substitution, two or more substituents may be the same or different from each other.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Nitrile group; Cyano group; Phosphine oxide group; Alkyl group; alkenyl group; Alkynyl group; Cycloalkyl group; heteroalkyl group; Aryl group; heterocyclic group; Aralkyl group; heteroaralkyl group; Aralkenyl group; Alkylaryl group; alkenyl aryl group; Alkoxy group; Aryloxy group; Arylphosphine oxide group; silyl group; Alkylamine group; Aralkylamine group; Arylamine group; Alkylarylamine group; or substituted or unsubstituted with one or more substituents selected from the group consisting of a heteroarylamine group, or substituted or unsubstituted with a substituent in which two or more of the above-exemplified substituents are linked. For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

In this specification, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but may be, for example, 1 to 100, 1 to 80, 1 to 50, or 1 to 20. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n. -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited to these.

In the present specification, the alkenyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but may be, for example, 2 to 100, 2 to 80, 2 to 50, or 2 to 30. Specific examples of alkenyl groups include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, and 3-methyl. -1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl- 2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, etc., but are not limited to these. .

In the present specification, the number of carbon atoms of the alkynyl group is not particularly limited, but may be 2 to 50, 2 to 30, or 2 to 20. Specifically, the alkynyl group may be an unsaturated aliphatic hydrocarbyl group containing a triple bond such as an ethynyl group, but is not limited thereto.

In the present specification, the number of carbon atoms of the cycloalkyl group is not particularly limited, but may be 3 to 100, 3 to 60, or 3 to 30. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, Examples include, but are not limited to, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, and cyclooctyl.

As used herein, a heteroalkyl group or heterocycloalkyl group refers to an alkyl group or a cycloalkyl group each having one or more carbon atoms substituted by a heteroatom. The heteroatoms are selected from O, S, N, P, B, Si, and Se, preferably O, S, or N.

In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group. When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but may be 6 to 80, 6 to 60, 6 to 50, or 6 to 30 carbon atoms. Specific monocyclic aryl groups may include phenyl groups, biphenyl groups, and terphenyl groups, but are not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure. When the fluorenyl group is substituted, , , , , and It can be etc. However, it is not limited to this.

In the present specification, examples of the arylphosphine oxide group include a substituted or unsubstituted monoarylphosphine oxide group, a substituted or unsubstituted diarylphosphine oxide group, or a substituted or unsubstituted triarylphosphine oxide group. . The aryl group in the arylphosphine oxide group may be a monocyclic aryl group or a polycyclic aryl group. The arylphosphine oxide group containing two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group simultaneously.

As used herein, an aralkyl group or heteroaralkyl group refers to an alkyl group substituted with an aryl group or heteroaryl group. The number of carbon atoms is not limited, but may be 3 to 20.

In the present specification, the silyl group may be represented by the formula -SiR _a R _b R _c , where R _a , R _b , and R _c are each hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or it may be a substituted or unsubstituted heteroaryl group. The silyl group specifically includes, but is not limited to, trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, and phenylsilyl group. No. The number of carbon atoms is not limited, but when R _a , R _b and R _c are each a substituted or unsubstituted alkyl group, the carbon number may be 1 to 30, and if they are a substituted or unsubstituted aryl group, the carbon number may be 6 to 30. In the case of a substituted or unsubstituted heteroaryl group, the number of carbon atoms may be 3 to 30.

In the present specification, the heterocyclic group is an aromatic or aliphatic heterocyclic group containing at least one of N, O, and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but has 2 to 80 carbon atoms, 2 to 60 carbon atoms, or 2 to 2 carbon atoms. It could be 40. Specific examples of heterocyclic groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridine group, bipyridine group, pyrimidine group, triazine group, and triazole group. , acridine group, pyridazine group, pyrazine group, quinoline group, quinazoline group, quinoxaline group, phthalazine group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group, carbazole group, carboline group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, and dibenzofuranyl group, but is not limited to these.

In the present specification, the heteroaryl group may be described as an aromatic heterocyclic group among heterocyclic groups. The number of carbon atoms is not particularly limited, but may be 3 to 30 carbon atoms. The heteroaryl group may include the structure below.

In the present specification, the alkoxy group may be straight chain, branched chain, or ring chain. The number of carbon atoms of the alkoxy group is not particularly limited, but may have 1 to 50 carbon atoms, 1 to 30 carbon atoms, or 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It may be possible, but it is not limited to this.

In this specification, the aryl group in the aryloxy group is the same as the example of the aryl group described above. Specifically, aryloxy groups include phenoxy, p-toryloxy, m-toryloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, p-tert-butylphenoxy, and 3-biphenyl. Oxy, 4-biphenyloxy, 1-naphthyloxy, 2-naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryl Oxy, 9-anthryloxy, 1-phenanthryloxy, 3-phenanthryloxy, 9-phenanthryloxy, etc. Arylthioxy groups include phenylthioxy, 2-methylphenylthioxy, and 4-tert-butylphenyl. There is a thioxy group, etc., but it is not limited thereto.

In the present specification, an alkylamine group, an aralkylamine group, an arylamine group, an alkylarylamine group, and a heteroarylamine group are amine groups substituted with an alkyl group, an aralkyl group, an aryl group, an alkylaryl group, and a heteroaryl group, respectively. Here, the description of the above-described alkyl group and aryl group may be applied to alkyl and aryl, and the description of the aromatic heterocyclic group among the above-described heterocyclic groups may be applied to the heteroaryl group. Specific examples of amine groups include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 3-methyl-phenylamine, 4 -Methyl-naphthylamine, 2-methyl-biphenylamine, 9-methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, etc. However, it is not limited to these.

In the present specification, an arylene group refers to an aryl group having two binding positions, that is, a bivalent group. The description of the aryl group described above can be applied, except that each of these is a divalent group.

In the present specification, a heteroarylene group refers to a heteroaryl group having two bonding positions, that is, a bivalent group. The description of the aromatic heterocyclic group described above can be applied, except that each of these is a divalent group.

In the present specification, forming a ring by bonding with adjacent groups means a substituted or unsubstituted aliphatic hydrocarbon ring by bonding with adjacent groups; Substituted or unsubstituted aromatic hydrocarbon ring; Substituted or unsubstituted aliphatic heterocycle; Substituted or unsubstituted aromatic heterocycle; Or it means forming a condensed ring thereof.

In this specification, “adjacent group” refers to a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located closest to the substituent in terms of structure, or another substituent substituted on the atom on which the substituent is substituted. It can mean. For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring can be interpreted as “adjacent groups”.

In the present specification, an aliphatic hydrocarbon ring refers to a non-aromatic ring consisting only of carbon and hydrogen atoms.

In the present specification, examples of aromatic hydrocarbon rings include phenyl groups, naphthyl groups, and anthracenyl groups, but are not limited to these.

As used herein, an aliphatic heterocycle refers to an aliphatic ring containing at least one of N, O, or S atoms as a heteroatom.

As used herein, an aromatic heterocycle refers to an aromatic ring containing at least one of N, O, or S atoms as a heteroatom.

In the present specification, the aliphatic ring, aromatic ring, aliphatic heterocycle, and aromatic heterocycle may be monocyclic or polycyclic.

The compound containing the structure of Formula 1 has three substituents connected to the pyrazine core, and thus has high luminous efficiency and excellent thermal stability.

According to one embodiment of the present invention, the compound of the present invention is represented by the following [Chemical Formula 2].

In Formula 2 above,

X ₁ and X ₂ , Ar ₁ and Ar ₂ are as defined in Formula 1 above,

L ₁ to L ₃ are the same or different from each other, and each independently represents a single bond or a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₆ -C ₃₀ arylene group, or a substituted or unsubstituted C 1 -C 10 alkylene group. selected from the group consisting of a C ₂ -C ₃₀ heteroarylene group, a substituted or unsubstituted C ₃ -C ₂₀ cycloalkylene, and a substituted or unsubstituted C ₂ -C ₂₀ heterocycloalkylene,

Ar ₃ is a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, or a substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group, substituted or unsubstituted C ₃ -C ₂₀ aralkyl group, substituted or unsubstituted C ₆ -C ₃₀ aryl group, Substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, substituted or unsubstituted C ₃ -C ₂₀ heteroaralkyl group, substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, substituted or unsubstituted Selected from the group consisting of a C ₆ -C ₃₀ arylsilyl group and a substituted or unsubstituted C ₃ -C ₃₀ heteroarylsilyl group,

n is an integer from 1 to 5,

When n is 2 or more, a plurality of L ₃ or Ar ₃ may each independently be the same or different from each other.

According to one embodiment of the present invention, at least one of Ar ₃ of Formula 2 includes an electron-withdrawing group (EWG).

According to one embodiment of the present invention, at least one of Ar ₃ in Formula 2 is represented by any one of Formulas 3 to 8 below.

In Formulas 3 to 8,

A ₁ to A ₃₂ are the same or different from each other, and are each independently CR ₂ or N, at least one of A ₁ to A ₆ , at least one of A ₇ to A ₁₄ , at least one of A ₁₅ to A ₂₄ , or A ₂₅ to A ₂₉ , at least one is N,

Y ₁ and Y ₂ are the same or different from each other and are each independently a single bond, CR ₃ R ₄ , NR ₅ , O or S, and neither Y ₁ nor Y ₂ can be a single bond;

R ₂ and R ₃ to R ₅ of CR ₂ as A ₁ to A ₃₂ are the same or different from each other, and are each independently hydrogen, deuterium, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted C ₁ -C ₂₀ alkyl group, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted Or an unsubstituted C ₁ -C ₂₀ heteroalkyl group, a substituted or unsubstituted C ₃ -C ₂₀ aralkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, substituted or unsubstituted C ₃ -C ₂₀ heteroaralkyl group, substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, substituted or unsubstituted C ₆ -C ₃₀ arylsilyl group , and substituted or unsubstituted C ₃ -C ₃₀ heteroarylsilyl groups, and adjacent groups may be bonded to each other to form a substituted or unsubstituted ring.

According to one embodiment of the present invention, at least one of L ₁ to L ₃ and Ar ₃ of Formula 2 is represented by Formula 9 or Formula 10 below.

In Formula 10 and Formula 11,

_{X 3 and _ _ _ _}

o and p are integers from 0 to 3,

r is an integer from 0 to 4,

R ₆ to R ₁₃ are the same or different from each other, and are each independently hydrogen, deuterium, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted C ₁ -C ₂₀ alkyl group, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group , a substituted or unsubstituted C ₃ -C ₂₀ aralkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, a substituted or unsubstituted C ₃ -C ₂₀ heteroaralkyl group, substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, substituted or unsubstituted C ₆ -C ₃₀ arylsilyl group, and substituted or unsubstituted C ₃ -C ₃₀ It is selected from the group consisting of heteroarylsilyl groups, and adjacent groups may be bonded to each other to form a substituted or unsubstituted ring.

According to one embodiment of the present invention, at least one of Ar ₃ in Formula 2 is a polycyclic-aromatic-hydrocarbon (PHA) having a C ₇ or higher. Specifically, at least one of Ar ₃ may be naphthalene, anthracene, phenanthrene, pyrene, or triphenylene.

According to one embodiment of the present invention, n in Formula 2 is 2.

According to one embodiment of the present invention, n in Formula 2 is 4 or 5.

For example, the compounds of the present invention include the following compounds.

Below, an organic electroluminescent device having one light-emitting stacked portion and an organic electroluminescent device having a plurality of light-emitting stacked portions according to an embodiment of the present invention will be described in detail based on the drawings.

Figure 1 is a schematic cross-sectional view showing an organic electroluminescent device having a structure in which one light-emitting stacked part is formed between a pair of electrodes, and Figures 2 and 3 show a structure in which a plurality of light-emitting stacked parts are formed between a pair of electrodes. This is a schematic cross-sectional view showing an organic electroluminescent device.

<Organic electroluminescent device with a structure having one light-emitting layered portion>

The organic electroluminescent device 1 shown in FIG. 1 includes an anode 110 (first electrode) installed on a substrate 100, a hole injection layer 120 installed on the anode 110, and a hole injection layer 120. ) a hole transport layer 130 installed on the hole transport layer 130, a light-emitting layer 140 installed on the hole transport layer 130, an electron transport layer 150 installed on the light-emitting layer 140, and an electron injection layer installed on the electron transport layer 150. (160) and a cathode (170, a second electrode) provided on the electron injection layer (160). In FIG. 1, the organic material layer portion including layers between the anode 110 and the cathode 170 constitutes one light-emitting stacked portion.

In addition, the organic electroluminescent element 1 has the stacked structure reversed (so-called inverted element), for example, a cathode provided on the substrate 100, an electron injection layer provided on the cathode, and an electron injection layer on the electron injection layer. It may be configured to include an electron transport layer provided on the electron transport layer, a light emitting layer provided on the electron transport layer, a hole transport layer provided on the light emitting layer, a hole injection layer provided on the hole transport layer, and an anode provided on the hole injection layer.

In the organic electroluminescent device of the present invention, not all of the above layers are essential, and the minimum structural unit is composed of an anode 110, a light emitting layer 140, and a cathode 170, and a hole injection layer 120 and a hole injection layer 120. At least one of the transport layer 130, the electron transport layer 150, and the electron injection layer 160 may be omitted.

For example, in addition to the configuration of “anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode” which describes the laminate structure of the organic electroluminescent element, “anode/hole transport layer/light-emitting layer/electron transport layer/electron injection” layer/cathode”, “anode/hole injection layer/light-emitting layer/electron transport layer/electron injection layer/cathode”, “anode/hole injection layer/hole transport layer/light-emitting layer/electron injection layer/cathode”, “anode/hole injection layer/ Hole transport layer/light-emitting layer/electron transport layer/cathode”, “anode/light-emitting layer/electron transport layer/electron injection layer/cathode”, “anode/hole transport layer/light-emitting layer/electron injection layer/cathode”, “anode/hole transport layer/light-emitting layer/electron” Transport layer/cathode”, “anode/hole injection layer/light-emitting layer/electron injection layer/cathode”, “anode/hole injection layer/light-emitting layer/electron transport layer/cathode”, “anode/light-emitting layer/electron transport layer/cathode”, “anode/ It may be configured as “light emitting layer/electron injection layer/cathode”.

In addition, for the purpose of controlling the balance of the concentration of holes and electrons in the light-emitting layer 140, the area between the anode 110 and the light-emitting layer 140 (hole transport area) and between the light-emitting layer 140 and the cathode 170. A separate layer (for example, a hole blocking layer (electron transport auxiliary layer) and/or an electron blocking layer (hole transport auxiliary layer), etc.) may be added to the region (electron transport region).

In this case, the organic electroluminescent device 1 has “anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode”, “anode/hole injection layer/hole transport layer/light emitting layer/ It can have a stacked structure such as “hole blocking layer/electron transport layer/electron injection layer/cathode”, “anode/hole injection layer/hole transport layer/electron blocking layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode”, etc. there is.

Additionally, each of the above layers may be composed of a single layer or may be composed of multiple layers.

Hereinafter, the substrate 100 used to manufacture the organic electroluminescent device 1 and each layer forming the organic electroluminescent device 1 will be described in detail.

The substrate 100 is a support that supports the organic electroluminescent element 1, and glass, metal, polymer, semiconductor (silicon), etc. are usually used. The substrate 100 is formed in a plate shape, a film shape, or a sheet shape depending on the purpose, and for example, a glass plate, a metal plate, a metal foil, a polymer film, a polymer sheet, etc. are used. Among them, glass plates and plates made of transparent synthetic resins such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable. When manufacturing a flexible display, a glass plate (also called carrier glass) coated with a highly thermally stable and flexible polymer material (eg, polyimide) can be used as the substrate 100.

If it is a glass substrate, soda-lime glass, alkali-free glass, etc. are used, and the thickness just needs to be sufficient to maintain mechanical strength, so for example, it can be 0.2 mm or more. The upper limit of the thickness is, for example, 2 mm or less, and preferably 1 mm or less. Regarding the material of glass, alkali-free glass is preferable because it is better to have fewer ions eluted from the glass, but soda-lime glass coated with a barrier coating such as SiO ₂ is also commercially available and can be used. Additionally, in order to increase gas barrier properties, the substrate 100 may be provided with a gas barrier film such as a dense silicon oxide film on at least one side. In particular, when a polymer plate, film or sheet with low gas barrier properties is used as the substrate 100, It is desirable to install a gas barrier film.

The anode 110 is an electrode that injects holes, and the anode material is preferably a material with a large work function to ensure smooth hole injection into the organic layer.

Examples of materials forming the anode 110 include inorganic compounds and organic compounds. Inorganic compounds include, for example, metals (aluminium, gold, silver, nickel, palladium, chromium, vanadium, copper, zinc, etc.) or alloys thereof, metal oxides (indium oxide, tin oxide, indium-tin oxide ( (ITO), indium-zinc oxide (IZO), etc.), ZnO:Al or _SNO2 : A combination of metals and oxides such as Sb, metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, Nesa glass, etc. You can. Organic compounds include, for example, polythiophenes such as poly(3-methylthiophene) and poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline. Conductive polymers, etc. can be mentioned. In addition, the material can be appropriately selected from materials used as anodes for organic electroluminescent devices.

The hole injection layer 120 serves to efficiently inject holes moving from the anode 110 into the light emitting layer 140 or the hole transport layer 130.

The hole transport layer 130 serves to efficiently transport holes injected from the anode 110 or holes injected from the anode 110 through the hole injection layer 120 to the light emitting layer 140. The hole injection layer 120 and the hole transport layer 130 are each formed by laminating or mixing one or two or more types of hole injection/transport materials or a mixture of a hole injection/transport material and a polymer binder. Additionally, an inorganic salt such as iron(III) chloride may be added to the hole injection/transport material to form a layer.

As a hole injection/transport material, it is desirable to have a high hole injection efficiency and to transport the injected holes efficiently. For this purpose, it is desirable to use a material that has a small ionization potential, a high hole mobility, and excellent stability, and in which impurities that become traps are unlikely to be generated during manufacture and use.

Materials forming the hole injection layer 120 and the hole transport layer 130 include compounds conventionally used as hole charge transport materials in photoconductive materials, p-type semiconductors, hole injection layers of organic electroluminescent devices, and Any compound can be selected and used among known compounds used in the hole transport layer.

These specific examples include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis(N-arylcarbazole) or bis(N-alkylcarbazole), and triarylamine derivatives. (Polymer having aromatic tertiary amino in the main or side chain, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N'-diphenyl-N,N'-di(3- Methylphenyl)-4,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, N,N'-diphenyl-N, N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine, N,N'-dinaphthyl-N,N'-diphenyl-4,4'-diphenyl- 1,1'-diamine, N ⁴ ,N ^{4 '} -diphenyl-N ⁴ ,N ^{4 '} -bis(9-phenyl-9H-carbazol-3-yl)-[1,1'-biphenyl]- 4,4'-diamine, N ⁴ ,N ⁴ ,N ^{4 '} ,N ^4' -tetra[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4 Triphenylamine derivatives such as '-diamine, 4,4',4"-tris(3-methylphenyl(phenyl)amino)triphenylamine, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (e.g., 1,4,5,8,9,12-hexaazatriphenylene) -2,3,6,7,10,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonate, styrene derivatives, and polyvinylcarboxylic compounds having the above-mentioned monomer in the side chain. Bazol, polysilane, etc. are preferred, but there is no particular limitation as long as it is a compound that forms a thin film necessary for manufacturing a light emitting device, can inject holes from the anode, and can transport holes.

Additionally, it is known that the conductivity of organic semiconductors is strongly influenced by their doping. This organic semiconductor matrix material is composed of a compound with good electron donating properties or a compound with good electron accepting properties. For doping of electron-donating materials, strong electron acceptors such as tetracyanoquinonedimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinonedimethane (F4TCNQ) are used. It is known (e.g., “M.Pfeiffer, A.Beyer, T.Fritz, K.Leo, Appl. Phys. Lett., 73(22), 3202-3204 (1998)” and “J.Blochwitz , M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(6), 729-731 (1998)). These generate so-called holes by an electron transfer process in an electron-donating base material (hole transport material). Depending on the number and mobility of holes, the conductivity of the base material changes significantly. As matrix materials with hole transport properties, for example, benzidine derivatives (TPD, etc.) or starburst amine derivatives (TDATA, etc.), or specific metal phthalocyanines (especially zinc phthalocyanine (ZnPc), etc.) are known (Japanese Patent Publication, 2005). -167175 Gazette).

An additional hole buffer layer may be provided between the hole injection layer 120 and the hole transport layer 130, and may include hole injection or transport materials known in the art.

The light-emitting layer 140 is a layer that emits light by recombining holes injected from the anode 110 and electrons injected from the cathode 170 between electrodes to which an electric field is applied. The material forming the light-emitting layer 140 may be any compound (luminescent compound) that is excited and emits light by recombination of holes and electrons, and can form a stable thin film shape and have strong luminescence (fluorescence) efficiency in the solid state. It is preferable that it is a visible compound.

The light emission mechanism of the light emitting layer 140 is divided into fluorescence and phosphorescence. Fluorescence is a mechanism in which excitons in the singlet state, among excitons created by the combination of holes and electrons, descend to the ground state and emit light, while phosphorescence is a mechanism in which excitons in the triplet state descend to the ground state and emit light. By combining holes and electrons, 25% of singlet excitons and 75% of triplet excitons are generated. Unlike fluorescence, where only 25% of singlet excitons contribute to light emission, in the case of phosphorescence, 75% of triplet excitons and 75% of triplet excitons are generated. Since all 25% of singlet excitons that can be converted to triplet excitons through intersystem transition contribute to light emission, it is theoretically possible to achieve 100% internal quantum efficiency.

The light emitting layer 140 may be a single layer or multiple layers, and may include a host and a dopant to improve color purity and quantum efficiency. In the light emitting layer 140 of this structure, excitons generated in the host transfer to dopants and emit light. The host material and the dopant material may be of one type or a combination of multiple types. The dopant material may be contained entirely or partially in the host material. As a doping method, it can be formed by co-deposition with a host material, but may be deposited simultaneously after pre-mixing with the host material, or may be deposited by pre-mixing with the host material with an organic solvent and then forming into a film by a wet film forming method.

The amount of host material used varies depending on the type of host material, and can be determined according to the characteristics of the host material. The standard for the usage amount of the host material is 50 to 99.999% by weight, 80 to 99.95% by weight, or 90 to 99.9% by weight of the total light emitting layer material.

The amount of dopant material used varies depending on the type of dopant material, and can be determined according to the characteristics of the dopant material. The standard for the usage amount of the dopant material is 0.001 to 50% by weight, 0.05 to 20% by weight, or 0.1 to 10% by weight of the total material for the light emitting layer. The above range is preferable because, for example, concentration quenching phenomenon can be prevented.

Host materials include condensed aromatic ring derivatives or heterocyclic ring-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder-type compounds. These include, but are not limited to, furan compounds and pyrimidine derivatives.

When the emitting layer emits red light, the dopants include PIQIr(acac)(bis(1-phenylsoquinoline)acetylacetonateiridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), and PQIr(tris(1-phenylquinoline)iridium). , phosphorescent materials such as octaethylporphyrin platinum (PtOEP) or fluorescent materials such as tris(8-hydroxyquinolino)aluminum (Alq3) may be used, but are not limited to these. If the emitting layer emits green light, a phosphor such as Ir(ppy)3 (fac tris(2-phenylpyridine)iridium) or a fluorescent material such as Alq3 (tris(8-hydroxyquinolino)aluminum) may be used as the dopant. , but is not limited to this. If the light-emitting layer emits blue light, the light-emitting dopant may be a phosphorescent material such as (4,6-F2ppy)2Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distrylarylene (DSA), or PFO. Fluorescent materials such as polymers and PPV-based polymers may be used, but are not limited to these.

For example, as a blue light-emitting dopant, a polycyclic aromatic compound represented by the following formula (BD-YX2) or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (BD-YX2) may be used.

In the above formula (BD-YX2), ring A, ring B, and ring C are each independently an aryl ring or heteroaryl ring, and at least one hydrogen in these rings may be substituted,

Y1 is B, P, P=O, P=S, Al, Ga, As, Si-R or Ge-R, and R of Si-R and Ge-R is aryl, alkyl or cycloalkyl,

X1 _and Optionally alkyl or optionally substituted cycloalkyl

and R in >C(-R) ₂ is hydrogen, optionally substituted aryl, optionally substituted alkyl, or optionally substituted cycloalkyl, and R in >NR and >C(-R) At least one of R in ₂ may be bonded to at least one of the A ring, B ring, and C ring through a linking group or single bond,

At least one hydrogen in the compound or structure represented by the formula (BD-YX2) may be substituted with deuterium, cyano, or halogen,

In the compound or structure represented by the formula (BD-YX2), at least one of A ring, B ring, C ring, aryl, and heteroaryl may be condensed with at least one cycloalkane, and At least one hydrogen may be substituted, and at least one -CH2- in the cycloalkane may be substituted with -O-.

In particular, in the formula (BD-YX2), the aryl ring or heteroaryl ring as the A ring, B ring, and C ring is a 5-membered ring that shares a bond with the condensed 2-ring structure in the center of the formula consisting of Y1, It is preferable that it is a 6-membered ring.

The electron injection layer 160 serves to efficiently inject electrons moving from the cathode 170 into the light emitting layer 140 or the electron transport layer 150.

The electron transport layer 150 serves to efficiently transport electrons injected from the cathode 170 or electrons injected from the cathode 170 through the electron injection layer 160 to the light emitting layer 140. A suitable material for the electron transport layer 150 is a compound that has electron acceptor properties and has high mobility for electrons. In addition, it must have a LUMO (Lowest Unoccupied Molecular Orbital) energy level suitable for injecting electrons into the light-emitting layer 140, and the HOMO of the light-emitting layer 140 is required to prevent holes from flowing from the light-emitting layer 140 to the electron transport layer 150. (Highest Occupied Molecular Orbital) It is desirable to have a large difference from the energy level.

The electron transport layer 150 and the electron injection layer 160 are formed by laminating and mixing one or two or more types of electron transport/injection materials, respectively.

The electron injection/transport layer, which performs the functions of both the electron injection layer and the electron transport layer, is a layer that promotes the injection of electrons from the cathode and transports electrons to the light emitting layer 140, and has high electron injection efficiency, It is desirable to transport the injected electrons efficiently. For this purpose, it is desirable to use a material that has high electron affinity, high electron mobility, excellent stability, and that impurities that become traps are unlikely to be generated during production and use. The electron injection/transport layer in this embodiment may have the function of a layer that can efficiently prevent the movement of holes.

Materials forming the electron transport layer 150 or the electron injection layer 160 include compounds conventionally used as electron transport compounds in photoconductive materials, and known compounds used in the electron injection layer and electron transport layer of organic electroluminescent devices. It can be used by arbitrarily selecting from among the compounds. In the present invention, a compound containing one or more structures represented by Formula 1 can be used as the electron transport material and/or electron injection material.

In general, the material used for the electron transport layer 150 or the electron injection layer 160 is a compound made of an aromatic ring or heteroaromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus. , pyrrole derivatives, condensed ring derivatives thereof, and metal complexes having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives such as 4,4'-bis(diphenylethenyl)biphenyl, perinone derivatives, coumarin derivatives, and naphthalimide derivatives. , quinone derivatives such as anthraquinone and diphenoquinone, phosphorus derivatives, carbazole derivatives, and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complex, azomethine complex, tropolone metal complex, flavonol metal complex, and benzoquinoline metal complex. These materials can be used alone, but may also be mixed with other materials.

Additionally, specific examples of other electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, and diphenylquinone. Derivatives, perylene derivatives, oxadiazole derivatives (1,3-bis[(4-tert-butylphenyl)1,3,4-oxadiazolyl]phenylene, etc.), thiophene derivatives, triazole derivatives (N- (naphthyl-2,5-diphenyl-1,3,4-triazole, etc.), thiadiazole derivatives, metal complexes of auxin derivatives, quinolinol-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazoles Compounds, gallium complex, pyrazole derivative, perfluorinated phenylene derivative, triazine derivative, pyrazine derivative, benzoquinoline derivative (2,2'-bis(benzo[h]quinolin-2-yl)-9,9' -spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzoimidazole derivatives (tris(N-phenylbenzoimidazol-2-yl)benzene, etc.), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives , oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (1,3-bis(4'-(2,2':6'2"-terpyridinyl))benzene, etc.), naphthyridine derivatives ( bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide, etc.), aldazine derivatives, carbazole derivatives, indole derivatives, phosphorus oxide derivatives, bistyryl derivatives, etc. I can hear it.

Additionally, a metal complex having an electron-accepting nitrogen can also be used, for example, a quinolinol-based metal complex, a hydroxyazole complex such as a hydroxyphenyloxazole complex, an azomethine complex, a tropolone metal complex, or a flavonol metal complex. and benzoquinoline metal complexes.

The above-mentioned materials can be used alone, but may also be used in combination with other materials.

Among the above-mentioned materials, borane derivatives, pyridine derivatives, fluoranthene derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, Phenanthroline derivatives and quinolinol-based metal complexes are preferred.

The electron transport layer or electron injection layer may also contain a material capable of reducing the material forming the electron transport layer or electron injection layer. A variety of reducing substances are used as long as they have a certain reducing property. For example, alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metal oxides, alkaline earth metals. At least one selected from the group consisting of halides, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals can be preferably used.

Preferred reducing substances include alkali metals such as Li (work function 2.3 eV), Na (work function 2.36 eV), K (work function 2.28 eV), Rb (work function 2.16 eV), or Cs (work function 1.95 eV). Examples include alkaline earth metals such as Ca (work function 2.9 eV), Sr (work function 2.0-2.5 eV), or Ba (work function 2.52 eV), and those with a work function of 2.9 eV or less are particularly preferable. Among these, more preferable reducing substances are alkali metals of K, Rb or Cs, more preferably Rb or Cs, and most preferable is Cs. These alkali metals have a particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or electron injection layer, the luminance of the organic EL device can be improved and its lifespan can be improved. In addition, as a reducing material with a work function of 2.9 eV or less, a combination of two or more of these alkali metals is also preferred, especially a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, or Cs and A combination of Na and K is preferred. By including Cs, the reducing ability can be efficiently exerted, and by adding it to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL device can be improved and its lifespan can be improved.

Additionally, other preferred reducing substances include organometallic compounds represented by the following structural formula.

Among the structural formulas above,

Ar ₆ is hydrogen; heavy hydrogen; halogen group; Nitrile group; nitro group; hydroxyl group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted arylsulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

The curve represents the bonds and 2 or 3 atoms required to form a 5- or 6-membered ring with M, said atoms being substituted or unsubstituted by one or more substituents identical to the definition of Ar ₆ ;

M is an alkali metal or alkaline earth metal.

More preferably, M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium, and even more preferably M is lithium. For example, the reducing organometallic compound represented by the above structural formula is unsubstituted lithium quinolinate.

The above-mentioned reducing material may be used as a mixture or composition within one layer with the material forming the electron transport layer or electron injection layer, or may be used by forming a separate layer continuous with the electron transport layer or electron injection layer.

The cathode 170 serves to inject electrons into the light emitting layer 140 through the electron injection layer 160 and the electron transport layer 150.

The material forming the cathode 170 is preferably a material with a small work function so that electrons can be efficiently injected into the organic layer. Specific examples of cathode materials include metals such as tin, indium, calcium, aluminum, silver, lithium, sodium, potassium, titanium, yttrium, gadolinium, lead, cesium, and magnesium, or alloys thereof (magnesium-silver alloy, magnesium-indium alloy) , aluminum-lithium alloys such as lithium fluoride/aluminum, etc.) are preferable. In order to improve device characteristics by increasing electron injection efficiency, alloys containing lithium, sodium, potassium, cesium, calcium, magnesium, or these low work function metals are effective. However, these low work function metals are generally unstable in the atmosphere. To improve this problem, there is a known method of using a highly stable electrode by, for example, doping a trace amount of lithium, cesium, or magnesium into the organic layer. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used. However, it is not limited to these.

The organic material layer may further include an electron blocking layer (or hole transport auxiliary layer) between the hole transport layer 130 and the light emitting layer 140, and a hole blocking layer (or electron transport auxiliary layer) between the electron transport layer 150 and the light emitting layer 140. An auxiliary layer) may be further included.

The electron blocking layer and the hole blocking layer allow the excitons generated in the light-emitting layer 140 to diffuse into the electron transport layer 150 or the hole transport layer 130 adjacent to the light-emitting layer 140, or do not recombine in the light-emitting layer 140 and form a hole transport layer ( 130) or the electron transport layer 150, which is a layer that prevents electrons or holes from passing over. As a result, the number of excitons contributing to light emission in the light-emitting layer increases, improving the light-emitting efficiency of the device and lowering the driving voltage. In addition, by preventing irreversible decomposition reactions due to oxidation by diffusion of holes into the electron transport layer 150, which moves electrons through reduction (electron reception), the durability and stability of the device are improved and the lifespan of the device is efficiently increased. can be increased.

Materials known in the art may be used as the electron blocking layer or hole blocking layer, and the compound containing the structure represented by Formula 1 of the present invention is preferably used as a material for the hole blocking layer (or electron transport auxiliary layer). can be used

The organic material layer may further include a light-emitting auxiliary layer (not shown) between the electron blocking layer and the light-emitting layer 140. The light-emitting auxiliary layer may serve to transport holes to the light-emitting layer 140 and adjust the thickness of the organic material layer. The light emitting auxiliary layer may be a hole transport material known in the art.

The materials used for the above hole injection layer, hole transport layer, light-emitting layer, electron transport layer, and electron injection layer can form each layer individually, but may be used as a polymer binder such as polyvinyl chloride, polycarbonate, polystyrene, or poly(N-vinylcarboxylic acid). Bazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS Used by dispersing with solvent-soluble resins such as resins and polyurethane resins, and curable resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, and silicone resins. It is also possible to do so.

<Organic electroluminescent device having a structure having a plurality of light-emitting stacked portions>

Figure 2 shows the structure of an organic electroluminescent device 2 having a plurality of light-emitting stacked parts according to an embodiment of the present invention, and includes two light-emitting stacked parts in the organic material layer between the anode 210 and the cathode 220. (230, 240) is formed.

Here, the light emitting stacked portions 230 and 240 are not particularly limited as long as they have a function of emitting light. For example, each of the light emitting stacked parts 230 and 240 may include one or more light emitting layers, and may also include one or more organic material layers other than the light emitting layer. The light-emitting stacked portions 230 and 240 are one or more organic material layers other than the light-emitting layer, and for example, a hole transport layer, a hole injection layer, and a hole transport/ It may include at least one of an injection layer, a buffer layer, an electron blocking layer, an electron transport layer, an electron injection layer, an electron transport/injection layer, and a hole blocking layer.

That is, each of the light-emitting stacked parts 230 and 240 may have a stacked structure of the light-emitting stacked parts shown in FIG. 1 and can emit light of different wavelengths. For example, the light-emitting stacked portion 230 may emit blue light, and the light-emitting stacked portion 240 may emit yellow-green light, and thereby the organic electroluminescent device 2 may emit white light.

A charge generation layer 250 is formed between the two light-emitting stacked parts 230 and 240 of the organic electroluminescent device 2. The charge generation layer 250 generates charges (holes and/or electrons) to form adjacent By injecting into the light-emitting stacked part, each light-emitting stacked part can emit light in a predetermined color range.

Specifically, the charge generation layer 250 includes an n-type charge generation layer 251 and a p-type charge generation layer 252, and the n-type charge generation layer 251 is a light emitting layer adjacent to the anode 210 ( 230) to generate/inject electrons into the light emitting stacked portion 230, and the p-type charge generation layer 252 is formed adjacent to the light emitting stacked portion 240 adjacent to the cathode 220 to form the light emitting stacked portion 230. Create/inject holes at (240). As a result, both holes and electrons are supplied to each light-emitting stacked part, allowing it to independently emit light in a predetermined color.

The n-type charge generation layer 251 may be a layer capable of n-type charge injection, n-type charge generation, or n-type charge injection/generation, and the p-type charge generation layer 252 may be a layer capable of p-type charge injection, p It may be a layer that can perform type charge generation or p-type charge injection/generation.

The n-type charge generation layer 251 is a host and an organic material layer doped with an alkali metal such as Li or an electron-deficient metal such as an alkaline earth metal as a dopant, or an organic metal compound containing an alkali metal such as Li or an alkaline earth metal. It may be made of a mixed composition layer, and the p-type charge generation layer 252 may be made of an organic semiconductor layer containing an organic material. A compound having one or more structures represented by Formula 1 of the present invention can be used as a material for the n-type charge generation layer 251.

Figure 2 shows a case where only two light-emitting stacked parts are provided in the organic material layer between the anode 210 and the cathode 220, but the present invention is not limited to this, and three or more light-emitting stacked parts may be provided.

For example, Figure 3 includes three light-emitting stacked parts (230, 240, 260) in the organic layer between the anode 210 and the cathode 220, and charge generation layers 250 and 270 between each light-emitting stacked part. The structure of an organic electroluminescent device is shown. In this structure, the light-emitting stacked part 260 may include a light-emitting layer that emits light in the same or different color range as the other light-emitting stacked parts 230 and 240. Like the charge generation layer 250, the charge generation layer 270 may include an n-type charge generation layer 271 and a p-type charge generation layer 272.

When three or more light-emitting stacked parts are formed between the anode 210 and the cathode 220, the amount of charge supplied may be different depending on the location of the light-emitting stacked parts, and the charge generation layer formed between these light-emitting stacked parts ( For example, by adjusting the amount of dopant of the n-type charge generation layer, the amount of charge supplied to the plurality of light-emitting stacked parts can be adjusted to be balanced.

In this specification, n-type refers to n-type semiconductor characteristics. In other words, n-type is a characteristic of injecting or transporting electrons through the LUMO (lowest unoccupied molecular orbital) energy level, and can be defined as a characteristic of a material in which the mobility of electrons is greater than that of holes. Conversely, p-type refers to p-type semiconductor characteristics. In other words, p-type is a characteristic of injecting or transporting holes through the HOMO (highest occupied molecular orbital) energy level, and this can be defined as a characteristic of a material in which the mobility of holes is greater than that of electrons. In this specification, an organic material layer having n-type characteristics may be referred to as an n-type organic material layer. Additionally, the organic material layer having p-type characteristics may be referred to as a p-type organic material layer. Additionally, n-type doping means that the material is doped to have n-type characteristics.

In this specification, adjacent refers to the arrangement relationship of the closest layers among the layers mentioned as adjacent. For example, two adjacent floors refers to the arrangement relationship of the two floors arranged closest among multiple floors. Here, adjacent may mean that two floors are in physical contact, depending on the case, or another unmentioned floor may be placed between the two floors. For example, the light-emitting stacked part adjacent to the cathode refers to the light-emitting stacked part disposed closest to the cathode among the light-emitting stacked parts. In addition, between the cathode 220 and the light emitting stacked portion 240 and between the anode 210 and the light emitting stacked portion 230 may be in physical contact, but between the cathode 220 and the light emitting stacked portion 240 and the anode. Another layer may be disposed between 210 and the light emitting layer 230. For example, a single p-type charge generation layer may be formed between the anode 210 and the light emitting layer 230.

<Method for manufacturing organic electroluminescent device>

Each layer constituting the organic electroluminescent device is made by using the materials that must make up each layer using methods such as deposition, resistance heating deposition, electron beam deposition, sputtering, molecular stacking, printing, spin coating or casting, and coating methods. It can be manufactured by forming a thin film. There is no particular limitation on the film thickness of each layer formed in this way, and it can be set appropriately depending on the properties of the material, but is usually in the range of 2 nm to 5 μm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like. When thinning a film using a vapor deposition method, the deposition conditions vary depending on the type of material, the target crystal structure and association structure of the film, etc. Deposition conditions are generally heating temperature of the deposition crucible +50~+400℃, vacuum degree 10 ^-6 ~10 ^-3 Pa, deposition speed 0.01~50nm/sec, substrate temperature -150~+300℃, film thickness 2nm. It is desirable to set it appropriately in the range of ~5㎛.

Next, as an example of a method for manufacturing an organic electroluminescent device, a method for manufacturing an organic electroluminescent device composed of an anode/hole injection layer/hole transport layer/host material and a light emitting layer/electron transport layer/electron injection layer/cathode made of a dopant material is included. Explain about it.

After producing an anode by forming a thin film of an anode material by a vapor deposition method or the like on a suitable substrate, thin films of a hole injection layer and a hole transport layer are formed on this anode. A host material and a dopant material are co-deposited on this to form a thin film to form a light-emitting layer. An electron transport layer and an electron injection layer are formed on this light-emitting layer, and a thin film made of a cathode material is formed by a deposition method or the like to serve as a cathode. By doing so, the desired organic electroluminescent device is obtained. In addition, when manufacturing the organic electroluminescent device described above, it is also possible to reverse the manufacturing order and manufacture the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer, and anode in that order.

<Application examples of organic electroluminescent devices>

Additionally, the present invention can be applied to a display device equipped with an organic electroluminescent element, a lighting device equipped with an organic electroluminescent element, etc.

A display device or lighting device equipped with an organic electroluminescent element is manufactured by a known method, such as connecting such an organic electroluminescent element and a known driving device (for example, a drain electrode or source electrode of a thin film transistor) in this embodiment. It can be driven using known driving methods such as direct current driving, pulse driving, and alternating current driving, as appropriate.

Examples of the display device include panel displays such as a color flat panel display, and flexible displays such as a flexible color organic electroluminescence (EL) display (for example, Japanese Patent Application Laid-Open No. 10-335066, See Japanese Patent Laid-Open No. 2003-321546, Japanese Patent Laid-Open No. 2004-281706, etc.). Additionally, examples of display methods include matrix and/or segment methods. Additionally, the matrix display and segment display may coexist in the same panel.

In a matrix, pixels for display are arranged two-dimensionally, such as in a grid or mosaic, and characters or images are displayed as a set of pixels. The shape and size of the pixel are determined depending on the purpose. For example, for image and text display on PCs, monitors, and televisions, square pixels with a side of 300㎛ or less are usually used, and in the case of large displays such as display panels, pixels on the order of mm are used. do. In the case of monochrome display, pixels of the same color can be arranged, but in the case of color display, red, green, and blue pixels are displayed in a row. In this case, there are typically delta types and stripe types. The driving method for this matrix may be either a line-sequential driving method or an active matrix driving method. Line-sequential driving has the advantage of having a simple structure, but when considering operating characteristics, the active matrix is sometimes superior, so it also needs to be used differently depending on the application.

In the segment method (type), a pattern is formed to display predetermined information, and a defined area is emitted. Examples include time and temperature displays in digital clocks and thermometers, operating status displays in audio devices and electronic cookers, and panel displays in automobiles.

Examples of lighting devices include lighting devices such as indoor lighting, backlights of liquid crystal displays, etc. (e.g., Japanese Patent Application Laid-Open No. 2003-257621, Japanese Patent Application Laid-Open No. 2003-277741, Japanese Patents (See Public Notice No. 2004-119211, etc.). Backlights are mainly used to improve the visibility of display devices that do not emit light themselves, and are used in liquid crystal displays, clocks, audio devices, automobile panels, display boards, and signs. In particular, considering that it is difficult to reduce the thickness of a backlight for a liquid crystal display device, especially for a PC, where thinness is an issue, because the conventional method consists of a fluorescent lamp or a light guide plate, the backlight using the light emitting element according to the present embodiment is thin. , characterized by light weight.

<Example>

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited to these.

[Synthesis example of cores 1 to 30]

7-(3-chlorophenyl)-9,9-dimethyl-9H-fluorene-2-carbonitrile (100g, 0.30mol), 4,4,4',4',5,5,5',5'-octamethyl- 2,2'-bi(1,3,2-dioxaborolane) (92.74g, 0.436mol) and Pd(dppf)Cl ₂ (6.65g, 0.2mmol), KOAc (59.50g, 1.21mol), X-Phos ( 14.45g, 3mmol) was added to 1,4-Dioxane (2000ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, the target compound Core1 (90.7g, yield 71%) was obtained using column chromatography.

H-NMR: δ 1.20(s, 12H), 1.69(s, 6H), 7.51(s, 1H), 7.54(d, 1H), 7.63(d, 1H), 7.67(s, 1H), 7.78(d , 1H), 7.80(s, 1H), 7.85(d, 1H), 7.89(d, 1H), 8.08(d, 1H), 8.09(d, 1H)

Cores 2 to 30 described below are 2-(5-chloro-[1, 1':3',1''-terphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 7-(4'-chloro-[1,1'- biphenyl]-3-yl)-9,9-dimethyl-9H-fluorene-2-carbonitrile, 5-(3'-chloro-[1,1'-biphenyl]-3-yl)-9,9-dimethyl- 9H-fluorene-2-carbonitrile, 5-(3'-chloro-[1,1'-biphenyl]-2-yl)-9,9-dimethyl-9H-fluorene-2-carbonitrile, 5-(2'- chloro-[1,1'-biphenyl]-2-yl)-9,9-dimethyl-9H-fluorene-2-carbonitrile, 9-(3-chloro-5-(naphthalen-1-yl)phenyl)phenanthrene, 3''-chloro-5''-(phenanthren-9-yl)-[1,1':3',1''-terphenyl]-4-carbonitrile, (3''-chloro-5''-( phenanthren-9-yl)-[1,1':3',1''-terphenyl]-4-yl)dimethylphosphine oxide, 3''-chloro-5''-(pyren-1-yl)-[1 ,1':3',1''-terphenyl]-4-carbonitrile, (3''-chloro-5''-(pyren-1-yl)-[1,1':3',1''- terphenyl]-4-yl)dimethylphosphine oxide, 9-(3-chloro-5-(naphthalen-2-yl)phenyl)phenanthrene, 3'-chloro-5'-(pyren-1-yl)-[1,1 '-biphenyl]-3-carbonitrile, (3'-chloro-5'-(pyren-1-yl)-[1,1'-biphenyl]-3-yl)dimethylphosphine oxide, (3'-chloro-5' -(phenanthren-9-yl)-[1,1'-biphenyl]-3-yl)dimethylphosphine oxide, 2-(3-chloro-5-(phenanthren-9-yl)phenyl)pyrene, 2-(5- chloro-[1,1':3',1''-terphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 9-(4-chlorophenyl)-10 -phenylanthracene, 9-([1,1'-biphenyl]-4-yl)-10-(4-chlorophenyl)anthracene, 4'-(4-(4-chlorophenyl)naphthalen-1-yl)-[1, 1'-biphenyl]-4-carbonitrile, 4'-(10-(4-chlorophenyl)anthracen-9-yl)-[1,1'-biphenyl]-4-carbonitrile, 4-(4-(3'- chloro-[1,1'-biphenyl]-3-yl)naphthalen-1-yl)benzonitrile, 4-(10-(3'-chloro-[1,1'-biphenyl]-3-yl)anthracen-9 -yl)benzonitrile, 2-(3-chloro-5-(pyren-1-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-(3-chloro-5 -(naphthalen-1-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-(3-chloro-5-(pyren-2-yl)phenyl)-4, 4,5,5-tetramethyl-1,3,2-dioxaborolane, 2-(3-chloro-5-(phenanthren-9-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2 -dioxaborolane, 2-(3-chloro-5-(naphthalen-2-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 9-(3-chloro-5-( It was prepared in the same manner as the synthesis example of Core 1, except that dibenzo[b,d]furan-4-yl)phenyl)-9H-carbazole was used, respectively.

[Synthesis example of cores 31 to 36]

5-chloro-2,3-diphenylpyrazine (100g, 0.374mol), Core18 (205.2g, 0.539mol) and Pd(pph ₃ ) ₄ (12.99g, 0.3mmol), K ₂ CO ₃ (103.6g, 1.49mol) was added to THF (2000ml) and H2O (500ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, the target compound Core 31 (149.1g, yield 71%) was obtained using column chromatography.

H-NMR: δ 1.20(s, 12H), 7.32(m, 5H), 7.35(d, 1H), 7.39(t, 1H), 7.52(d, 1H), 7.59(t, 2H), 7.77(t , 1H), 7.87(s, 1H), 8.03(d, 2H), 8.09(d, 1H), 8.20(d, 1H), 8.33(s, 1H), 8.50(d, 1H), 8.57(s, 1H), 8.79(m, 1H), 8.95(d, 1H)

Cores 32 to 36 below were performed in the same manner as the synthesis example of Core 31, except that Core 25, Core 26, Core27, Core28, Core29, etc. were used instead of Core 18 in the synthesis example of Core 31. Manufactured.

[Synthesis example of cores 37 to 99]

2-(5-chloro-5'-phenyl-[1,1':3',1''-terphenyl]-3-yl)naphthalene (100g, 0.21mol), 4,4,4',4', 5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) (65.50g, 0.308mol) and Pd(dppf)Cl ₂ (4.70g, 0.19mmol), KOAc (42.02g, 0.85mol) and X-Phos (10.20g, 2mmol) were added to 1,4-Dioxane (2000ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, the target compound Core 37 (84.9 g, yield 71%) was obtained using column chromatography.

H-NMR: δ 1.20(s, 12H), 7.38(d, 1H), 7.41(t, 2H), 7.49(t, 4H), 7.55(d, 2H), 7.60(t, 1H), 7.63(t , 1H), 7.75(d, 4H), 7.79(d, 1H), 8.04(s, 3H), 8.06(d, 1H), 8.09(d, 1H)

Cores 38 to 99 described below are substituted for 2-(5-chloro-5'-phenyl-[1,1':3',1''-terphenyl]-3-yl) used in the synthesis example of core 37. , 2-(5-chloro-4'-phenyl-[1,1':3',1''-terphenyl]-3-yl)naphthalene, 9-(5-chloro-5'-phenyl-[1, 1':3',1''-terphenyl]-3-yl)phenanthrene, 9-(5-chloro-4'-phenyl-[1,1':3',1''-terphenyl]-3-yl )phenanthrene, 2-(5-chloro-5'-phenyl-[1,1':3',1''-terphenyl]-3-yl) naphthalene, 2-(5-chloro-4'-phenyl-[ 1,1':3',1''-terphenyl]-3-yl)naphthalene, 2-(5-chloro-4'-phenyl-[1,1':3',1''-terphenyl]-2 -yl)naphthalene, 2-(5-chloro-4'-phenyl-[1,1':2',1''-terphenyl]-2-yl)naphthalene, 2-(4-chloro-4'-phenyl -[1,1':3',1''-terphenyl]-2-yl)naphthalene, 2-(5-chloro-4'-phenyl-[1,1':2',1''-terphenyl] -2-yl)naphthalene, 9-(5-chloro-[1,1':3',1''-terphenyl]-3-yl)-10-phenylanthracene, 9-(5-chloro-5'-phenyl -[1,1':3',1''-terphenyl]-3-yl)-10-phenylanthracene, 1-(5-chloro-[1,1':3',1''-terphenyl]-3 -yl)pyrene, 1-(5-chloro-5'-phenyl-[1,1':3',1''-terphenyl]-3-yl)pyrene, 1-(5-chloro-5'-phenyl -[1,1':3',1''-terphenyl]-3-yl)triphenylene, 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-9,9-dimethyl -9H-fluorene, 4-(4'-chloro-[1,1'-biphenyl]-3-yl)-9,9-dimethyl-9H-fluorene, 4-(3'-chloro-[1,1' -biphenyl]-3-yl)-9,9-dimethyl-9H-fluorene, 2-(3''-chloro-[1,1':3',1''-terphenyl]-3-yl)-9 ,9-dimethyl-9H-fluorene, 2'-(3'-chloro-[1,1'-biphenyl]-3-yl)spiro[cyclohexane-1,9'-fluorene], 4'-(4'- chloro-[1,1'-biphenyl]-3-yl)spiro[cyclohexane-1,9'-fluorene], 4'-(3'-chloro-[1,1'-biphenyl]-3-yl)spiro [cyclohexane-1,9'-fluorene], 2'-(3''-chloro-[1,1':3',1''-terphenyl]-3-yl)spiro[cyclohexane-1,9'- fluorene], 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-9,9'-spirobi[fluorene], 4-(4'-chloro-[1,1'-biphenyl ]-3-yl)-9,9'-spirobi[fluorene], 4-(3'-chloro-[1,1'-biphenyl]-3-yl)-9,9'-spirobi[fluorene], 2 -(3''-chloro-[1,1':3',1''-terphenyl]-3-yl)-9,9'-spirobi[fluorene], 2-(3'-chloro-[1, 1'-biphenyl]-3-yl) spiro[fluorene-9,9'-xanthene], 4-(4'-chloro-[1,1'-biphenyl]-3-yl) spiro[fluorene-9,9 '-xanthene], 4-(3'-chloro-[1,1'-biphenyl]-3-yl) spiro[fluorene-9,9'-xanthene], 2-(3''-chloro-[1, 1':3',1''-terphenyl]-3-yl) spiro[fluorene-9,9'-xanthene], 2'-(3'-chloro-[1,1'-biphenyl]-3-yl ) spiro[fluorene-9,9'-xanthene], 2'-(4'-chloro-[1,1'-biphenyl]-3-yl) spiro[fluorene-9,9'-xanthene], 2'- (3'-chloro-[1,1'-biphenyl]-2-yl)spiro[fluorene-9,9'-xanthene], 2'-(3-chlorophenyl)spiro[fluorene-9,9'-xanthene] , 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-9,9-diphenyl-9H-fluorene, 4-(4'-chloro-[1,1'-biphenyl]- 3-yl)-9,9-diphenyl-9H-fluorene, 4-(3'-chloro-[1,1'-biphenyl]-3-yl)-9,9-diphenyl-9H-fluorene, 2-( 3''-chloro-[1,1':3',1''-terphenyl]-3-yl)-9,9-diphenyl-9H-fluorene, 1-(4'-chloro-[1,1' -biphenyl]-3-yl)-9,9-dimethyl-6,7-diphenyl-9H-fluorene, 1-(3'-chloro-[1,1'-biphenyl]-3-yl)-9,9 -dimethyl-6,7-diphenyl-9H-fluorene, 2-(3-chlorophenyl)-9,9-dimethyl-1,3-diphenyl-9H-fluorene, 2-(3'-chloro-[1,1' -biphenyl]-3-yl)-9,9-dimethyl-1,3-diphenyl-9H-fluorene, 2-(4'-chloro-[1,1'-biphenyl]-3-yl)-9,9 -dimethyl-1,3-diphenyl-9H-fluorene, 1-(4'-chloro-[1,1'-biphenyl]-3-yl)-9,9-dimethyl-2,3-diphenyl-9H-fluorene , 1-(3'-chloro-[1,1'-biphenyl]-3-yl)-9,9-dimethyl-2,3-diphenyl-9H-fluorene, 3-(3-chlorophenyl)-2,4 -diphenyldibenzo[b,d]furan, 3-(3'-chloro-[1,1'-biphenyl]-3-yl)-2,4-diphenyldibenzo[b,d]furan, 4-(3-chlorophenyl) -2,3-diphenyldibenzo[b,d]furan, 4-(3'-chloro-[1,1'-biphenyl]-3-yl)-2,3-diphenyldibenzo[b,d]furan, 6-( 3-chlorophenyl)-2,3-diphenyldibenzo[b,d]furan, 6-(3'-chloro-[1,1'-biphenyl]-3-yl)-2,3-diphenyldibenzo[b,d]furan , 5'-(3-chlorophenyl)-3'-phenyl-1,1':2',1''-terphenyl, 3-chloro-4',6'-diphenyl-1,1':2',1 ''-terphenyl, 3'''-chloro-3',5'-diphenyl-1,1':2',1'':3'',1'''-quaterphenyl, 4-chloro-3', 4',5'-triphenyl-1,1':2',1''-terphenyl, 4-chloro-3',5',6'-triphenyl-1,1':2',1''-terphenyl , 3-chloro-3',4',5'-triphenyl-1,1':2',1''-terphenyl, 3'''-chloro-4',5',6'-triphenyl-1, 1':2',1'':3'',1'''-quaterphenyl, 2-(3'-chloro-[1,1'-biphenyl]-4-yl)-3,4,5-triphenylthiophene , 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-3,4,5-triphenylthiophene, 2-(3'-chloro-[1,1'-biphenyl]-4- Except for using yl)-3,4,5-triphenylfuran, 2-(3'-chloro-[1,1'-biphenyl]-3-yl)-3,4,5-triphenylfuran, etc., respectively. It was manufactured in the same manner as the synthesis example of Core 37.

[Synthesis example of cores 100 to 108]

5-(3-chlorophenyl)-2,3-diphenylpyrazine (100g, 0.29mol), 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1 ,3,2-dioxaborolane) (89.22g, 0.420mol) and Pd(dppf)Cl ₂ (6.40g, 0.26mmol), KOAc (57.25g, 1.166mol), X-Phos (13.9g, 2mmol) in 1, It was added to 4-Dioxane (2000ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, the target compound Core 100 (89.9g, yield 71%) was obtained using column chromatography.

H-NMR: δ 1.20(s, 12H), 7.32(m, 4H), 7.35(d, 1H), 7.58(t, 1H), 7.59(t, 1H), 8.03(d, 1H), 8.23(s , 1H), 8.40(d, 1H), 8.79(d, 1H), 8.98(d, 2H)

Cores 101 to 108 described below contain 5-(4-chlorophenyl)-2,3-diphenylpyrazine, 5-(3) instead of 5-(3-chlorophenyl)-2,3-diphenylpyrazine used in the synthesis example of Core 100. '-methyl-[1,1'-biphenyl]-4-yl)-2,3-diphenylpyrazine, 5-(3'-chloro-[1,1'-biphenyl]-3-yl)-2,3- diphenylpyrazine, 5-(4'-chloro-[1,1'-biphenyl]-3-yl)-2,3-diphenylpyrazine, 5-(4''-chloro-[1,1':2',1' '-terphenyl]-4-yl)-2,3-diphenylpyrazine, 5-(4-(1-(4-chlorophenyl)naphthalen-2-yl)phenyl)-2,3-diphenylpyrazine, 2-(4-( 6-(4-chlorophenyl)dibenzo[b,d]furan-4-yl)phenyl)-4,6-diphenyl-1,3,5-triazine, 2-(4-(6-chlorodibenzo[b,d] It was prepared in the same manner as in the synthesis example of Core 100, except that furan-4-yl)phenyl)-4,6-diphenyl-1,3,5-triazine, etc. was used.

[Examples of synthesis of compounds of the present invention]

[Synthesis Example 1] Synthesis of Compound L-100

Core31 (10g, 17mmol), 5-chloro-2,3-diphenylpyrazine (5.71g, 25mmol), Pd(pph ₃ ) ₄ (0.61g, 0.016mmol), K ₂ CO ₃ (4.93g, 71mmol) were mixed with THF ( 200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound L-100 (8.0 g, yield 68%) was obtained using column chromatography. [LCMS] : 664

Instead of 5-chloro-2,3-diphenylpyrazine used in Synthesis Example 1, 4-chloro-2,6-diphenylpyrimidine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6- phenyl-1,3,5-triazine or 2-chloro-4,6-diphenyl-1,3,5-triazine, 4-([1,1'-biphenyl]-4-yl)-6-chloro-2 -phenylpyrimidine or 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine or 4-([1,1'-biphenyl]-3- yl)-6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-2-yl)-4-chloro-6-phenyl-1,3,5-triazine or 4-([1, Use 1'-biphenyl]-2-yl)-6-chloro-2-phenylpyrimidine or 4-chloro-2-phenylquinazoline or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d]pyrimidine Compounds M-6, N-6, O-6, P-6, Q-6, R-6, S-6, T-6, and U-6 were prepared in the same manner.

In addition, Core 32 to 36 is used instead of Core 31, and 5-chloro-2,3-diphenylpyrazine, 4-chloro-2,6-diphenylpyrimidine or 2-([1,1'- biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-4,6-diphenyl-1,3,5-triazine, 4-([1,1' -biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine or 4-([1,1'-biphenyl]-3-yl)-6-chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-2-yl)-4-chloro-6-phenyl- 1,3,5-triazine or 4-([1,1'-biphenyl]-2-yl)-6-chloro-2-phenylpyrimidine or 4-chloro-2-phenylquinazoline or 4-chloro-2-phenylbenzo[4 ,5]In the same manner as the synthesis example of L-100 using thieno[3,2-d]pyrimidine, compounds L-105, L-106, L-125, L-31, M-11, M-12 , M-31, N-11, N-12, O-11, O-12, O-30, P-11, P-12, P-30, Q-11, Q-12, Q-30, R -11, R-12, R-30, S-11, S-12, S-30, T-11, T-12, T-30, U-11, U-12, U-30, V-11 , V-12, and V-30 were manufactured.

[Synthesis Example 2] Synthesis of Compound W-1

Core 30 (10g, 18mmol), 5-chloro-2,3-diphenylpyrazine (5.97g, 26mmol), Pd(pph ₃ ) ₄ (0.64g, 0.016mmol), K ₂ CO ₃ (5.16g, 74mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound W-1 (8.1 g, yield 68%) was obtained using column chromatography. [LCMS] : 639

Additionally, instead of 5-chloro-2,3-diphenylpyrazine, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1'-biphenyl] Compounds W-33 and W-49 were prepared in the same manner as above using -2-yl)-5-chloropyrazine.

[Synthesis Example 3] Synthesis of compound par-2

Core 1 (10g, 23mmol), 5-chloro-2,3-diphenylpyrazine (7.59g, 34mmol), Pd(pph ₃ ) ₄ (0.82g, 0.021mmol), K ₂ CO ₃ (6.5g, 94mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound par-2 (8.4 g, yield 68%) was obtained using column chromatography. [LCMS] : 525

Also, instead of the 5-chloro-2,3-diphenylpyrazine, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1'-biphenyl] Compounds Par-54 and Par-80 were obtained in the same manner using -2-yl)-5-chloropyrazine.

Also, use Core 3 to Core 7 instead of Core 1 and use 5-chloro-2,3-diphenylpyrazine or 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3 -di([1,1'-biphenyl]-2-yl)-5-chloropyrazine was used in the same manner as above to produce compounds Par-5, Par-8, Par-20, Par-21, and Par-24. We got green onions - 57, green onions - 60, green onions - 72, green onions - 73, green onions - 76, green onions - 83, green onions - 86, green onions - 98, green onions - 99, green onions - 102.

[Synthesis Example 4] Synthesis of Compound E-2

Core 8 (10g, 19mmol), 5-chloro-2,3-diphenylpyrazine (6.31g, 28mmol), Pd(pph ₃ ) ₄ (0.68g, 0.017mmol), K ₂ CO ₃ (5.45g, 78mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound E-2 (8.2 g, yield 68%) was obtained using column chromatography. [LCMS] : 610

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds G-2 and H-2 were prepared in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

Also, use Core 13 or Core 17 instead of Core 8 and use 5-chloro-2,3-diphenylpyrazine or 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3 -di([1,1'-biphenyl]-2-yl)-5-chloropyrazine was used in the same manner as above to produce compounds E-5, G-5, H-5, J-32, and J-144, Got J-167.

[Synthesis Example 5] Synthesis of compound K-58

Core 9 (10g, 17mmol), 5-chloro-2,3-diphenylpyrazine (5.74g, 25mmol), Pd(pph ₃ ) ₄ (0.62g, 0.016mmol), K ₂ CO ₃ (4.95g, 71mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound K-58 (8.0 g, yield 68%) was obtained using column chromatography. [LCMS] : 661

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds K-151 and L-88 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

Also, use Core 11 or Core 14 instead of Core 9 and use 5-chloro-2,3-diphenylpyrazine or 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine, respectively. Compounds K-97 and K-74 were obtained in the same manner.

[Synthesis Example 6] Synthesis of compound L-96

Core 2 (10g, 20mmol), 5-chloro-2,3-diphenylpyrazine (6.63g, 29mmol), Pd(pph ₃ ) ₄ (0.71g, 0.018mmol), K ₂ CO ₃ (5.73g, 82mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound L-96 (8.0 g, yield 68%) was obtained using column chromatography.

[LCMS] : 689

[Synthesis Example 7] Synthesis of compound K-60

Core10 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.25g, 23mmol), Pd(pph ₃ ) ₄ (0.56g, 0.014mmol), K ₂ CO ₃ (4.54g, 65mmol) were mixed with THF ( 200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound K-60 (7.9 g, yield 68%) was obtained using column chromatography.

[LCMS] : 712

In addition, compound L-23 was obtained in the same manner using 2,3-di([1,1'-biphenyl]-2-yl)-5-chloropyrazine instead of the 5-chloro-2,3-diphenylpyrazine used above. .

[Synthesis Example 8] Synthesis of compound K-111

Core 12 (10g, 15mmol), 5-chloro-2,3-diphenylpyrazine (5.06g, 22mmol), Pd(pph ₃ ) ₄ (0.54g, 0.014mmol), K ₂ CO ₃ (4.36g, 63mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound K-111 (7.9 g, yield 68%) was obtained using column chromatography.

[LCMS] : 736

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds K-205 and L-90 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 9] Synthesis of compound K-179

Core 15 (10g, 17mmol), 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine (9.03g, 25mmol), Pd(pph ₃ ) ₄ (0.62g, 0.016mmol) ), K ₂ CO ₃ (4.96 g, 71 mmol) was added to a mixed solvent of THF (200 ml) and H ₂ O (50 ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound K-179 (9.9 g, yield 68%) was obtained using column chromatography.

[LCMS] : 812

In addition, compound L-48 was obtained in the same manner using 2,3-di([1,1'-biphenyl]-2-yl)-5-chloropyrazine instead of the 5-chloro-2,3-diphenylpyrazine used above. .

[Synthesis Example 10] Synthesis of compound Y-45

Core 19 (10g, 21mmol), 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine (11.0g, 31mmol), Pd(pph ₃ ) ₄ (0.76g, 0.019mmol) ), K ₂ CO ₃ (6.06 g, 87 mmol) were added to a mixed solvent of THF (200 ml) and H ₂ O (50 ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Y-45 (10.6 g, yield 68%) was obtained using column chromatography.

[LCMS] : 712

In addition, compound Y-61 was obtained in the same manner using 2,3-di([1,1'-biphenyl]-2-yl)-5-chloropyrazine instead of the 5-chloro-2,3-diphenylpyrazine used above. .

[Synthesis Example 11] Synthesis of compound Y-35

Core 20 (10g, 18mmol), 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine (9.4g, 27mmol), Pd(pph ₃ ) ₄ (0.65g, 0.016mmol) ), K ₂ CO ₃ (5.19 g, 75 mmol) were added to a mixed solvent of THF (200 ml) and H ₂ O (50 ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Y-35 (10.6 g, yield 68%) was obtained using column chromatography.

[LCMS] : 788

In addition, compound Y-51 was obtained in the same manner using 2,3-di([1,1'-biphenyl]-2-yl)-5-chloropyrazine instead of the 5-chloro-2,3-diphenylpyrazine used above. .

[Synthesis Example 12] Synthesis of Compound Y-4

Core 21 (10g, 19mmol), 5-chloro-2,3-diphenylpyrazine (6.3g, 28mmol), Pd(pph ₃ ) ₄ (0.68g, 0.017mmol), K ₂ CO ₃ (5.44g, 78mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Y-4 (8.1 g, yield 68%) was obtained using column chromatography.

[LCMS] : 611

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Y-36 and Y-52 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 13] Synthesis of Compound Y-6

Core22 (10g, 17mmol), 5-chloro-2,3-diphenylpyrazine (5.74g, 25mmol), Pd(pph ₃ ) ₄ (0.62g, 0.016mmol), K ₂ CO ₃ (0.62g, 0.016mmol) synthesized in [Preparation Example 22] 4.95 g, 71 mmol) was added to a mixed solvent of THF (200 ml) and H ₂ O (50 ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Y-6 (8.0 g, yield 68%) was obtained using column chromatography.

[LCMS] : 661

Also, instead of 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1'- Y-38 and Y-54 were obtained in the same manner using biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 14] Synthesis of compound Z-11

Core 23 (10g, 19mmol), 5-chloro-2,3-diphenylpyrazine (6.30g, 28mmol), Pd(pph ₃ ) ₄ (0.68g, 0.017mmol), K ₂ CO ₃ (5.44g, 78mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Z-11 (8.1 g, yield 68%) was obtained using column chromatography.

[LCMS] : 611

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Z-43 and Z-59 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 15] Synthesis of compound Z-16

Core 24 (10g, 17mmol), 5-chloro-2,3-diphenylpyrazine (5.74g, 25mmol), Pd(pph ₃ ) ₄ (0.62g, 0.016mmol), K ₂ CO ₃ (4.95g, 71mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Z-16 (8.07 g, yield 68%) was obtained using column chromatography.

[LCMS] : 661

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Z-48 and Z-64 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 16] Synthesis of Compound A-29

Core 37 (10g, 17mmol), 5-chloro-2,3-diphenylpyrazine (5.73g, 25mmol), Pd(pph ₃ ) ₄ (0.62g, 0.016mmol), K ₂ CO ₃ (4.94g, 71mmol) in THF (200ml) and H ₂ O (50ml) in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound A-29 (8.07 g, yield 68%) was obtained using column chromatography.

[LCMS] : 662

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds C-29 and D-29 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 17] Synthesis of Compound A-32

Core 38 (10g, 17mmol), 5-chloro-2,3-diphenylpyrazine (5.73g, 25mmol), Pd(pph ₃ ) ₄ (0.62g, 0.016mmol), K ₂ CO ₃ (4.94g, 71mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound A-32 (8.07 g, yield 68%) was obtained using column chromatography.

[LCMS] : 662

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds C-32 and D-32 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 18] Synthesis of Compound E-10

Core 39 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.25g, 23mmol), Pd(pph ₃ ) ₄ (0.56g, 0.014mmol), K ₂ CO ₃ (4.54g, 65mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound E-10 (7.96 g, yield 68%) was obtained using column chromatography.

[LCMS] : 712

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds G-10 and H-10 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 19] Synthesis of Compound E-25

Core 40 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.25g, 23mmol), Pd(pph ₃ ) ₄ (0.56g, 0.014mmol), K ₂ CO ₃ (4.54g, 65mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound E-25 (7.96 g, yield 68%) was obtained using column chromatography.

[LCMS] : 712

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds G-25 and H-25 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 20] Synthesis of Compound A-47

Core 43 (10g, 17mmol), 5-chloro-2,3-diphenylpyrazine (5.73g, 25mmol), Pd(pph ₃ ) ₄ (0.62g, 0.016mmol), K ₂ CO ₃ (4.94g, 71mmol) in THF (200ml) and H ₂ O (50ml) in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound A-47 (8.06 g, yield 68%) was obtained using column chromatography.

[LCMS] : 662

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds C-43 and D-44 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 21] Synthesis of Compound A-50

Core 44 (10g, 17mmol), 5-chloro-2,3-diphenylpyrazine (5.73g, 25mmol), Pd(pph ₃ ) ₄ (0.62g, 0.016mmol), K ₂ CO ₃ (4.94g, 71mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound A-50 (8.06 g, yield 68%) was obtained using column chromatography.

[LCMS] : 662

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds C-45 and D-49 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 22] Synthesis of Compound I-4

Core 47 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.25g, 23mmol), Pd(pph ₃ ) ₄ (0.56g, 0.014mmol), K ₂ CO ₃ (4.54g, 65mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound I-4 (7.96 g, yield 68%) was obtained using column chromatography.

[LCMS] : 712

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds I-43 and I-94 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 23] Synthesis of Compound I-10

Core 48 (10g, 14mmol), 5-chloro-2,3-diphenylpyrazine (4.67g, 21mmol), Pd(pph ₃ ) ₄ (0.50g, 0.013mmol), K ₂ CO ₃ (4.03g, 58mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound I-10 (7.83 g, yield 68%) was obtained using column chromatography.

[LCMS] : 788

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds I-40 and I-100 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 24] Synthesis of Compound J-4

Core 49 (10g, 17mmol), 5-chloro-2,3-diphenylpyrazine (5.75g, 25mmol), Pd(pph ₃ ) ₄ (0.62g, 0.016mmol), K ₂ CO ₃ (4.96g, 71mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound J-4 (8.07 g, yield 68%) was obtained using column chromatography.

[LCMS] : 660

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds J-95 and J-116 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 25] Synthesis of compound J-25

Core 50 (10g, 15mmol), 5-chloro-2,3-diphenylpyrazine (5.05g, 22mmol), Pd(pph ₃ ) ₄ (0.54g, 0.014mmol), K ₂ CO ₃ (4.36g, 63mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound J-25 (7.92 g, yield 68%) was obtained using column chromatography.

[LCMS] : 736

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds J-137 and J-160 were obtained in the same manner using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 26] Synthesis of Compound X-44

4,4,5,5-tetramethyl-2-(5'-phenyl-[1,1':3',1''-terphenyl]-3-yl)-1,3,2-dioxaborolane (10g, 23mmol ), 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine (11.62g, 33mmol), Pd(pph ₃ ) ₄ (0.80g, 0.020mmol), K ₂ CO ₃ (6.39g, 92mmol) was added to a mixed solvent of THF (200ml) and H ₂ O (50ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound X-44 (10.83 g, yield 68%) was obtained using column chromatography.

[LCMS] : 688

In addition, instead of 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine used above, 2,3-di([1,1'-biphenyl]-4-yl)-5 Compounds X-29 and

[Synthesis Example 27] Synthesis of Compound X-36

2-(3-(dibenzo[b,d]furan-2-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (10g, 27mmol), 2,3-di( [1,1'-biphenyl]-3-yl)-5-chloropyrazine (13.57g, 38mmol), Pd(pph ₃ ) ₄ (0.93g, 0.024mmol), K ₂ CO ₃ (7.46g, 108mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound X-36 (11.51 g, yield 68%) was obtained using column chromatography.

[LCMS] : 626

In addition, instead of 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine used above, 2,3-di([1,1'-biphenyl]-4-yl)-5 Compounds X-27 and

[Synthesis Example 28] Synthesis of Compound A-8

Core 52 (10g, 21mmol), 5-chloro-2,3-diphenylpyrazine (6.77g, 30mmol), Pd(pph ₃ ) ₄ (0.73g, 0.019mmol), K ₂ CO ₃ (5.85g, 84mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound A-8 (8.30 g, yield 68%) was obtained using column chromatography.

[LCMS]: 576

In addition, compounds A-17, A-20, A-25, Na-8, Na-17, Na-20, and Na-25 were prepared in the same manner as above using Core 53 to Core 7 instead of Core 52. , C-8, C-17, C-20, C-25, D-8, D-17, D-20, D-25, D-107, D-109, D-111, D-117, D I got -8, Ma-17, Ma-20, Ma-25.

[Synthesis Example 29] Synthesis of compound bar-54

2-(3-(dibenzo[b,d]furan-3-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (10g, 27mmol), 2,3-di( [1,1'-biphenyl]-3-yl)-5-chloropyrazine (13.57g, 38mmol), Pd(pph ₃ ) ₄ (0.93g, 0.024mmol), K ₂ CO ₃ (7.46g, 108mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound bar-54 (11.51 g, yield 68%) was obtained using column chromatography.

[LCMS] : 626

Additionally, instead of 2-(3-(dibenzo[b,d]furan-3-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane used above, 2-(3' -(dibenzo[b,d]furan-3-yl)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane or 2-( 3-(dibenzo[b,d]furan-1-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane or 2-(3'-(dibenzo[b,d]furan Compound Ba-60 was prepared in the same manner as above using -1-yl)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. , Bar-66, Bar-77 were obtained.

[Synthesis Example 30] Synthesis of compound bar-80

2-(3-(dibenzo[b,d]furan-3-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (10g, 27mmol), 2,3-di( [1,1'-biphenyl]-2-yl)-5-chloropyrazine (13.57g, 38mmol), Pd(pph ₃ ) ₄ (0.93g, 0.024mmol), K ₂ CO ₃ (7.46g, 108mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound bar-80 (11.51 g, yield 68%) was obtained using column chromatography.

[LCMS] : 626

Additionally, instead of 2-(3-(dibenzo[b,d]furan-3-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane used above, 2-(3'- (dibenzo[b,d]furan-3-yl)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane or 2-(3 -(dibenzo[b,d]furan-1-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane or 2-(3'-(dibenzo[b,d]furan- Compound Ba-86 was prepared in the same manner as above using 1-yl)-[1,1'-biphenyl]-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, Got bar-92 and bar-98.

[Synthesis Example 31] Synthesis of Compound A-1

Core89 (10g, 19mmol), 5-chloro-2,3-diphenylpyrazine (6.29g, 28mmol), Pd(pph ₃ ) ₄ (0.68g, 0.017mmol), K ₂ CO ₃ (5.43g, 78mmol) were mixed with THF ( 200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound A-1 (8.19 g, yield 68%) was obtained using column chromatography.

[LCMS] : 612

In addition, compounds A-4, A-13, A-2, and A-9 were obtained in the same manner as above using Core90, Core91, Core94, and Core95 instead of Core 89.

[Synthesis Example 32] Synthesis of compound 4-30

Core92 (10g, 17mmol), 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine (8.59g, 24mmol), Pd(pph ₃ ) ₄ (0.59g, 0.015mmol) , K ₂ CO ₃ (4.72 g, 68 mmol) was added to a mixed solvent of THF (200 ml) and H ₂ O (50 ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Sa-30 (9.78 g, yield 68%) was obtained using column chromatography.

[LCMS] : 841

In addition, instead of Core 92 used above, Core89, Core90, Core91, Core93, Core94, and Core95 were used to produce compounds Sa-33, A-31, A-34, A-43, A-32, and A in the same manner as above. I got -39.

[Synthesis Example 33] Synthesis of compound 4-42

Core 92 (10g, 17mmol), 2,3-di([1,1'-biphenyl]-2-yl)-5-chloropyrazine (8.59g, 24mmol), Pd(pph ₃ ) ₄ (0.59g, 0.015mmol) ), K ₂ CO ₃ (4.72 g, 68 mmol) was added to a mixed solvent of THF (200 ml) and H ₂ O (50 ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Sa-42 (9.78 g, yield 68%) was obtained using column chromatography.

[LCMS] : 841

In addition, compounds Sa-42, Sa-45, A-46, A-49, A-58, A-47, and A-54 were prepared in the same manner as above using Core 89 to Core 95 instead of Core92, respectively. got it

[Synthesis Example 34] Synthesis of compound Ka-5

Core 81 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.12g, 23mmol), Pd(pph ₃ ) ₄ (0.55g, 0.014mmol), K ₂ CO ₃ (4.42g, 64mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Ka-5 (7.93 g, yield 68%) was obtained using column chromatography.

[LCMS] : 728

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Ka-29 and Ka-41 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 35] Synthesis of compound Ka-8

Core 82 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.12g, 23mmol), Pd(pph ₃ ) ₄ (0.55g, 0.014mmol), K ₂ CO ₃ (4.42g, 64mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Ka-8 (7.93 g, yield 68%) was obtained using column chromatography.

[LCMS] : 728

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Ka-32 and Ka-44 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 36] Synthesis of compound cha-2

Core 85 (10g, 19mmol), 5-chloro-2,3-diphenylpyrazine (6.12g, 27mmol), Pd(pph ₃ ) ₄ (0.66g, 0.017mmol), K ₂ CO ₃ (5.29g, 76mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Cha-2 (8.15 g, yield 68%) was obtained using column chromatography.

[LCMS] : 626

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Cha-26 and Cha-38 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 37] Synthesis of compound cha-8

Core 86 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.34g, 24mmol), Pd(pph ₃ ) ₄ (0.57g, 0.015mmol), K ₂ CO ₃ (4.61g, 66mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Cha-8 (7.98 g, yield 68%) was obtained using column chromatography.

[LCMS] : 702

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Cha-32 and Cha-44 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 38] Synthesis of compound Cha-98

Core 83 (10g, 19mmol), 5-chloro-2,3-diphenylpyrazine (6.12g, 27mmol), Pd(pph ₃ ) ₄ (0.66g, 0.017mmol), K ₂ CO ₃ (5.29g, 76mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Cha-98 (8.15 g, yield 68%) was obtained using column chromatography.

[LCMS] : 626

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Cha-122 and Cha-134 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 39] Synthesis of compound Cha-104

Core 84 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.34g, 24mmol), Pd(pph ₃ ) ₄ (0.57g, 0.015mmol), K ₂ CO ₃ (4.61g, 66mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Cha-104 (7.98 g, yield 68%) was obtained using column chromatography.

[LCMS] : 702

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Cha-128 and Cha-140 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 40] Synthesis of compound Ta-6

Core 97 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.42g, 24mmol), Pd(pph ₃ ) ₄ (0.58g, 0.015mmol), K ₂ CO ₃ (4.68g, 67mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Ta-6 (8.00 g, yield 68%) was obtained using column chromatography.

[LCMS] : 694

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Ta-30 and Ta-42 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 41] Synthesis of compound Ta-5

Core 96 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.42g, 24mmol), Pd(pph ₃ ) ₄ (0.58g, 0.015mmol), K ₂ CO ₃ (4.68g, 67mmol) in THF (200ml) and H ₂ O (50ml) in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Ta-5 (8.00 g, yield 68%) was obtained using column chromatography.

[LCMS] : 694

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Ta-29 and Ta-41 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 42] Synthesis of compound Ta-53

Core 98 (10g, 17mmol), 5-chloro-2,3-diphenylpyrazine (5.57g, 25mmol), Pd(pph ₃ ) ₄ (0.60g, 0.015mmol), K ₂ CO ₃ (4.81g, 69mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Ta-53 (8.03 g, yield 68%) was obtained using column chromatography.

[LCMS] : 678

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Ta-77 and Ta-89 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 43] Synthesis of compound Ta-54

Core 99 (10g, 17mmol), 5-chloro-2,3-diphenylpyrazine (5.57g, 25mmol), Pd(pph ₃ ) ₄ (0.60g, 0.015mmol), K ₂ CO ₃ (4.81g, 69mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Ta-54 (8.03 g, yield 68%) was obtained using column chromatography.

[LCMS] : 678

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Ta-78 and Ta-90 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 44] Synthesis of compound Ka-98

Core 78 (10g, 18mmol), 5-chloro-2,3-diphenylpyrazine (5.83g, 26mmol), Pd(pph ₃ ) ₄ (0.63g, 0.016mmol), K ₂ CO ₃ (5.03g, 72mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Ka-98 (8.09 g, yield 68%) was obtained using column chromatography.

[LCMS] : 652

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Ka-122 and Ka-134 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 45] Synthesis of compound Ka-101

Core 80 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.12g, 23mmol), Pd(pph ₃ ) ₄ (0.55g, 0.014mmol), K ₂ CO ₃ (4.42g, 64mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Ka-101 (7.93 g, yield 68%) was obtained using column chromatography.

[LCMS] : 728

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Ka-125 and Ka-137 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 46] Synthesis of compound Ka-104

Core 79 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.12g, 23mmol), Pd(pph ₃ ) ₄ (0.55g, 0.014mmol), K ₂ CO ₃ (4.42g, 64mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Ka-104 (7.93 g, yield 68%) was obtained using column chromatography.

[LCMS] : 728

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Ka-128 and Ka-140 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 47] Synthesis of compound Ka-53

Core76 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.12g, 23mmol), Pd(pph ₃ ) ₄ (0.55g, 0.014mmol), K ₂ CO ₃ (4.42g, 64mmol) were mixed with THF ( 200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Ka-53 (7.93 g, yield 68%) was obtained using column chromatography.

[LCMS] : 728

Also, instead of 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1'- Compounds Ka-77 and Ka-89 were obtained in the same manner as above using [biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 48] Synthesis of compound Ka-56

Core 77 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.12g, 23mmol), Pd(pph ₃ ) ₄ (0.55g, 0.014mmol), K ₂ CO ₃ (4.42g, 64mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Ka-56 (7.93 g, yield 68%) was obtained using column chromatography.

[LCMS] : 728

Additionally, instead of the 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1' Compounds Ka-80 and Ka-92 were obtained in the same manner as above using -biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 49] Synthesis of compound Cha-50

Core87 (10g, 19mmol), 5-chloro-2,3-diphenylpyrazine (6.12g, 27mmol), Pd(pph ₃ ) ₄ (0.66g, 0.017mmol), K ₂ CO ₃ (5.29g, 76mmol) were mixed with THF ( 200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Cha-50 (8.15 g, yield 68%) was obtained using column chromatography.

[LCMS] : 626

Also, instead of 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1'- Compounds Cha-74 and Cha-86 were obtained in the same manner as above using [biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 50] Synthesis of compound Cha-56

Core 88 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.34g, 24mmol), Pd(pph ₃ ) ₄ (0.57g, 0.015mmol), K ₂ CO ₃ (4.61g, 66mmol) in THF (200ml) and H ₂ O (50ml) in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound Cha-56 (7.98 g, yield 68%) was obtained using column chromatography.

[LCMS] : 702

Also, instead of 5-chloro-2,3-diphenylpyrazine used above, 2,3-di([1,1'-biphenyl]-3-yl)-5-chloropyrazine or 2,3-di([1,1'- Compounds Cha-80 and Cha-92 were obtained in the same manner as above using [biphenyl]-2-yl)-5-chloropyrazine.

[Synthesis Example 51] Synthesis of compound lnv 2

Core 100 (10g, 23mmol), 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (9.49g, 33mmol), Pd(pph ₃ ) ₄ (0.79g, 0.02mmol) and K ₂ CO ₃ (6.36g, 92mmol) were added to a mixed solvent of THF (200ml) and H ₂ O (50ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound lnv 2 (9.63 g, yield 68%) was obtained using column chromatography.

[LCMS] : 615

Additionally, instead of the 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine used above, 2-([1,1'-biphenyl]- Compound lnv 3 was obtained in the same manner as above using 3-yl)-4-chloro-6-phenyl-1,3,5-triazine.

[Synthesis Example 52] Synthesis of compound lnv 19

Core101 (10g, 23mmol), 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine (9.49g, 33mmol), Pd(pph ₃ ) ) ₄ (0.79g, 0.02mmol) and K ₂ CO ₃ (6.36g, 92mmol) were added to a mixed solvent of THF (200ml) and H ₂ O (50ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound lnv 19 (9.63 g, yield 68%) was obtained using column chromatography.

[LCMS] : 615

Also, instead of 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine used above, 2-([1,1'-biphenyl]-4 Compound lnv 18 was obtained in the same manner as above using -yl)-4-chloro-6-phenyl-1,3,5-triazine.

[Synthesis Example 53] Synthesis of compound lnv 145

Core102 (10g, 19mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (6.29g, 28mmol), Pd(pph ₃ ) ₄ (0.67g, 0.017mmol), K ₂ CO ₃ ( 5.4g, 78mmol) was added to a mixed solvent of THF (200ml) and H ₂ O (50ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound lnv 145 (8.2 g, yield 68%) was obtained using column chromatography.

[LCMS] : 615

Also, instead of 2-chloro-4,6-diphenyl-1,3,5-triazine used above, 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3 ,5-triazine or 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine or 4-([1,1'-biphenyl]- Compounds lnv 146, lnv 147, and lnv 152 were obtained in the same manner as above using 3-yl)-6-chloro-2-phenylpyrimidine.

[Synthesis Example 54] Synthesis of compound lnv 154

Core103 (10g, 19mmol), 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (8.08g, 28mmol), Pd(pph ₃ ) ₄ (0.67g, 0.017mmol) and K ₂ CO ₃ (5.4g, 78mmol) were added to a mixed solvent of THF (200ml) and H ₂ O (50ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound lnv 154 (9.2 g, yield 68%) was obtained using column chromatography.

[LCMS] : 691

Also, instead of 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine used above, 2-([1,1'-biphenyl]-3 Compound lnv 155 was obtained in the same manner as above using -yl)-4-chloro-6-phenyl-1,3,5-triazine.

[Synthesis Example 55] Synthesis of compound lnv 193

Core104 (10g, 19mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (6.29g, 28mmol), Pd(pph ₃ ) ₄ (0.67g, 0.017mmol), K ₂ CO ₃ ( 5.4g, 78mmol) was added to a mixed solvent of THF (200ml) and H ₂ O (50ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound lnv 193 (8.2 g, yield 68%) was obtained using column chromatography.

[LCMS] : 615

Also, instead of 2-chloro-4,6-diphenyl-1,3,5-triazine used above, 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3 Compound lnv 195 or lnv 228 was obtained in the same manner as above using ,5-triazine or 4-chloro-2-phenylbenzo[4,5]thieno[3,2-d]pyrimidine.

[Synthesis Example 56] Synthesis of compound lnv 241

Core105 (10g, 17mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.47g, 24mmol), Pd(pph ₃ ) ₄ (0.59g, 0.015mmol), K ₂ CO ₃ ( 4.7g, 68mmol) was added to a mixed solvent of THF (200ml) and H ₂ O (50ml) and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound lnv 241 (8.0 g, yield 68%) was obtained using column chromatography.

[LCMS] : 691

Also, instead of 2-chloro-4,6-diphenyl-1,3,5-triazine used above, 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3 Compound lnv 243 or lnv 273 or I got lnv 274.

[Synthesis Example 57] Synthesis of compound lnv 338

Core106 (10g, 15mmol), 5-chloro-2,3-diphenylpyrazine (5.02g, 22mmol), Pd(pph ₃ ) ₄ (0.54g, 0.014mmol), K ₂ CO ₃ (4.3g, 62mmol) with THF ( 200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound lnv 338 (7.9 g, yield 68%) was obtained using column chromatography.

[LCMS] : 740

Also, instead of 5-chloro-2,3-diphenylpyrazine used above, 4-chloro-2-phenylquinazoline or 4-chloro-2,6-diphenylpyrimidine or 4-([1,1'-biphenyl]-3-yl)-6 -chloro-2-phenylpyrimidine or 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine or 2-chloro-4,6-diphenyl- Compound using the same method as above using 1,3,5-triazine or 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine I got lnv 333 or lnv 301 or lnv 304 or lnv 299 or lnv 297 or lnv 298.

[Synthesis Example 58] Synthesis of compound lnv 400

Core108 (10g, 16mmol), 5-chloro-2,3-diphenylpyrazine (5.32g, 23mmol), Pd(pph ₃ ) ₄ (0.57g, 0.015mmol), K ₂ CO ₃ (4.5g, 66mmol) were mixed with THF ( 200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound lnv 400 (7.9 g, yield 68%) was obtained using column chromatography.

[LCMS]: 705

[Synthesis Example 59] Synthesis of compound lnv 401

Core 107 (10g, 14mmol), 5-chloro-2,3-diphenylpyrazine (4.72g, 21mmol), Pd(pph ₃ ) ₄ (0.51g, 0.013mmol), K ₂ CO ₃ (4.0g, 59mmol) in THF (200ml) and H ₂ O (50ml) were placed in a mixed solvent and heated to reflux for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent in the filtered organic layer, compound lnv 401 (7.9 g, yield 68%) was obtained using column chromatography.

[LCMS] : 780

By appropriately changing the raw material compounds, other compounds of the present invention can be synthesized by a method similar to the above-described synthesis example.

[Examples 1-87] Fabrication of blue organic electroluminescent device

Among the compounds synthesized in the synthesis example, the compounds shown in [Table 1] below were purified to high purity by sublimation according to a commonly known method, and then a blue organic electroluminescent device was manufactured as follows.

First, a glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,500 Å was washed with distilled water ultrasonic waves. After cleaning with distilled water, ultrasonic cleaning with solvents such as isopropyl alcohol, acetone, and methanol, drying, transferring to a UV OZONE cleaner (Power sonic 405, Hwashin Tech), and then cleaning the substrate for 5 minutes using UV. The substrate was transferred to a vacuum evaporator.

On the ITO transparent electrode prepared as above, anode (ITO) / hole injection layer (100Å, compound HTL1 and P1 at a weight ratio of 97:3) / hole transport layer (1350Å, compound HTL1) / electron blocking layer (50Å, compound HTL2) / Light-emitting layer (190Å, weight ratio of compounds BH and BD of 97:3) / Electron transport auxiliary layer (50Å, compound xETL1) / Electron transport layer (300Å, example compounds and ETL1 (comparative example) and N1 to N3 specified in Table 1 Weight ratio of 7:3 to 3:7 with one of the following, (specifically, 50:50 weight ratio with N1) / electron injection layer (10Å, Yb) / cathode (100Å, magnesium and silver weight ratio of 10:1) ) / A capping layer (800Å, compound CPL)-based light emitting device was produced.

The structure of the compound used at this time is as follows.

[Comparative Examples 1 to 4] Fabrication of blue organic electroluminescent device

In Comparative Example 1, a blue organic electroluminescent device was manufactured in the same manner as Example 1, except that Alq3 was deposited to a thickness of 300 Å instead of the compound of the Example as the electron transport layer material.

In Comparative Example 2, ETL1 was deposited at 300 Å as the electron transport layer material instead of the compound of the example.

In Comparative Example 3, a blue organic electroluminescent device was manufactured by depositing only the example compound to a thickness of 300 Å without containing N1 as the electron transport layer material.

In Comparative Example 4, a blue organic electroluminescent device was manufactured in the same manner as Example 1, except that ETL2 was deposited at 300 Å instead of the compound of the example as the electron transport layer material.

The driving voltage, current efficiency, and luminescence peak at a current density of 10 mA/cm ² were measured for the blue organic electroluminescent devices manufactured in Examples 1 to 87 and Comparative Examples 1 to 4, and the lifespan results of the devices are shown in Table 1 below. indicated.

[Table 1]

As shown in Table 1, the blue organic electroluminescent devices of Examples 1 to 87 in which the compound of the present invention was applied as the electron transport layer were compared with the conventional Alq3 compound ETL1 and ETL1 without N1 as the electron transport layer material, respectively. Compared to the blue organic electroluminescent devices of Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4, it was found to exhibit better performance in terms of driving voltage, emission peak, current efficiency, and lifespan.

[Examples 88-164] Fabrication of blue organic electroluminescent device

Among the compounds synthesized in the synthesis example, the compounds shown in [Table 2] below were purified by high purity by sublimation according to a commonly known method, and then a blue organic electroluminescent device was manufactured as follows.

First, a glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,500 Å was washed with distilled water ultrasonic waves. After cleaning with distilled water, ultrasonic cleaning with solvents such as isopropyl alcohol, acetone, and methanol, drying, transferring to a UV OZONE cleaner (Power sonic 405, Hwashin Tech), and then cleaning the substrate for 5 minutes using UV. The substrate was transferred to a vacuum evaporator.

On the ITO transparent electrode prepared as above, anode (ITO) / hole injection layer (100Å, compound HTL1 and P1 at a weight ratio of 97:3) / hole transport layer (1350Å, compound HTL1) / electron blocking layer (50Å, compound HTL2) / Light-emitting layer (190Å, weight ratio of compounds BH and BD of 97:3) / Electron transport auxiliary layer (or hole blocking layer) (50Å, example compounds in Table 2 and comparative example compounds (xETL1) / Electron transport layer (300Å, Table 2) A weight ratio of 7:3 to 3:7 between the example compound and ETL1 (comparative example) specified in 1 and one of N1 to N3 (specifically, a weight ratio of 50:50 with N1) / electron injection layer (10 Å, A light emitting device based on Yb) / cathode (100 Å, magnesium and silver at a weight ratio of 10:1) / capping layer (800 Å, compound CPL) was manufactured.

The structure of the compound used at this time is as follows.

[Comparative Examples 5-7] Fabrication of blue organic electroluminescent device

In Comparative Example 5, a blue organic electroluminescent device was manufactured in the same manner as Example 88, except that Alq3 was deposited to 50 Å as an electron transport auxiliary layer (hole blocking layer) material instead of the compound of the example.

In Comparative Example 6, xETL1 as indicated above was deposited to a thickness of 50 Å instead of the compound of the example as the electron transport auxiliary layer material.

In Comparative Example 7, xETL2 as indicated above was deposited to 50 Å as an electron transport auxiliary layer material instead of the compound of the example.

For the blue organic electroluminescent devices manufactured in Examples 88 to 164 and Comparative Examples 5 to 7, the driving voltage, current efficiency, and luminescence peak at a current density of 10 mA/cm ² were measured, and the lifespan results of the devices are shown in Table 2 below. indicated.

[Table 2]

As shown in Table 2, the blue organic electroluminescent devices of Examples 88 to 164 in which the compound of the present invention was applied as an electron transport auxiliary layer (or hole blocking layer) used conventional Alq3 and compounds xETL1 and xETL2 as electron transport auxiliary layers, respectively. Compared to the blue organic electroluminescent devices of Comparative Examples 5 to 7 used as layer materials, it was found to exhibit better performance in terms of driving voltage, luminous peak, current efficiency, and lifespan.

100 substrate
110 Anode (first electrode)
120 hole injection layer
130 Hole transport layer
140 light emitting layer
150 electron transport layer
160 electron injection layer
170 cathode (second electrode)
230, 240, 260 light emitting layer
250, 270 charge generation unit

Claims (21)

A compound containing a structure represented by the following formula (1);

In Formula 1,
X ₁ and X ₂ are the same or different from each other, and are each independently CR ₁ or N, and at least one of X ₁ and X ₂ is N,
Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents deuterium, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted alkyl group of C ₁ -C ₂₀ , substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group, substituted or an unsubstituted aralkyl group of C ₃ -C ₂₀ , a substituted or unsubstituted aryl group of C ₆ -C ₃₀ , a substituted or unsubstituted heteroaryl group of C ₃ -C ₃₀ , or a substituted or unsubstituted C ₃ - C ₂₀ heteroaralkyl group, substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, substituted or unsubstituted C ₆ -C ₃₀ arylsilyl group and substituted or unsubstituted C ₃ -C ₃₀ heteroaryl It is selected from the group consisting of silyl groups. According to paragraph 1,
A compound represented by the following formula (2);

In Formula 2 above,
X ₁ and X ₂ , Ar ₁ and Ar ₂ are as defined in Formula 1 above,
L ₁ to L ₃ are the same or different from each other, and each independently represents a single bond or a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₆ -C ₃₀ arylene group, or a substituted or unsubstituted C 1 -C 10 alkylene group. selected from the group consisting of a C ₂ -C ₃₀ heteroarylene group, a substituted or unsubstituted C ₃ -C ₂₀ cycloalkylene, and a substituted or unsubstituted C ₂ -C ₂₀ heterocycloalkylene,
Ar ₃ is a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, or a substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group, substituted or unsubstituted C ₃ -C ₂₀ aralkyl group, substituted or unsubstituted C ₆ -C ₃₀ aryl group, Substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, substituted or unsubstituted C ₃ -C ₂₀ heteroaralkyl group, substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, substituted or unsubstituted Selected from the group consisting of a C ₆ -C ₃₀ arylsilyl group and a substituted or unsubstituted C ₃ -C ₃₀ heteroarylsilyl group,
n is an integer from 1 to 5,
When n is 2 or more, a plurality of L ₃ or Ar ₃ may each independently be the same or different from each other. According to paragraph 2,
A compound in which at least one of Ar ₃ of Formula 2 contains an electron-withdrawing group (EWG). According to paragraph 3,
A compound in which at least one of Ar ₃ in Formula 2 is represented by any one of Formulas 3 to 8 below.

In Formulas 3 to 8,
A ₁ to A ₃₂ are the same or different from each other, and are each independently CR ₂ or N, at least one of A ₁ to A ₆ , at least one of A ₇ to A ₁₄ , at least one of A ₁₅ to A ₂₄ , or A ₂₅ to A ₂₉ , at least one is N,
Y ₁ and Y ₂ are the same or different from each other and are each independently a single bond, CR ₃ R ₄ , NR ₅ , O or S, and neither Y ₁ nor Y ₂ can be a single bond;
R ₂ and R ₃ to R ₅ of CR ₂ as A ₁ to A ₃₂ are the same or different from each other, and are each independently hydrogen, deuterium, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted C ₁ -C ₂₀ alkyl group, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted Or an unsubstituted C ₁ -C ₂₀ heteroalkyl group, a substituted or unsubstituted C ₃ -C ₂₀ aralkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, substituted or unsubstituted C ₃ -C ₂₀ heteroaralkyl group, substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, substituted or unsubstituted C ₆ -C ₃₀ arylsilyl group , and substituted or unsubstituted C ₃ -C ₃₀ heteroarylsilyl groups, and adjacent groups may be bonded to each other to form a substituted or unsubstituted ring. According to paragraph 2,
A compound in which at least one of L ₁ to L ₃ and Ar ₃ of Formula 2 is represented by Formula 9 or Formula 10 below.

In Formula 10 and Formula 11,
_{X 3 and _ _ _ _}
o and p are integers from 0 to 3,
r is an integer from 0 to 4,
R ₆ to R ₁₃ are the same or different from each other, and are each independently hydrogen, deuterium, trifluoromethyl group, nitro group, halogen group, hydroxy group, substituted or unsubstituted C ₁ -C ₂₀ alkyl group, substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group , a substituted or unsubstituted C ₃ -C ₂₀ aralkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, a substituted or unsubstituted C ₃ -C ₂₀ heteroaralkyl group, substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, substituted or unsubstituted C ₆ -C ₃₀ arylsilyl group, and substituted or unsubstituted C ₃ -C ₃₀ It is selected from the group consisting of heteroarylsilyl groups, and adjacent groups may be bonded to each other to form a substituted or unsubstituted ring. According to paragraph 2,
Ar ₃ of Formula 2 A compound in which at least one of the compounds is a polyaromatic group (PHA; Polycyclic-Aromatic-hydrocarbon) of C ₇ or more. According to paragraph 2,
A compound in which n of Formula 2 is 2. According to paragraph 2,
A compound in which n of Formula 2 is 4 or 5. A composition for an organic electroluminescent device comprising the compound of any one of claims 1 to 8, and an organometallic compound of an alkali metal or an alkaline earth metal. According to clause 9,
The organometallic compound is a composition for an organic electroluminescent device represented by the following formula (11);

In the above formula 11,
Ar ₆ is hydrogen; heavy hydrogen; halogen group; Nitrile group; nitro group; hydroxyl group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted arylsulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
The curve represents the bonds and 2 or 3 atoms required to form a 5- or 6-membered ring with M, said atoms being substituted or unsubstituted by one or more substituents identical to the definition of Ar ₆ ;
M is an alkali metal or alkaline earth metal. According to clause 10,
A composition for an organic electroluminescent device, wherein M is an alkali metal selected from lithium, sodium, potassium, rubidium, or cesium. According to clause 11,
A composition for an organic electroluminescent device where M is lithium. a first electrode,
a second electrode opposite the first electrode;
Comprising an organic material layer formed between the first electrode and the second electrode,
The organic material layer portion includes one or more organic material layers, and the organic material layer includes the compound of any one of claims 1 to 8. According to clause 13,
The first electrode is an anode,
The second electrode is a cathode,
The organic layer,
i) luminescent layer,
ii) a hole transport region interposed between the first electrode and the light emitting layer and including at least one of a hole injection layer, a hole transport layer, and an electron blocking layer; and
iii) interposed between the light-emitting layer and the second electrode, and comprising an electron transport region including at least one of a hole blocking layer, an electron transport layer, an electron injection layer, and an electron injection/transport layer,
wherein the electron transport region includes the compound,
Organic electroluminescent device. According to clause 14,
An organic electroluminescent device wherein the electron transport layer or the hole blocking layer includes the compound. According to clause 14,
Any one of the electron transport layer, the electron injection layer, or the electron injection/transport layer is made of an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, or an alkaline earth metal. An organic electroluminescent element containing at least one selected from the group consisting of a halide, an oxide of a rare earth metal, a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal. According to clause 13,
An organic electroluminescent device in which any one of the electron transport layer, the electron injection layer, or the electron injection/transport layer includes an organometallic compound represented by the following formula (11);

In the above formula 11,
Ar ₆ is hydrogen; heavy hydrogen; halogen group; Nitrile group; nitro group; hydroxyl group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted aryloxy group; Substituted or unsubstituted alkylthioxy group; Substituted or unsubstituted arylthioxy group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted arylsulfoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
The curve represents the bonds and 2 or 3 atoms required to form a 5- or 6-membered ring with M, said atoms being substituted or unsubstituted by one or more substituents identical to the definition of Ar ₆ ;
M is an alkali metal or alkaline earth metal. According to clause 13,
The organic material layer includes a plurality of light-emitting stacked parts, each of which includes a light-emitting layer, and a charge generation layer formed between the plurality of light-emitting stacked parts,
An organic electroluminescent device wherein the charge generation layer includes the compound. According to clause 18,
The charge generation layer includes an n-type charge generation layer, and the n-type charge generation layer includes the compound. According to clause 19,
The n-type charge generation layer further contains an alkali metal or an alkaline earth metal. A display device comprising the organic electroluminescent device of claim 13, wherein a first electrode of the organic electroluminescent device is electrically connected to a source electrode or a drain electrode of a thin film transistor.