TW201722939A - Hetero-cyclic compound and organic light emitting device using the same - Google Patents

Abstract

The present application provides a hetero-cyclic compound which may significantly improve the service life, efficiency, electrochemical stability, and thermal stability of an organic light emitting device, and an organic light emitting device in which the hetero-cyclic compound is contained in an organic compound layer.

Description

Heterocyclic 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 electric fluorescent device is a type of self-luminous display device, and has the advantages of wide viewing angle, excellent contrast, and fast reaction speed.

An organic light-emitting device has a structure of an organic thin film disposed between two electrodes, and when a voltage is applied to the organic light-emitting device having the structure, electrons and holes injected from the two electrodes are combined with each other to form a pair in the organic thin film, and then Lights up when it is extinguished. The organic film may be composed of a single layer or a plurality of layers as needed.

The material for the organic film can have a light-emitting function as needed. For example, as the material for the organic thin film, a compound which can constitute the light-emitting layer itself can be used, or a compound which is a host or an additive in the host-additive light-emitting layer can be used, and as a material for the organic thin film, Compounds that perform functions such as hole injection, electron blocking, hole blocking, electron transfer, or electron injection can also be used.

In order to improve the performance, service life or efficiency of organic light-emitting devices, there is a continuing need for the development of materials for organic thin films.

It is necessary to conduct research on an organic light-emitting device comprising a compound having a chemical structure, which can satisfy conditions required for materials for an organic light-emitting device, for example, appropriate energy level, electrochemical stability, thermal stability, and the like. And various functions required for the organic light-emitting device can be performed depending on the substituent.

An exemplary embodiment of the present invention provides a heterocyclic compound represented by any one of the following Chemical Formulas 1 to 3:

[Chemical Formula 2]

In Chemical Formulas 1 to 3, Ar1-Ar6 are the same or different from each other, and each independently is a substituted or unsubstituted C ₆ -C ₆₀ aryl group; or a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group R1, R1 are the same or different from each other, and are each independently selected from hydrogen; hydrazine; halogen; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted C ₂ -C Alkenyl group of ₆₀ ; substituted or unsubstituted C ₂ -C ₆₀ alkynyl group; substituted or unsubstituted C ₁ -C ₆₀ alkoxy group; substituted or unsubstituted C ₃ -C ₆₀ naphthenic group a substituted or unsubstituted C ₂ -C ₆₀ heterocycloalkyl; a substituted or unsubstituted C ₆ -C ₆₀ aryl; a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR'R";-P(=O)RR'; unsubstituted or C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ a group consisting of a heteroaryl-substituted amine group, R, R', R" are the same or different from each other, and each independently is hydrogen; hydrazine; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkane group; a substituted or unsubstituted of C ₃ -C ₆₀ cycloalkyl group; a substituted or unsubstituted C ₆ -C ₆₀ aryl of ; Integer or a substituted or unsubstituted of C ₂ -C ₆₀ heteroaryl group, and m, n, o, p, q, r, s, t and u are each independently 0-4.

Further, another exemplary embodiment of the present invention provides an organic light emitting device including a positive electrode, a negative electrode, and an organic material layer having one or more layers disposed between the positive electrode and the negative electrode, wherein the one or more layers The organic material layer contains the heterocyclic compound represented by any one of Chemical Formulas 1 to 3.

Furthermore, another exemplary embodiment of the present invention provides an organic light-emitting device, wherein the organic material layer containing the heterocyclic compound further contains a compound represented by the following Chemical Formula 4 or 5.

Wherein in Chemical Formula 4, L1 and L2 are the same or different from each other, and each independently is a bonded or substituted or unsubstituted C ₆ -C ₆₀ arylene group, and Ar7 is substituted or not comprising at least one N; By substituting a heteroaryl group of C ₂ -C ₆₀ , Ar 8 is represented by the following Chemical Formula 6 or 7.

Wherein Y1-Y4 are the same or different from each other, and each independently is a substituted or unsubstituted C ₆ -C ₆₀ aromatic hydrocarbon ring; or a substituted or unsubstituted C ₂ -C ₆₀ aromatic heterocyclic ring, R10- R16 are the same or different from each other, and are each independently selected from hydrogen; hydrazine; halogen; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted C ₂ -C ₆₀ alkenyl Substituted or unsubstituted C ₂ -C ₆₀ alkynyl; substituted or unsubstituted C ₁ -C ₆₀ alkoxy; substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl; substituted Or unsubstituted C ₂ -C ₆₀ heterocycloalkyl; substituted or unsubstituted C ₆ -C ₆₀ aryl; substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR'R ";-P(=O)RR'; unsubstituted or substituted by C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ heteroaryl An amine group, or a group of two or more adjacent groups bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring, and R, R' and R" are the same or different from each other And each independently hydrogen; 氘; -CN; substituted or unsubstituted C ₁ -C ₆₀ Alkyl; substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl; substituted or unsubstituted C ₆ -C ₆₀ aryl; or substituted or unsubstituted C ₂ -C ₆₀ heteroaryl Base, and

In Chemical Formula 5, at least one of X1 to X3 is N, and the others are each independently N or CR35, and R17, R18 and R35 are the same or different from each other, and are each independently selected from hydrogen; hydrazine; halogen; -CN; Or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted C ₂ -C ₆₀ alkenyl; substituted or unsubstituted C ₂ -C ₆₀ alkynyl; substituted or unsubstituted C _1- C ₆₀ alkoxy; substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl; substituted or unsubstituted C ₂ -C ₆₀ heterocycloalkyl; substituted or unsubstituted C ₆ -C ₆₀ aryl; substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR'R";-P(=O)RR'; unsubstituted or C ₁ -C ₂₀ alkane a substituted, unsubstituted or unsubstituted C ₆ -C ₆₀ aryl group or a C ₂ -C ₆₀ heteroaryl substituted amine group, or two or more adjacent groups bonded to each other to form a substituted or unsubstituted group a group consisting of aliphatic or aromatic hydrocarbon rings, R19-R21 and R27-R30 are the same or different from each other, and are each independently selected from hydrogen; hydrazine; halogen, -CN; substituted or unsubstituted C ₁ - C ₆₀ alkyl; substituted or unsubstituted C ₂ -C ₆₀ alkenyl; substituted Or unsubstituted C ₂ -C ₆₀ alkynyl; substituted or unsubstituted C ₁ -C ₆₀ alkoxy; substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl; substituted or not Substituted C ₂ -C ₆₀ heterocycloalkyl; substituted or unsubstituted C ₆ -C ₆₀ aryl; substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR'R";- P(=O)RR'; an amine group which is unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₆ -C ₆₀ aryl group or a C ₂ -C ₆₀ heteroaryl group The group consisting of R31-R34 are the same or different from each other, and are each independently selected from hydrogen; hydrazine; halogen; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted Alkenyl C ₂ -C ₆₀ ; substituted or unsubstituted C ₂ -C ₆₀ alkynyl; substituted or unsubstituted C ₁ -C ₆₀ alkoxy; substituted or unsubstituted C ₃ -C _a cycloalkyl group of ₆₀ ; a substituted or unsubstituted C ₂ -C ₆₀ heterocycloalkyl; a substituted or unsubstituted C ₆ -C ₆₀ aryl group; a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR'R "; - P (= O) RR '; unsubstituted or alkyl group of C ₁ -C _20, a substituted or unsubstituted C ₆ -C ₆₀ aryl of Or the substituted C ₂ -C ₆₀ hetero aryl group of group, or two or more adjacent groups bonded to each other to form the group consisting of a substituted or unsubstituted hydrocarbon ring or heterocyclic ring, R22-R26 least One is -CN, and the others are each independently selected from hydrogen; hydrazine; halogen; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted C ₂ -C ₆₀ alkenyl Substituted or unsubstituted C ₂ -C ₆₀ alkynyl; substituted or unsubstituted C ₁ -C ₆₀ alkoxy; substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl; substituted Or unsubstituted C ₂ -C ₆₀ heterocycloalkyl; substituted or unsubstituted C ₆ -C ₆₀ aryl; substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR'R ";-P(=O)RR'; unsubstituted or substituted by C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ heteroaryl An amine group, or a group of two or more adjacent groups bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring, R, R' and R" are the same or different from each other, And each independently is hydrogen; 氘; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; a substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group; a substituted or unsubstituted C ₆ -C ₆₀ aryl group; or a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group.

The heterocyclic compound according to an exemplary embodiment of the present invention may be used as a material for an organic material layer of an organic light-emitting device which can be used as a hole injection layer, a hole transfer layer, or the like in an organic light-emitting device. A material such as a light-emitting layer, an electron transport layer, or an electron injection layer. In particular, the heterocyclic compound represented by any one of Chemical Formulas 1 to 3 can be used as a material for an electron transport layer, a hole transport layer or a light-emitting layer of an organic light-emitting device, and further, any one of Chemical Formulas 1 to 3 When the heterocyclic compound is used in an organic light-emitting device, the driving voltage of the device can be lowered, the luminous efficiency of the device can be improved, and the service life of the device can be improved due to the thermal stability of the compound.

In particular, according to an exemplary embodiment of the present invention, the organic light-emitting device includes, as a host material for a light-emitting layer, a heterocyclic compound represented by any one of Chemical Formulas 1 to 3; and a compound represented by Chemical Formula 4 or 5. Therefore, compared with an organic light-emitting device using a single compound as a host material, it is possible to exhibit characteristics that are significantly improved in driving, efficiency, and service life.

100‧‧‧Substrate

200‧‧‧ positive electrode

300‧‧‧ organic material layer

301‧‧‧ hole injection layer

302‧‧‧ hole transfer layer

303‧‧‧Lighting layer

304‧‧‧ hole barrier

305‧‧‧Electronic transmission layer

306‧‧‧Electronic injection layer

400‧‧‧negative electrode

1 to 3 each schematically illustrate a view of a stacked structure of an organic light-emitting device according to an exemplary embodiment of the present invention.

The invention will be described in detail herein.

According to an exemplary embodiment of the present invention, the heterocyclic compound represented by any one of Chemical Formulas 1 to 3, more specifically, the heterocyclic compound is represented by any one of Chemical Formulas 1 to 3, and can be constituted by a core structure and The structural characteristics of the above substituents are used as materials for the organic light-emitting device for the organic material layer.

In an exemplary embodiment of the present invention, R1 to R9 of Chemical Formulas 1 to 3 are each independently hydrogen or hydrazine.

In the present invention, the substituent of the formula will be described more specifically below.

In the present invention, "substituted or unsubstituted" means unsubstituted or substituted by one or more substituents selected from the group consisting of hydrazine; halogen; -CN; C ₁ -C ₆₀ alkyl; C ₂ -C ₆₀ alkenyl; C ₂ -C ₆₀ alkynyl; C ₃ -C ₆₀ cycloalkyl; C ₂ -C ₆₀ heterocycloalkyl; C ₆ -C ₆₀ aryl; C ₂ -C ₆₀ heteroaryl; -SiRR'R";-P(=O)RR'; C ₁ -C ₂₀ alkylamine; C ₆ -C ₆₀ arylamine: and C ₂ -C ₆₀ heteroaryl a group consisting of an amine group, or a substituent which is unsubstituted or bonded by two or more substituents in the substituent, or which represents unsubstituted or selected from two or more of the substituents The substituent is substituted with a substituent. For example, "a substituent in which two or more substituents are bonded" may be a biphenyl group, that is, a biphenyl group may also be an aryl group, and may be interpreted as a substitution of two phenyl groups. base. Additional substituents may also be additionally substituted. R, R' and R" are mutually or different and each independently hydrogen; hydrazine; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted C ₃ -C ₆₀ a cycloalkyl group; a substituted or unsubstituted C ₆ -C ₆₀ aryl group; or a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group.

According to an exemplary embodiment of the invention, "substituted or unsubstituted" means unsubstituted or substituted by one or more substituents selected from the group consisting of hydrazine, halogen, -CN, -SiRR'R", -P(=O)RR', a group of C ₁ -C ₂₀ linear or branched alkyl groups, a C ₆ -C ₆₀ aryl group, and a C ₂ -C ₆₀ heteroaryl group, and R , R' and R" are the same or different from each other, and are each independently hydrogen; hydrazine; -CN; unsubstituted or fluorene, halogen, -CN, C ₁ -C ₂₀ alkyl, C ₆ -C ₆₀ Alkyl, C ₂ -C ₆₀ heteroaryl substituted C ₁ -C ₆₀ alkyl; unsubstituted or fluorenyl, halogen, -CN, C ₁ -C ₂₀ alkyl, C ₆ -C ₆₀ Aryl, C ₂ -C ₆₀ heteroaryl substituted C ₃ -C ₆₀ cycloalkyl; unsubstituted or fluorenyl, halogen, -CN, C ₁ -C ₂₀ alkyl, C ₆ -C ₆₀ An aryl group, a C ₆ -C ₆₀ heteroaryl substituted C ₆ -C ₆₀ aryl group; or an unsubstituted or fluorene, halogen, -CN, C ₁ -C ₂₀ alkyl group, C ₆ -C ₆₀ aryl, C ₂ -C ₆₀ heteroaryl substituted C ₂ -C ₆₀ heteroaryl.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound becomes another substituent, and the position to be substituted is not limited as long as the position is the position at which the hydrogen atom is substituted, that is, the position at which the substituent is substituted. And when two or more are substituted, the two or more substituents may be the same or different from each other.

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

In the present specification, the alkyl group contains a straight chain or a branched chain having 1 to 60 carbon atoms, and may be additionally substituted with another substituent, and the alkyl group may have 1 to 60 carbon atoms, specifically 1 to 40. More specifically 1-20. Specific examples thereof include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, t-butyl, t-butyl, 1-methyl-butyl, 1 -ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-amyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl -2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, N-octyl, trioctyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-decyl, 2,2-dimethylheptyl, 1-ethyl-propyl 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.

In the present specification, the alkenyl group contains a straight chain or a branched chain having 2 to 60 carbon atoms, and may be additionally substituted with another substituent, and the alkenyl group may have a carbon number of 2 to 60, specifically 2 to 40. More specifically 2-20. Specific examples thereof include a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, and a 3-pentene group. , 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylethen-1-yl, 2-phenylethen-1-yl, 2,2- Diphenylethylene-1-yl, 2-phenyl-2-(naphthalen-1-yl)ethen-1-yl, 2,2-biphenyl-1-ylvinyl-1-yl, diphenyl Ethylene, styrene, etc., but not limited thereto.

In the present specification, an alkynyl group contains a straight chain or a branched chain having 2 to 60 carbon atoms, and may be additionally substituted with another substituent, and the alkynyl group may have a carbon number of 2 to 60, specifically 2 to 40. More specifically 2-20.

In the present specification, a cycloalkyl group contains a monocyclic or polycyclic ring having 3 to 60 carbon atoms, and may be additionally substituted with another substituent, where the polycyclic ring means that the cycloalkyl group is directly bonded or fused to another A group of a ring group, wherein the other ring group may also be a cycloalkyl group, but may be another type of ring group such as a heterocycloalkyl group, an aryl group, a heteroaryl group or the like. The cycloalkyl group may have a carbon number of from 3 to 60, specifically from 3 to 40, more specifically from 5 to 20. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclo Hexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are not limited thereto.

In the present specification, a heterocycloalkyl group includes a monocyclic or polycyclic ring having O, S, Se, N or Si as a hetero atom and having 2 to 60 carbon atoms, and may be additionally substituted by another substituent. Thus, the polycyclic ring means a group in which a heterocycloalkyl group is directly bonded or fused to another ring group, and the other ring group may also be a heterocycloalkyl group, but may be another type of ring group, such as a ring. Alkyl, aryl, heteroaryl, and the like. The heterocycloalkyl group may have a carbon number of from 2 to 60, specifically from 2 to 40, more specifically from 3 to 20.

In the present specification, an aryl group contains a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be additionally substituted with another substituent, where the polycyclic ring means that the aryl group is directly bonded or fused to another cyclic group. The group here may also be an aryl group, but may be another type of ring group such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group or the like, and the aryl group contains a spiro ring group. The aryl group may have a carbon number of 6 to 60, specifically 6 to 40, more specifically 6 to 25. Specific examples of the aryl group include phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, chrysenyl, phenanthrenyl, perylenyl, fluoranthenyl , stretching triphenylenyl, phenalenyl, pyrenyl, tetracenyl, pentacenyl, fluorenyl, indenyl, Acenaphthylenyl, benzofluorenyl, spirobifluorenyl, 2,3-dihydro-1H-indenyl, fused ring groups thereof, and the like, but not limited thereto .

In the present specification, a spiro group is a group containing a spiro ring structure and has 15 to 60 carbon atoms, and for example, the spiro group may include a 2-2-3 dihydro-1H-indenyl group or a cyclohexyl group and an anthracene. The structure of the base spiro-bond, in particular, the spiro group may comprise any of the following structural groups.

In the present specification, a heteroaryl group contains a single or polycyclic ring having S, O, Se, N or Si as a hetero atom and having 2 to 60 carbon atoms, and may be additionally substituted with another substituent, The polycyclic ring represents a group in which a heteroaryl group is directly bonded or fused to another ring group, and the other ring group may also be a heteroaryl group, but may be another type of ring group, such as a cycloalkyl group, Heterocycloalkyl, aryl, and the like. The heteroaryl group may have a carbon number of from 2 to 60, specifically from 2 to 40, more specifically from 3 to 25. Specific examples of the heteroaryl group include pyridyl, pyrrolyl, pyrimidyl, pyridazinyl, furanyl, thiophene, imidazolyl, Pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, three Triazolyl, furazanyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, Thiopyranyl, diazinyl, oxazinyl, thiazinyl, dioxynyl, triazinyl, tetrazinyl Tetrazinyl), quinolyl, isoquinolyl, quinazolinyl, isoquinazolinyl, quinozolilyl, naphthyridyl, Acridinyl, phenanthridinyl, imidazopyridinyl, diaza naphthalenyl, triazaindene, indolyl, pyridazine Indolizinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothiophene, benzofuran, dibenzothiophene ), dibenzofuran, carbazolyl, benzocarbazo Lyl), dibenzocarbazolyl, phenazinyl, dibenzosilole, spirobi(dibenzosilole), dihydromorphazine Dihydrophenazinyl, phenoxazinyl, phenanthridyl, thienyl, 吲哚[2,3-a]oxazolyl, 吲哚[2,3-b]carbazole , porolinyl, 10,11-dihydro-dibenzo[b,f]azepin, 9,10-dihydroanthracene Pyridyl, phenanthrazinyl, phenothiazinyl, phthalazinyl, naphthylidinyl, phenanthrolinyl, benzo[c][1,2, 5] thiadiazolyl, 5,10-dihydrodibenzo[b,e][1,4]fluorenyl (5,10-dihydrodibenzo[b,e][1,4]azasilinyl), pyrazole And [1,5-c]quinazolinyl, pyrido[1,2-b]oxazolyl, pyrido[1,2-a]imidazo[1,2-e]porphyrinyl, 5 , 11-dihydroindeno[1,2-b]oxazolyl and the foregoing approximation, but not limited thereto.

In the present specification, the amine group may be selected from a monoalkylamino group; a monoarylamine group; a monoheteroarylamino group; -NH2; a dialkylamino group; a diarylamino group; a diheteroarylamino group. The group consisting of an alkylarylamino group; an alkylheteroarylamino group; and an arylheteroarylamino group, and the number of carbon atoms thereof is not particularly limited, but is preferably from 1 to 30. Specific examples of the amine group include a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a phenylamino group, a naphthylamino group, a biphenylamino group, a diphenylamine group. Base, mercaptoamine group, 9-methyl-decylamino group, diphenylamino group, phenylnaphthylamino group, xylylamino group, phenyltolylamino group, triphenylamino group, linked Phenylnaphthylamino, phenylbiphenylamino, biphenylnonylamino, phenyl-terminated triphenylamine, biphenyltriphenylenylamine, and the foregoing approximations, but Not limited to this.

In the present specification, arylene means that there are two bonding positions in the phenyl group, that is, a divalent group, except for a divalent arylene group, the above description of the aryl group. It can be applied to an arylene group. Further, the heteroarylene means that there are two bonding positions in the heteroaryl group, that is, a divalent group, except for the divalent heteroarylene group, the above description of the heteroaryl group It can be applied to an arylene group.

According to an exemplary embodiment of the present invention, the compound represented by any one of Chemical Formulas 1 to 3 may be represented by any of the following compounds, but is not limited thereto.

Further, a compound having an intrinsic property of introducing a substituent can be synthesized by introducing various substituents into the structure of any of Chemical Formulas 1 to 3. For example, a material for a hole injection layer, a material for transmitting a hole, a material of a light-emitting layer, and an electron transport layer, which are generally used for an organic light-emitting device, can be introduced into a core structure to synthesize each organic material layer. Materials required.

Further, by introducing various substituents into the structure of any of Chemical Formulas 1 to 3, the energy gap is finely adjusted, and at the same time, the characteristics at the interface between the organic materials can be improved, and the use of the materials can be diversified.

At the same time, the heterocyclic compound has a high glass transition temperature (Tg), and thus has excellent thermal stability, and an increase in thermal stability is an important factor for the device to provide driving stability.

The heterocyclic compound according to an exemplary embodiment of the present invention can be produced by a multi-step chemical reaction, first preparing some intermediate compounds, and any of Chemical Formulas 1 to 3 can be prepared from an intermediate compound, more specifically, according to the present invention. The heterocyclic compound of one exemplary embodiment can be prepared from the preparation examples described below.

An exemplary embodiment of the present invention provides an organic light-emitting device comprising the compound represented by any one of Chemical Formulas 1 to 3.

Another exemplary embodiment of the present invention provides an organic light emitting device including a positive electrode, a negative electrode, and a layer of organic material having one or more layers disposed between a positive electrode and a negative electrode, wherein the organic material layer A light-emitting layer comprising: a heterocyclic compound represented by any one of Chemical Formulas 1 to 3; and a compound represented by Chemical Formula 4 or 5.

In Chemical Formulas 6 and 7, * represents a position to which L2 of Chemical Formula 4 is bonded.

According to an exemplary embodiment of the present invention, Chemical Formula 6 may be represented by any of the following structural formulas.

In the formula, X1-X6 are the same or different from each other, and are each independently NR, S, O or CR'R", R8-R14 are the same or different from each other, and are each independently selected from hydrogen; hydrazine; halogen; CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted C ₂ -C ₆₀ alkenyl; substituted or unsubstituted C ₂ -C ₆₀ alkynyl; substituted or Unsubstituted C ₁ -C ₆₀ alkoxy; substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl; substituted or unsubstituted C ₂ -C ₆₀ heterocycloalkyl; substituted or not Substituted C ₆ -C ₆₀ aryl; substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR'R";-P(=O)RR'; and unsubstituted or via C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ heteroaryl substituted amine, or two or more adjacent groups bonded to each other to form A group of substituted or unsubstituted aliphatic or aromatic hydrocarbon rings.

R, R' and R" are the same or different from each other and are each independently hydrogen; hydrazine; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted C ₃ -C ₆₀ a cycloalkyl group; a substituted or unsubstituted C ₆ -C ₆₀ aryl group; or a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group, and m is an integer from 0 to 8, and n, o , p, q, r and s are each independently an integer from 0 to 6.

According to an exemplary embodiment of the present invention, Chemical Formula 7 may be represented by any of the following structural formulas.

In the formula, X7 and X8 are the same or different from each other, and are each independently NR, S, O or CR'R", R15-R18 are the same or different from each other, and are each independently selected from hydrogen; hydrazine; halogen; CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted C ₂ -C ₆₀ alkenyl; substituted or unsubstituted C ₂ -C ₆₀ alkynyl; substituted or Unsubstituted C ₁ -C ₆₀ alkoxy; substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl; substituted or unsubstituted C ₂ -C ₆₀ heterocycloalkyl; substituted or via Substituting a C ₆ -C ₆₀ aryl group; a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group; -SiRR'R";-P(=O)RR'; and unsubstituted or C ₁ - An alkyl group of C ₂₀ , a substituted or unsubstituted C ₆ -C ₆₀ aryl group or a C ₂ -C ₆₀ heteroaryl substituted amine group, or two or more adjacent groups bonded to each other to form a substituted or a group consisting of unsubstituted aliphatic or aromatic hydrocarbon rings, R, R' and R" are the same or different from each other and are each independently hydrogen; hydrazine; -CN; substituted or unsubstituted C ₁ - C ₆₀ alkyl; substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl; substituted or not An aryl group substituted with C ₆ -C ₆₀ ; or a heteroaryl group substituted or unsubstituted with C ₂ -C ₆₀ , and t is an integer from 0 to 7.

In an exemplary embodiment of the invention, R10-R15 of Chemical Formula 4 are each independently hydrogen or deuterium.

According to an exemplary embodiment of the present invention, the compound represented by Chemical Formula 4 may be represented by any of the following compounds, but is not limited thereto.

In an exemplary embodiment of the present invention, in Chemical Formula 5, one of X1-X3 may be N, X1-X3 may be N, and X1-X3 may all be N.

In an exemplary embodiment of the present invention, R17 and R18 of Chemical Formula 5 may each independently be a substituted or unsubstituted C _6- C ₆₀ aryl group; or a substituted or unsubstituted C ₂ -C ₆₀ hetero Aryl.

In an exemplary embodiment of the present invention, R19-R21 of Chemical Formula 5 may each independently be hydrogen or deuterium.

In an exemplary embodiment of the present invention, either of R22 to R26 of Chemical Formula 5 may be -CN, and the remainder may each independently be hydrogen or hydrazine.

According to an exemplary embodiment of the present invention, the compound represented by Chemical Formula 5 may be represented by any of the following compounds, but is not limited thereto.

The organic light-emitting device according to an exemplary embodiment of the present invention may contain, as a host material for the light-emitting layer, a heterocyclic compound represented by any one of Chemical Formulas 1 to 3; and a compound represented by Chemical Formula 4 or 5. In this case, the doping material for the light-emitting layer may use a material well known in the art.

In the host material, the heterocyclic compound represented by any one of Chemical Formulas 1 to 3: the compound represented by Chemical Formula 4 or 5 may have a weight ratio of 1:10 to 10:1, 1:8 to 8:1. 1,5-5:1, 1:2-2:1 and 1:1, but not limited to this.

The host material is a form in which two or more compounds are simply mixed, and the powdery host material may be mixed before the organic material layer of the organic light-emitting device is formed, and the compound in a liquid state may be mixed at a temperature equal to or higher than a suitable temperature. The host material is in a solid state at a temperature equal to or less than the melting point of each material, and can be maintained in the liquid by adjusting the temperature.

An organic light-emitting device according to an exemplary embodiment of the present invention, except that one or more organic material layers are formed by using a heterocyclic compound represented by any one of Chemical Formulas 1 to 3 and a compound represented by Chemical Formula 4 or In addition, it can be prepared by general methods and materials for fabricating organic light-emitting devices.

When the organic light-emitting device is manufactured, the heterocyclic compound can be formed as an organic material layer not only by a vacuum deposition method but also by a solution application method. Here, the solution application method means spin coating, dip coating, ink jet printing, screen printing, spray coating, roll coating, and the like, but is not limited thereto.

The compound represented by Chemical Formulas 1 to 3 can be used as a material for an electron transport layer, a hole barrier layer, or a light-emitting layer in an organic light-emitting device, for example, a compound represented by Chemical Formulas 1 to 3 can be used as an organic light-emitting device. The material of the electron transport layer, the hole transport layer or the light-emitting layer.

Further, the compound represented by Chemical Formulas 1 to 3 can be used as a material for the light-emitting layer in the organic light-emitting device, and for example, the compound represented by Chemical Formulas 1 to 3 can be used as a material for the phosphorescent host for the light-emitting layer in the organic light-emitting device. .

Further, the organic material layer containing the compound represented by Chemical Formulas 1 to 3 may additionally contain other materials if necessary.

The compound represented by Chemical Formulas 1 to 3 can be used as a material for the charge generating layer in the organic light-emitting device.

The compound represented by Chemical Formulas 1 to 3 can be used as an electron transporting layer, an electroconductive barrier layer, a light-emitting layer, or the like as an approximation in an organic light-emitting device. For example, a compound represented by Chemical Formulas 1 to 3 can be used as an organic light-emitting device. The material of the electron transport layer, the hole transport layer, or the light-emitting layer.

Further, the compound represented by Chemical Formulas 1 to 3 can be used as a material for the light-emitting layer in the organic light-emitting device, and for example, the compound represented by Chemical Formulas 1 to 3 can be used as a material for the phosphorescent host for the light-emitting layer in the organic light-emitting device. .

1 to 3 illustrate stacked sequences of electrodes and organic material layers in an organic light-emitting device according to an exemplary embodiment of the present invention, however, the scope of the present invention is not limited to the drawings, and may be well known in the field of the present invention. The structure of the organic hair device is applied to the present invention.

According to FIG. 1, an organic light-emitting device in which a positive electrode 200, an organic material layer 300, and a negative electrode 400 are sequentially stacked on a substrate 100 is illustrated. However, the organic light-emitting device is not limited to this one As shown in FIG. 2, an organic light-emitting device in which a negative electrode, an organic material layer, and a positive electrode are sequentially stacked on a substrate can also be implemented.

Figure 3 illustrates the case where the organic material layer is a plurality of layers. The organic light-emitting device according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, a light-emitting layer 303, a hole barrier layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present invention is not limited to the above-described stacked structure, and if necessary, other layers may be omitted except for the luminescent material layer, and another necessary functional layer may be further added.

An organic light-emitting device according to an exemplary embodiment of the present invention will exemplify materials other than the compounds of Chemical Formulas 1 to 5, but the materials are for illustrative purposes only, are not intended to limit the scope of the present invention, and may be well known in the art. Replaced by the material.

As the material of the positive electrode, a material having a relatively high work function can be used, and a transparent conductive oxide, a metal or a conductive polymer can be used, and specific examples of the positive electrode material include: metals such as vanadium, chromium, copper, zinc, gold. Or an alloy thereof; a metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); a combination of a metal and an oxide such as ZnO:Al or SnO ₂ :Sb; a conductive polymer Such as poly(3-methyl compound), poly[3,4-(ethylene-1,2-dioxy)thiophene (PEDT), Polypyrrole and polyaniline, etc., but are not limited thereto.

As the material of the negative electrode, a material having a relatively low work function can be used, and a metal, a metal oxide or a conductive polymer can be used, and specific examples of the negative electrode material include: metals such as magnesium, calcium, sodium, potassium, titanium, Indium, antimony, lithium, antimony, aluminum, silver, tin, lead or alloys thereof; multilayer structural materials such as LiF/Al or LiO ₂ /Al, and their approximations, but are not limited thereto.

As the material of the electric injection layer, a hole injection material which is well known in the public can be used, and for example, phthalocyanine, such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429, or in the literature [Advanced Material, 6 , a starburst-type amine derivative described in p. 677 (1994), such as tris(4-carbazol-9-ylphenyl) Amine, TCTA), 4,4',4"-tris[phenyl(o-tolyl)amine]triphenylamine, 4,4',4"-tris(phenyl(m-tolyl)amino)triphenylamine, m-MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamine)phenyl]benzene, 1,3,5-tris[4-(3-metylphenylphenylamino)phenyl]benzene, m-MTDAPB), polyaniline/dodecylbenzenesulfonic acid, or soluble conductive polymer poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate), polyaniline/camphor Sulfonic acid, or polyaniline/poly(4-styrene-sulfonate), and similar approximations.

As the material of the hole transport layer, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative or the like can be used, and a low molecular weight or polymerization can also be used. Material.

As the material of the electron transport layer, an oxadiazole derivative, anthraquinodimethane and a derivative thereof, benzoquinone and a derivative thereof, naphthoquinone and a derivative thereof can be used. , anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone and its derivatives, diphenyldicyanoethylene and its derivatives, two As the diphenoquinone derivative, the metal complex of 8-hydroxyquinoline, and the above derivatives, a low molecular weight material and a polymer material can also be used.

As a material of the electron injecting layer, for example, LiF is typically used in the art, but the present invention is not limited thereto.

The organic light-emitting device according to an exemplary embodiment of the present invention may be a top emission type, a bottom emission type, or a dual emission type depending on the material used.

The heterocyclic compound according to an exemplary embodiment of the present invention can be applied to an organic electronic device based on a similar principle applied to an organic light-emitting device, and includes an organic solar cell, an organic photoconductor, an organic transistor, and the like.

The description of the present invention will be described in more detail by way of example only, but the description of the present invention is only intended to be illustrative of the invention.

<Example>

[Synthesis Example 1] Preparation of Compound H

Preparation of Compound H

2-Bromodibenzofuran (30 g, 121.41 mmol) and tetrahydrofuran (300 ml) were placed in a reaction flask, the temperature was cooled to -78 ° C, and lithium diisopropylamide (LDA) solution (1.8 M) was slowly added dropwise. , 88 ml), the temperature was maintained at -78 ° C for 1 hour, followed by the addition of solid iodine (33.9 g, 133.55 mmol) at room temperature for 4 hours, extracted with distilled water and dichloromethane, and the extract was dissolved in dichloromethane. The resulting solution was filtered with EtOAc (EtOAc) and EtOAc (EtOAc).

[Preparation Example 1-1] Preparation of Compound 1-1

Preparation of Compound 1-1-1

Compound H (20 g, 53.62 mmol), (9-phenyl-9H-indazol-2-yl)boronic acid (15.4 g, 53.62 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ , 3.1 g, 2.68 mmol), potassium carbonate (14.82 g, 107.24 mmol), 1,4-dioxane (300 ml), water (60 ml) in a reaction flask, and the mixture was heated to 120 ° C for 12 hours to form The product was cooled to room temperature and extracted with distilled water and dichloromethane, then the extract was dissolved in dichloromethane, and the resulting solution was filtered with silica gel, diatomaceous earth and magnesium silicate (florisil) and the solvent was removed through the column layer. The title compound 1-1-1 (7.5 g, 40%) was obtained by chromatography.

Preparation of Compound 1-1

Compound 1-1-1 (5 g, 10.24 mmol), (9-phenyl-9H-indazol-2-yl)boronic acid (5.88 g, 20.48 mmol), Pd(PPh ₃ ) ₄ (0.59 g, 0.51 mmol) , potassium carbonate (4.25g, 30.72mmol), cesium fluoride (3.1g, 20.48mmol) in toluene / ethanol / water (60 / 10/10ml) solution, the mixture is heated to 100 ° C for 12 hours, will The resulting product was cooled to room temperature and extracted with distilled water and dichloromethane, then the extract was dissolved in dichloromethane, and the resulting solution was filtered over silica gel, diatomaceous earth, magnesium silicate, and solvent was removed through the column layer. The title compound 1-1 (4.1 g, 65%) was obtained.

In addition to the preparation of the compound 1-1-1 in Preparation Example 1-1, the (9-phenyl-9H-carbazol-2-yl)boronic acid was replaced with the intermediate in the following Table 1, and Preparation Example 1 1 The same preparation method was used to synthesize the target compound A.

[Table 1]

[Preparation Example 2-1] Preparation of Compound 2-1

Preparation of Compound 2-1-1

Compound H (30 g, 61.40 mmol), (9-phenyl-9H-indazol-2-yl)boronic acid (17.63 g, 61.40 mmol), Pd(PPh ₃ ) ₄ (3.1 g, 3.55 mmol), potassium carbonate (25.46g, 184.2mmol), 1,4-dioxane (300ml) and water (60ml) in a reaction flask, the mixture is heated to 120 ° C for 12 hours, the product is cooled to room temperature, and distilled water And dichloromethane extraction, and then the extract is dissolved in dichloromethane, the resulting solution is filtered with silica gel, diatomaceous earth and magnesium silicate (florisil) and the solvent is removed, and the target compound 2-1- is obtained by column chromatography. 1 (17.95 g, 60%).

Preparation of Compound 2-1

Compound 2-1-1 (7 g, 14.33 mmol), (9-phenyl-9H-indazol-2-yl)boronic acid (8.23 g, 28.66 mmol), Pd(PPh ₃ ) ₄ (0.83 g, 0.72 mmol) ), potassium carbonate (5.94 g, 42.99 mmol), cesium fluoride (3.1 g, 20.48 mmol) in a solution of toluene / ethanol / water (80 / 16 / 16 ml), the mixture is heated to 100 ° C for 12 hours, will The resulting product was cooled to room temperature and extracted with distilled water and dichloromethane, then the extract was dissolved in dichloromethane, and the resulting solution was filtered over silica gel, diatomaceous earth, magnesium silicate, and solvent was removed through the column layer. The title compound 2-1 (6.5 g, 70%) was obtained.

The title compound A was synthesized in the same manner as in Preparation 2-1 except for the preparation of the compound 2-1-1 in Preparation 2-1, using the intermediate A in the following Table 2 (9-phenyl- 9H-indazol-2-yl)boronic acid, and in the preparation of compound 2-1, (B-phenyl-9H-indazol-2-yl)boronic acid was replaced with the intermediate B in the following Table 2.

[Preparation Example 3-1] Preparation of Compound 3-1

Preparation of Compound 3-1-1

Compound H (20 g, 53.62 mmol), (9-phenyl-9H-indazol-2-yl)boronic acid (15.4 g, 53.62 mmol), Pd(PPh ₃ ) ₄ (3.1 g, 2.68 mmol), potassium carbonate (14.82g, 107.24mmol), 1,4-dioxane (300ml) and water (60ml) in a reaction flask, the mixture is heated to 120 ° C for 12 hours, the product is cooled to room temperature, and distilled water And dichloromethane extraction, and then the extract is dissolved in dichloromethane, and the resulting solution is filtered with silica gel, diatomaceous earth and magnesium silicate (florisil) and the solvent is removed, and the target compound 3-1- is obtained by column chromatography. 1 (7.5 g, 40%).

Preparation of Compound 3-1

Compound 3-1-1 (8 g, 16.37 mmol), (9-phenyl-9H-indazol-3-yl)boronic acid (9.4 g, 32.76 mmol), Pd(PPh ₃ ) ₄ (0.94 g, 0.82 mmol) ), potassium carbonate (6.79 g, 49.14 mmol), cesium fluoride (4.9 g, 32.76 mmol) in toluene / ethanol / water (60 / 10/10 ml), the mixture is heated to 100 ° C for 12 hours, will The resulting product was cooled to room temperature and extracted with distilled water and dichloromethane, then the extract was dissolved in dichloromethane, and the resulting solution was filtered over silica gel, diatomaceous earth, magnesium silicate, and solvent was removed through the column layer. The title compound 3-1 (6.9 g, 65%) was obtained.

The title compound A was synthesized in the same manner as in Preparation Example 3-1 except that the preparation of the compound 3-1-1 in Preparation Example 3-1 was substituted with the intermediate A in the following Table 3 (9-phenyl- 9H-carbazol-2-yl)boronic acid, and in the preparation of compound 3-1, (B-phenyl-9H-carbazol-3-yl)boronic acid was replaced with the intermediate B in the following Table 3.

[Preparation Example 4-1] Preparation of Compound 4-11

Preparation of Compound 4-11-2

2-Bromodibenzo[b,d]thiophene (5.0 g, 19.0 mmol), 9H-carbazole (2.6 g, 15.8 mmol), copper iodide (3.0 g, 15.8 mmol), trans-1,2- Diaminocyclohexane (1.9 ml, 15.8 mmol), potassium phosphate (3.3 g, 31.6 mmol) was dissolved in 1,4-dioxane (100 ml), and the mixed solution was refluxed for 24 hours. Distilled water and dichloromethane were added at room temperature, the organic layer was dried over magnesium sulfate, and the solvent was evaporated on a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane:hexane = 1:3) Recrystallization from methanol gave the title compound 4-11-2 (4.7 g, 85%).

Preparation of Compound 4-11-1

A mixed solution of the compound 4-11-2 (5 g, 14.3 mmol) and tetrahydrofuran (100 ml) was formed at -78 ° C, and n-butyllithium (n-BuLi, 2.5 M, 7.4 ml, 18.6 mmol) was added dropwise, and The mixture was stirred at room temperature for 1 hour, then trimethyl borate (B(OMe) ₃ , 4.8 ml, 42.9 mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours until the reaction was completed. After that, extraction was carried out by adding distilled water and dichloromethane at room temperature, the organic layer was dried over magnesium sulfate and solvent was evaporated on a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane: methanol = 100: 3), and recrystallized from dichloromethane to give the title compound 4-11-1 (3.9 g, 70%).

Preparation of Compound 4-11

Take compound 4-11-1 (7.5 g, 19.0 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1 g, 19.0 mmol), Pd(PPh ₃ ) ₄ ( 1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours, after the reaction was completed, in the room. Extraction was carried out by adding distilled water and dichloromethane under temperature, and the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane:hexane = 1:3). Recrystallization from methanol gave the title compound 4-11 (7.7 g, 70%).

[Preparation Example 4-2] Preparation of Compound 4-11

Take compound 4-11-1 (7.5 g, 19.0 mmol), 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-tri Pyridine (6.5 g, 19.0 mmol), Pd(PPh ₃ ) ₄ (1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) dissolved in a solution of toluene/ethanol/water (100/20/20 ml). The resulting solution was then refluxed for 12 hours. After the reaction was completed, distilled water and dichloromethane were added at room temperature for extraction, the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator. Purification by chromatography (dichloromethane:hexane = 1 : 3), and then crystallised from methanol to afford title compound 4-12 (8.7 g, 70%).

[Preparation Example 4-3] Preparation of Compound 4-28

Take compound 4-11-1 (7.5 g, 19.0 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5 triazine (7.4 g, 19.0 mmol), Pd ( PPh ₃ ) ₄ (1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours until the reaction After completion, extraction was carried out by adding distilled water and dichloromethane at room temperature, and the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane:hexane =1:3), and recrystallized from methanol to give the title compound 4-28 (8.7 g, 70%).

[Preparation Example 4-4] Preparation of Compound 4-36

Take compound 4-11-1 (7.5 g, 19.0 mmol), 2-(4-bromophenyl)-4,6-diphenyl-1,3,5 triazine (7.4 g, 19.0 mmol), Pd ( PPh ₃ ) ₄ (1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours until the reaction After completion, extraction was carried out by adding distilled water and dichloromethane at room temperature, and the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane:hexane =1:3), and recrystallized from methanol to give the title compound 4-36 (8.7 g, 70%).

[Preparation Example 4-5] Preparation of Compound 4-39

Preparation of Compound 4-39-2

Take 2-bromodibenzo[b,d]thiophene (5.0 g, 19.0 mmol), 2-benzyl-9H-carbazole (3.8 g, 15.8 mmol), copper iodide (3.0 g, 15.8 mmol), reverse -1,2-Diaminocyclohexane (1.9 ml, 15.8 mmol), potassium phosphate (3.3 g, 31.6 mmol) was dissolved in 1,4-dioxane (100 ml), and the mixture was refluxed for 24 hours. After the reaction was completed, distilled water and dichloromethane were added thereto at room temperature, and the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane:hexane =1:3), and recrystallized from methanol to give the title compound 4-39-2 (5.7 g, 85%).

Preparation of Compound 4-39-1

A mixed solution of the compound 4-39-2 (6.1 g, 14.3 mmol) and tetrahydrofuran (100 ml) was formed at -78 ° C, and n-butyllithium (n-BuLi, 2.5 M, 7.4 ml, 18.6 mmol) was added dropwise. The mixture was stirred at room temperature for 1 hour, and then trimethyl borate (B(OMe) 3, 4.8 ml, 42.9 mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours until the reaction. After completion, extraction was carried out by adding distilled water and dichloromethane at room temperature, and the organic layer was dried over magnesium sulfate and the solvent was removed by a rotary evaporator. Purification by column chromatography (dichloromethane:methanol = 100:3).

Preparation of Compound 4-39

Take compound 4-39-1 (8.9 g, 19.0 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1 g, 19.0 mmol), Pd(PPh ₃ ) ₄ ( 1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours, after the reaction was completed, in the room. Extraction was carried out by adding distilled water and dichloromethane under temperature, and the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane:hexane = 1:3). Recrystallization from methanol gave the title compound 4-39 (8.7 g, 70%).

[Preparation Example 4-6] Preparation of Compound 4-40

Take compound 4-39-1 (8.9 g, 19.0 mmol), 2-([1,1'-biphenyl]-3-yl)-4-bromo-6-phenyl-1,3,5-tri Pyridine (7.4 g, 19.0 mmol), Pd(PPh ₃ ) ₄ (1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) dissolved in a solution of toluene/ethanol/water (100/20/20 ml). The resulting solution was then refluxed for 12 hours. After the reaction was completed, distilled water and dichloromethane were added at room temperature for extraction, the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator. Purification by chromatography (dichloromethane:hexane = 1 : 3), and then crystallised from methanol to afford the desired compound 4-40 (9.7 g, 70%).

[Preparation Example 4-7] Preparation of Compound 4-41

Take compound 4-39-1 (8.9 g, 19.0 mmol), 2-([1,1'-biphenyl]-4-yl)-4-bromo-6-phenyl-1,3,5-tri Pyridine (7.4 g, 19.0 mmol), Pd(PPh ₃ ) ₄ (1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) dissolved in a solution of toluene/ethanol/water (100/20/20 ml). The resulting solution was then refluxed for 12 hours. After the reaction was completed, distilled water and dichloromethane were added at room temperature for extraction, the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator. Purification by chromatography (dichloromethane:hexane = 1 :3).

[Preparation Example 4-8] Preparation of Compound 4-42

Compound 4-39-1 (8.9 g, 19.0 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7.4 g, 19.0 mmol), Pd (PPh ₃ ) ₄ (1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours. After completion of the reaction, extraction was carried out by adding distilled water and dichloromethane at room temperature, the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane: Alkane = 1:3), and recrystallized from methanol to give the title compound 4-42 (9.7 g, 70%).

[Preparation Example 4-9] Preparation of Compound 4-43

Compound 4-39-1 (8.9 g, 19.0 mmol), 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7.4 g, 19.0 mmol), Pd (PPh ₃ ) ₄ (1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours. After completion of the reaction, extraction was carried out by adding distilled water and dichloromethane at room temperature, the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane: Alkane = 1:3), and recrystallized from methanol to give the title compound 4-43 (9.7 g, 70%).

[Preparation Example 4-10] Preparation of Compound 4-47

Preparation of Compound 4-47-2

2-Bromodibenzo[b,d]thiophene (5.0 g, 19.0 mmol), 2,7-diphenyl-9H-carbazole (5.0 g, 15.8 mmol), copper iodide (3.0 g, 15.8 mmol) ), trans-1,2-diaminocyclohexane (1.9 ml, 15.8 mmol), potassium phosphate (3.3 g, 31.6 mmol) dissolved in 1,4-dioxane (100 ml), and the mixed solution was refluxed 24 After the reaction was completed, distilled water and dichloromethane were added at room temperature to extract, the organic layer was dried over magnesium sulfate, and the solvent was removed on a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane) :hexane = 1:3), and recrystallized from methanol to give the title compound 4-47-2 (6.7 g, 85%).

Preparation of Compound 4-47-1

A mixed solution of the compound 4-47-2 (7.2 g, 14.3 mmol) and tetrahydrofuran (100 ml) was formed at -78 ° C, and n-butyllithium (n-BuLi, 2.5 M, 7.4 ml, 18.6 mmol) was added dropwise. The mixture was stirred at room temperature for 1 hour, and then trimethyl borate (B(OMe) 3, 4.8 ml, 42.9 mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours until the reaction. After completion, extraction was carried out by adding distilled water and dichloromethane at room temperature, the organic layer was dried over magnesium sulfate and solvent was evaporated on a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane: methanol = 100) :3), and recrystallized from dichloromethane to give the title compound 4-47-1 (60%).

Preparation of Compound 4-47

Take compound 4-47-1 (10.4 g, 19.0 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1 g, 19.0 mmol), Pd(PPh ₃ ) ₄ ( 1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours, after the reaction was completed, in the room. Extraction was carried out by adding distilled water and dichloromethane under temperature, and the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane:hexane = 1:3). Recrystallization from methanol gave the title compound 4-47 (9.7 g, 70%).

[Preparation Example 4-11] Preparation of Compound 4-66

Preparation of Compound 4-66-2

Take 2-bromodibenzo[b,d]thiophene (5.0 g, 19.0 mmol), 7,7-dimethyl-5,7-dihydroindolo[2,1-b]carbazole (4.5 g, 15.8 mmol), copper iodide (3.0 g, 15.8 mmol), trans-1,2-diaminocyclohexane (1.9 ml, 15.8 mmol), potassium phosphate (3.3 g, 31.6 mmol) in 1,4-two Dissolve in methane (100 ml), reflux the mixed solution for 24 hours. After the reaction is completed, add distilled water and dichloromethane at room temperature, extract the organic layer with magnesium sulfate, and remove the solvent by a rotary evaporator. Purification by column chromatography (dichloromethane:hexane = 1 : 3) and recrystallised from methanol to afford titled compound 4-66-2 (7.3 g, 85%).

Preparation of Compound 4-66-1

A mixed solution of the compound 4-66-2 (6.7 g, 14.3 mmol) and tetrahydrofuran (100 ml) was formed at -78 ° C, and n-butyllithium (n-BuLi, 2.5 M, 7.4 ml, 18.6 mmol) was added dropwise. The mixture was stirred at room temperature for 1 hour, and then trimethyl borate (B(OMe) 3, 4.8 ml, 42.9 mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours until the reaction. After completion, extraction was carried out by adding distilled water and dichloromethane at room temperature, and the organic layer was dried over magnesium sulfate and the solvent was removed by a rotary evaporator. Purification by column chromatography (dichloromethane:methanol = 100:3).

Preparation of Compound 4-66

Compound 4-66-1 (9.7 g, 19.0 mmol), 2-bromo-4,6-diphenylpyrimidine (5.9 g, 19.0 mmol), Pd(PPh ₃ ) ₄ (1.1 g, 0.95 mmol), carbonic acid Potassium (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours. After the reaction was completed, distilled water and dichloromethane were added at room temperature. The extraction was carried out, the organic layer was dried over magnesium sulfate, and the solvent was removed on a rotary evaporator. The solvent was purified by column chromatography (dichloromethane:hexane = 1:3) and recrystallized from methanol to give the target. Compound 4-66 (9.3 g, 70%).

[Preparation Example 4-12] Preparation of Compound 4-68

Take compound 4-66-1 (9.7 g, 19.0 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1 g, 19.0 mmol), Pd(PPh ₃ ) ₄ ( 1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours, after the reaction was completed, in the room. Extraction was carried out by adding distilled water and dichloromethane under temperature, and the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane:hexane = 1:3). Recrystallization from methanol gave the title compound 4-68 (9.3 g, 70%).

[Preparation Example 4-13] Preparation of Compound 4-71

Compound 4-66-1 (9.7 g, 19.0 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7.4 g, 19.0 mmol), Pd (PPh ₃ ) ₄ (1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours. After completion of the reaction, extraction was carried out by adding distilled water and dichloromethane at room temperature, the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane: Alkane = 1:3), and recrystallized from methanol to give the title compound 4-71 (10.3 g, 70%).

[Preparation Example 4-14] Preparation of Compound 4-74

Compound 4-66-1 (9.7 g, 19.0 mmol), 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7.4 g, 19.0 mmol), Pd (PPh ₃ ) ₄ (1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours. After completion of the reaction, extraction was carried out by adding distilled water and dichloromethane at room temperature, the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane: Alkane = 1:3), and recrystallized from methanol to give the title compound 4-74 (10.3 g, 70%).

[Preparation Example 4-15] Preparation of Compound 4-79

Preparation of Compound 4-79-2

Take 2-bromodibenzo[b,d]thiophene (5.0 g, 19.0 mmol), 11,11-dimethyl-5,11-dihydroindeno[1,2-b]carbazole (4.5 g, 15.8 mmol), copper iodide (3.0 g, 15.8 mmol), trans-1,2-diaminocyclohexane (1.9 ml, 15.8 mmol), potassium phosphate (3.3 g, 31.6 mmol) in 1,4-two Dissolve in methane (100 ml), reflux the mixed solution for 24 hours. After the reaction is completed, add distilled water and dichloromethane at room temperature, extract the organic layer with magnesium sulfate, and remove the solvent by a rotary evaporator. Purification by column chromatography (dichloromethane:hexane = 1 : 3), and recrystallized from methanol to afford title compound 4-79-2 (5.9 g, 80%).

Preparation of Compound 4-79-1

A mixed solution of the compound 4-79-2 (6.7 g, 14.3 mmol) and tetrahydrofuran (100 ml) was formed at -78 ° C, and n-butyllithium (n-BuLi, 2.5 M, 7.4 ml, 18.6 mmol) was added dropwise. And will mix at room temperature After stirring for 1 hour, trimethyl borate (4.8 ml, 42.9 mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, distilled water and dichloromethane were added at room temperature for extraction. The organic layer was dried over magnesium sulfate and the solvent was evaporated on a rotary evaporator. -1 (5.1 g, 70%).

Preparation of Compound 4-79

Take compound 4-79-1 (9.7 g, 19.0 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1 g, 19.0 mmol), Pd(PPh ₃ ) ₄ ( 1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours, after the reaction was completed, in the room. Extraction was carried out by adding distilled water and dichloromethane under temperature, and the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane:hexane = 1:3). Recrystallization from methanol gave the title compound 4-79 (9.3 g, 70%).

[Preparation Example 4-16] Preparation of Compound 4-83

Preparation of Compound 4-83-2

2-Bromodibenzo[b,d]thiophene (5.0 g, 19.0 mmol), 5-phenyl-5,7-dihydroindolo[2,3-b]carbazole (5.3 g, 15.8 mmol) ), copper iodide (3.0 g, 15.8 mmol), trans-1,2-diaminocyclohexane (1.9 ml, 15.8 mmol), potassium phosphate (3.3 g, 31.6 mmol) in 1,4-dioxane The solution was dissolved under (100 ml), and the mixed solution was refluxed for 24 hours. After the reaction was completed, distilled water and dichloromethane were added at room temperature to extract, the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator. Purification by column chromatography (dichloromethane:hexane = 1 :3)

Preparation of Compound 4-83-1

Compound 4-83-2 (7.4 g, 14.3 mmol) and tetrahydrofuran (100 ml) were combined to form a mixed solution at -78 ° C, n-butyllithium (2.5 M, 7.4 ml, 18.6 mmol) was added dropwise and mixed After stirring at room temperature for 1 hour, trimethyl borate (4.8 ml, 42.9 mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, distilled water and dichloromethane were added at room temperature. The organic layer was dried over magnesium sulfate and the solvent was evaporated on a rotary evaporator. The solvent was purified by column chromatography (dichloromethane:methanol = 100:3) 4-83-1 (5.6 g, 70%).

Preparation of Compound 4-83

Compound 4-83-1 (10.6 g, 19.0 mmol), 2-bromo-4,6-diphenylpyrimidine (5.9 g, 19.0 mmol), Pd(PPh ₃ ) ₄ (1.1 g, 0.95 mmol), carbonic acid Potassium (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours. After the reaction was completed, distilled water and dichloromethane were added at room temperature. The extraction was carried out, the organic layer was dried over magnesium sulfate, and the solvent was removed on a rotary evaporator. The solvent was purified by column chromatography (dichloromethane:hexane = 1:3) and recrystallized from methanol to give the target. Compound 4-83 (9.3 g, 70%).

[Preparation Example 4-17] Preparation of Compound 4-85

Compound 4-83-1 (10.6 g, 19.0 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1 g, 19.0 mmol), Pd(PPh ₃ ) ₄ ( 1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours, after the reaction was completed, in the room. Extraction was carried out by adding distilled water and dichloromethane under temperature, and the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane:hexane = 1:3). Recrystallization from methanol gave the title compound 4-85 (9.3 g, 70%).

[Preparation Example 4-18] Preparation of Compound 4-99

Preparation of Compound 4-99-2

Take 2-bromodibenzo[b,d]thiophene (5.0 g, 19.0 mmol), 5H-benzo[4,5]thieno[3,2-c]carbazole (4.3 g, 15.8 mmol), iodine Copper (3.0 g, 15.8 mmol), trans-1,2-diaminocyclohexane (1.9 ml, 15.8 mmol), potassium phosphate (3.3 g, 31.6 mmol) in 1,4-dioxane (100 ml) Dissolved, the mixed solution was refluxed for 24 hours. After the reaction was completed, distilled water and dichloromethane were added at room temperature to extract, the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator. Purification by chromatography (dichloromethane:hexane = 1 :3)

Preparation of Compound 4-99-1

A mixed solution of the compound 4-99-2 (6.5 g, 14.3 mmol) and tetrahydrofuran (100 ml) was formed at -78 ° C, and n-butyllithium (n-BuLi, 2.5 M, 7.4 ml, 18.6 mmol) was added dropwise. The mixture was stirred at room temperature for 1 hour, then trimethyl borate (4.8 ml, 42.9 mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, distilled water was added at room temperature. The organic layer was dried over magnesium sulfate and the solvent was evaporated on a rotary evaporator. The residue was purified by column chromatography (dichloromethane:methanol = 100:3) Crystallization gave the title compound 4-99-1 (5.0 g, 70%).

Preparation of Compound 4-99

Taking compound 4-99-1 (9.5 g, 19.0 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1 g, 19.0 mmol), Pd(PPh ₃ ) ₄ ( 1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours, after the reaction was completed, in the room. Extraction was carried out by adding distilled water and dichloromethane under temperature, and the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane:hexane = 1:3). Recrystallization from methanol gave the title compound 4-99 (8.9 g, 70%).

[Preparation Example 4-19] Preparation of Compound 4-164

Preparation of Compound 4-164-2

2-Bromodibenzo[b,d]thiophene (5.0 g, 19.0 mmol), (4-(9H-indazol-9-yl)phenyl)boronic acid (5.5 g, 19.0 mmol), Pd (PPh _{3) 4} (1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours, after the reaction was completed. Extraction was carried out by adding distilled water and dichloromethane at room temperature, and the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane:hexane = 1) :3), and recrystallized from methanol to give the title compound 4-164-2 (8.9 g, 70%).

Preparation of Compound 4-164-1

A mixed solution of the compound 4-164-2 (6.09 g, 14.3 mmol) and tetrahydrofuran (100 ml) was formed at -78 ° C, and n-butyllithium (n-BuLi, 2.5 M, 7.4 ml, 18.6 mmol) was added dropwise. The mixture was stirred at room temperature for 1 hour, then trimethyl borate (4.8 ml, 42.9 mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, distilled water was added at room temperature. Extraction with methylene chloride, organic layer Drying over magnesium sulfate and removing the solvent by a rotary evaporator, the reaction was purified by column chromatography (dichloromethane:methanol = 100:3) and recrystallized from dichloromethane to give the title compound 4-164-1 (4.7g, 70%).

Preparation of Compound 4-164

Take compound 4-164-1 (8.9 g, 19.0 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (6.1 g, 22.8 mmol), Pd(PPh ₃ ) ₄ ( 1.1 g, 0.95 mmol), potassium carbonate (5.2 g, 38.0 mmol) was dissolved in a solution of toluene/ethanol/water (100/20/20 ml), and the resulting solution was refluxed for 12 hours, after the reaction was completed, in the room. Extraction was carried out by adding distilled water and dichloromethane under temperature, and the organic layer was dried over magnesium sulfate, and the solvent was removed by a rotary evaporator, and the reaction was purified by column chromatography (dichloromethane:hexane = 1:3). Recrystallization from methanol gave the title compound 4-164 (9.0 g, 72%).

[Preparation Example 5-1] Preparation of Compound 5-87

Preparation of Compound 5-87-3

9H-carbazole (8.9 g, 52.93 mmol), 1-bromo-3-chloro-5-fluorobenzene (22.1 g, 105.8 mmol), sodium hydride (1.9 g, 79.40 mmol), dimethylformamide DMF, 200 ml) in a reaction flask, the mixture was heated to 120 ° C for 8 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane. The extract was then dissolved in dichloromethane, and the resulting solution was filtered with silica gel and Florisil, and solvent was removed to give the objective compound 5-87-3 (13.2 g, 70%).

Preparation of Compound 5-87-2

Compound 5-87-3 (14.3 g, 40.18 mmol), bis(pinacolato) diboron (13.26 g, 52.24 mmol), (1,1'-bis(diphenylphosphine) Ferrocene) palladium dichloride (0.8 g, 1.205 mmol), potassium acetate (11.8 g, 120.5 mmol), 1,4-dioxane (150 ml) in a reaction flask, and the mixture was heated to 120 ° C for 5 hours. The resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, and then the extract was dissolved in dichloromethane, and the resulting solution was filtered with silica gel, diatomaceous earth and magnesium silicate, and solvent was removed. The title compound 5-87-2 (12.7 g, 78%) was obtained.

Preparation of compound 5-87-1

Compound 5-87-2 (14 g, 34.6 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (11.2 g, 41.5 mmol), Pd(PPh ₃ ) ₄ (2 g) , 1.7 mmol), potassium carbonate (14.3 g, 103.8 mmol), toluene (120 ml), ethanol (20 ml) and water (20 ml) in a reaction flask, the mixture was heated to 120 ° C for 8 hours, and the resulting product was cooled to The mixture was extracted with distilled water and dichloromethane, and the extract was dissolved in dichloromethane. The resulting solution was filtered over silica gel, diatomaceous earth and magnesium hydride. The filtrate was recrystallized from dichloromethane and methanol to give the title compound 5- 87-1 (14.1 g, 80%).

Preparation of Compound 5-87

Compound 5-87-1 (4.9 g, 9.582 mmol), (2-cyanophenyl)boronic acid (2.1 g, 14.37 mmol), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ , 0.61 g, 0.67 mmol), potassium phosphate (6.1 g, 28.7 mmol), 2-dicyclohexylphosphino-2', 4',6'-triisopropylbiphenyl (Xphos, 0.91 g, 1.91 mmol), toluene (60 ml) and water (10 ml) in a reaction flask, the mixture was subjected to nitrogen displacement, and the resulting product was refluxed for 12 hours, followed by extraction with distilled water and dichloromethane, and the organic layer was dried over magnesium sulfate and evaporated. The solvent was removed, and the obtained product was purified by column chromatography (dichloromethane:hexane = 1:1) to give the object compound 5-87 (4.0 g, 73%).

[Preparation Example 5-2] Preparation of Compound 5-99

Preparation of Compound 5-99-1

Compound 5-203-2 (18 g, 34.6 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (11.2 g, 41.5 mmol), Pd(PPh ₃ ) ₄ (2 g) , 1.7 mmol), potassium carbonate (14.3 g, 103.8 mmol), toluene (120 ml), ethanol (20 ml) and water (20 ml) in a reaction flask, the mixture was heated to 120 ° C for 8 hours, and the resulting product was cooled to The mixture was extracted with distilled water and dichloromethane at room temperature, and then the extract was dissolved in dichloromethane, and the resulting solution was obtained from silica gel, diatomaceous earth and magnesium niobate (filtered, and the filtrate was recrystallized from dichloromethane and methanol to give the target compound 5 -99-1 (16 g, 77%).

Preparation of Compound 5-99

Compound 5-99-1 (6 g, 9.582 mmol), (2-cyanophenyl)boronic acid (2.1 g, 14.37 mmol), Pd ₂ (dba) ₃ (0.61 g, 0.67 mmol), potassium phosphate (6.1 g, 28.7 mmol), Xphos (0.91 g, 1.91 mmol), toluene (60 ml) and water (10 ml) were placed in a reaction flask, the mixture was subjected to nitrogen displacement, and the resulting product was refluxed for 12 hours, followed by extraction with distilled water and dichloromethane. The organic layer was dried over magnesium sulfate, and the solvent was removed on a rotary evaporator, and the product was purified by column column (dichloromethane:hexane = 1:1) to give the title compound 5-99 (4.1 g, 73%) ).

[Preparation Example 5-3] Preparation of Compound 5-203

Preparation of Compound 5-203-3

Take 7,7-dimethyl-5,7-dihydroindeno[2,1-b]carbazole (15 g, 52.93 mmol), 1-bromo-3-chloro-5-fluorobenzene (22.1 g, 105.8) Methyl hydride (1.9 g, 79.4 mmol), DMF (200 ml) in a reaction flask, the mixture was heated to 120 ° C for 8 hours, and the resulting product was cooled to room temperature and extracted with distilled water and dichloromethane. The extract was then dissolved in dichloromethane, and the resulting solution was filtered over silica gel and Florisil, and solvent was removed to give the title compound 5-203-3 (19 g, 76%).

Preparation of Compound 5-203-2

Compound 5-203-3 (19 g, 40.18 mmol), bispinacol borate (13.26 g, 52.24 mmol), PdCl ₂ (dppf) (0.8 g, 1.21 mmol), potassium acetate (11.8 g, 120.5) Ment), 1,4-dioxane (150 ml) in a reaction flask, the mixture was heated to 120 ° C for 5 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, followed by extract The methylene chloride was dissolved, and the resulting solution was filtered through silica gel, celite, and magnesium sulfate, and the solvent was removed to give the title compound 5-203-2 (18 g, 76%).

Preparation of compound 5-203-1

Taking compound 5-203-2 (18 g, 34.6 mmol), 2-chloro-4,6-diphenylpyrimidine (11.0 g, 41.5 mmol), Pd(PPh ₃ ) ₄ (2 g, 1.7 mmol), potassium carbonate ( 14.3g, 103.8mmol), toluene (120ml), ethanol (20ml) and water (20ml) in a reaction flask, the mixture is heated to 120 ° C for 8 hours, the product is cooled to room temperature, and distilled water and two The methyl chloride was extracted, and the extract was dissolved in dichloromethane. The resulting solution was filtered over silica gel, diatomaceous earth and magnesium hydride. The filtrate was recrystallized from dichloromethane and methanol to give the title compound 5-203-1 (15 g, 78%) ).

Preparation of compound 5-203

Compound 5-203-1 (5 g, 7.98 mmol), (3-cyanophenyl)boronic acid (1.5 g, 10.38 mmol), Pd ₂ (dba) ₃ (0.36 g, 0.39 mmol), potassium phosphate (5.2 g, 23.9 mmol), 2-cyclohexylphosphine-2',6'-dimethoxybiphenyl (Sphos, 0.33 g, 0.79 mmol), toluene (60 ml) and water (10 ml) were placed in a reaction flask, and the mixture was subjected to nitrogen. After the replacement, the resulting product was refluxed for 12 hours, then extracted with distilled water and dichloromethane. The organic layer was dried over magnesium sulfate, and the solvent was removed on a rotary evaporator, and the product was purified by column (dichloromethane: Hexane = 1:1) The title compound 5-203 (3.4 g, 61%) was obtained.

[Preparation Example 5-4] Preparation of Compound 5-260

Compound 5-99-1 (5 g, 7.98 mmol), (3-cyanophenyl)boronic acid (1.5 g, 10.38 mmol), Pd ₂ (dba) ₃ (0.36 g, 0.39 mmol), potassium phosphate (5.2 g, 23.9 mmol), Sphos (0.33 g, 0.79 mmol), toluene (60 ml) and water (10 ml) were placed in a reaction flask, the mixture was subjected to nitrogen displacement, and the resulting product was refluxed for 12 hours, followed by extraction with distilled water and dichloromethane. The organic layer was dried over magnesium sulfate, and the solvent was removed on a rotary evaporator, and the product was purified by column column (dichloromethane:hexane = 1:1) to give the title compound 5- ).

[Preparation Example 5-5] Preparation of Compound 5-262

Preparation of compound 5-262-3

Take 11,11-dimethyl-5,11-dihydroindolo[2,1-b]carbazole (15 g, 53 mmol), 1-bromo-3-chloro-5-fluorobenzene (24.3 g, 106.01 mmol) , sodium hydride (3.1 g, 79.54 mmol), DMF (200 ml) in a reaction flask, the mixture was heated to 120 ° C for 8 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, followed by extraction The extract was dissolved in dichloromethane, and the resulting solution was filtered through silica gel and magnesium sulfate, and solvent was evaporated to give the desired compound 5-262-3 (17 g, 71%).

Preparation of compound 5-262-2

Compound 5-262-3 (17 g, 40.25 mmol), bis(pinacolato diboron, 15.2 g, 60.81 mmol), PdCl ₂ (dppf) (1.4 g, 2.01 mmol), acetic acid Potassium (11.8g, 120.7mmol), 1,4-dioxane (150ml) in a reaction flask, the mixture was heated to 120 ° C for 5 hours, the resulting product was cooled to room temperature, and distilled water and dichloromethane After extraction, the extract was dissolved in dichloromethane, and the resulting solution was filtered over silica gel, diatomaceous earth, and Florisil, and solvent was removed to give the title compound 5-262-2 (16 g, 72%).

Preparation of compound 5-262-1

Compound 5-262-2 (16 g, 34.68 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (19.4 g, 52.02 mmol), Pd(PPh ₃ ) ₄ (2.6) g, 1.7 mmol), potassium carbonate (14.3 g, 109.8 mmol), toluene (120 ml), ethanol (20 ml) and water (20 ml) were placed in a reaction flask, and the mixture was heated to 120 ° C for 8 hours to cool the product. The mixture was extracted with distilled water and dichloromethane, and the extract was dissolved in dichloromethane. The resulting solution was filtered over silica gel, diatomaceous earth and magnesium hydride. The filtrate was recrystallized from dichloromethane and methanol to give the title compound 5 -262-1 (16 g, 75%).

Preparation of Compound 5-262

Compound 5-262-1 (6 g, 9.648 mmol), (3-cyanophenyl)boronic acid (2.1 g, 14.42 mmol), Pd ₂ (dba) ₃ (0.44 g, 0.48 mmol), potassium phosphate (6.1 g, 28.9 mmol), Sphos (0.39 g, 0.94 mmol), toluene (60 ml) and water (10 ml) were placed in a reaction flask, the mixture was subjected to nitrogen substitution, and the resulting product was refluxed for 12 hours, followed by extraction with distilled water and dichloromethane. The organic layer was dried over magnesium sulfate, and the solvent was removed on a rotary evaporator, and the product was purified by column chromatography (dichloromethane:hexane = 1:1) to afford the title compound 5-262 (4.6 g, 77% ).

[Preparation Example 5-6] Preparation of Compound 5-264

Preparation of compound 5-264-3

Take 11,11-dimethyl-5,11-dihydroindeno[1,2-b]carbazole (15 g, 53 mmol), 1-bromo-3-chloro-5-fluorobenzene (24.3 g, 106.01 mmol) , sodium hydride (3.1 g, 79.54 mmol), DMF (200 ml) in a reaction flask, the mixture was heated to 120 ° C for 8 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, followed by extraction The extract was dissolved in dichloromethane, and the resulting solution was filtered with silica gel and Florisil, and solvent was removed to give the title compound 5-264-3 (19 g, 78%).

Preparation of compound 5-264-2

Compound 5-264-3 (19 g, 40.25 mmol), bispinacol borate (15.2 g, 60.81 mmol), PdCl ₂ (dppf) (1.4 g, 2.01 mmol), potassium acetate (11.8 g, 120.7) Ment), 1,4-dioxane (150 ml) in a reaction flask, the mixture was heated to 120 ° C for 5 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, followed by extract The methylene chloride was dissolved, and the resulting solution was filtered through silica gel, celite, and magnesium sulfate, and solvent was evaporated to give the desired compound 5-264-2 (18 g, 73%).

Preparation of compound 5-264-1

Compound 5-264-2 (18 g, 34.68 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (19.4 g, 52.02 mmol), Pd(PPh ₃ ) ₄ (2.6) g, 1.7 mmol), potassium carbonate (14.3 g, 109.8 mmol), toluene (120 ml), ethanol (20 ml) and water (20 ml) were placed in a reaction flask, and the mixture was heated to 120 ° C for 8 hours to cool the product. The mixture was extracted with distilled water and dichloromethane, and the extract was dissolved in dichloromethane. The resulting solution was filtered over silica gel, diatomaceous earth and magnesium hydride. The filtrate was recrystallized from dichloromethane and methanol to give the title compound 5 -264-1 (16g, 74%).

Preparation of compound 5-264

Compound 5-264-1 (6 g, 9.64 mmol), (3-cyanophenyl)boronic acid (2.1 g, 14.42 mmol), Pd ₂ (dba) ₃ (0.44 g, 0.48 mmol), potassium phosphate (6.1 g, 28.9 mmol), Sphos (0.39 g, 0.94 mmol), toluene (60 ml) and water (10 ml) were placed in a reaction flask, the mixture was subjected to nitrogen substitution, and the resulting product was refluxed for 12 hours, followed by extraction with distilled water and dichloromethane. The organic layer was dried over magnesium sulfate, and the solvent was evaporated on a rotary evaporator, and the product was purified by column column (dichloromethane:hexane = 1:1) to give the title compound 5-264 (4.6 g, 75%) ).

[Preparation Example 5-7] Preparation of Compound 5-267

Preparation of Compound 5-267-3

5H-benzo[4,5]thieno[3,2-c]carbazole (15 g, 54.94 mmol), 1-bromo-3-chloro-5-fluorobenzene (22.9 g, 109.89 mmol), sodium hydride (3.2g, 82.41mmol), DMF (200ml) in the reaction bottle, will The mixture was heated to 120 ° C for 8 hours, and the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, then the extract was dissolved in dichloromethane, and the resulting solution was filtered with silica gel and magnesium silicate. After removing the solvent, the title compound 5-267-3 (17 g, 76%) was obtained.

Preparation of Compound 5-267-2

Compound 5-267-3 (17 g, 41.12 mmol), bispinacol borate (15.6 g, 61.68 mmol), PdCl ₂ (dppf) (1.5 g, 2.056 mmol), potassium acetate (12.08 g, 123.3) Ment), 1,4-dioxane (150 ml) in a reaction flask, the mixture was heated to 120 ° C for 5 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, followed by extract The methylene chloride was dissolved, and the resulting solution was obtained from silica gel, diatomaceous earth and magnesium niobate (filtered, and solvent was removed to give the title compound 5-267-2 (19 g, 76%).

Preparation of compound 5-267-1

Take compound 5-267-2 (17.7 g, 34.68 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (19.4 g, 52.02 mmol), Pd(PPh ₃ ) ₄ ( 2.6 g, 1.7 mmol), potassium carbonate (14.3 g, 109.8 mmol), toluene (120 ml), ethanol (20 ml) and water (20 ml) were placed in a reaction flask, and the mixture was heated to 120 ° C for 8 hours to form a product. After cooling to room temperature, and extracting with distilled water and dichloromethane, the extract is dissolved in dichloromethane, and the resulting solution is filtered with cerium, diatomaceous earth and magnesium silicate, and the filtrate is recrystallized from dichloromethane and methanol to give the target compound. 5-267-1 (15.8 g, 74%).

Preparation of Compound 5-267

Compound 5-267-1 (5.9 g, 9.64 mmol), (3-cyanophenyl)boronic acid (2.1 g, 14.42 mmol), Pd ₂ (dba) ₃ (0.44 g, 0.48 mmol), potassium phosphate (6.1 g) , 28.9 mmol), Sphos (0.39 g, 0.94 mmol), toluene (60 ml) and water (10 ml) were placed in a reaction flask, and the mixture was subjected to nitrogen substitution, and the resulting product was refluxed for 12 hours, followed by distilled water and dichloromethane. The organic layer was dried over magnesium sulfate, and the solvent was removed on a rotary evaporator, and the product was purified by column chromatography (dichloromethane:hexane = 1:1) to give the title compound 5- %).

[Preparation Example 5-8] Preparation of Compound 5-271

Preparation of compound 5-271-3

Take 5H-benzofuro[3,2-c]carbazole (15g, 58.36mmol), 1-bromo-3-chloro-5-fluorobenzene (24.3g, 116.73mmol), sodium hydride (3.5g, 87.54) Ment), DMF (200 ml) in a reaction flask, the mixture was heated to 120 ° C for 8 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, then the extract was dissolved in dichloromethane to give The solution was filtered with silica gel and florisil, and the solvent was removed to give the title compound 5-271-3 (18 g, 73%).

Preparation of compound 5-271-2

Compound 5-271-3 (18 g, 42.6 mmol), bispinacol borate (15.6 g, 63.90 mmol), PdCl ₂ (dppf) (1.5 g, 2.13 mmol), potassium acetate (12.08 g, 127.9) Ment), 1,4-dioxane (150 ml) in a reaction flask, the mixture was heated to 120 ° C for 5 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, followed by extract The methylene chloride was dissolved, and the resulting solution was filtered through silica gel, celite, and Florisil, and the solvent was removed to give the title compound 5-271-2 (17 g, 78%).

Preparation of compound 5-271-1

Compound 5-271-2 (17 g, 36.51 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (19.4 g, 73.02 mmol), Pd(PPh ₃ ) ₄ (2.6) g, 1.7 mmol), potassium carbonate (14.3 g, 106.0 mmol), toluene (120 ml), ethanol (20 ml) and water (20 ml) were placed in a reaction flask, and the mixture was heated to 120 ° C for 8 hours to cool the product. The mixture was extracted with distilled water and dichloromethane, and the extract was dissolved in dichloromethane. The resulting solution was obtained from silica gel, diatomaceous earth and magnesium niobate (filtered, and the filtrate was recrystallized from dichloromethane and methanol to give the title compound. 5-271-1 (18g, 71%).

Preparation of Compound 5-271

Compound 5-271-1 (6 g, 8.34 mmol), (3-cyanophenyl)boronic acid (1.8 g, 12.52 mmol), Pd ₂ (dba) ₃ (0.38 g, 0.41 mmol), potassium phosphate (5.3 g, 25.1 mmol), Sphos (0.34 g, 0.83 mmol), toluene (60 ml) and water (10 ml) were placed in a reaction flask, the mixture was subjected to nitrogen displacement, and the resulting product was refluxed for 12 hours, followed by extraction with distilled water and dichloromethane. The organic layer was dried over magnesium sulfate, and the solvent was removed on a rotary evaporator, and the product was purified by column column (dichloromethane:hexane = 1:1) to afford the title compound 5-271 (4.6 g, 72% ).

[Preparation Example 5-9] Preparation of Compound 5-416

Compound 5-99-1 (5 g, 7.98 mmol), (4-cyanophenyl)boronic acid (1.5 g, 10.38 mmol), Pd ₂ (dba) ₃ (0.36 g, 0.39 mmol), potassium phosphate (5.2 g, 23.9 mmol), Sphos (0.33 g, 0.79 mmol), toluene (60 ml) and water (10 ml) were placed in a reaction flask, the mixture was subjected to nitrogen displacement, and the resulting product was refluxed for 12 hours, followed by extraction with distilled water and dichloromethane. The organic layer was dried over magnesium sulfate, and the solvent was removed on a rotary evaporator, and the product was purified by column column (dichloromethane:hexane = 1:1) to give the title compound 5-416 (4.1 g, 73%) ).

[Preparation Example 5-10] Preparation of Compound 5-421

Preparation of Compound 5-421-3

Taking 12H-benzo[4,5]thieno[3,2-a]carbazole (15 g, 54.94 mmol), 1-bromo-3-chloro-5-fluorobenzene (22.9 g, 109.89 mmol), sodium hydride (3.2g, 82.41mmol), DMF (200ml) in a reaction flask, the mixture was heated to 120 ° C for 8 hours, the product was cooled to room temperature, and extracted with distilled water and dichloromethane, followed by extract The methyl chloride was dissolved, and the resulting solution was filtered through silica gel and Florisil, and solvent was removed to give the title compound 5-421-3 (17 g, 76%).

Preparation of compound 5-421-2

Compound 5-421-3 (17 g, 41.12 mmol), bispinacol borate (15.6 g, 61.68 mmol), PdCl ₂ (dppf) (1.5 g, 2.056 mmol), potassium acetate (12.08 g, 123.3) Ment), 1,4-dioxane (150 ml) in a reaction flask, the mixture was heated to 120 ° C for 5 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, followed by extract The methylene chloride was dissolved, and the resulting solution was filtered through silica gel, diatomaceous earth, and magnesium sulfate, and the solvent was removed to give the objective compound 5-421-2 (19 g, 76%).

Preparation of Compound 5-421-1

Compound 5-421-2 (19 g, 35.36 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (14.1 g, 53.04 mmol), Pd(PPh ₃ ) ₄ (2 g) , 1.7 mmol), potassium carbonate (14.3 g, 106.0 mmol), toluene (120 ml), ethanol (20 ml) and water (20 ml) in a reaction flask, the mixture was heated to 120 ° C for 8 hours, and the resulting product was cooled to The mixture was extracted with distilled water and dichloromethane, and the extract was dissolved in dichloromethane. The resulting solution was filtered over silica gel, diatomaceous earth and magnesium hydride. The filtrate was recrystallized from dichloromethane and methanol to give the title compound 5- 421-1 (15 g, 77%).

Preparation of compound 5-421

Compound 5-421-1 (5 g, 8.13 mmol), (4-cyanophenyl)boronic acid (1.7 g, 12.19 mmol), Pd ₂ (dba) ₃ (0.36 g, 0.40 mmol), potassium phosphate (5.8 g, 24.39 mmol), Sphos (0.33 g, 0.79 mmol), toluene (60 ml) and water (10 ml) were placed in a reaction flask, the mixture was subjected to nitrogen displacement, and the resulting product was refluxed for 12 hours, followed by extraction with distilled water and dichloromethane. The organic layer was dried over magnesium sulfate, and the solvent was removed on a rotary evaporator, and the product was purified by column chromatography (dichloromethane:hexane = 1:1) to give the title compound 5-422 (4.5 g, 78%) ).

[Preparation Example 5-11] Preparation of Compound 5-422

Compound 5-267-1 (5 g, 8.13 mmol), (4-cyanophenyl)boronic acid (1.7 g, 12.19 mmol), Pd ₂ (dba) ₃ (0.36 g, 0.40 mmol), potassium phosphate (5.8 g, 24.39 mmol), Sphos (0.33 g, 0.79 mmol), toluene (60 ml) and water (10 ml) were placed in a reaction flask, the mixture was subjected to nitrogen displacement, and the resulting product was refluxed for 12 hours, followed by extraction with distilled water and dichloromethane. The organic layer was dried over magnesium sulfate, and the solvent was evaporated on a rotary evaporator, and the product was purified by column column (dichloromethane:hexane = 1:1) to give the title compound 5-422 (4.3 g, 72%) ).

[Preparation Example 5-12] Preparation of Compound 5-450

Preparation of compound 5-450-3

2-Phenyl-9H-carbazole (12.8 g, 52.89 mmol), 1-bromo-3-chloro-5-fluorobenzene (22.1 g, 105.8 mmol), sodium hydride (1.9 g, 79.40 mmol), DMF 200 ml) in a reaction flask, the mixture was heated to 120 ° C for 8 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, and then the extract was dissolved in dichloromethane to give a solution of The magnesium ruthenate was filtered and the solvent was removed to give the title compound 5-450-3 (17.2 g, 74%).

Preparation of compound 5-450-2

Taking compound 5-450-3 (17.3 g, 40.09 mmol), bispinacol borate (13.26 g, 52.24 mmol), PdCl ₂ (dppf) (0.8 g, 1.205 mmol), potassium acetate (11.8 g, 120.5 mmol), 1,4-dioxane (150 ml) in a reaction flask, the mixture was heated to 120 ° C for 5 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, followed by extract The solution was dissolved in dichloromethane, and the resulting solution was filtered over silica gel, celite, and magnesium sulfate, and the solvent was removed to give the title compound 5-450-2 (14.8 g, 74%).

Preparation of compound 5-450-1

Take compound 5-450-2 (11.7 g, 24.53 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (7.9 g, 29.48 mmol), Pd(PPh ₃ ) ₄ ( 1.4 g, 1.2 mmol), potassium carbonate (10.1 g, 73.7 mmol), toluene (120 ml), ethanol (20 ml) and water (20 ml) were placed in a reaction flask, and the mixture was heated to 120 ° C for 8 hours to form a product. After cooling to room temperature, and extracting with distilled water and dichloromethane, the extract was dissolved in dichloromethane, and the resulting solution was filtered with silica gel, diatomaceous earth and magnesium silicate (florisil), and the filtrate was recrystallized from dichloromethane and methanol. The title compound 5-450-1 (10 g, 70%) was obtained.

Preparation of compound 5-450

Take compound 5-450-1 (5.6 g, 9.582 mmol), 3,5-dicyanophenylboronic acid pinacol ester (3.7 g, 14.37 mmol), Pd ₂ (dba) ₃ (0.61 g, 0.67 mmol), potassium phosphate (6.1 g, 28.7 mmol), Xphos (0.91 g, 1.91 mmol), toluene (60 ml) and water (10 ml) were placed in a reaction flask, and the mixture was replaced with nitrogen to form The product was refluxed for 12 hours, then extracted with distilled water and dichloromethane. The organic layer was dried over magnesium sulfate and solvent was evaporated on a rotary evaporator, and the product was purified by column (dichloromethane:hexane = 1) :1) The target compound 5-450 (3.8 g, 58%) was obtained.

[Comparative Preparation Example 1] Preparation of Reference 5

Preparation by reference 5-1

Compound H (30 g, 61.40 mmol), (9-phenyl-9H-indazol-3-yl)boronic acid (17.63 g, 61.40 mmol), Pd(PPh ₃ ) ₄ (3.1 g, 3.55 mmol), potassium carbonate (25.46g, 184.2mmol), 1,4-dioxane (300ml) and water (60ml) in a reaction flask, the mixture is heated to 120 ° C for 12 hours, the product is cooled to room temperature, and distilled water And extracting with methylene chloride, and then extracting the solution in dichloromethane, the resulting solution is filtered with phthalocyanine, diatomaceous earth and magnesium citrate and the solvent is removed, and the target compound is obtained by column chromatography to obtain 5-1 (17.9 g, 60%).

Preparation of reference 5

Reference compound 5-1 (6 g, 12.28 mmol), (9-phenyl-9H-indazol-3-yl)boronic acid (7.08 g, 24.57 mmol), Pd(PPh ₃ ) ₄ (0.71 g, 0.61 mmol) Potassium carbonate (5.09 g, 36.84 mmol), cesium fluoride (3.7 g, 24.57 mmol), toluene (60 ml), ethanol (10 ml) and water (60 ml) were placed in a reaction flask, and the mixture was heated to 100 ° C for 12 hours. The resulting product was cooled to room temperature and extracted with distilled water and dichloromethane, then the extract was dissolved in dichloromethane, and the resulting solution was filtered over silica gel, diatomaceous earth and magnesium sulphate, and solvent was removed. The target compound reference 5 (1 g, 63%) was obtained by column chromatography.

The compounds were prepared in the same manner as in the Preparation, and the results of their synthesis were determined in Tables 4-7 below. Table 4 shows the NMR values, and Table 5 shows the measured values by field absorption mass spectrometry (FD-MS).

<Experimental example>

1) Manufacture of organic light-emitting devices

Ultrasonic cleaning of a glass substrate distilled water having a thickness of 1500 Å indium tin oxide (ITO) coating, followed by ultrasonic cleaning and drying of the glass substrate with a solvent such as acetone, methanol and isopropyl alcohol, followed by UV washing machine UVO treatment with UV for 5 minutes, after which the substrate was transferred to a plasma washing machine (PT) for plasma treatment, and for vacuum The work function is performed and the indium tin oxide (ITO) is removed for plasma treatment to be transferred to a thermal deposition apparatus for organic deposition.

On the ITO prepared as described above, 4,4',4"-tris[2-naphthyl(phenyl)amine]triphenylamine (2-TNATA) forms a hole injection layer, and N,N'- Bis(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPB) forms a hole transport layer by means of a hole Thermal vacuum lamination is performed on the transport layer to form a light-emitting layer having a thickness of 400 Å. For the light-emitting layer, the compound described in the following table is used as a host and doped with 7% of tris(2-phenylpyridine) ruthenium (Ir(ppy) ₃ ) As a phosphorescent dopant, BCP having a thickness of 60 Å is deposited as a hole barrier layer, and Alq ₃ having a thickness of 200 Å is deposited thereon as an electron transport layer, and finally, lithium fluoride having a thickness of 10 Å (LiF) An electron injecting layer is deposited on the electron transporting layer, and aluminum (Al) having a thickness of 1200 Å is deposited on the electron injecting layer to form a negative electrode, thereby fabricating an organic light-emitting device.

At the same time, all of the organic compounds required for the manufacture of OLEDs were subjected to vacuum sublimation purification at 10 ^-6 to 10 ^-8 torr and then used in OLED fabrication.

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

For the organic light-emitting device manufactured as described above, an electroluminescence (EL) characteristic was measured by M7000 manufactured by McScience Inc., and based on the measurement result, when the reference luminescence value was 6000 cd/m ² , it was manufactured by McScience Inc. The life measuring device (M6000) measures T ₉₀ . The characteristics of the organic light-emitting device of the present invention are shown in Tables 8 and 9 below.

When the evaluation results of the present invention were compared with Comparative Examples 1-6, in the case of Reference 1, Reference 2, and Reference 3, it was determined that when the position 2 of dibenzofuran was substituted with carbazole-N, the service life was poor. Since the oxygen of dibenzofuran is in the para position, it can be activated by the nitrogen as an electron-providing group to attenuate the resonance effect, so that the stability of the molecule is deteriorated. In the case of Reference 4, it is determined that when the position 4 of the dibenzofuran is an electron-extracting heteroaryl group, the service life is reduced because the oxygen atom of the dibenzofuran provides electrons to make the electrons unstable along the LUMO injection. . Reference 5 has a molecular structure similar to the present invention, However, it is determined that when the positions 2 and 4 of the dibenzofuran are simultaneously substituted with the oxazole at the position 3, the service life is reduced, and the reason is the same as Reference 1, Reference 2 and Reference 3.

As shown by the results, in particular, an organic light-emitting device according to an exemplary embodiment of the present invention includes a host material as an organic light-emitting layer: both compounds are represented by any one of Chemical Formulas 1 to 3. As shown, and the compound is represented by Chemical Formula 4 or 5, there is a significant improvement in all items of driving voltage, efficiency, and service life as compared with the organic light-emitting device using a single compound as a host material, however, in Comparative Example 7 In the case of -16, even if the light-emitting layer is composed of two main bodies, the holes and the electrons are not balanced, and in particular, the service life is remarkably deteriorated as compared with the embodiment.

The organic light-emitting device of the present invention comprises a light-emitting layer using a host and a phosphorescent dopant, and the host is composed of a host compound (pn type) in which two or more compounds are mixed, and thus, the organic light-emitting device of the present invention and the related art Compared with an organic light-emitting device in which a single compound constitutes a host compound, it has a better service life.

In particular, the pn-type body of the present invention has an advantage that the ratio of the body can be adjusted to increase the luminescent characteristics, and the advantage is by appropriately combining a p-type body having a good hole mobility and an n-type body having a good electron mobility. The result achieved.

100‧‧‧Substrate

200‧‧‧ positive electrode

300‧‧‧ organic material layer

301‧‧‧ hole injection layer

302‧‧‧ hole transfer layer

303‧‧‧Lighting layer

304‧‧‧ hole barrier

305‧‧‧Electronic transmission layer

306‧‧‧Electronic injection layer

400‧‧‧negative electrode

Claims (11)

A heterocyclic compound represented by any one of the following Chemical Formulas 1 to 3: [Chemical Formula 3] Wherein in Chemical Formulas 1 to 3, Ar1-Ar6 are the same or different from each other, and each independently is a substituted or unsubstituted C ₆ -C ₆₀ aryl group; or a substituted or unsubstituted C ₂ -C ₆₀ hetero Aryl, R1-R9 are the same or different from each other, and are each independently selected from hydrogen; hydrazine; halogen; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted C ₂ - Alkenyl C ₆₀ ; substituted or unsubstituted C ₂ -C ₆₀ alkynyl; substituted or unsubstituted C ₁ -C ₆₀ alkoxy; substituted or unsubstituted C ₃ -C ₆₀ ring Alkyl; substituted or unsubstituted C ₂ -C ₆₀ heterocycloalkyl; substituted or unsubstituted C ₆ -C ₆₀ aryl; substituted or unsubstituted C ₂ -C ₆₀ heteroaryl ;-SiRR'R";-P(=O)RR'; unsubstituted or C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ a group consisting of a heteroaryl-substituted amine group, R, R', R" are the same or different from each other, and each independently is hydrogen; hydrazine; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl group; a substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group of; a substituted or unsubstituted C ₆ -C ₆₀ of Group; or substituted or unsubstituted of C ₂ -C ₆₀ heteroaryl group, and m, n, o, p, q, r, s, t and u are each independently an integer of 0-4. The heterocyclic compound according to claim 1, wherein R1 to R9 of Chemical Formulas 1 to 3 are each independently hydrogen or hydrazine. The heterocyclic compound according to claim 1, wherein the chemical formulas 1 to 3 are represented by any one of the following compounds: An organic light-emitting device comprising: a positive electrode; a negative electrode; and a layer of organic material having one or more layers disposed between the positive electrode and the negative electrode, wherein one or more layers of the organic material layer are included in the patent application scope The heterocyclic compound according to any one of items 1 to 3. The organic light-emitting device of claim 4, wherein the organic material layer comprises at least one of a hole barrier layer, an electron injection layer and an electron transport layer, and the hole barrier layer, the electron At least one of the injection layer and the electron transport layer contains the heterocyclic compound. The organic light-emitting device of claim 4, wherein the organic material layer comprises a light-emitting layer, and the light-emitting layer comprises the heterocyclic compound. The organic light-emitting device of claim 4, wherein the organic material layer comprises one or more layers of a hole injection layer, a hole transfer layer, and a layer for simultaneously injecting and transferring holes, and wherein the layer is One layer contains the heterocyclic compound. The organic light-emitting device according to claim 4, wherein the organic material layer containing the heterocyclic compound further comprises a compound represented by the following Chemical Formula 4 or 5: Wherein in Chemical Formula 4, L1 and L2 are the same or different from each other, and each independently is a bonded or substituted or unsubstituted C ₆ -C ₆₀ arylene group, and Ar7 is substituted or not comprising at least one N; By substituting a heteroaryl group of C ₂ -C ₆₀ , Ar 8 is represented by the following Chemical Formula 6 or 7, [Chemical Formula 6] Wherein Y1-Y4 are the same or different from each other, and each independently is a substituted or unsubstituted C ₆ -C ₆₀ aromatic hydrocarbon ring; or a substituted or unsubstituted C ₂ -C ₆₀ aromatic heterocyclic ring, R10- R16 are the same or different from each other, and are each independently selected from hydrogen; hydrazine; halogen; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted C ₂ -C ₆₀ alkenyl Substituted or unsubstituted C ₂ -C ₆₀ alkynyl; substituted or unsubstituted C ₁ -C ₆₀ alkoxy; substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl; substituted Or unsubstituted C ₂ -C ₆₀ heterocycloalkyl; substituted or unsubstituted C ₆ -C ₆₀ aryl; substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR'R ";-P(=O)RR'; unsubstituted or substituted by C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ heteroaryl An amine group, or a group of two or more adjacent groups bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring, R, R' and R" are the same or different from each other, And each independently is hydrogen; 氘; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkane a substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group; a substituted or unsubstituted C ₆ -C ₆₀ aryl group; or a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group, And [Chemical Formula 5] Wherein in Chemical Formula 5, at least one of X1 - X3 is N, and the others are each independently N or CR35, and R17, R18 and R35 are the same or different from each other, and are each independently selected from hydrogen; hydrazine; halogen; -CN; Substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted C ₂ -C ₆₀ alkenyl; substituted or unsubstituted C ₂ -C ₆₀ alkynyl; substituted or unsubstituted C ₁ -C ₆₀ alkoxy; substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl; substituted or unsubstituted C ₂ -C ₆₀ heterocycloalkyl; substituted or unsubstituted C _6- C ₆₀ aryl; substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR'R";-P(=O)RR'; unsubstituted or C ₁ -C ₂₀ An alkyl group, a substituted or unsubstituted C ₆ -C ₆₀ aryl group or a C ₂ -C ₆₀ heteroaryl substituted amine group, or two or more adjacent groups bonded to each other to form a substituted or unsubstituted a group consisting of substituted aliphatic or aromatic hydrocarbon rings, R19-R21 and R27-R30 are the same or different from each other, and are each independently selected from hydrogen; hydrazine; halogen, -CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted C ₂ -C ₆₀ alkenyl; Substituted or unsubstituted C ₂ -C ₆₀ alkynyl; substituted or unsubstituted C ₁ -C ₆₀ alkoxy; substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl; substituted or not Substituted C ₂ -C ₆₀ heterocycloalkyl; substituted or unsubstituted C ₆ -C ₆₀ aryl; substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR'R";-P(=O)RR'; an amine which is unsubstituted or substituted with a C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₆ -C ₆₀ aryl group or a C ₂ -C ₆₀ heteroaryl group a group consisting of: R31-R34 are the same or different from each other, and are each independently selected from hydrogen; hydrazine; halogen; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted Substituted C ₂ -C ₆₀ alkenyl; substituted or unsubstituted C ₂ -C ₆₀ alkynyl; substituted or unsubstituted C ₁ -C ₆₀ alkoxy; substituted or unsubstituted C ₃ - a C ₆ cycloalkyl group; a substituted or unsubstituted C ₂ -C ₆₀ heterocycloalkyl group; a substituted or unsubstituted C ₆ -C ₆₀ aryl group; a substituted or unsubstituted C ₂ -C ₆₀ the heteroaryl; -SiRR'R "; - P (= O) RR '; unsubstituted or alkyl group of C ₁ -C _20, a substituted or unsubstituted C ₆ -C ₆₀ The substituted aryl or C ₂ -C ₆₀ heteroaryl group the aryl group, or two or more adjacent groups bonded to each other to form the group consisting of a substituted or unsubstituted hydrocarbon ring or heterocyclic ring, R22- at least one of R26 is -CN, and the remaining are each independently selected from hydrogen; deuterium; halo; -CN; a substituted or unsubstituted of C ₁ -C ₆₀ alkyl; a substituted or unsubstituted C ₂ -C _60's Alkenyl; substituted or unsubstituted C ₂ -C ₆₀ alkynyl; substituted or unsubstituted C ₁ -C ₆₀ alkoxy; substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl; Substituted or unsubstituted C ₂ -C ₆₀ heterocycloalkyl; substituted or unsubstituted C ₆ -C ₆₀ aryl; substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR 'R';-P(=O)RR'; unsubstituted or C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ heteroaryl a group substituted with an amine group, or a group of two or more adjacent groups bonded to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring, R, R' and R" are the same or not identical, and are each independently hydrogen; deuterium; -CN; a substituted or unsubstituted alkyl of C ₁ -C _60; A substituted or unsubstituted of C ₃ -C ₆₀ cycloalkyl group; a substituted or unsubstituted C ₆ -C ₆₀ aryl group; or a substituted or unsubstituted C ₂ -C _60, aryl, heteroaryl. The organic light-emitting device according to claim 8, wherein the compound represented by Chemical Formula 4 is represented by any one of the following compounds: The organic light-emitting device according to claim 8, wherein the compound represented by Chemical Formula 5 is represented by any one of the following compounds: The organic light-emitting device according to claim 8, wherein the organic light-emitting device comprises, as a host material for the light-emitting layer: the heterocyclic compound; and a compound represented by Chemical Formula 4 or 5.