KR102572372B1 - Hetero-cyclic compound and organic light emitting device using same - Google Patents

Abstract

The present application provides a heterocyclic compound capable of significantly improving lifespan, efficiency, electrochemical stability and thermal stability of an organic light emitting device, and an organic light emitting device in which the heterocyclic compound is contained in an organic material layer.

Description

Heterocyclic compound and organic light emitting device using the same {HETERO-CYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE USING SAME}

The present application relates to a heterocyclic compound and an organic light emitting device using the same.

The electroluminescent device is a type of self-luminous display device, and has advantages such as a wide viewing angle, excellent contrast, and fast response speed.

The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes are combined in the organic thin film to form a pair, and then emit light while disappearing. The organic thin film may be composed of a single layer or multiple layers as needed.

The material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound capable of constituting the light emitting layer by itself may be used, or a compound capable of serving as a host or dopant of the host-dopant type light emitting layer may be used. In addition, as a material for the organic thin film, a compound capable of performing functions such as hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection may be used.

In order to improve the performance, lifespan or efficiency of organic light emitting devices, the development of materials for organic thin films is continuously required.

U.S. Patent No. 4,356,429

The present invention is to provide a heterocyclic compound and an organic light emitting device including the same.

An exemplary embodiment of the present application provides a heterocyclic compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

N-Het is a substituted or unsubstituted, monocyclic or polycyclic heterocyclic group containing one or more N,

L ₁ and L ₂ are the same as or different from each other, and are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,

X is O; or S,

R ₁ and R ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; Or a substituted or unsubstituted amine group, wherein at least one of R ₁ and R ₂ is a substituted or unsubstituted amine group,

R _m and R _n are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; Or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms,

a and b are each an integer from 0 to 3, and when a and b are each 2 or more, the substituents in parentheses are the same as or different from each other,

m is 1 or 2, and when m is 2, the substituents in parentheses are the same as or different from each other;

n is each an integer of 1 to 3, and when n is 2 or more, the substituents in parentheses are the same as or different from each other.

In addition, another exemplary embodiment of the present application is an organic light emitting device including an anode, a cathode, and one or more organic material layers provided between the anode and the cathode, wherein at least one layer of the organic material layer is a heterocyclic compound represented by Formula 1 It provides an organic light emitting device comprising a.

The heterocyclic compound according to an exemplary embodiment of the present application may be used as a material for an organic material layer of an organic light emitting device. The heterocyclic compound may be used as a material for a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or a charge generating layer in an organic light emitting device. In particular, the heterocyclic compound represented by Chemical Formula 1 may be used as a material for a light emitting layer of an organic light emitting device. In addition, when the heterocyclic compound represented by Chemical Formula 1 is used in an organic light emitting device, the driving voltage of the device is lowered, the light efficiency is improved, and the lifespan characteristics of the device can be improved due to the thermal stability of the compound.

1 to 3 are diagrams schematically illustrating a stacked structure of an organic light emitting device according to an exemplary embodiment of the present application.

Hereinafter, this application will be described in detail.

An exemplary embodiment of the present application provides a heterocyclic compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

N-Het is a substituted or unsubstituted, monocyclic or polycyclic heterocyclic group containing one or more N,

L ₁ and L ₂ are the same as or different from each other, and are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,

X is O; or S,

R ₁ and R ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; Or a substituted or unsubstituted amine group, wherein at least one of R ₁ and R ₂ is a substituted or unsubstituted amine group,

R _m and R _n are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; Or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms,

a and b are each an integer from 0 to 3, and when a and b are each 2 or more, the substituents in parentheses are the same as or different from each other,

m is 1 or 2, and when m is 2, the substituents in parentheses are the same as or different from each other;

n is each an integer of 1 to 3, and when n is 2 or more, the substituents in parentheses are the same as or different from each other.

Formula 1 has a structure in which dibenzofuran or dibenzothiophene is substituted with three specific substituents including an amine group (hereinafter, also referred to as a trisubstituted structure), so that electrons are more abundant, and thus the formula (1) When the compound is used in the device, the current flow is improved and the driving voltage is lowered. In addition, since Formula 1 has an amine group having hole characteristics as a substituent and thus has excellent hole transport capability, when the compound represented by Formula 1 is used in a device, a driving voltage is reduced.

In the present specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the hydrogen atom is substituted, that is, the position where the substituent can be substituted, When two or more are substituted, two or more substituents may be the same as or different from each other.

In the present specification, "substituted or unsubstituted" is a straight-chain or branched-chain alkyl having 1 to 60 carbon atoms; straight-chain or branched-chain alkenyl having 2 to 60 carbon atoms; straight or branched alkynyl having 2 to 60 carbon atoms; monocyclic or polycyclic cycloalkyl having 3 to 60 carbon atoms; monocyclic or polycyclic heterocycloalkyl having 2 to 60 carbon atoms; monocyclic or polycyclic aryl having 6 to 60 carbon atoms; monocyclic or polycyclic heteroaryl having 2 to 60 carbon atoms; -SiRR'R"; -P(=O)RR'; alkylamines having 1 to 20 carbon atoms; monocyclic or polycyclic arylamines having 6 to 60 carbon atoms; and monocyclic or polycyclic heteroarylamines having 2 to 60 carbon atoms. It means substituted or unsubstituted with one or more substituents selected from the group, or substituted or unsubstituted with substituents in which two or more substituents selected from the above exemplified substituents are connected.

In the present specification, the halogen may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group includes a straight or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically, 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl- 2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , Isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, etc., but is not limited thereto.

In the present specification, the alkenyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The alkenyl group may have 2 to 60 carbon atoms, specifically 2 to 40, and more specifically, 2 to 20. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1 -butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, styrenyl group, etc., but is not limited thereto.

In the present specification, the alkynyl group includes a straight chain or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically, 2 to 20.

In the present specification, the alkoxy group may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, 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 is not limited.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic group having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which a cycloalkyl group is directly connected or condensed with another ring group. Here, the other ring group may be a cycloalkyl group, but may also be another type of ring group, such as a heterocycloalkyl group, an aryl group, a heteroaryl group, and the like. The number of carbon atoms in the cycloalkyl group may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2 ,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, etc., but are not limited thereto.

In the present specification, the heterocycloalkyl group as a hetero atom is O, S, Se,

It includes N or Si, and includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted with other substituents. Here, the polycyclic means a group in which a heterocycloalkyl group is directly connected or condensed with another ring group. Here, the other ring group may be a heterocycloalkyl group, but may also be another type of ring group, such as a cycloalkyl group, an aryl group, a heteroaryl group, and the like. The heterocycloalkyl group may have 2 to 60, specifically 2 to 40, and more specifically 3 to 20 carbon atoms.

In the present specification, the aryl group is a monocyclic or polycyclic group having 6 to 60 carbon atoms.

and may be further substituted by other substituents. Here, the polycyclic means a group in which an aryl group is directly connected or condensed with another cyclic group. Here, the other ring group may be an aryl group, but may also be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, and the like. The aryl group includes a spiro group. The number of carbon atoms of the aryl group may be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of the aryl group include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a chrysenyl group, a phenanthrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a phenalenyl group, and a pyrene group. Nyl group, tetracenyl group, pentacenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, condensed ring groups thereof and the like, but is not limited thereto.

In the present specification, the phosphine oxide group is represented by -P(=O)R101R102, R101 and R102 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; an alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. The phosphine oxide group specifically includes a diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like, but is not limited thereto.

In the present specification, the silyl group includes Si and is a substituent to which the Si atom is directly connected as a radical, represented by -SiR104R105R106, R104 to R106 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; an alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specific examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. It is not limited.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may bond to each other to form a ring.

In the present specification, the spiro group is a group including a spiro structure, and may have 15 to 60 carbon atoms. For example, the spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro bonded to a fluorenyl group. Specifically, the following spiro group may include any one of groups of the following structural formula.

In the present specification, the heteroaryl group is a hetero atom as S, O, Se, N or

contains Si, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which a heteroaryl group is directly connected or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may also be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, an aryl group, and the like. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40, and more specifically 3 to 25 carbon atoms. Specific examples of the heteroaryl group include a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, and a thiazolyl group. group, isothiazolyl group, triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , thiazinyl group, dioxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolilyl group, naphthyridyl group, acridinyl group, phenanthridi Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triazaindene group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , Dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, A phenoxazinyl group, a phenanthridyl group, an imidazopyridinyl group, a thienyl group, an indolo[2,3-a]carbazolyl group, an indolo[2,3-b]carbazolyl group, an indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenantrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthyridinyl group, phenanthrolinyl group, Benzo [c] [1,2,5] thiadiazolyl group, 5,10-dihydrodibenzo [b, e] [1,4] azasilinyl group, pyrazolo [1,5-c] quinazolinyl group , pyrido [1,2-b] indazolyl group, pyrido [1,2-a] imidazo [1,2-e] indolinyl group, 5,11-dihydroindeno [1,2-b ] carbazolyl group and the like, but is not limited thereto.

In the present specification, the amine group is a monoalkylamine group; monoarylamine group; mono

heteroarylamine group; -NH ₂ ; Dialkylamine group; Diaryl amine group; Diheteroarylamine group; an alkyl arylamine group; Alkylheteroarylamine group; And it may be selected from the group consisting of an arylheteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, a dibiphenylamine group, an anthracenylamine group, a 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenylfluorene Examples include a ylamine group, a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group, and the like, but are not limited thereto.

In the present specification, the arylene group means that the aryl group has two bonding sites, that is, a divalent group. Except that each of these is a divalent group, the description of the above-mentioned aryl group is

can be applied In addition, the heteroarylene group means a heteroaryl group having two bonding sites, that is, a divalent group. The above description of the heteroaryl group may be applied except that each is a divalent group.

As used herein, "adjacent" refers to a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located sterically closest to the substituent, or another substituent substituted on the atom on which the substituent is substituted. can For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as “adjacent” to each other.

The heterocyclic compound according to an exemplary embodiment of the present application is characterized in that it is represented by Formula 1 above. More specifically, the heterocyclic compound represented by Chemical Formula 1 may be used as an organic material layer material of an organic light emitting device due to the structural characteristics of the core structure and the substituent.

In an exemplary embodiment of the present application, L ₁ and L ₂ of Formula 1 are the same as or different from each other, and are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or it may be a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, the L ₁ and L ₂ are the same as or different from each other, and are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 40 carbon atoms; Or it may be a substituted or unsubstituted heteroarylene group having 2 to 40 carbon atoms.

In an exemplary embodiment of the present application, the L ₁ and L ₂ are the same as or different from each other, and are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 20 carbon atoms; Or it may be a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms.

In an exemplary embodiment of the present application, L ₁ is a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or it may be a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms.

In another exemplary embodiment, L ₁ is a direct bond.

In another exemplary embodiment, L ₁ is an arylene group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms.

In another exemplary embodiment, L ₁ is a phenylene group or a biphenyl group.

In another exemplary embodiment, L ₁ is a phenylene group.

In an exemplary embodiment of the present application, the L ₂ is a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or it may be a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms.

In another exemplary embodiment, L ₂ is a direct bond.

In another exemplary embodiment, L ₂ is an arylene group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms.

In another exemplary embodiment, L ₂ is a phenylene group or a biphenyl group.

In another exemplary embodiment, L ₂ is a phenylene group.

In an exemplary embodiment of the present application, X in Formula 1 is O; or S.

In another exemplary embodiment, X in Formula 1 is O.

In another exemplary embodiment, X in Formula 1 is S.

In an exemplary embodiment of the present application, R ₁ and R ₂ in Formula 1 are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; or a substituted or unsubstituted amine group, and at least one of R ₁ and R ₂ may be a substituted or unsubstituted amine group.

In an exemplary embodiment of the present application, R ₁ is a substituted or unsubstituted amine group, and R ₂ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R ₁ is a substituted or unsubstituted amine group, and R ₂ is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In an exemplary embodiment of the present application, R ₁ is a substituted or unsubstituted amine group, and R ₂ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In an exemplary embodiment of the present application, R ₁ is a substituted or unsubstituted amine group, and R ₂ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In an exemplary embodiment of the present application, R ₁ is a substituted or unsubstituted amine group, and R ₂ is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuran group; Or it may be a substituted or unsubstituted dibenzothiophenyl group.

In an exemplary embodiment of the present application, R ₁ is a substituted or unsubstituted amine group, and R ₂ is a phenyl group; biphenyl group; terphenyl group; naphthyl group; A fluorenyl group substituted with one or more selected from the group consisting of an alkyl group having 1 to 10 carbon atoms; Dibenzofuran group; or a dibenzothiophenyl group.

In an exemplary embodiment of the present application, R ₁ is substituted or unsubstituted with one or more selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 60 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms. An amine group, wherein R ₂ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; It may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R ₁ is substituted or unsubstituted with one or more selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms. An amine group, wherein R ₂ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; It may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R ₁ is substituted or unsubstituted with one or more selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 20 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms. An amine group, wherein R ₂ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; It may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R ₁ is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted unsubstituted dibenzofuran group, and a substituted or an amine group unsubstituted or substituted with one or more selected from the group consisting of an unsubstituted dibenzothiophenyl group, wherein R ₂ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; It may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R ₁ is a fluorenyl group substituted with one or more selected from the group consisting of a phenyl group, a biphenyl group, an alkyl group having 1 to 10 carbon atoms, a dibenzofuran group, and a dibenzothiophenyl group. An amine group unsubstituted or substituted with at least one selected group, wherein R ₂ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; It may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R ₁ is a fluorenyl group substituted with one or more selected from the group consisting of a phenyl group, a biphenyl group, an alkyl group having 1 to 10 carbon atoms, a dibenzofuran group, and a dibenzothiophenyl group. An amine group unsubstituted or substituted with at least one selected group, wherein R ₂ is a phenyl group; biphenyl group; terphenyl group; naphthyl group; A fluorenyl group substituted with one or more selected from the group consisting of an alkyl group having 1 to 10 carbon atoms; Dibenzofuran group; or a dibenzothiophenyl group.

In an exemplary embodiment of the present application, R ₂ is a substituted or unsubstituted amine group, and R ₁ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R ₂ is a substituted or unsubstituted amine group, and R ₁ is a substituted or unsubstituted aryl group having 6 to 40 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In an exemplary embodiment of the present application, R ₂ is a substituted or unsubstituted amine group, and R ₁ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In an exemplary embodiment of the present application, R ₂ is a substituted or unsubstituted amine group, and R ₁ is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In an exemplary embodiment of the present application, R ₂ is a substituted or unsubstituted amine group, and R ₁ is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted dibenzofuran group; Or it may be a substituted or unsubstituted dibenzothiophenyl group.

In an exemplary embodiment of the present application, R ₂ is a substituted or unsubstituted amine group, and R ₁ is a phenyl group; biphenyl group; terphenyl group; naphthyl group; A fluorenyl group substituted with one or more selected from the group consisting of an alkyl group having 1 to 10 carbon atoms; Dibenzofuran group; or a dibenzothiophenyl group.

In an exemplary embodiment of the present application, R ₂ is substituted or unsubstituted with one or more selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 60 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms. An amine group, wherein R ₁ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; It may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R ₂ is substituted or unsubstituted with one or more selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 40 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms. An amine group, wherein R ₁ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; It may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R ₂ is substituted or unsubstituted with one or more selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 20 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms. An amine group, wherein R ₁ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; It may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R ₂ is a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted unsubstituted dibenzofuran group, and a substituted or an amine group unsubstituted or substituted with one or more selected from the group consisting of an unsubstituted dibenzothiophenyl group, wherein R ₁ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; It may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R ₂ is a fluorenyl group substituted with one or more selected from the group consisting of a phenyl group, a biphenyl group, an alkyl group having 1 to 10 carbon atoms, a dibenzofuran group, and a dibenzothiophenyl group. An amine group unsubstituted or substituted with one or more selected groups, wherein R ₁ is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; It may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In an exemplary embodiment of the present application, R ₂ is a fluorenyl group substituted with one or more selected from the group consisting of a phenyl group, a biphenyl group, an alkyl group having 1 to 10 carbon atoms, a dibenzofuran group, and a dibenzothiophenyl group. An amine group unsubstituted or substituted with at least one selected group, wherein R ₁ is a phenyl group; biphenyl group; terphenyl group; naphthyl group; A fluorenyl group substituted with one or more selected from the group consisting of an alkyl group having 1 to 10 carbon atoms; Dibenzofuran group; or a dibenzothiophenyl group.

When an amine group and an aryl group are respectively substituted at the positions of R ₁ and R ₂ in Formula 1, appropriate homo energy levels for hole injection and transport may be formed.

In addition, when the aryl group is phenyl or biphenyl, conjugation expansion is suppressed and the thin film and interfacial arrangement of molecules are excellent, compared to the case where the aryl group is a naphthyl group. elements can be implemented.

In an exemplary embodiment of the present application, N-Het of Chemical Formula 1 may be a substituted or unsubstituted, monocyclic or polycyclic heterocyclic group containing one or more N atoms.

In an exemplary embodiment of the present application, N-Het of Chemical Formula 1 may be a group represented by any one of the following Chemical Formulas A-1 to A-3.

[Formula A-1]

[Formula A-2]

[Formula A-3]

In the above formulas A-1 to A-3,

X1 is CR11 or N, X2 is CR12 or N, X3 is CR13 or N, X4 is CR14 or N, X5 is CR15 or N, and at least one of X1 to X5 is N,

R11 to R15 and R17 to R22 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; A substituted or unsubstituted phosphine oxide group; And it is selected from the group consisting of a substituted or unsubstituted amine group, is a site connected to Formula 1 above.

In an exemplary embodiment of the present application, Formula A-1 may be represented by Group A below.

[Group A]

In another exemplary embodiment, R _m and R _n in Formula 1 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; Or it may be a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In another exemplary embodiment, R _m and R _n in Formula 1 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; Alternatively, it may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In another exemplary embodiment, R _m and R _n are the same as or different from each other, and each independently hydrogen; or deuterium.

In another exemplary embodiment, R _m and R _n are the same as or different from each other, and each independently represents hydrogen.

In one embodiment of the present application, a and b in Formula 1 are each an integer of 0 to 3, and when a and b are each 2 or more, the substituents in parentheses may be the same as or different from each other.

In another exemplary embodiment, a is 0.

In another exemplary embodiment, a is 1.

In another exemplary embodiment, a is 2.

In another exemplary embodiment, a is 3.

In one embodiment of the present application, when a is 2 or more, the substituents in parentheses may be the same as or different from each other.

In another exemplary embodiment, b is 0.

In another exemplary embodiment, b is 1.

In another exemplary embodiment, b is 2.

In another exemplary embodiment, b is 3.

In one embodiment of the present application, when b is 2 or more, the substituents in parentheses may be the same as or different from each other.

In one embodiment of the present application, m in Formula 1 is 1 or 2, and when m is 2, the substituents in parentheses may be the same as or different from each other.

In another exemplary embodiment, m is 1.

In another exemplary embodiment, m is 2.

In one embodiment of the present application, when m is 2, the substituents in parentheses may be the same as or different from each other.

In an exemplary embodiment of the present application, each n in Formula 1 is an integer of 1 to 3, and when n is 2 or more, substituents in parentheses may be the same as or different from each other.

In another exemplary embodiment, n is 1.

In another exemplary embodiment, n is 2.

In another exemplary embodiment, n is 2.

In one embodiment of the present application, when n is 2, the substituents in parentheses may be the same as or different from each other.

In an exemplary embodiment of the present application, Formula 1 may be represented by any one of Formulas 2 to 4 below.

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4, the definition of the substituent is the same as in Formula 1 above.

The 4th position of dibenzofuran and dibenzothiophene is adjacent to an oxygen atom (O) or sulfur atom (S) whose electronegativity is greater than that of a carbon atom (C), so electrons are relatively scarce. When an electron-rich substituent R is placed in this position, the molecule itself becomes more electron-rich. Accordingly, in Chemical Formulas 2 and 3, the flow of electrons tends to be smoother and the driving voltage tends to be lowered.

Since dibenzofuran and dibenzothiophene are resonant structures, there is a relative lack of electrons in the 1st and 3rd positions. As shown in Formula 4, when an electron-rich substituent R is present at this position, the stability of the molecular structure increases and the lifetime tends to increase. In addition, when the position of the substituent corresponds to the position of Chemical Formulas 3 and 4, the homo (HOMO, Highest Occupied Molecular Orbital) energy level and LUMO (Lowest Unoccupied Molecular Orbital) energy level have an energy level suitable for use in the device, , it has a high T1 value and has excellent hole transport ability.

The 1st, 3rd and 4th positions respectively mean positions indicated by numbers in the following formula (B).

[Formula B]

In Formula B, X is O; or S, and each number means a digit of the corresponding number. That is, for example, a part marked with 1 means the first digit.

According to an exemplary embodiment of the present application, Formula 1 may be represented by any one of the following compounds, but is not limited thereto.

In addition, by introducing various substituents into the structure of Chemical Formula 1, compounds having unique characteristics of the introduced substituents can be synthesized. For example, by introducing substituents mainly used in hole injection layer materials, hole transport materials, light emitting layer materials, electron transport layer materials, and charge generation layer materials used in the manufacture of organic light emitting devices into the core structure, the requirements of each organic layer are met. substances can be synthesized.

In addition, by introducing various substituents into the structure of Chemical Formula 1, it is possible to finely control the energy band gap, while improving the properties of the interface between organic materials and diversifying the use of the material.

Meanwhile, the heterocyclic compound has a high glass transition temperature (Tg) and excellent thermal stability. This increase in thermal stability is an important factor in providing driving stability to the device.

The heterocyclic compound according to an exemplary embodiment of the present application may be prepared through a multi-step chemical reaction. Some intermediate compounds are prepared first, and the compound of Formula 1 can be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to an exemplary embodiment of the present application may be prepared based on Preparation Examples described below.

Another exemplary embodiment of the present application provides an organic light emitting device including the heterocyclic compound represented by Formula 1 above. The "organic light emitting device" may be expressed in terms such as "organic light emitting diode", "organic light emitting diodes (OLED)", "OLED device", and "organic electroluminescent device".

The heterocyclic compound may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

Specifically, the organic light emitting device according to an exemplary embodiment of the present application includes an anode, a cathode, and one or more organic material layers provided between the anode and the cathode, and at least one layer of the organic material layers is a heterocyclic ring represented by Chemical Formula 1 above. contains a compound When the organic material layer includes the heterocyclic compound represented by Chemical Formula 1, the organic light emitting device has excellent light emitting efficiency and lifespan.

In addition, the organic material layer includes one or more light emitting layers, and the light emitting layer includes the heterocyclic compound represented by Chemical Formula 1 above. Among the organic material layers, when the light emitting layer includes the heterocyclic compound represented by Chemical Formula 1, the light emitting efficiency and lifetime of the organic light emitting device are more excellent.

In the organic light emitting device of the present application, the organic material layer includes a light emitting layer, and the light emitting layer may include the heterocyclic compound as a host material of the light emitting material.

In the organic light emitting device of the present application, the light emitting layer may include two or more host materials, and at least one of the host materials may include the heterocyclic compound as a host material of the light emitting material.

In the organic light emitting device of the present application, the light emitting layer may be used by pre-mixing two or more host materials, and at least one of the two or more host materials uses the heterocyclic compound as a host material of the light emitting material. can include

The pre-mixing means that the light emitting layer mixes two or more host materials before depositing them on the organic material layer and mixes them in a single park.

In the organic light emitting device of the present application, the light emitting layer may include two or more host materials, each of the two or more host materials includes one or more p-type host materials and one or more n-type host materials, and at least one of the host materials One may include the heterocyclic compound as a host material of the light emitting material. In this case, driving, efficiency, and lifespan of the organic light emitting device may be improved.

The organic light emitting device of the present invention may further include one or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole auxiliary layer, and a hole blocking layer.

An organic light emitting device according to an exemplary embodiment of the present application may be manufactured by a conventional organic light emitting device manufacturing method and material, except for forming an organic material layer using the aforementioned heterocyclic compound.

1 to 3 illustrate the stacking order of the electrode and the organic material layer of the organic light emitting device according to an exemplary embodiment of the present application. However, it is not intended that the scope of the present application be limited by these drawings, and structures of organic light emitting devices known in the art may be applied to the present application as well.

According to FIG. 1 , an organic light emitting device in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is shown. However, it is not limited to such a structure, and as shown in FIG. 2, an organic light emitting device in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate may be implemented.

3 illustrates a case where the organic material layer is multi-layered. The organic light emitting device according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, an emission layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present application is not limited by such a laminated structure, and layers other than the light emitting layer may be omitted as necessary, and other necessary functional layers may be further added.

In the organic light emitting device according to an exemplary embodiment of the present application, materials other than the heterocyclic compound of Chemical Formula 1 are exemplified below, but these are for illustrative purposes only and are not intended to limit the scope of the present application. may be substituted with known materials.

Materials having a relatively high work function may be used as the anode material, and transparent conductive oxides, metals, or conductive polymers may be used. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline, but are not limited thereto.

Materials having a relatively low work function may be used as the cathode material, and metals, metal oxides, or conductive polymers may be used. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

As the hole injection material, a known hole injection material may be used. For example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or described in [Advanced Material, 6, p.677 (1994)] starburst amine derivatives, such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4',4"-tri[phenyl(m-tolyl)amino]triphenylamine (m- MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), polyaniline/dodecylbenzenesulfonic acid, a soluble conductive polymer, or poly( 3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate) (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), Polyaniline/Camphor sulfonic acid or Polyaniline/ Poly(4-styrene-sulfonate) or the like can be used.

As the hole transport material, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, and the like may be used, and low molecular weight or high molecular weight materials may also be used.

Examples of the electron transport material include oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, and fluorenone. Derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, etc. may be used, and high molecular materials as well as low molecular materials may be used.

As an electron injection material, for example, LiF is typically used in the art, but the present application is not limited thereto.

A red, green or blue light emitting material may be used as the light emitting material, and if necessary, two or more light emitting materials may be mixed and used. In addition, a fluorescent material can be used as a light emitting material, but it can also be used as a phosphorescent material. As the light emitting material, a material that emits light by combining holes and electrons respectively injected from the anode and the cathode may be used, but materials in which a host material and a dopant material are involved in light emission may also be used.

An organic light emitting device according to an exemplary embodiment of the present application may be a top emission type, a bottom emission type, or a double side emission type depending on materials used.

The heterocyclic compound according to an exemplary embodiment of the present application may act on a principle similar to that applied to an organic light emitting device in an organic electronic device including an organic solar cell, an organic photoreceptor, and an organic transistor.

Hereinafter, the present specification will be described in more detail through examples, but these are only for exemplifying the present application, and are not intended to limit the scope of the present application.

<Preparation Example 1> Preparation of Compound 1 (D)

1) Preparation of Compound 1-1

(3-bromo-2-methoxyphenyl)boronic acid (14.73g, 0.064mol) in a One neck round bottom flask (hereinafter referred to as One neck rbf) ), 4-chloro-2-fluoro-1-iodobenzene (4-chloro-2-fluoro-1-iodobenzene) (15g, 0.058mol), tetrakis (triphenylphosphine) palladium (0) (Tetrakis (triphenylphosphine)palladium(0)) (3.35g, 0.0029mol), Sodium hydroxide (4.64g, 0.12mol), and 1,4-Dioxane/water (150mL /50 mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After drying, the mixture was concentrated through a silica gel filter to obtain compound 1-1. (15.92g, 87%)

2) Preparation of compound 1-2

Compound 1-1, 3-bromo-4'-chloro-2'-fluoro-2-methoxy-1,1'-biphenyl (3-bromo-4 A mixture of '-chloro-2'-fluoro-2-methoxy-1,1'-biphenyl) (15.92 g, 0.050 mol) and methyl chloride (MC) (150 mL) was cooled to 0 ^o C BBr ₃ (25.05g, 0.10mol) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 3 hours. The reaction of the stirred mixture was terminated with distilled water, extracted with dichloromethane, and dried with MgSO ₄ . After drying, the mixture was concentrated through a silica gel filter to obtain compound 1-2. (14.32g, 95%)

3) Preparation of compound 1-3

Compound 1-2, 3-bromo-4'-chloro-2'-fluoro-[1,1'-biphenyl]-2-ol (3-bromo- 4'-chloro-2'-fluoro-[1,1'-biphenyl]-2-ol) (14.32 g, 0.048 mol), Cs ₂ CO ₃ (31.28 g, 0.096 mol), and dimethylacetamide (140 mL) was stirred at 180 ^° C. After cooling the stirred mixture, the mixture was filtered, the solvent of the filtrate was removed, and the mixture was filtered through silica gel to obtain compound 1-3. (10.95g, 81%)

4) Preparation of compounds 1-4

6-bromo-3-chlorodibenzo[b,d]furan (10.95 g of compounds 1-3, 6-bromo-3-chlorodibenzo[b,d]furan) in a one-necked round bottom flask (One neck rbf) , 0.039mol), Phenylboronic acid (A) (5.24g, 0.043mol), Tetrakis(triphenylphosphine)palladium(0) (2.25g, 0.0020 mol), potassium carbonate (10.78 g, 0.078 mol), and 1,4-dioxane/water (100 mL/30 mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After drying, column purification was performed to obtain compounds 1-4. (10.11g, 93%)

5) Preparation of compounds 1-5

Compounds 1-4, 7-chloro-N,N-diphenyldibenzo[b,d]furan-4-amine (7-chloro-N,N-diphenyldibenzo[b ,d] furan-4-amine) (10.11 g, 0.027 mol), 1-bromo-2,5-pyrrolidinedione (1-Bromo-2,5-pyrrolidinedione) (9.61 g, 0.054 mol), and A mixture of dichloromethane (100mL) was stirred at room temperature. The stirred mixture was extracted with distilled water and dried over MgSO ₄ . After concentrating the dry mixture, it was filtered through silica gel. After filtering through silica gel, concentrating, and then treating with dichloromethane/methanol to obtain compound 1-5. (12.61g, 98%)

6) Preparation of compounds 1-6

Compounds 1-5, 2-bromo-7-chloro-4-phenyldibenzo[b,d]furan (2-bromo-7-chloro-4-phenyldibenzo[b ,d]furan) (12.61g, 0.035mol), Diphenylamine (B) (6.52g, 0.039mol), Bis(dibenzylideneacetone)palladium(0) (Bis(dibenzylideneacetone)palladium(0) ) (2.01g, 0.0035mol), Tri-tert-butylphosphine (7.08g, 0.035mol), Sodium tert-butoxide (6.73g, 0.07mol), and Toluene (120mL) mixture was refluxed at 120 ^° C. The solid obtained by vacuum filtering the refluxed mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain compound 1-6. (12.33g, 79%)

7) Preparation of compounds 1-7

Compounds 1-6, 7-chloro-N,N,4-triphenyldibenzo[b,d]furan-2-amine (7-chloro-N,N,4 -triphenyldibenzo[b,d]furan-2-amine) (12.33g, 0.027mol), Bis(pinacolato)diboron (13.71g, 0.054mol), Pd ₂ (dba) ₃ (1.24g, 0.0014mol), SPhos (2.22g, 0.0054mol), Potassium acetate (7.95g, 0.081mol), and a mixture of 1,4-Dioxane (120mL) was refluxed at 140 ^° C. The refluxed mixture was extracted with dichloromethane, concentrated, and filtered through silica gel. After concentration, compound 1-7 was obtained by treatment with dichloromethane/methanol. (14.22g, 98%)

8) Preparation of Compound 1 (D)

Compounds 1-7, N,N,4-triphenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl)dibenzo[b,d]furan-2-amine (N,N,4-triphenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) dibenzo[b,d]furan-2-amine) (14.22g, 0.026mol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl- 1,3,5-triazine) (C) (7.76g, 0.029mol), Tetrakis(triphenylphosphine)palladium(0) (1.50g, 0.0013mol), carbonate A mixture of Potassium carbonate (7.19g, 0.052mol) and 1,4-Dioxane/water (140mL/40mL) was stirred at 120 ^° C. The stirred mixture was vacuum The solid obtained by vacuum filter was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain Compound 1 (D) (12.03 g, 72%).

In Preparation Example 1, phenylboronic acid (Intermediate A), diphenylamine (Intermediate B) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2- chloro-4,6-diphenyl-1,3,5-triazine) (Intermediate C) was used to synthesize target compound D in Table 1 in the same manner except for using Intermediates A, B and C in Table 1 below. .

<Preparation Example 2> Preparation of compound 11 (E)

1) Preparation of Compound 11-4

6-bromo-3-chlorodibenzo[b,d]furan (6-bromo-3-chlorodibenzo[b,d], which is compound 1-3 of Preparation Example 1, was placed in a one-necked round bottom flask (One neck rbf) furan) (10.95g, 0.039mol), Diphenylamine (A) (7.26g, 0.043mol), Bis(dibenzylideneacetone)palladium(0) (Bis(dibenzylideneacetone)palladium(0)) (2.24 g, 0.0039 mol), Tri-tert-butylphosphine (7.89 g, 0.039 mol), Sodium tert-butoxide (7.50 g, 0.078 mol), and toluene ( Toluene) (100 mL) mixture was refluxed at 120 ^° C. The solid obtained by vacuum filtering the refluxed mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain compound 11-4. (10.39g, 72%)

2) Preparation of compound 11-5

Compound 11-4, 2-bromo-7-chloro-N, N-diphenyldibenzo[b,d]furan-4-amine (2-bromo-7- A mixture of chloro-N,N-diphenyldibenzo[b,d]furan-4-amine (10.39g, 0.028mol), 1-Bromo-2,5-pyrrolidinedione (1.00g, 0.0056mol), and dichloromethane (100mL) was mixed at room temperature. The stirred mixture was extracted with distilled water and dried with MgSO _4. After drying, it was concentrated and filtered through silica gel. After filtering, it was concentrated and treated with dichloromethane/methanol to obtain compound 11-5. .(11.35g, 90%)

3) Preparation of compound 11-6

Compound 11-5, 7-chloro-N,N,2-triphenyldibenzo[b,d]furan-4-amine (7-chloro-N,N,2 -triphenyldibenzo[b,d]furan-4-amine) (11.35g, 0.025mol), Phenylboronic acid (B) (3.35g, 0.028mol), tetrakis(triphenylphosphine)palladium(0 ) (Tetrakis(triphenylphosphine)palladium(0)) (1.44g, 0.0013mol), Potassium carbonate (6.91g, 0.05mol), and 1,4-Dioxane/water ) (100 mL/30 mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After drying, column purification was performed to obtain compound 11-6. (9.25g, 83%)

4) Preparation of compound 11-7

Compound 11-6, 7-chloro-N,N,2-triphenyldibenzo[b,d]furan-4-amine (7-chloro-N,N,2 -triphenyldibenzo[b,d]furan-4-amine) (9.25g, 0.021mol), Bis(pinacolato)diboron (10.67g, 0.042mol), Pd ₂ (dba) ₃ (0.96g, 0.0011mol), SPhos (1.72g, 0.0042mol), Potassium acetate (6.18g, 0.0063mol), and a mixture of 1,4-Dioxane (90mL) was refluxed at 140 ^° C. The refluxed mixture was extracted with dichloromethane, concentrated, and filtered through silica gel. Filtered, concentrated, and treated with dichloromethane/methanol to obtain compound 11-7. (10.84g, 96%)

5) Preparation of Compound 11 (E)

Compound 11-7, N,N,2-triphenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl)dibenzo[b,d]furan-4-amine (N,N,2-triphenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) dibenzo[b,d]furan-4-amine) (10.84g, 0.020mol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl- 1,3,5-triazine) (C) (5.89g, 0.022mol), Tetrakis(triphenylphosphine)palladium(0) (1.16g, 0.001mol), carbonate A mixture of Potassium carbonate (5.53g, 0.040mol) and 1,4-Dioxane/water (100mL/30mL) was stirred at 120 ^° C. The solid obtained by vacuum filtering the stirred mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain Compound 11 (E). (10.28g, 80%)

In Preparation Example 2, diphenylamine (Intermediate A), phenylboronic acid (Intermediate B) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2- chloro-4,6-diphenyl-1,3,5-triazine) (Intermediate C) was used to synthesize target compound E in Table 2 in the same manner except for using Intermediates A, B and C in Table 2 below. .

<Preparation Example 3> Preparation of compound 23 (F)

1) Preparation of compound 23-1

Phenylboronic acid (A) (5.64g, 0.046mol), (6-bromo-3-iodo-2-methoxyphenyl)boronic acid (( 6-bromo-3-iodo-2-methoxyphenyl)boronic acid) (15g, 0.042mol), tetrakis(triphenylphosphine)palladium(0) (2.43g, 0.0021mol) ), potassium carbonate (11.61g, 0.084mol), and 1,4-dioxane/water (150mL/45mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After filtering through silica gel, the mixture was concentrated to obtain compound 23-1. (8.12g, 63%)

2) Preparation of compound 23-2

Compound 23-1 (4-bromo-2-methoxy-[1,1'-biphenyl]-3-yl)boronic acid ((4-bromo-2 -methoxy-[1,1'-biphenyl]-3-yl)boronic acid) (8.12g, 0.026mol), 4-chloro-2-fluoro-1-iodobenzene (4-chloro-2-fluoro- 1-iodobenzene) (6.78g, 0.029mol), Tetrakis(triphenylphosphine)palladium(0) (1.50g, 0.0013mol), Sodium hydroxide (2.08 g, 0.052 mol), and 1,4-Dioxane/water (80mL/24mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried over MgSO ₄ . After drying, the mixture was concentrated through a silica gel filter to obtain compound 23-2. (6.21g, 61%)

3) Preparation of compound 23-3

In a one-necked round bottom flask (One neck rbf), compound 23-2, 6'-bromo-4-chloro-2-fluoro-2'-methoxy-1,1':3',1''-ter Phenyl (6'-bromo-4-chloro-2-fluoro-2'-methoxy-1,1': 3', 1''-terphenyl (6.21 g, 0.016 mol), and methyl chloride (MC) (60mL) was cooled to 0 ^o C, BBr ₃ (8.02g, 0.032mol) was added dropwise, and the temperature was raised to room temperature and stirred for 3 hours.Then, the reaction was terminated with distilled water, extracted with dichloromethane, and MgSO dried over _4. Filtered with silica gel and concentrated to obtain compound 23-3 (5.86 g, 97%).

4) Preparation of Compound 23-4

Compound 23-3, 6'-bromo-4-chloro-2-fluoro-[1,1':3',1''-terphenyl]-2', was added to a one-neck round bottom flask (One neck rbf). -ol (6'-bromo-4-chloro-2-fluoro-[1,1':3',1''-terphenyl]-2'-ol) (5.86 g, 0.016 mol), Cs ₂ CO ₃ ( 10.11 g, 0.031 mol), and Dimethylacetamide (50 mL) was stirred at 180 ^° C. After cooling the stirred mixture, the mixture was filtered, the solvent of the filtrate was removed, and the mixture was filtered through silica gel to obtain compound 23-4. (4.75g, 83%)

5) Preparation of Compound 23-5

Compound 23-4, 1-bromo-7-chloro-4-phenyldibenzo[b,d]furan (1-bromo-7-chloro-4-phenyldibenzo[b ,d]furan) (4.75g, 0.013mol), Diphenylamine (B) (2.47g, 0.015mol), Bis(dibenzylideneacetone)palladium(0)(Bis(dibenzylideneacetone)palladium(0) ) (0.75g, 0.00065mol), Tri-tert-butylphosphine (6.27g, 0.031mol), Sodium tert-butoxide (5.96g, 0.062mol), and Toluene (50mL) mixture was refluxed at 120 ^° C. The solid obtained by vacuum filtering the refluxed mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain compound 23-5. (4.17g, 72%)

6) Preparation of compound 23-6

Compound 23-5, 7-chloro-N,N,4-triphenyldibenzo[b,d]furan-1-amine (7-chloro-N,N,4 -triphenyldibenzo[b,d]furan-1-amine) (4.17g, 0.0094mol), Bis(pinacolato)diboron (4.77g, 0.019mol), Pd ₂ (dba) ₃ (0.43g, 0.00047mol), SPhos (0.77g, 0.0019mol), Potassium acetate (2.77g, 0.028mol), and a mixture of 1,4-Dioxane (40mL) was refluxed at 140 ^° C. The refluxed mixture was extracted with dichloromethane, concentrated, and filtered through silica gel. Filtered with silica gel, concentrated, and treated with dichloromethane/methanol to obtain compound 23-6. (5.00g, 99%)

7) Preparation of Compound 23 (F)

Compound 23-6, N,N,4-triphenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl)dibenzo[b,d]furan-1-amine (N,N,4-triphenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) dibenzo[b,d]furan-1-amine) (5.00g, 0.0093mol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl- 1,3,5-triazine) (C) (2.74g, 0.010mol), tetrakis(triphenylphosphine)palladium(0) (0.54g, 0.00047mol), carbonic acid A mixture of Potassium carbonate (2.57g, 0.019mol) and 1,4-Dioxane/water (50mL/15mL) was stirred at 120 ^° C. The solid obtained by vacuum filtering the stirred mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain Compound 23 (F). (5.02g, 84%)

In Preparation Example 3, phenylboronic acid (Intermediate A), diphenylamine (Intermediate B) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2- chloro-4,6-diphenyl-1,3,5-triazine) (Intermediate C) was used to synthesize target compound F in Table 3 in the same manner except for using Intermediates A, B and C in Table 3 below. .

<Preparation Example 4> Preparation of compound 32 (G)

1) Preparation of compound 32-1

Phenylboronic acid (A) (7.52g, 0.062mol), (3-bromo-6-iodo-2-methoxyphenyl)boronic acid (( 3-bromo-6-iodo-2-methoxyphenyl)boronic acid) (20g, 0.056mol), tetrakis(triphenylphosphine)palladium(0) (3.24g, 0.0028mol) ), potassium carbonate (15.48 g, 0.11 mol), and 1,4-dioxane/water (200 mL/60 mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After filtering through silica gel, the mixture was concentrated to obtain compound 32-1. (11.17g, 65%)

2) Preparation of Compound 32-2

Compound 32-1, (4-bromo-3-methoxy-[1,1'-biphenyl]-2-yl)boronic acid ((4-bromo-3 -methoxy-[1,1'-biphenyl]-2-yl)boronic acid) (11.17g, 0.036mol), 4-chloro-2-fluoro-1-iodobenzene (4-chloro-2-fluoro- 1-iodobenzene) (10.16g, 0.040mol), Tetrakis(triphenylphosphine)palladium(0) (2.31g, 0.002mol), Sodium hydroxide (2.88 g, 0.072 mol), and 1,4-Dioxane/water (110 mL/30 mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After filtering with silica gel, the mixture was concentrated to obtain compound 32-2. (9.59g, 68%)

3) Preparation of Compound 32-3

In a one-necked round bottom flask (One neck rbf), compound 32-2, 5'-bromo-4-chloro-2-fluoro-6'-methoxy-1,1':2',1''-ter Phenyl (5'-bromo-4-chloro-2-fluoro-6'-methoxy-1,1': 2', 1''-terphenyl) (9.59 g, 0.025 mol), and methyl chloride (MC ) (95mL) was cooled to 0 ^° C, BBr ₃ (12.53g, 0.05mol) was added dropwise, and the temperature was raised to room temperature and stirred for 3 hours. The reaction was terminated with distilled water, extracted with dichloromethane, and dried with MgSO ₄ . After drying, the mixture was concentrated through a silica gel filter to obtain compound 32-3. (8.97g, 95%)

4) Preparation of Compound 32-4

Compound 32-3, 4'-bromo-4''-chloro-2''-fluoro-[1,1':2',1''-terphenyl, was added to a one-necked round bottom flask (One neck rbf). ]-3'-ol (4'-bromo-4''-chloro-2''-fluoro-[1,1':2',1''-terphenyl]-3'-ol) (8.97 g, 0.024 mol), Cs ₂ CO ₃ (15.64 g, 0.048 mol), and dimethylacetamide (90 mL) were stirred at 180 ^° C. After cooling the stirred mixture, the mixture was filtered, the solvent of the filtrate was removed, and the mixture was filtered through silica gel to obtain compound 32-4. (7.47g, 87%)

5) Preparation of Compound 32-5

Compound 32-4, 4-bromo-7-chloro-1-phenyldibenzo[b,d]furan (4-bromo-7-chloro-1-phenyldibenzo[b ,d]furan) (7.47g, 0.021mol), N-phenyl-[1,1'-biphenyl]-3-amine (N-phenyl-[1,1'-biphenyl]-3-amine) (B ) (5.64 g, 0.023 mol), bis (dibenzylideneacetone) palladium (0) (Bis (dibenzylideneacetone) palladium (0)) (1.21 g, 0.0021 mol), tri-tert-butylphosphine (Tri-tert- A mixture of butylphosphine) (4.25 g, 0.021 mol), sodium tert-butoxide (4.04 g, 0.042 mol), and toluene (75 mL) was refluxed at 120 ^° C. The solid obtained by vacuum filtering the refluxed mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain compound 32-5. (7.02g, 75%)

6) Preparation of Compound 32-6

Compound 32-5, 7-chloro-N,N,1-triphenyldibenzo[b,d]furan-4-amine (7-chloro-N,N,1 -triphenyldibenzo[b,d]furan-4-amine) (7.02g, 0.016mol), Bis(pinacolato)diboron (8.13g, 0.032mol), Pd ₂ (dba) ₃ (0.73g, 0.0008mol), SPhos (1.31g, 0.0032mol), Potassium acetate (3.14g, 0.032mol), and a mixture of 1,4-Dioxane (70mL) was refluxed at 140 ^° C. The refluxed mixture was extracted with dichloromethane, concentrated, and filtered through silica gel. After filtering through silica gel, concentration and dichloromethane/methanol treatment, compound 32-6 was obtained. (8.26g, 96%)

7) Preparation of Compound 32 (G)

Compound 32-6, N-([1,1'-biphenyl]-3-yl)-N,1-diphenyl-7-(4,4,5, 5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-4-amine (N-([1,1'-biphenyl]-3-yl)- N,1-diphenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-4-amine) (8.26g, 0.013mol) , 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) (C) (4.53 g, 0.017 mol), Tetrakis(triphenylphosphine)palladium(0) (0.75g, 0.00065mol), Potassium carbonate (3.59g, 0.026mol), and 1,4-di A mixture of 1,4-Dioxane/water (80mL/24mL) was stirred at 120 ^° C. The solid obtained by vacuum filtering the stirred mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain Compound 32 (G). (9.27g, 86%)

In Preparation Example 4, Phenylboronic acid (Intermediate A), N-phenyl-[1,1'-biphenyl]-3-amine (N-phenyl-[1,1'-biphenyl]-3- amine) (intermediate B) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) (intermediate C) instead Target compound G in Table 4 was synthesized in the same manner except for using Intermediates A, B and C in Table 4 below.

<Preparation Example 5> Preparation of compound 41 (H)

1) Preparation of compound 41-1

Phenylboronic acid (A) (7.52g, 0.062mol), (2-bromo-4-iodo-6-methoxyphenyl)boronic acid (( 2-bromo-4-iodo-6-methoxyphenyl)boronic acid) (20g, 0.056mol), Tetrakis(triphenylphosphine)palladium(0) (3.24g, 0.0028mol) ), potassium carbonate (15.48 g, 0.11 mol), and 1,4-dioxane/water (200 mL/60 mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After filtering through silica gel, the mixture was concentrated to obtain compound 41-1. (12.20g, 71%)

2) Preparation of compound 41-2

Compound 41-1 (3-bromo-5-methoxy-[1,1'-biphenyl]-4-yl)boronic acid ((3-bromo-5 -methoxy-[1,1'-biphenyl]-4-yl)boronic acid) (12.20g, 0.040mol), 4-chloro-2-fluoro-1-iodobenzene (4-chloro-2-fluoro- 1-iodobenzene) (11.28g, 0.044mol), Tetrakis(triphenylphosphine)palladium(0) (2.31g, 0.002mol), Sodium hydroxide (3.20 g, 0.08 mol), and 1,4-Dioxane/water (120 mL/35 mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After filtering through silica gel, the mixture was concentrated to obtain compound 41-2. (11.44g, 73%)

3) Preparation of compound 41-3

In a one-neck round-bottom flask (One neck rbf), compound 41-2, 2'-bromo-4-chloro-2-fluoro-6'-methoxy-1,1':4',1''-ter Phenyl (2'-bromo-4-chloro-2-fluoro-6'-methoxy-1,1': 4', 1''-terphenyl) (11.44 g, 0.029 mol), and methyl chloride (MC ) (110 mL) was cooled to 0 ^° C, BBr ₃ (14.53 g, 0.058 mol) was added dropwise, and the temperature was raised to room temperature and stirred for 3 hours. The reaction was terminated with distilled water, extracted with dichloromethane, and dried with MgSO ₄ . After filtering through silica gel, the mixture was concentrated to obtain compound 41-3. (10.08g, 92%)

4) Preparation of Compound 41-4

Compound 41-3, 6'-bromo-4-chloro-2-fluoro-[1,1':4',1''-terphenyl]-2' -ol (6'-bromo-4-chloro-2-fluoro-[1,1':4',1''-terphenyl]-2'-ol) (10.08 g, 0.027 mol), Cs ₂ CO ₃ ( 17.39 g, 0.053 mol), and Dimethylacetamide (100 mL) was stirred at 180 ^° C. After cooling the stirred mixture, the mixture was filtered, the solvent of the filtrate was removed, and the mixture was filtered through silica gel to obtain compound 41-4. (7.63g, 79%)

5) Preparation of Compound 41-5

Compound 41-4, 1-bromo-7-chloro-3-phenyldibenzo[b,d]furan (1-bromo-7-chloro-3-phenyldibenzo[b ,d]furan) (7.63g, 0.021mol), Diphenylamine (B) (3.91g, 0.023mol), Bis(dibenzylideneacetone)palladium(0) ) (1.21g, 0.0021mol), Tri-tert-butylphosphine (4.25g, 0.021mol), Sodium tert-butoxide (4.04g, 0.042mol), and Toluene (75mL) mixture was refluxed at 120 ^° C. The solid obtained by vacuum filtering the refluxed mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain compound 41-5. (7.49g, 80%)

6) Preparation of compound 41-6

Compound 41-5, 7-chloro-N,N,3-triphenyldibenzo[b,d]furan-1-amine (7-chloro-N,N,3 -triphenyldibenzo[b,d]furan-1-amine) (7.49g, 0.017mol), Bis(pinacolato)diboron (8.53g, 0.034mol), Pd ₂ (dba) ₃ (0.78g, 0.00085mol), SPhos (1.40g, 0.0034mol), Potassium acetate (4.70g, 0.034mol), and a mixture of 1,4-Dioxane (70mL) was refluxed at 140 ^° C. The refluxed mixture was extracted with dichloromethane, concentrated, and filtered through silica gel. After filtering through silica gel, concentration and dichloromethane/methanol treatment, compound 41-6 was obtained. (8.41g, 92%)

7) Preparation of Compound 41 (H)

Compound 41-6, N,N,3-triphenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl)dibenzo[b,d]furan-1-amine (N,N,3-triphenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) dibenzo[b,d]furan-1-amine) (8.41g, 0.016mol), chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1, 3,5-triazine) (C) (4.61g, 0.017mol), tetrakis(triphenylphosphine)palladium(0) (0.92g, 0.0008mol), potassium carbonate ( A mixture of Potassium carbonate) (4.42g, 0.032mol), and 1,4-Dioxane/water (80mL/24mL) was stirred at 120 ^° C. The solid obtained by vacuum filtering the stirred mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain compound 41 (H). (8.95g, 87%)

In Preparation Example 5, phenylboronic acid (Intermediate A), diphenylamine (Intermediate B) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2- chloro-4,6-diphenyl-1,3,5-triazine) (Intermediate C) was used to synthesize target compound H in Table 5 in the same manner except for using Intermediates A, B and C in Table 5 below. .

<Preparation Example 6> Preparation of compound 61 (I)

1) Preparation of Compound 61-1

(3-bromo-2-methoxyphenyl)boronic acid (14.73g, 0.064mol), 1-chloro- 3-fluoro-2-iodobenzene (1-chloro-3-fluoro-2-iodobenzene) (15g, 0.058mol), Tetrakis(triphenylphosphine)palladium(0) )) (3.35g, 0.0029mol), Sodium hydroxide (4.64g, 0.12mol), and 1,4-Dioxane/water (150mL/50mL) mixture was added to 120 reflux at ^o C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After drying, the mixture was concentrated through a silica gel filter to obtain compound 61-1. (11.71g, 64%)

2) Preparation of Compound 61-2

Compound 61-1, 3-bromo-2'-chloro-6'-fluoro-2-methoxy-1,1'-biphenyl (3-bromo-2 A mixture of '-chloro-6'-fluoro-2-methoxy-1,1'-biphenyl) (11.71 g, 0.037 mol) and methyl chloride (MC) (100 mL) was cooled to 0 ^o C BBr ₃ (18.54g, 0.074mol) was added dropwise, the temperature was raised to room temperature, and the mixture was stirred for 3 hours. After stirring, the reaction was terminated with distilled water, extracted with dichloromethane, and dried with MgSO ₄ . After drying, the mixture was concentrated through a silica gel filter to obtain compound 61-2. (10.49g, 94%)

3) Preparation of compound 61-3

Compound 61-2, 3-bromo-2'-chloro-6'-fluoro-[1,1'-biphenyl]-2-ol (3-bromo- 2'-chloro-6'-fluoro-[1,1'-biphenyl]-2-ol) (10.49g, 0.035mol), Cs ₂ CO ₃ (22.67g, 0.070mol), and dimethylacetamide (100 mL) was stirred at 180 ^° C. After stirring, the mixture was cooled, filtered, and the filtrate was filtered with silica gel to obtain compound 61-3 after removing the solvent. (8.38g, 85%)

4) Preparation of Compound 61-4

Compound 61-3, 6-bromo-1-chlorodibenzo[b,d]furan (8.38g) in a one-necked round bottom flask (One neck rbf) , 0.030mol), Phenylboronic acid (A) (3.99g, 0.033mol), Tetrakis(triphenylphosphine)palladium(0) (1.73g, 0.0015 mol), potassium carbonate (8.29g, 0.060mol), and 1,4-dioxane/water (80mL/24mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After drying, compound 61-4 was obtained by column purification. (6.61g, 79%)

5) Preparation of Compound 61-5

Compound 61-4, 1-chloro-6-phenyldibenzo[b,d]furan (1-chloro-6-phenyldibenzo[b,d]furan) (6.61 g, A mixture of 0.024 mol), 1-Bromo-2,5-pyrrolidinedione (8.54 g, 0.048 mol), and dichloromethane (60 mL) was stirred at room temperature. did. After stirring, the mixture was extracted with distilled water and dried with MgSO ₄ . After concentration, a silica gel filter was applied. After concentration, compound 61-5 was obtained by treatment with dichloromethane/methanol. (8.07g, 94%)

6) Preparation of compound 61-6

Compound 61-5, 8-bromo-1-chloro-6-phenyldibenzo[b,d]furan (8-bromo-1-chloro-6-phenyldibenzo[b ,d]furan) (8.07g, 0.023mol), Diphenylamine (B) (4.20g, 0.025mol), Bis(dibenzylideneacetone)palladium(0) ) (1.32g, 0.0023mol), Tri-tert-butylphosphine (4.65g, 0.023mol), Sodium tert-butoxide (4.42g, 0.046mol), and Toluene (80mL) mixture was refluxed at 120 ^° C. The solid obtained by vacuum filtering the refluxed mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain compound 61-6. (8.72g, 85%)

7) Preparation of compound 61-7

Compound 61-6, 9-chloro-N,N,4-triphenyldibenzo[b,d]furan-2-amine (9-chloro-N,N,4 -triphenyldibenzo[b,d]furan-2-amine) (8.72g, 0.020mol), Bis(pinacolato)diboron (10.16g, 0.040mol), Pd ₂ (dba) ₃ (0.92g, 0.001mol), SPhos (1.64g, 0.004mol), Potassium acetate (5.53g, 0.040mol), and a mixture of 1,4-Dioxane (80mL) was refluxed at 140 ^° C. The refluxed mixture was extracted with dichloromethane, concentrated, and filtered through silica gel. After filtering through silica gel, concentration and dichloromethane/methanol treatment, compound 61-7 was obtained. (10.00g, 93%)

8) Preparation of Compound 61 (I)

Compound 61-7, N,N,4-triphenyl-9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl)dibenzo[b,d]furan-2-amine (N,N,4-triphenyl-9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) dibenzo[b,d]furan-2-amine) (10.00g, 0.019mol), chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1, 3,5-triazine) (C) (5.48g, 0.020mol), tetrakis(triphenylphosphine)palladium(0) (1.10g, 0.00095mol), potassium carbonate ( A mixture of Potassium carbonate) (5.25g, 0.038mol), and 1,4-Dioxane/water (100mL/30mL) was stirred at 120 ^° C. The solid obtained by vacuum filtering the stirred mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain compound 61(I). (9.53g, 78%)

In Preparation Example 6, phenylboronic acid (Intermediate A), diphenylamine (Intermediate B) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2- chloro-4,6-diphenyl-1,3,5-triazine) (Intermediate C) was used to synthesize target compound I in Table 6 in the same manner except for using Intermediates A, B and C in Table 6 below. .

<Preparation Example 7> Preparation of compound 72 (J)

1) Preparation of Compound 72-4

6-bromo-1-chlorodibenzo[b,d]furan (6-bromo-1-chlorodibenzo[b,d], which is the compound 61-3 of Preparation Example 6, was placed in a one-necked round bottom flask (One neck rbf). furan) (8.38 g, 0.030 mol), N-phenyl-[1,1'-biphenyl]-3-amine (A) (8.10 g, 0.033 mol), Bis (dibenzylideneacetone) palladium (0) (1.73 g, 0.003 mol), Tri-tert-butylphosphine ( 6.07 g, 0.030 mol), sodium tert-butoxide (5.77 g, 0.060 mol), and toluene (80 mL) mixture was refluxed at 120 ^° C. The solid obtained by vacuum filtering the refluxed mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain compound 72-4. (8.43g, 63%)

2) Preparation of Compound 72-5

Compound 72-4, N-([1,1'-biphenyl]-3-yl)-9-chloro-N-phenyldibenzo[b,d]furan- 4-amine (N-([1,1'-biphenyl]-3-yl)-9-chloro-N-phenyldibenzo[b,d]furan-4-amine) (8.43g, 0.019mol), 1-broth A mixture of 1-Bromo-2,5-pyrrolidinedione (6.76g, 0.038mol) and dichloromethane (80mL) was stirred at room temperature. After stirring, the mixture was extracted with distilled water and dried with MgSO ₄ . After concentration, a silica gel filter was applied. After concentration, compound 72-5 was obtained by treatment with dichloromethane/methanol. (8.78g, 88%)

3) Preparation of Compound 72-6

Compound 72-5, N-([1,1'-biphenyl]-3-yl)-2-bromo-9-chloro-N-phenyldibenzo[b ,d] furan-4-amine (N-([1,1'-biphenyl]-3-yl)-2-bromo-9-chloro-N-phenyldibenzo[b,d]furan-4-amine) (8.78 g, 0.017mol), Phenylboronic acid (B) (2.28g, 0.019mol), Tetrakis(triphenylphosphine)palladium(0) (0.98g, A mixture of 0.0009 mol), potassium carbonate (4.70 g, 0.034 mol), and 1,4-Dioxane/water (80 mL/24 mL) was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After drying, the mixture was concentrated through a silica gel filter to obtain compound 72-6. (6.83g, 77%)

4) Preparation of Compound 72-7

Compound 72-6, N-([1,1'-biphenyl]-3-yl)-9-chloro-N,2-diphenyldibenzo[b,d ]furan-4-amine (N-([1,1'-biphenyl]-3-yl)-9-chloro-N,2-diphenyldibenzo[b,d]furan-4-amine) (6.83g, 0.013mol ), Bis(pinacolato)diboron (6.60g, 0.026mol), Pd ₂ (dba) ₃ (0.60g, 0.0007mol), SPhos (1.07g, 0.003mol), potassium acetate A mixture of (Potassium acetate) (3.59g, 0.026mol) and 1,4-dioxane (65mL) was refluxed at 140 ^° C. The refluxed mixture was extracted with dichloromethane, concentrated, and filtered through silica gel. After filtering through silica gel, concentration and treatment with dichloromethane/methanol, compound 72-7 was obtained. (7.58g, 95%)

5) Preparation of Compound 72 (J)

Compound 72-7, N-([1,1'-biphenyl]-3-yl)-N,2-diphenyl-9-(4,4,5, 5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-4-amine (N-([1,1'-biphenyl]-3-yl)- N,2-diphenyl-9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-4-amine) (7.58g, 0.012mol) , 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) (C) (3.53 g, 0.013 mol), Tetrakis(triphenylphosphine)palladium(0) (0.69g, 0.0006mol), Potassium carbonate (3.32g, 0.024mol), and 1,4-di A mixture of 1,4-Dioxane/water (75mL/20mL) was refluxed at 120 ^° C. After filtering the precipitated solid under reflux, it was dissolved in 1,2-dichlorobenzene, filtered through silica gel, and concentrated to obtain compound 72 (J). (6.04g, 70%)

In Preparation Example 7, N-phenyl-[1,1'-biphenyl]-3-amine (Intermediate A), phenylboronic acid (Phenylboronic acid) (intermediate B) and 2-chloro-4,6-diphenyl-1,3,5-triazine (intermediate C) Target compound J in Table 7 was synthesized in the same manner except for using Intermediates A, B and C in Table 7 below.

<Preparation Example 8> Preparation of compound 91 (K)

1) Preparation of Compound 91-1

Phenylboronic acid (A) (5.63g, 0.046mol), (3-bromo-6-iodo-2-methoxyphenyl)boronic acid (( 3-bromo-6-iodo-2-methoxyphenyl)boronic acid) (15g, 0.042mol), Tetrakis(triphenylphosphine)palladium(0) (2.43g, 0.0021mol) ), potassium carbonate (11.61 g, 0.084 mol), and 1,4-dioxane/water (150 mL/45 mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After filtering with silica gel, the mixture was concentrated to obtain compound 91-1. (9.41g, 73%)

2) Preparation of compound 91-2

Compound 91-1 (4-bromo-3-methoxy-[1,1'-biphenyl]-2-yl)boronic acid ((4-bromo-3 -methoxy-[1,1'-biphenyl]-2-yl)boronic acid) (9.41g, 0.031mol), 1-chloro-3-fluoro-2-iodobenzene 2-iodobenzene) (8.74g, 0.034mol), Tetrakis(triphenylphosphine)palladium(0) (1.79g, 0.0016mol), Sodium hydroxide (2.48 g, .062 mol), and 1,4-Dioxane/water (90mL/27mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After drying, the mixture was concentrated through a silica gel filter to obtain compound 91-2. (7.28g, 60%)

3) Preparation of compound 91-3

In a one-necked round bottom flask (One neck rbf), compound 91-2, 5'-bromo-2-chloro-6-fluoro-6'-methoxy-1,1':2',1''-ter Phenyl (5'-bromo-2-chloro-6-fluoro-6'-methoxy-1,1': 2', 1''-terphenyl) (7.28 g, 0.019 mol), and methyl chloride (MC ) (70mL) was cooled to 0 ^° C, BBr ₃ (9.52g, 0.038mol) was added dropwise, and the temperature was raised to room temperature and stirred for 3 hours. After stirring, the reaction was terminated with distilled water, extracted with dichloromethane, and dried with MgSO ₄ . After drying, the mixture was concentrated through a silica gel filter to obtain compound 91-3. (6.53g, 91%)

4) Preparation of Compound 91-4

In a one neck round bottom flask (One neck rbf), compound 91-3, 4'-bromo-2''-chloro-6''-fluoro-[1,1':2',1''-terphenyl ]-3'-ol (4'-bromo-2''-chloro-6''-fluoro-[1,1':2',1''-terphenyl]-3'-ol) (6.53 g, 0.017 mol), Cs ₂ CO ₃ (11.27 g, 0.035 mol), and dimethylacetamide (65 mL) was stirred at 180 ^° C. After stirring, the mixture was cooled, filtered, and the filtrate was filtered with silica gel to obtain compound 91-4 after removing the solvent. (5.29g, 87%)

5) Preparation of Compound 91-5

Compound 91-4, 4-bromo-9-chloro-1-phenyldibenzo[b,d]furan (4-bromo-9-chloro-1-phenyldibenzo[b ,d] furan) (5.29g, 0.015mol), N-phenyl-[1,1'-biphenyl]-3-amine (N-phenyl-[1,1'-biphenyl]-3-amine) (B ) (3.93 g, 0.016 mol), bis (dibenzylideneacetone) palladium (0) (Bis (dibenzylideneacetone) palladium (0)) (0.86 g, 0.0015 mol), tri-tert-butylphosphine (Tri-tert- A mixture of butylphosphine) (3.03 g, 0.015 mol), sodium tert-butoxide (2.88 g, 0.03 mol), and toluene (50 mL) was refluxed at 120 ^° C. The solid obtained by vacuum filtering the refluxed mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain compound 91-5. (5.87g, 75%)

6) Preparation of Compound 91-6

Compound 91-5, N-([1,1'-biphenyl]-3-yl)-9-chloro-N,1-diphenyldibenzo[b,d ]Furan-4-amine (N-([1,1'-biphenyl]-3-yl)-9-chloro-N,1-diphenyldibenzo[b,d]furan-4-amine) (5.87g, 0.011mol ), Bis(pinacolato)diboron (5.59g, 0.022mol), Pd ₂ (dba) ₃ (0.50g, 0.00055mol), SPhos (0.90g, 0.0022mol), potassium acetate A mixture of (Potassium acetate) (3.24g, 0.033mol) and 1,4-dioxane (50mL) was refluxed at 140 ^° C. The refluxed mixture was extracted with dichloromethane, concentrated, and filtered through silica gel. After filtering through silica gel, concentration and dichloromethane/methanol treatment, compound 91-6 was obtained. (6.41g, 95%)

7) Preparation of Compound 91 (K)

Compound 91-5, N-([1,1′-biphenyl]-3-yl)-N,1-diphenyl-9-(4,4,5, 5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-4-amine (N-([1,1'-biphenyl]-3-yl)- N,1-diphenyl-9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]furan-4-amine) (6.41g, 0.010mol) , chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) (C) (2.94g, 0.011mol), tetrakis (triphenylphosphine)palladium(0) (Tetrakis(triphenylphosphine)palladium(0)) (0.58g, 0.0005mol), Potassium carbonate (2.76g, 0.02mol), and 1,4-dioxane/ A mixture of water (1,4-Dioxane/water) (60mL/18mL) was stirred at 120 ^° C. The solid obtained by vacuum filtering the stirred mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain compound 91 (K). (5.82g, 81%)

In Preparation Example 8, Phenylboronic acid (Intermediate A), N-phenyl-[1,1'-biphenyl]-3-amine (N-phenyl-[1,1'-biphenyl]-3- amine) (intermediate B) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1,3,5-triazine) (intermediate C) instead The target compound K in Table 8 was synthesized in the same manner except for using Intermediates A, B and C in Table 8 below.

<Preparation Example 9> Preparation of compound 111 (L)

1) Preparation of Compound 111-1

Phenylboronic acid (A) (7.52g, 0.062mol), (4-bromo-2-iodo-6-methoxyphenyl)boronic acid (4 -bromo-2-iodo-6-methoxyphenyl)boronic acid) (20g, 0.056mol), Tetrakis(triphenylphosphine)palladium(0) (3.24g, 0.0028mol) , Potassium carbonate (15.48g, 0.11mol), and 1,4-Dioxane/water (200mL/60mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After filtering through silica gel, the mixture was concentrated to obtain compound 111-1. (10.83g, 63%)

2) Preparation of compound 111-2

Compound 111-1 (5-bromo-3-methoxy-[1,1'-biphenyl]-2-yl)boronic acid ((5-bromo-3 -methoxy-[1,1'-biphenyl]-2-yl)boronic acid) (10.83g, 0.035mol), 1-chloro-3-fluoro-2-iodobenzene 2-iodobenzene) (9.87g, 0.039mol), Tetrakis(triphenylphosphine)palladium(0) (2.02g, 0.0018mol), Sodium hydroxide (2.80 g, 0.07 mol), and 1,4-Dioxane/water (100 mL/30 mL) mixture was refluxed at 120 ^° C. The refluxed mixture was extracted with dichloromethane and dried with MgSO ₄ . After drying, the mixture was concentrated through a silica gel filter to obtain compound 111-2. (8.36g, 61%)

3) Preparation of compound 111-3

In a one-necked round bottom flask (One neck rbf), compound 111-2, 4'-bromo-2-chloro-6-fluoro-6'-methoxy-1,1':2',1''-ter Phenyl (4'-bromo-2-chloro-6-fluoro-6'-methoxy-1,1': 2', 1''-terphenyl) (8.36 g, 0.021 mol), and methyl chloride (MC ) (80mL) was cooled to 0 ^° C, BBr ₃ (10.52g, 0.042mol) was added dropwise, and the temperature was raised to room temperature and stirred for 3 hours. After stirring, the reaction was terminated with distilled water, extracted with dichloromethane, and dried with MgSO ₄ . After drying, the mixture was concentrated through a silica gel filter to obtain compound 111-3. (7.53g, 95%)

4) Preparation of Compound 111-4

Compound 111-3, 5'-bromo-2''-chloro-6''-fluoro-[1,1':2',1''-terphenyl, was added to a one-necked round bottom flask (One neck rbf). ]-3'-ol (5'-bromo-2''-chloro-6''-fluoro-[1,1':2',1''-terphenyl]-3'-ol) (7.53 g, 0.020 mol), Cs ₂ CO ₃ (13.03 g, 0.040 mol), and dimethylacetamide (75 mL) were stirred at 180 ^° C. After cooling the stirred mixture, the mixture was filtered, the solvent of the filtrate was removed, and the mixture was filtered through silica gel to obtain compound 111-4. (4.12g, 80%)

5) Preparation of compound 111-5

Compound 111-4, 3-bromo-9-chloro-1-phenyldibenzo[b,d]furan (3-bromo-9-chloro-1-phenyldibenzo[b ,d]furan) (4.12g, 0.012mol), Diphenylamine (B) (2.23g, 0.013mol), Bis(dibenzylideneacetone)palladium(0) ) (0.69g, 0.0012mol), Tri-tert-butylphosphine (2.43g, 0.012mol), Sodium tert-butoxide (2.31g, 0.024mol), and Toluene (40mL) mixture was refluxed at 120 ^° C. The solid obtained by vacuum filtering the refluxed mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain compound 111-5. (4.55g, 85%)

6) Preparation of compound 111-6

Compound 111-5, 9-chloro-N,N,1-triphenyldibenzo[b,d]furan-3-amine (9-chloro-N,N,1 -triphenyldibenzo[b,d]furan-3-amine) (4.55g, 0.010mol), Bis(pinacolato)diboron (5.08g, 0.020mol), Pd ₂ (dba) ₃ (0.46g, 0.0005mol), SPhos (0.82g, 0.002mol), Potassium acetate (1.96g, 0.020mol), and a mixture of 1,4-Dioxane (45mL) was refluxed at 140 ^° C. The refluxed mixture was extracted with dichloromethane, concentrated, and filtered through silica gel. After filtering through silica gel, concentration and dichloromethane/methanol treatment, compound 111-6 was obtained. (5.27g, 98%)

7) Preparation of Compound 111 (L)

Compound 111-6, N,N,1-triphenyl-9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl)dibenzo[b,d]furan-3-amine (N,N,1-triphenyl-9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) dibenzo[b,d]furan-3-amine) (5.27g, 0.010mol), chloro-4,6-diphenyl-1,3,5-triazine (2-chloro-4,6-diphenyl-1, 3,5-triazine) (C) (2.94g, 0.011mol), tetrakis(triphenylphosphine)palladium(0) (0.58g, 0.0005mol), potassium carbonate ( Potassium carbonate) (2.76g, 0.020mol), and 1,4-Dioxane/water (50mL/15mL) were stirred at 120 ^° C. The solid obtained by vacuum filtering the stirred mixture was dissolved in dichlorobenzene, filtered through silica gel, and then concentrated to obtain compound 111 (H). (5.40g, 84%)

In Preparation Example 9, phenylboronic acid (Intermediate A), diphenylamine (Intermediate B) and 2-chloro-4,6-diphenyl-1,3,5-triazine (2- chloro-4,6-diphenyl-1,3,5-triazine) (Intermediate C) was used to synthesize target compound L in Table 9 in the same manner except for using intermediates A, B and C in Table 9 below. .

In order to prepare the compounds described herein in the same manner as in the above preparations, and to confirm the synthesis confirmation results of the prepared compounds, ¹ H NMR (CDCl ₃ , 200 Mz) and FD-mass spectrometer (FD-MS: Field desorption mass spectrometry) was measured and the measured values are shown in Tables 10 and 11 below. Table 10 below shows ¹ H NMR (CDCl ₃ , 200 Mz) measurement values of some of the prepared compounds, and Table 11 below shows FD-mass spectrometry (FD-MS) measurement values of the prepared compounds. indicates

compound ¹ H NMR (CDCl ₃ , 200 Mz) One δ = 8.32~8.36 (5H, m), 8.26 (1H, s), 8.03 (1H, d), 7.82 (1H, d), 7.76 (1H, s), 7.41~7.51 (11H, m), 7.24 ( 4H, m), 7.00~7.08 (6H, m) 2 δ = 8.32~8.36 (5H, m), 8.26 (1H, s), 8.03 (1H, d), 7.75~7.82 (4H, m), 7.41~7.55 (15H, m), 7.17~7.27 (5H, m) ), 7.00~7.08 (3H, m) 3 δ = 8.32~8.36 (5H, m), 8.26 (1H, s), 7.98~8.03 (3H, m), 7.76~7.82 (3H, m), 7.24~7.54 (16H, m), 7.00~7.08 (3H , m), 6.91 (1H, d) 5 δ = 8.32~8.36 (5H, m), 8.03 (1H, d), 7.75~7.82 (4H, m), 7.37~7.55 (18H, m), 7.24 (2H, t), 7.00~7.08 (3H, m) ) 7 δ = 8.32~8.36 (5H, m), 8.26 (1H, s), 8.03 (1H, d), 7.75~7.82 (4H, m), 7.41~7.50 (9H, m), 7.24~7.25 (8H, m) ), 7.00~7.08 (6H, m) 8 δ = 8.32~8.36 (5H, m), 8.26 (1H, s), 7.98~8.03 (2H, m), 7.76~7.88 (5H, m), 7.50~7.54 (7H, m), 7.24~7.39 (6H , m), 7.00~7.08 (6H, m), 9 δ = 8.32~8.36 (5H, m), 8.26 (1H, s), 8.03 (1H, d), 7.94 (1H, s), 7.73~7.82 (5H, m), 7.61 (2H, d), 7.41~ 7.50 (9H, m), 7.24 (4H, m), 7.00~7.08 (6H, m) 10 δ = 8.32~8.36 (5H, m), 8.26 (1H, s), 8.03~8.04 (4H, m), 7.75~7.82 (6H, m), 7.41~7.50 (12H, m), 7.24 (4H, t) ), 7.00~7.08 (6H, m) 11 δ = 8.36 (4H, m), 8.26 (1H, s), 8.03 (1H, d), 7.75 to 7.82 (4H, m), 7.41 to 7.50 (10H, m), 7.24 (4H, t), 7.00 to 7.08 (6H, m) 15 δ = 8.36 (4H, m), 8.26 (1H, s), 8.03 (1H, d), 7.75 to 7.82 (6H, m), 7.37 to 7.55 (17H, m), 7.24 (2H, t), 7.00 to 7.08 (3H, m) 16 δ = 8.36 (4H, m), 8.26 (1H, s), 8.03 (1H, d), 7.75~7.82 (8H, m), 7.60 (1H, s), 7.37~7.50 (18H, m), 7.24 ( 2H, t), 7.00~7.08 (3H, m) 20 δ = 8.36 (4H, m), 8.26 (1H, s), 8.03 to 8.04 (4H, d), 7.75 to 7.82 (6H, m), 7.41 to 7.50 (13H, m), 7.24 (4H, t), 7.00~7.08 (6H, m) 23 δ = 8.45 (1H, d), 8.36 (4H, m), 8.12 (2H, m), 7.93 to 8.03 (3H, m), 7.76 to 7.84 (3H, m), 7.49 to 7.50 (8H, m), 7.24 (4H, t), 7.00~7.10 (7H, m) 27 δ = 8.56 (1H, d), 8.03 (1H, d), 7.75 to 7.84 (6H, m), 7.38 to 7.62 (15H, m), 7.00 to 7.28 (10H, m) 29 δ = 8.45 (1H, d), 8.36 (4H, m), 8.03 (1H, d), 7.93 to 7.95 (2H, m), 7.82 to 7.85 (3H, m), 7.76 (1H, s), 7.41 to 7.56 (14H, m), 7.24 (2H, t), 7.00~7.10 (4H, m) 32 δ = 8.36 (4H, m), 8.03 (1H, d), 7.75 to 7.82 (7H, m), 7.41 to 7.55 (13H, m), 7.16 to 7.27 (6H, m), 7.00 to 7.08 (3H, m) ) 34 δ = 8.36 (4H, m), 8.18 (1H, s), 8.03 (1H, d), 7.90 (1H, d), 7.68-7.82 (5H, m), 7.50-7.55 (7H, m), 7.38 ( 1H, t), 7.16~7.28 (6H, m), 7.00~7.08 (6H, m) 38 δ = 8.36 (4H, m), 8.01 to 8.07 (3H, m), 7.76 to 7.82 (4H, m), 7.41 to 7.55 (10H, m), 7.18 to 7.24 (7H, m), 7.00 to 7.08 (6H , m) 41 δ = 8.36 (4H, m), 8.20 (1H, s), 8.03 (1H, d), 7.75 to 7.82 (4H, m), 7.41 to 7.50 (10H, m), 7.24 (4H, m), 7.00 to 7.08 (6H, m) 43 δ = 8.36 (4H, m), 8.20 (1H, s), 8.03 (1H, d), 7.75 to 7.82 (4H, m), 7.41 to 7.50 (10H, m), 7.24 to 7.25 (8H, m), 7.00~7.08 (6H, m) 48 δ = 8.45 (1H, d), 8.36 (4H, m), 8.20 (1H, s), 8.01~8.03 (2H, m), 7.93 (1H, d), 7.75~7.82 (4H, m), 7.64 ( 1H, s), 7.41~7.56 (13H, m), 7.24 (2H, t), 7.00~7.08 (3H, m) 49 δ = 8.36 (4H, m), 8.20 (1H, s), 8.03 (1H, d), 7.94 (1H, s), 7.73 to 7.82 (5H, m), 7.61 (2H, d), 7.41 to 7.50 ( 9H, m), 7.24 (4H, m), 7.00~7.08 (6H, m) 61 δ = 8.32~8.36 (5H, m), 7.82 (1H, d), 7.69 (1H, d), 7.41~7.57 (12H, m), 7.24 (4H, m), 7.00~7.08 (6H, m) 63 δ = 8.32~8.36 (5H, m), 8.26 (1H, s), 7.98~8.03 (2H, m), 7.80~7.82 (2H, m), 7.69 (1H, d), 7.24~7.57 (17H, m) ), 7.00~7.08 (3H, m), 6.91 (1H, d) 66 δ = 8.32~8.38 (4H, m), 8.26 (1H, s), 7.94 (1H, s), 7.69~7.82 (5H, m), 7.41~7.61 (13H, m), 7.24 (4H, m), 7.00~7.08 (6H, m) 72 δ = 8.36 (4H, m), 8.26 (1H, s), 7.69 to 7.82 (6H, m), 7.41 to 7.57 (15H, m), 7.17 to 7.27 (5H, m), 7.00 to 7.08 (3H, m) ) 75 δ = 8.36 (4H, m), 8.26 (1H, s), 7.69 to 7.82 (6H, m), 7.37 to 7.57 (18H, m), 7.24 (2H, t), 7.00 to 7.08 (3H, m) 80 δ = 8.36 (4H, m), 8.26 (1H, s), 8.04 (3H, s), 7.69 to 7.82 (6H, m), 7.41 to 7.57 (14H, m), 7.24 (4H, t), 7.00 to 7.08 (6H, m) 91 δ = 8.36 (4H, m), 7.78 to 7.82 (4H, m), 7.69 (1H, d), 7.41 to 7.57 (10H, m), 7.16 to 7.24 (5H, m), 7.00 to 7.08 (6H, m) ) 95 δ = 8.36 (4H, m), 8.22 (1H, s), 7.98 (1H, d), 7.78 to 7.82 (4H, m), 7.69 (1H, d), 7.16 to 7.57 (17H, m), 6.97 to 7.08 (4H, m) 111 δ = 8.36 (4H, m), 8.20 (1H, s), 8.13 (1H, s), 7.79-7.82 (3H, m), 7.69 (1H, d), 7.41-7.57 (10H, m), 7.24 ( 4H, t), 7.00~7.08 (6H, m) 112 δ = 8.36 to 8.38 (3H, m), 8.20 (1H, s), 8.13 (1H, s), 7.94 (1H, s), 7.69 to 7.82 (7H, m), 7.41 to 7.61 (11H, m), 7.24 (4H, t), 7.00~7.08 (6H, m) 113 δ = 8.36 (4H, m), 8.20 (1H, s), 8.13 (1H, s), 7.69 to 7.82 (4H, m), 7.41 to 7.57 (10H, m), 7.24 to 7.25 (8H, m), 7.00~7.08 (6H, m) 116 δ = 8.45 (1H, d), 8.36 (4H, m), 8.13–8.24 (5H, m), 7.93 (1H, d), 7.82 (1H, d), 7.9 (1H, d), 7.49–7.57 ( 9H, m), 7.24 (4H, m), 7.00~7.08 (6H, m) 119 δ = 8.36 (4H, m), 8.20 (1H, s), 8.13 (1H, s), 7.94 (1H, s), 7.69-7.82 (5H, m), 7.41-7.61 (12H, m), 7.24 ( 4H, m), 7.00~7.08 (6H, m) 120 δ = 8.20~8.23 (2H, m), 8.13 (1H, s), 7.94 (4H, m), 7.69~7.82 (4H, m), 7.41~7.57 (10H, m), 7.24~7.25 (8H, m) ), 7.00~7.08 (6H, m)

compound FD-Mass compound FD-Mass One m/z= 642.76 (C45H30N4O=642.24) 2 m/z = 718.86 (C51H34N4O=718.27) 3 m/z= 732.84 (C51H32N4O2=732.25) 5 m/z = 718.86 (C51H34N4O=718.27) 7 m/z = 718.86 (C51H34N4O=718.27) 8 m/z= 732.84 (C51H32N4O2=732.25) 9 m/z = 718.86 (C51H34N4O=718.27) 10 m/z = 794.96 (C57H38N4O=794.30) 11 m/z= 642.76 (C45H30N4O=642.24) 15 m/z = 718.86 (C51H34N4O=718.27) 16 m/z = 794.96 (C57H38N4O=794.30) 20 m/z = 794.96 (C57H38N4O=794.30) 23 m/z= 748.90 (C51H32N4OS=748.23) 27 m/z= 679.82 (C49H33N3O=679.26) 29 m/z= 748.90 (C51H32N4OS=748.23) 32 m/z = 718.86 (C51H34N4O=718.27) 34 m/z= 758.93 (C54H38N4O=758.30) 38 m/z = 718.86 (C51H34N4O=718.27) 41 m/z= 642.76 (C45H30N4O=642.24) 43 m/z = 718.86 (C51H34N4O=718.27) 48 m/z= 748.90 (C51H32N4OS=748.23) 49 m/z = 718.86 (C51H34N4O=718.27) 61 m/z= 642.76 (C45H30N4O=642.24) 63 m/z= 732.84 (C51H32N4O2=732.25) 66 m/z = 718.86 (C51H34N4O=718.27) 72 m/z = 718.86 (C51H34N4O=718.27) 75 m/z = 718.86 (C51H34N4O=718.27) 80 m/z = 794.96 (C57H38N4O=794.30) 91 m/z= 642.76 (C45H30N4O=642.24) 95 m/z= 732.84 (C51H32N4O2=732.25) 111 m/z= 642.76 (C45H30N4O=642.24) 112 m/z = 718.86 (C51H34N4O=718.27) 113 m/z = 718.86 (C51H34N4O=718.27) 116 m/z= 748.90 (C51H32N4OS=748.23) 119 m/z = 718.86 (C51H34N4O=718.27) 120 m/z= 717.87 (C52H35N3O=717.28)

<Experimental example>

(1) Manufacture of organic light emitting device

A glass substrate coated with ITO thin film to a thickness of 1,500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, ultrasonic cleaning was performed with solvents such as acetone, methanol, and isopropyl alcohol, and after drying, UVO treatment was performed for 5 minutes using UV in a UV cleaner. Thereafter, the substrate was transferred to a plasma cleaner (PT), plasma treated to remove the ITO work function and residual film in a vacuum state, and transferred to a thermal evaporation equipment for organic deposition.

A hole injection layer 2-TNATA (4,4′,4′′-Tris [2-naphthyl (phenyl) amino] triphenylamine) and a hole transport layer NPB (N, N′-Di) as a common layer on the ITO transparent electrode (anode) (1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) was formed.

A light emitting layer was thermally vacuum deposited thereon as follows. The light emitting layer was deposited at 400 Å by doping 7wt% of Ir(ppy) _{3 on the host using a compound listed in Table 12 below and Ir(ppy) 3 (} tris(2-phenylpyridine)iridium) as a green phosphorescent dopant. Thereafter, 60 Å of bathocuproine (BCP) was deposited as a hole blocking layer, and 200 Å of Alq ₃ was deposited thereon as an electron transport layer. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode is deposited on the electron injection layer to a thickness of 1200 Å to form a cathode. Organic light emitting devices of 1 to 36 and Comparative Examples 1 to 6 were prepared.

On the other hand, all organic compounds required for OLED device fabrication were purified by vacuum sublimation under 10 ⁻⁶ to 10 ⁻⁸ torr for each material and used for OLED fabrication.

In addition, compounds A to F used as hosts in Comparative Examples 1 to 6 in the table below are as follows

(2) Driving voltage and luminous efficiency of organic light emitting device

Examples 1 to 36 and Comparative Examples 1 to 6 prepared as described above The electroluminescence (EL) characteristics of the organic light emitting devices were measured with McSyers' M7000, and with the measurement results, the standard luminance was 6,000 cd/m ² When , the lifetime T ₉₀ (unit: h, time), which is the time to reach 90% of the initial luminance, was measured.

The characteristics of the organic light emitting diodes of the present invention shown by the above measurement results are shown in Table 12 below.

compound drive voltage
(V) efficiency
(cd/A) color coordinates
(x, y) life span
(T ₉₀ ) Comparative Example 1 A 5.75 46.0 (0.273, 0.686) 53 Comparative Example 2 B 5.72 45.7 (0.275, 0.674) 54 Comparative Example 3 C 5.60 50.6 (0.271, 0.685) 67 Comparative Example 4 D 5.30 52.3 (0.276, 0.681) 66 Comparative Example 5 E 5.25 55.6 (0.274, 0.667) 80 Comparative Example 6 F 5.12 56.1 (0.287, 0.674) 78 Example 1 One 5.05 56.5 (0.278, 0.685) 90 Example 2 2 4.87 55.9 (0.283, 0.680) 85 Example 3 3 4.65 58.1 (0.279, 0.674) 83 Example 4 5 4.77 57.6 (0.269, 0.683) 88 Example 5 7 4.83 58.9 (0.274, 0.667) 86 Example 6 8 4.66 56.8 (0.285, 0.675) 83 Example 7 9 4.89 58.8 (0.287, 0.677) 88 Example 8 10 4.61 56.5 (0.278, 0.666) 87 Example 9 11 4.05 30.3 (0.273, 0.679) 90 Example 10 15 4.45 64.5 (0.277, 0.671) 93 Example 11 16 4.41 63.1 (0.271, 0.673) 94 Example 12 20 4.13 62.5 (0.274, 0.675) 95 Example 13 23 4.77 55.9 (0.287, 0.675) 90 Example 14 27 4.65 58.7 (0.274, 0.662) 84 Example 15 29 4.97 56.9 (0.268, 0.682) 88 Example 16 32 2.57 90.5 (0.285, 0.680) 145 Example 17 34 2.68 97.6 (0.274, 0.688) 157 Example 18 38 2.64 98.0 (0.279, 0.677) 159 Example 19 41 3.15 76.8 (0.274, 0.678) 120 Example 20 43 3.48 83.4 (0.273, 0.677) 116 Example 21 48 3.50 86.9 (0.271, 0.687) 120 Example 22 49 3.44 76.1 (0.281, 0.683) 119 Example 23 61 2.87 85.9 (0.283, 0.688) 125 Example 24 63 2.64 86.2 (0.277, 0.686) 130 Example 25 66 2.59 79.4 (0.285, 0.669) 122 Example 26 72 3.01 88.5 (0.283, 0.672) 140 Example 27 75 2.89 87.9 (0.277, 0.682) 135 Example 28 80 2.63 89.2 (0.288, 0.682) 133 Example 29 91 2.51 97.5 (0.274, 0.671) 168 Example 30 95 2.63 98.0 (0.275, 0.674) 165 Example 31 111 3.85 75.3 (0.277, 0.673) 110 Example 32 112 3.79 74.2 (0.279, 0.673) 106 Example 33 113 3.62 72.9 (0.275, 0.675) 98 Example 34 116 4.01 70.5 (0.281, 0.675) 99 Example 35 119 3.53 74.8 (0.277, 0.670) 100 Example 36 120 3.65 73.2 (0.270, 0.662) 107

As can be seen from the structures of the compounds A to F, compounds A to D in which dibenzofuran is substituted with two specific substituents (hereinafter referred to as disubstituted structure) and dibenzofuran with three specific substituents substituted. It was confirmed that the compounds E and F, which had a trisubstituted structure but did not include an amine group in the specific substituent, were used in Comparative Examples 1 to 6, respectively.

From the above experimental examples, the compound according to the present application has a trisubstituted structure in which three specific substituents including an amine group are substituted for dibenzofuran or dibenzothiophene, so that electrons are more abundant and have an amine group having hole characteristics as a substituent Since the hole transport ability is excellent, in the case of the organic light emitting devices of Examples 1 to 36 using the compound according to the present application as a host of the light emitting layer of the organic light emitting device, current flow is better than that of the organic light emitting devices of Comparative Examples 1 to 6. It was confirmed that the driving voltage was lowered.

In addition, since the compound according to the present application has a trisubstituted structure in which three specific substituents including an amine group are substituted with dibenzofuran or dibenzothiophene, the stability of the structure is increased. In the case of the organic light emitting device of Examples 1 to 36 used as a host of the light emitting layer of, it was confirmed that the lifetime was superior to that of the organic light emitting device of Comparative Examples 1 to 6.

That is, it was confirmed that the organic light emitting devices of Examples 1 to 36 using the compound according to the present application as a host of the light emitting layer of the organic light emitting device had better luminous efficiency and lifetime than the organic light emitting devices of Comparative Examples 1 to 6.

Specifically, since dibenzofuran or dibenzothiophene has a trisubstituted structure in which three specific substituents are substituted, electrons are more abundant and the stability of the structure is increased, so that two specific substituents are substituted in this case than Compounds A to D substituted. When the compound according to the application was used in the organic light emitting device, it was confirmed that the light emitting efficiency and lifespan of the device were excellent. In particular, in the case of compound D, despite having an amine group as a substituent, when the compound according to the present application was used in an organic light emitting device, it was confirmed that the light emitting efficiency and lifespan of the device were more excellent.

In addition, since the compound according to the present application has excellent hole transport ability by having an amine group having hole characteristics as a substituent, it has a trisubstituted structure in which three specific substituents are substituted, but the specific substituent does not contain an amine group It was confirmed that the luminous efficiency and lifetime of the device were more excellent when the compound according to the present application was used in the organic light emitting device than when compounds E and F were used in the organic light emitting device.

100: substrate
200: anode
300: organic material layer
301: hole injection layer
302: hole transport layer
303: light emitting layer
304: hole blocking layer
305: electron transport layer
306: electron injection layer
400: cathode

Claims (9)

A heterocyclic compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
N-Het is a group represented by any one of the following formulas A-1 to A-3,
L ₁ and L ₂ are the same as or different from each other, and are each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,
X is O; or S,
R ₁ and R ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; Or a substituted or unsubstituted amine group, wherein at least one of R ₁ and R ₂ is a substituted or unsubstituted amine group,
R _m and R _n are the same as or different from each other, and each independently hydrogen; or deuterium;
a and b are each an integer from 0 to 3, and when a and b are each 2 or more, the substituents in parentheses are the same as or different from each other,
m is 1 or 2, and when m is 2, the substituents in parentheses are the same as or different from each other;
n is each an integer of 1 to 3, and when n is 2 or more, the substituents in parentheses are the same as or different from each other;
[Formula A-1]

[Formula A-2]

[Formula A-3]

In the above formulas A-1 to A-3,
X1 is CR11 or N, X2 is CR12 or N, X3 is CR13 or N, X4 is CR14 or N, X5 is CR15 or N, and at least one of X1 to X5 is N,
R11 to R15 and R17 to R22 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen; cyano group; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; A substituted or unsubstituted phosphine oxide group; And it is selected from the group consisting of a substituted or unsubstituted amine group, is a site connected to Formula 1 above. delete The method according to claim 1, wherein Formula 1 is a heterocyclic compound represented by any one of Formulas 2 to 4:
[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4, the definition of the substituent is the same as in Formula 1 above. delete The heterocyclic compound according to claim 1, wherein Formula 1 is represented by any one of the following compounds:





An organic light emitting device comprising an anode, a cathode, and at least one organic material layer provided between the anode and the cathode, wherein at least one layer of the organic material layer includes the heterocyclic compound according to any one of claims 1, 3, and 5. The organic light emitting device of claim 6, wherein the organic material layer includes one or more light emitting layers, and the light emitting layer includes the heterocyclic compound. The organic light emitting device of claim 7, wherein the light emitting layer includes two or more host materials, and at least one of the host materials includes the heterocyclic compound as a host material of the light emitting material. The method according to claim 6, wherein the organic light emitting device further comprises one layer or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole auxiliary layer, and a hole blocking layer. phosphorus organic light emitting device.