TWI713625B - 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 the same

This application relates to a heterocyclic compound and an organic light-emitting device using it.

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

An organic light-emitting device has a structure of an organic thin film disposed between two electrodes. When a voltage is applied to the organic light-emitting device with this structure, the electrons and holes injected from the two electrodes combine with each other in the organic thin film to form a pair, and then Glows when it goes out. The organic thin film may have a single-layer or multilayer structure as required.

The material used for the organic thin film may have a light-emitting function as required. For example, as a material for the organic thin film, a compound that itself can constitute the light-emitting layer can also be used, or a compound that serves as a host or an additive in the host-additive light-emitting layer can also be used. In addition, 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 continuous demand for the development of materials for organic thin films.

It is necessary to conduct research on organic light-emitting devices containing compounds with chemical structures, which can meet the conditions required for materials used in organic light-emitting devices, such as appropriate energy levels, electrochemical stability, thermal stability, etc., And according to the substituents, various functions required by the organic light-emitting device can be performed.

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 the chemical formulas 1 to 3, Ar1-Ar6 are the same or different from each other, and are each independently a substituted or unsubstituted C ₆ -C ₆₀ aryl group; or a substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group Group, R1-R9 are the same or different from each other, and are each independently selected from hydrogen; deuterium; 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 cycloalkane C ₂ -C ₆₀ substituted or unsubstituted 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 heteroaryl substituted amine groups, R, R', R" are the same or different from each other, and are each independently hydrogen; deuterium; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkane Group; 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, And m, n, o, p, q, r, s, t and u are each independently an integer of 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 includes a heterocyclic compound represented by any one of Chemical Formulas 1 to 3.

In addition, another exemplary embodiment of the present invention provides an organic light-emitting device, wherein the organic material layer including the heterocyclic compound further includes a compound represented by the following chemical formula 4 or 5.

Wherein in the chemical formula 4, L1 and L2 are the same or different from each other, and each independently is a bond or a substituted or unsubstituted C ₆ -C ₆₀ arylene group, and Ar7 is a substituted or unsubstituted C ₆ -C ₆₀ group containing at least one N The substituted C ₂ -C ₆₀ heteroaryl group, Ar8 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; deuterium; 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 The amine group, or two or more adjacent groups are bonded to each other to form a group consisting of substituted or unsubstituted aliphatic or aromatic hydrocarbon rings, and R, R'and R" are the same or different from each other , And each independently is hydrogen; deuterium; -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, and

In chemical formula 5, at least one of X1-X3 is N, and the others are each independently N or CR35, R17, R18, and R35 are the same or different from each other, and are each independently selected from hydrogen; deuterium; 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 alkane Group, substituted or unsubstituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ heteroaryl substituted amine group, or two or more adjacent groups are bonded to each other to form substituted or unsubstituted R19-R21 and R27-R30 are the same or different from each other, and are each independently selected from hydrogen; deuterium; 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 group; substituted or unsubstituted C ₂ -C ₆₀ heterocycloalkyl group; substituted or unsubstituted C ₆ -C ₆₀ aryl group; Substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR'R";-P(=O)RR'; unsubstituted or C ₁ -C ₂₀ alkyl, substituted or unsubstituted A group consisting of substituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ heteroaryl substituted amine groups, R31-R34 are the same or different from each other, and are each independently selected from hydrogen; deuterium; 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 Substituted C ₆ -C ₆₀ aryl group; substituted or unsubstituted C ₂ -C ₆₀ heteroaryl group; -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 substituted amine group, or two or more adjacent groups are bonded to each other to form substituted Or unsubstituted hydrocarbon ring or heterocyclic ring, at least one of R22-R26 is -CN, and The rest are each independently selected from hydrogen; deuterium; 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 substituted amine group, or two or Multiple adjacent groups are bonded to each other to form a group consisting of substituted or unsubstituted aliphatic or aromatic hydrocarbon rings, R, R'and R" are the same or different from each other, and each is independently hydrogen; deuterium ; -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.

The heterocyclic compound according to an exemplary embodiment of the present invention can be used as a material for an organic material layer of an organic light-emitting device, and the heterocyclic compound can be used as a hole injection layer, a hole transport layer, and a hole transport layer in an organic light-emitting device. Materials for the light-emitting layer, electron transport layer, electron injection layer, etc. In particular, the heterocyclic compound represented by any one of Chemical Formulas 1 to 3 can be used as a material for the electron transport layer, hole transport layer, or light emitting layer of an organic light-emitting device. In addition, when 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 reduced, 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 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 Therefore, compared with the organic light-emitting device using a single compound as the host material, it can show all the characteristics of significantly improved driving, efficiency and service life.

100‧‧‧Substrate

200‧‧‧Positive electrode

300‧‧‧Organic material layer

301‧‧‧hole injection layer

302‧‧‧Electric hole transfer layer

303‧‧‧Light-emitting layer

304‧‧‧electric hole barrier

305‧‧‧Electron transport layer

306‧‧‧Electron 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 present invention will be described in detail here.

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, can be represented by the core structure and The structural characteristics of the above substituents are used as materials for the organic material layer of the organic light-emitting device.

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

In the present invention, the substituents of the chemical formula will be described in more detail below.

In the present invention, "substituted or unsubstituted" means unsubstituted or substituted by one or more substituents selected from deuterium; 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 alkylamino group; C ₆ -C ₆₀ arylamino group: and C ₂ -C ₆₀ heteroaryl A group consisting of an amine group, or means unsubstituted or substituted by a substituent connected by two or more substituents in the substituent, or means unsubstituted or substituted by two or more selected from the substituent Substituents connected by substituents are substituted. For example, "substituents connected by two or more substituents" can be biphenyl, that is to say, biphenyl can also be aryl, and can be interpreted as a substitution in which two phenyl groups are connected base. Additional substituents may also be additionally substituted. R, R'and R" are mutually or different, and are each independently hydrogen; deuterium; -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.

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

The term "substitution" means that the hydrogen atom bonded to the carbon atom of the compound becomes another substituent, and the position of substitution is not limited, as long as the position is the position where the hydrogen atom is substituted, that is, the position where 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 this specification, halogen may be fluorine, chlorine, bromine or iodine.

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

In the present specification, the alkenyl group includes a straight or branched chain with 2-60 carbon atoms, and may be additionally substituted by another substituent. The number of carbon atoms of the alkenyl group may be 2-60, specifically 2-40, More specifically 2-20. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentene Group, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvin-1-yl, 2-phenylvin-1-yl, 2,2- Diphenylethylene-1-yl, 2-phenyl-2-(naphthalene-1-yl)ethylene-1-yl, 2,2-bi(diphenyl-1-yl)ethylene-1-yl, diphenyl But not limited to vinyl, styrene, etc.

In the present specification, an alkynyl group includes a straight or branched chain having 2-60 carbon atoms, and may be additionally substituted by another substituent. The number of carbon atoms of the alkynyl group may be 2-60, specifically 2-40, More specifically, it is 2-20.

In the present specification, a cycloalkyl group includes a monocyclic or polycyclic ring having 3-60 carbon atoms, and may be additionally substituted by another substituent. Here, the polycyclic ring means that the cycloalkyl group is directly connected or fused to another A cyclic group. Here, the other cyclic group can also be a cycloalkyl group, but it can also be another type of cyclic group, such as a heterocycloalkyl group, an aryl group, and a heteroaryl group. The number of carbon atoms of the cycloalkyl group may be 3-60, specifically 3-40, more specifically 5-20. 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 not limited thereto.

In this specification, heterocycloalkyl groups contain O, S, Se, N or Si as heteroatoms, and have a monocyclic or polycyclic ring with 2-60 carbon atoms, and may be additionally substituted by another substituent. Here, the polycyclic ring means a group in which a heterocycloalkyl group is directly connected or fused to another ring group. Here, the other ring group may also be a heterocycloalkyl group, but may also be another type of ring group, such as a ring group. Alkyl, aryl, heteroaryl, etc. The number of carbon atoms of the heterocycloalkyl group can be 2-60, specifically 2-40, more specifically 3-20.

In this specification, an aryl group includes a monocyclic or polycyclic ring having 6-60 carbon atoms, and may be additionally substituted by another substituent. Here, the polycyclic group means that the aryl group is directly connected or fused to another ring group Here, the other cyclic group can also be an aryl group, but it can also be another type of cyclic group, such as cycloalkyl, heterocycloalkyl, heteroaryl, etc. The aryl group includes a spirocyclic group. The number of carbon atoms of the aryl group may be 6-60, specifically 6-40, and more specifically 6-25. Specific examples of the aryl group include phenyl, biphenyl, triphenyl, naphthyl, anthracenyl, chrysenyl, phenanthrenyl, perylenyl, fluoranthenyl ), triphenylenyl (triphenylenyl), phenalenyl (phenalenyl), pyrenyl (pyrenyl), tetracenyl (tetracenyl), pentacenyl (pentacenyl), fluorenyl, indenyl, Acenaphthylenyl (acenaphthylenyl), benzofluorenyl (benzofluorenyl), spirobifluorenyl (spirobifluorenyl), 2,3-dihydro-1H-indenyl, its fused ring group and the foregoing approximation, but not limited to .

In this specification, a spirocyclic group is a group containing a spirocyclic structure and has 15-60 carbon atoms. For example, the spirocyclic group may include 2-3-dihydro-1H-indenyl or cyclohexyl and fluorene The spiro ring-bonded structure, specifically, the spiro ring group may include any of the following structural formula groups.

In this specification, the heteroaryl group contains S, O, Se, N or Si as the heteroatom, and has a monocyclic or polycyclic ring with 2-60 carbon atoms, and may be additionally substituted by another substituent, here , The polycyclic ring means a group in which a heteroaryl group is directly connected or fused to another ring group. Here, the other ring group can also be a heteroaryl group, but it can also be another type of ring group, such as cycloalkyl, Heterocycloalkyl, aryl, etc. The number of carbon atoms of the heteroaryl group may be 2-60, specifically 2-40, more specifically 3-25. Specific examples of the heteroaryl group include pyridyl, pyrrolyl, pyrimidyl, pyridazinyl, furanyl, thiophene, imidazolyl, imidazolyl, Pyrazolyl (pyrazolyl), oxazolyl (oxazolyl), isoxazolyl (isoxazolyl), thiazolyl (thiazolyl), isothiazolyl (isothiazolyl), three Triazolyl, furazanyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, Thiopyranyl (thiopyranyl), diazinyl (diazinyl), oxazinyl (oxazinyl), thiazinyl (thiazinyl), dioxynyl (dioxynyl), triazinyl (triazinyl), tetrazinyl ( tetrazinyl, quinolyl, isoquinolyl, quinazolinyl, isoquinazolinyl, quinozolilyl, naphthyridyl, Acridinyl, phenanthridinyl, imidazopyridinyl, diaza naphthalenyl, triazaindene, indolyl, indolazine Indolizinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothiophene, benzofuran, dibenzothiophene ), dibenzofuran (dibenzofuran), carbazolyl (carbazolyl), benzocarbazolyl (benzocarbazolyl), dibenzocarbazolyl (dibenzocarbazolyl), phenazinyl, dibenzosilole ), spirobi (dibenzosilole), dihydrophenazinyl, phenoxazinyl, phenanthridyl, thienyl, indole Indole[2,3-a]carbazolyl, indole[2,3-b]carbazolyl, indolinyl, 10,11-dihydro-dibenzo[b,f]acridine (10,11-dihydro-dibenzo(b,f)azepin), 9,10-dihydroacridinyl, phenanthrazinyl, phenothiazinyl, phthalazinyl, naphthalene Pyridyl (naphthylidinyl), phenanthrolinyl, benzo[c][1,2,5]thiadiazolyl, 5,10-dihydrodibenzo[b,e][1,4]azilsilyl (5,10-dihydrodibenzo[b,e][1,4]azasilinyl), pyrazolo[1,5-c]quinazolinyl, pyrido[1,2-b]indazolyl, pyrido[ 1,2-a]imidazo[1,2-e]indolinyl, 5,11-dihydroindeno[1,2-b]carbazolyl and the foregoing approximations, but not limited thereto.

In this specification, the amine group may be selected from monoalkylamino; monoarylamino; monoheteroarylamino; -NH2; dialkylamino; diarylamino; diheteroarylamino : An alkylarylamino group; an alkylheteroarylamino group; and an arylheteroarylamino group, and the number of carbon atoms is not particularly limited, but is preferably 1-30. Specific examples of the amino group include methylamino, dimethylamino, ethylamino, diethylamino, phenylamino, naphthylamino, biphenylamino, diphenylamine Group, anthrylamino group, 9-methyl-anthrylamino group, diphenylamino group, phenylnaphthylamino group, xylylamino group, phenyltolylamino group, triphenylamino group, biphenyl Phenylnaphthylamino, phenylbiphenylamino, biphenylfluorenylamino, phenylbiphenyltriphenylenylamine, biphenyltriphenylenylamine and similar to the foregoing, but Not limited to this.

In this specification, arylene means that there are two bonding positions in the phenyl group, that is, a divalent group, except for the divalent arylene group, the above description of the aryl group Can be applied to arylene. Further, the heteroarylene group (heteroarylene) means that there are two bonding positions in the heteroaryl group, that is, the divalent group, except for the divalent heteroarylene group, the above description of the heteroarylene group Can be applied to arylene.

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

In addition, by introducing various substituents into the structure of any one of Chemical Formulae 1 to 3, a compound having the inherent characteristic of introducing substituents can be synthesized. For example, materials for hole injection layers, materials for hole transport, materials for light-emitting layers, and materials for electron transport layers that are commonly used in organic light-emitting devices can be introduced into the core structure to synthesize each organic material layer. Materials of the required conditions.

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

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

The heterocyclic compound according to an exemplary embodiment of the present invention can be prepared by a multi-step chemical reaction. First, some intermediate compounds are prepared. Any one of Chemical Formulas 1 to 3 can be prepared from the intermediate compound. More specifically, according to the present invention An exemplary embodiment of the heterocyclic compound can be prepared from the following preparation examples.

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

Another exemplary embodiment of the present invention provides an organic light-emitting device comprising 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 organic material layer A light-emitting layer is included, and the light-emitting layer includes: 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 the position connected to L2 of chemical formula 4.

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

In the structural 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; deuterium; 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 Substituted C ₆ -C ₆₀ aryl; substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR'R";-P(=O)RR'; and unsubstituted or C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ heteroaryl substituted amine group, or two or more adjacent groups are bonded to each other to form a 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; deuterium; -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, and m is an integer of 0-8, and n, o , P, q, r and s are each independently an integer of 0-6.

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

In the structural formula, X7 and X8 are the same or different from each other, and are each independently NR, S, O or CR'R", and R15-R18 are the same or different from each other, and are each independently selected from hydrogen; deuterium; 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 C ₆ -C ₆₀ substituted aryl; substituted or unsubstituted C ₂ -C ₆₀ heteroaryl; -SiRR'R";-P(=O)RR'; and unsubstituted or C _1- C ₂₀ alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ heteroaryl substituted amine group, or two or more adjacent groups are 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; deuterium; -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, and t is an integer of 0-7.

In an exemplary embodiment of the present 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 can 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, two of X1-X3 may be N, and all of X1-X3 may 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, any one of R22-R26 of Chemical Formula 5 may be -CN, and the rest may be hydrogen or deuterium independently.

According to an exemplary embodiment of the present invention, the compound represented by Chemical Formula 5 can 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 include 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 dopant material used for the light-emitting layer can use materials well known in the art.

In the host material, the weight ratio of the heterocyclic compound represented by any one of chemical formulas 1 to 3: the compound represented by chemical formula 4 or 5 can be 1:10-10:1, 1:8-8:1 , 1:5-5:1, 1:2-2:1 and 1:1, but not limited to this.

The host material is a simple mixture of two or more compounds. The powdered host material can be mixed before the organic material layer of the organic light-emitting device is formed, and the compound in the liquid state can be mixed when the temperature is equal to or higher than the appropriate temperature. The host material is in a solid state when the temperature is equal to or lower than the melting point of each material, and can be maintained in a liquid state by adjusting the temperature.

The 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 5 In addition, it can be prepared by general methods and materials used to manufacture organic light-emitting devices.

When manufacturing an organic light-emitting device, 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, inkjet printing, screen printing, spraying method, roll coating, and the foregoing approximation, but is not limited thereto.

The compounds represented by chemical formulas 1 to 3 can be used as materials for electron transport layers, hole blocking layers, or light emitting layers in organic light-emitting devices. For example, the compounds represented by chemical formulas 1 to 3 can be used as organic light-emitting devices. Materials used in the electron transport layer, hole transport layer or light emitting layer.

In addition, the compounds represented by chemical formulas 1 to 3 can be used as materials for the light-emitting layer in organic light-emitting devices. For example, the compounds represented by chemical formulas 1 to 3 can be used as phosphorescent host materials for the light-emitting layer in organic light-emitting devices. .

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

The compounds represented by Chemical Formulas 1 to 3 can be used as materials for the charge generation layer in organic light emitting devices.

The compounds represented by chemical formulas 1 to 3 can be used as an electron transport layer, electrokinetic barrier layer, light-emitting layer, or similar materials in organic light-emitting devices. For example, the compounds represented by chemical formulas 1 to 3 can be used as organic light-emitting devices The material of the electron transport layer, hole transport layer, or light-emitting layer.

In addition, the compounds represented by chemical formulas 1 to 3 can be used as materials for the light-emitting layer in organic light-emitting devices. For example, the compounds represented by chemical formulas 1 to 3 can be used as the phosphorescent host material for the light-emitting layer in organic light-emitting devices. .

Figures 1 to 3 illustrate the stacking sequence 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 this figure, and can also 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 junction As shown in Figure 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 demonstrates the case where the organic material layer is multilayered. 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 blocking 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-mentioned stack structure, and if necessary, other layers except the light-emitting material layer can be omitted, and another necessary functional layer can be further added.

According to the organic light-emitting device of an exemplary embodiment of the present invention, the following will exemplify materials other than the compounds shown in chemistry 1 to 5, but the materials are only for illustration, not limiting the scope of the present invention, and can be well known in the art The material replaces.

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

As the material of the negative electrode, materials with relatively low work function can be used, and metals, metal oxides, or conductive polymers can be used. Specific examples of negative electrode materials include metals such as magnesium, calcium, sodium, potassium, titanium, Indium, yttrium, lithium, gamma, aluminum, silver, tin, lead or alloys thereof; multilayer structure materials, such as LiF/Al or LiO ₂ /Al, and similar, but not limited to.

As the material of the electromotive injection layer, a well-known hole injection material can be used, or phthalocyanine, such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or in the literature [Advanced Material, 6 , p.677 (1994)] described in starburst-type amine derivatives, such as tris (4-carbazol-9-ylphenyl) amine (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-methylphenylphenylamino)phenyl]benzene (1,3,5-tris[4-(3-metylphenylphenylamino)phenyl]benzene, m-MTDAPB), polyaniline/dodecylbenzene sulfonic acid, or soluble conductive polymer poly(3,4-ethylenedioxythiophene)/poly(4-styrene sulfonate), polyaniline/camphor Sulfonic acid, or polyaniline/poly(4-styrene-sulfonate), and similar.

As the material for the hole transport layer, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives and the like can be used, and low molecular weight or polymerized materials can also be used.物材料。 Material.

As the material of the electron transport layer, oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives can be used , Anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone and its derivatives, diphenyldicyanoethylene and its derivatives, two Diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline, and the aforementioned derivatives, low molecular weight materials and polymer materials can also be used.

As the material of the electron injection layer, for example, LiF is typically used in the art, but the present invention is not limited to this.

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

The heterocyclic compound according to an exemplary embodiment of the present invention, based on a principle similar to that applied to organic light-emitting devices, can even act on organic electronic devices, including organic solar cells, organic photoconductors, and organic transistors.

Here, this specification will be described in more detail through examples, but these examples are only provided as illustrations of the present invention, and do not limit the scope of the present invention.

<Example>

[Synthesis Example 1] Preparation of Compound H

Preparation of compound H

Take 2-bromodibenzofuran (30g, 121.41mmol) and tetrahydrofuran (300ml) in the reaction flask, cool the temperature to -78℃, and slowly add dropwise lithium diisopropylamide (LDA) solution (1.8M) , 88ml), the temperature was maintained at -78°C for 1 hour, then solid iodine (33.9g, 133.55mmol) was added and stirred at room temperature for 4 hours, extracted with distilled water and dichloromethane, the extract was dissolved in dichloromethane, and The resulting solution was filtered with silica gel and magnesium silicate (florisil), and the residue was filtered with methanol after the solvent was removed to obtain the target compound H (23.1g, 51%).

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

Preparation of compound 1-1-1

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

Preparation of compound 1-1

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

In addition to the preparation of compound 1-1-1 in Preparation Example 1-1, the intermediate in Table 1 below was used to substitute (9-phenyl-9H-carbazol-2-yl)boronic acid to compare with Preparation Example 1- 1 The target compound A was synthesized by the same preparation method.

[Table 1]

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

Preparation of compound 2-1-1

Take compound H (30g, 61.40mmol), (9-phenyl-9H-carbazol-2-yl)boronic acid (17.63g, 61.40mmol), Pd(PPh ₃ ) ₄ (3.1g, 3.55mmol), potassium carbonate (25.46g, 184.2mmol), 1,4-dioxane (300ml) and water (60ml) in a reaction flask, heat the mixture to 120°C for 12 hours, cool the resulting product to room temperature, and distilled water And dichloromethane extraction, 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 2-1-2 is obtained by column chromatography. 1 (17.95g, 60%).

Preparation of compound 2-1

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

The target compound A was synthesized by the same preparation method as the preparation example 2-1, except for the preparation of the compound 2-1-1 in the preparation example 2-1, the intermediate A in the following Table 2 was substituted for (9-phenyl- 9H-carbazol-2-yl)boronic acid, and in the preparation of compound 2-1, (9-phenyl-9H-carbazol-2-yl)boronic acid was substituted with intermediate B in Table 2 below.

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

Preparation of compound 3-1-1

Take compound H (20g, 53.62mmol), (9-phenyl-9H-carbazol-2-yl)boronic acid (15.4g, 53.62mmol), Pd(PPh ₃ ) ₄ (3.1g, 2.68mmol), potassium carbonate (14.82g, 107.24mmol), 1,4-dioxane (300ml) and water (60ml) in a reaction flask, the mixture was heated to 120℃ for 12 hours, the resulting product was cooled to room temperature, and distilled water And dichloromethane extraction, 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 3-1-1 is obtained by column chromatography. 1 (7.5g, 40%).

Preparation of compound 3-1

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

The target compound A was synthesized by the same preparation method as the preparation example 3-1, except for the preparation of the compound 3-1-1 in the preparation example 3-1, the intermediate A in the following Table 3 was substituted for (9-phenyl- 9H-carbazol-2-yl)boronic acid, and in the preparation of compound 3-1, intermediate B in Table 3 below was used to replace (9-phenyl-9H-carbazol-3-yl)boronic acid.

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

Preparation of compound 4-11-2

Take 2-bromodibenzo[b,d]thiophene (5.0g, 19.0mmol), 9H-carbazole (2.6g, 15.8mmol), copper iodide (3.0g, 15.8mmol), trans-1,2- Diaminocyclohexane (1.9ml, 15.8mmol) and potassium phosphate (3.3g, 31.6mmol) were dissolved in 1,4-dioxane (100ml), and the mixed solution was refluxed for 24 hours. After the reaction was completed, Distilled water and dichloromethane were added at room temperature for extraction, the organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator. The reactant was purified by column chromatography (dichloromethane:hexane=1:3) And recrystallized with methanol to obtain the target compound 4-11-2 (4.7g, 85%).

Preparation of compound 4-11-1

Take compound 4-11-2 (5g, 14.3mmol) and tetrahydrofuran (100ml) to form a mixed solution at -78°C, add n-butyllithium (n-BuLi, 2.5M, 7.4ml, 18.6mmol) dropwise, and The mixture was stirred at room temperature for 1 hour, then trimethyl borate ((B(OMe) ₃ , 4.8ml, 42.9mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours, until the reaction was complete After that, distilled water and dichloromethane were added at room temperature for extraction, the organic layer was dried over magnesium sulfate and the solvent was removed with a rotary evaporator, and the reactant was purified by column chromatography (dichloromethane: methanol = 100: 3), and recrystallize with dichloromethane to obtain the target compound 4-11-1 (3.9 g, 70%).

Preparation of compound 4-11

Take compound 4-11-1 (7.5g, 19.0mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1g, 19.0mmol), Pd(PPh ₃ ) ₄ ( 1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) were dissolved in toluene/ethanol/water (100/20/20ml) solution, and then the resulting solution was refluxed for 12 hours. After the reaction was completed, Distilled water and dichloromethane were added at low temperature for extraction, the organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator, and the reactant was purified by column chromatography (dichloromethane: hexane=1:3) And recrystallized with methanol to obtain the target compound 4-11 (7.7g, 70%).

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

Take compound 4-11-1 (7.5g, 19.0mmol), 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-tri Pyrazine (6.5g, 19.0mmol), Pd(PPh ₃ ) ₄ (1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) are dissolved in a toluene/ethanol/water (100/20/20ml) solution, Then the resulting solution was 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 with magnesium sulfate and the solvent was removed by a rotary evaporator. The reactants were passed through the column Purified by chromatography (dichloromethane:hexane=1:3), and recrystallized from methanol to obtain the target compound 4-12 (8.7g, 70%).

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

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

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

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

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

Preparation of compound 4-39-2

Take 2-bromodibenzo[b,d]thiophene (5.0g, 19.0mmol), 2-benzyl-9H-carbazole (3.8g, 15.8mmol), copper iodide (3.0g, 15.8mmol), reverse -1,2-Diaminocyclohexane (1.9ml, 15.8mmol), potassium phosphate (3.3g, 31.6mmol) were dissolved in 1,4-dioxane (100ml), and the mixed solution was refluxed for 24 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. =1:3), and recrystallized with methanol to obtain the target compound 4-39-2 (5.7g, 85%).

Preparation of compound 4-39-1

Take compound 4-39-2 (6.1g, 14.3mmol) and tetrahydrofuran (100ml) to form a mixed solution at -78°C, add n-butyllithium (n-BuLi, 2.5M, 7.4ml, 18.6mmol) dropwise, The mixture was stirred at room temperature for 1 hour, then trimethyl borate ((B(OMe)3, 4.8ml, 42.9mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After completion, distilled water and dichloromethane were added at room temperature for extraction, the organic layer was dried with magnesium sulfate, and the solvent was removed by a rotary evaporator. The product was purified by column chromatography (dichloromethane:methanol=100:3), and recrystallized from dichloromethane to obtain the target compound 4-39-1 (4.7 g, 70%).

Preparation of compound 4-39

Take compound 4-39-1 (8.9g, 19.0mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1g, 19.0mmol), Pd(PPh ₃ ) ₄ ( 1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) were dissolved in toluene/ethanol/water (100/20/20ml) solution, and then the resulting solution was refluxed for 12 hours. After the reaction was completed, Distilled water and dichloromethane were added at low temperature for extraction, the organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator, and the reactant was purified by column chromatography (dichloromethane: hexane=1:3) And recrystallized with methanol to obtain the target compound 4-39 (8.7g, 70%).

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

Take compound 4-39-1 (8.9g, 19.0mmol), 2-([1,1'-biphenyl]-3-yl)-4-bromo-6-phenyl-1,3,5-tri Pyrazine (7.4g, 19.0mmol), Pd(PPh ₃ ) ₄ (1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) are dissolved in a toluene/ethanol/water (100/20/20ml) solution, Then the resulting solution was 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 with magnesium sulfate and the solvent was removed by a rotary evaporator. The reactants were passed through the column Purified by chromatography (dichloromethane:hexane=1:3), and recrystallized from methanol to obtain the target compound 4-40 (9.7g, 70%).

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

Take compound 4-39-1 (8.9g, 19.0mmol), 2-([1,1'-biphenyl]-4-yl)-4-bromo-6-phenyl-1,3,5-tri Pyrazine (7.4g, 19.0mmol), Pd(PPh ₃ ) ₄ (1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) are dissolved in a toluene/ethanol/water (100/20/20ml) solution, Then the resulting solution was 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 with magnesium sulfate and the solvent was removed by a rotary evaporator. The reactants were passed through the column Purified by chromatography (dichloromethane:hexane=1:3), and recrystallized from methanol to obtain the target compound 4-41 (9g, 65%).

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

Take compound 4-39-1 (8.9g, 19.0mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7.4g, 19.0mmol), Pd (PPh ₃ ) ₄ (1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) were dissolved in a toluene/ethanol/water (100/20/20ml) solution, and then the resulting solution was 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. The reactant was purified by column chromatography (dichloromethane: hexane). Alkane=1:3), and recrystallized from methanol to obtain the target compound 4-42 (9.7g, 70%).

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

Take compound 4-39-1 (8.9g, 19.0mmol), 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7.4g, 19.0mmol), Pd (PPh ₃ ) ₄ (1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) were dissolved in a toluene/ethanol/water (100/20/20ml) solution, and then the resulting solution was 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. The reactant was purified by column chromatography (dichloromethane: hexane). Alkane=1:3), and recrystallized with methanol to obtain the target compound 4-43 (9.7g, 70%).

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

Preparation of compound 4-47-2

Take 2-bromodibenzo[b,d]thiophene (5.0g, 19.0mmol), 2,7-diphenyl-9H-carbazole (5.0g, 15.8mmol), copper iodide (3.0g, 15.8mmol) ), trans-1,2-diaminocyclohexane (1.9ml, 15.8mmol), potassium phosphate (3.3g, 31.6mmol) were dissolved in 1,4-dioxane (100ml), and the mixed solution was refluxed for 24 After the reaction is completed, add distilled water and dichloromethane to extract at room temperature, dry the organic layer with magnesium sulfate, and remove the solvent with a rotary evaporator. The reactant is purified by column chromatography (dichloromethane : Hexane=1:3), and recrystallized from methanol to obtain the target compound 4-47-2 (6.7 g, 85%).

Preparation of compound 4-47-1

Take compound 4-47-2 (7.2g, 14.3mmol) and tetrahydrofuran (100ml) to form a mixed solution at -78°C, add n-butyllithium (n-BuLi, 2.5M, 7.4ml, 18.6mmol) dropwise, The mixture was stirred at room temperature for 1 hour, then trimethyl borate ((B(OMe)3, 4.8ml, 42.9mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After completion, distilled water and dichloromethane were added at room temperature for extraction. The organic layer was dried with magnesium sulfate and the solvent was removed by a rotary evaporator. The reactant was purified by column chromatography (dichloromethane: methanol = 100 : 3), and recrystallized with dichloromethane to obtain the target compound 4-47-1 (60%).

Preparation of compound 4-47

Take compound 4-47-1 (10.4g, 19.0mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1g, 19.0mmol), Pd(PPh ₃ ) ₄ ( 1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) were dissolved in toluene/ethanol/water (100/20/20ml) solution, and then the resulting solution was refluxed for 12 hours. After the reaction was completed, Distilled water and dichloromethane were added at low temperature for extraction, the organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator, and the reactant was purified by column chromatography (dichloromethane: hexane=1:3) And recrystallized with methanol to obtain the target compound 4-47 (9.7g, 70%).

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

Preparation of compound 4-66-2

Take 2-bromodibenzo[b,d]thiophene (5.0g, 19.0mmol), 7,7-dimethyl-5,7-dihydroindeno[2,1-b]carbazole (4.5g, 15.8mmol), copper iodide (3.0g, 15.8mmol), trans-1,2-diaminocyclohexane (1.9ml, 15.8mmol), potassium phosphate (3.3g, 31.6mmol) in 1,4-bis Dissolve in oxane (100ml), reflux the mixed solution for 24 hours. After the reaction is complete, add distilled water and dichloromethane for extraction at room temperature, dry the organic layer with magnesium sulfate, and remove the solvent with a rotary evaporator. The product was purified by column chromatography (dichloromethane:hexane=1:3), and recrystallized from methanol to obtain the target compound 4-66-2 (7.3g, 85%).

Preparation of compound 4-66-1

Take compound 4-66-2 (6.7g, 14.3mmol) and tetrahydrofuran (100ml) to form a mixed solution at -78°C, add n-butyllithium (n-BuLi, 2.5M, 7.4ml, 18.6mmol) dropwise, The mixture was stirred at room temperature for 1 hour, then trimethyl borate ((B(OMe)3, 4.8ml, 42.9mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After completion, distilled water and dichloromethane were added at room temperature for extraction, the organic layer was dried with magnesium sulfate, and the solvent was removed by a rotary evaporator. The product was purified by column chromatography (dichloromethane: methanol = 100: 3), and recrystallized with dichloromethane to obtain the target compound 4-66-1 (5.1 g, 70%).

Preparation of compound 4-66

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

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

Take compound 4-66-1 (9.7g, 19.0mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1g, 19.0mmol), Pd(PPh ₃ ) ₄ ( 1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) were dissolved in toluene/ethanol/water (100/20/20ml) solution, and then the resulting solution was refluxed for 12 hours. After the reaction was completed, Distilled water and dichloromethane were added at low temperature for extraction, the organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator, and the reactant was purified by column chromatography (dichloromethane: hexane=1:3) And recrystallized with methanol to obtain the target compound 4-68 (9.3g, 70%).

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

Take compound 4-66-1 (9.7g, 19.0mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7.4g, 19.0mmol), Pd (PPh ₃ ) ₄ (1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) were dissolved in a toluene/ethanol/water (100/20/20ml) solution, and then the resulting solution was 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. The reactant was purified by column chromatography (dichloromethane: hexane). Alkane=1:3), and recrystallized with methanol to obtain the target compound 4-71 (10.3g, 70%).

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

Take compound 4-66-1 (9.7g, 19.0mmol), 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (7.4g, 19.0mmol), Pd (PPh ₃ ) ₄ (1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) were dissolved in a toluene/ethanol/water (100/20/20ml) solution, and then the resulting solution was 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. The reactant was purified by column chromatography (dichloromethane: hexane). Alkane=1:3), and recrystallized with methanol to obtain the target compound 4-74 (10.3g, 70%).

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

Preparation of compound 4-79-2

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

Preparation of compound 4-79-1

Take compound 4-79-2 (6.7g, 14.3mmol) and tetrahydrofuran (100ml) to form a mixed solution at -78°C, add n-butyllithium (n-BuLi, 2.5M, 7.4ml, 18.6mmol) dropwise, And mix at room temperature Stir for 1 hour, then add trimethyl borate (4.8ml, 42.9mmol) dropwise, and stir the mixture at room temperature for 2 hours. After the reaction is complete, add distilled water and dichloromethane at room temperature for extraction. The organic layer was dried with magnesium sulfate and the solvent was removed with a rotary evaporator. The reactant was purified by column chromatography (dichloromethane:methanol=100:3) and recrystallized with dichloromethane to obtain the target compound 4-79 -1 (5.1g, 70%).

Preparation of compound 4-79

Take compound 4-79-1 (9.7g, 19.0mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1g, 19.0mmol), Pd(PPh ₃ ) ₄ ( 1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) were dissolved in toluene/ethanol/water (100/20/20ml) solution, and then the resulting solution was refluxed for 12 hours. After the reaction was completed, Distilled water and dichloromethane were added at low temperature for extraction, the organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator, and the reactant was purified by column chromatography (dichloromethane: hexane=1:3) And recrystallized with methanol to obtain the target compound 4-79 (9.3g, 70%).

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

Preparation of compound 4-83-2

Take 2-bromodibenzo[b,d]thiophene (5.0g, 19.0mmol), 5-phenyl-5,7-indoline[2,3-b]carbazole (5.3g, 15.8mmol) ), copper iodide (3.0g, 15.8mmol), trans-1,2-diaminocyclohexane (1.9ml, 15.8mmol), potassium phosphate (3.3g, 31.6mmol) in 1,4-dioxane (100ml), the mixed solution was refluxed for 24 hours. After the reaction was completed, distilled water and dichloromethane were added for extraction at room temperature. The organic layer was dried with magnesium sulfate, and the solvent was removed by a rotary evaporator. Purified by column chromatography (dichloromethane:hexane=1:3), and recrystallized from methanol to obtain the target compound 4-83-2 (6.9 g, 85%).

Preparation of compound 4-83-1

Take compound 4-83-2 (7.4g, 14.3mmol) and tetrahydrofuran (100ml) to form a mixed solution at -78°C, add n-butyllithium (2.5M, 7.4ml, 18.6mmol) dropwise, and mix in Stir at room temperature for 1 hour, then add trimethyl borate (4.8ml, 42.9mmol) dropwise, and mix at room temperature and stir for 2 hours. After the reaction is complete, add distilled water and dichloromethane at room temperature to proceed. After extraction, the organic layer was dried with magnesium sulfate and the solvent was removed by a rotary evaporator. The reactant was purified by column chromatography (dichloromethane:methanol=100:3) and recrystallized with dichloromethane to obtain the target compound 4-83-1 (5.6g, 70%).

Preparation of compound 4-83

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

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

Take compound 4-83-1 (10.6g, 19.0mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1g, 19.0mmol), Pd(PPh ₃ ) ₄ ( 1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) were dissolved in toluene/ethanol/water (100/20/20ml) solution, and then the resulting solution was refluxed for 12 hours. After the reaction was completed, Distilled water and dichloromethane were added at low temperature for extraction, the organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator, and the reactant was purified by column chromatography (dichloromethane: hexane=1:3) And recrystallized with methanol to obtain the target 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 (5.0g, 19.0mmol), 5H-benzo[4,5]thieno[3,2-c]carbazole (4.3g, 15.8mmol), iodine Copper chloride (3.0g, 15.8mmol), trans-1,2-diaminocyclohexane (1.9ml, 15.8mmol), potassium phosphate (3.3g, 31.6mmol) in 1,4-dioxane (100ml) Dissolve the mixed solution under reflux for 24 hours. After the reaction is completed, add distilled water and dichloromethane for extraction at room temperature. The organic layer is dried with magnesium sulfate, and the solvent is removed by a rotary evaporator. The reactants are passed through the column Purified by chromatography (dichloromethane:hexane=1:3), and recrystallized from methanol to obtain the target compound 4-99-2 (7.2 g, 85%).

Preparation of compound 4-99-1

Take compound 4-99-2 (6.5g, 14.3mmol) and tetrahydrofuran (100ml) to form a mixed solution at -78°C, add n-butyllithium (n-BuLi, 2.5M, 7.4ml, 18.6mmol) dropwise, The mixture was stirred at room temperature for 1 hour, then trimethyl borate (4.8ml, 42.9mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, distilled water and Dichloromethane was used for extraction, the organic layer was dried with magnesium sulfate and the solvent was removed by a rotary evaporator. The reactant was purified by column chromatography (dichloromethane: methanol = 100:3), and then reprocessed with dichloromethane The target compound 4-99-1 (5.0 g, 70%) was obtained by crystallization.

Preparation of compound 4-99

Take compound 4-99-1 (9.5g, 19.0mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (5.1g, 19.0mmol), Pd(PPh ₃ ) ₄ ( 1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) were dissolved in toluene/ethanol/water (100/20/20ml) solution, and then the resulting solution was refluxed for 12 hours. After the reaction was completed, Distilled water and dichloromethane were added at low temperature for extraction, the organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator, and the reactant was purified by column chromatography (dichloromethane: hexane=1:3) And recrystallized with methanol to obtain the target compound 4-99 (8.9 g, 70%).

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

Preparation of compound 4-164-2

Take 2-bromodibenzo[b,d]thiophene (5.0g, 19.0mmol), (4-(9H-carbazol-9-yl)phenyl)boronic acid (5.5g, 19.0mmol), Pd(PPh ₃ ) ₄ (1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) are dissolved in toluene/ethanol/water (100/20/20ml) solution, then the resulting solution is refluxed for 12 hours, after the reaction is complete Add distilled water and dichloromethane at room temperature for extraction, dry the organic layer with magnesium sulfate, and remove the solvent with a rotary evaporator. The reactant is purified by column chromatography (dichloromethane: hexane=1 : 3), and recrystallized with methanol to obtain the target compound 4-164-2 (8.9 g, 70%).

Preparation of compound 4-164-1

Take compound 4-164-2 (6.09g, 14.3mmol) and tetrahydrofuran (100ml) to form a mixed solution at -78°C, add n-butyllithium (n-BuLi, 2.5M, 7.4ml, 18.6mmol) dropwise, The mixture was stirred at room temperature for 1 hour, then trimethyl borate (4.8ml, 42.9mmol) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, distilled water and Dichloromethane for extraction, the organic layer Dry with magnesium sulfate and remove the solvent with a rotary evaporator. The reactant was purified by column chromatography (dichloromethane:methanol=100:3) and recrystallized with dichloromethane to obtain the target compound 4-164-1 (4.7g, 70%).

Preparation of compound 4-164

Take compound 4-164-1 (8.9g, 19.0mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (6.1g, 22.8mmol), Pd(PPh ₃ ) ₄ ( 1.1g, 0.95mmol), potassium carbonate (5.2g, 38.0mmol) were dissolved in toluene/ethanol/water (100/20/20ml) solution, and then the resulting solution was refluxed for 12 hours. After the reaction was completed, Distilled water and dichloromethane were added at low temperature for extraction, the organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator, and the reactant was purified by column chromatography (dichloromethane: hexane=1:3) , And recrystallized from methanol to obtain the target compound 4-164 (9.0 g, 72%).

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

Preparation of compound 5-87-3

Take 9H-carbazole (8.9g, 52.93mmol), 1-bromo-3-chloro-5-fluorobenzene (22.1g, 105.8mmol), sodium hydride (1.9g, 79.40mmol), dimethylformamide ( DMF, 200ml) in a reaction flask, heat the mixture to 120°C for 8 hours, cool the resulting product to room temperature, and extract with distilled water and dichloromethane. Then the extract was dissolved in dichloromethane, the resulting solution was filtered with silica gel and magnesium silicate (florisil), and the solvent was removed to obtain the target compound 5-87-3 (13.2g, 70%).

Preparation of compound 5-87-2

Take compound 5-87-3 (14.3g, 40.18mmol), double pinacolato diboron (bis(pinacolato) diboron, 13.26g, 52.24mmol), (1,1'-bis(diphenylphosphine) Ferrocene) palladium dichloride (0.8g, 1.205mmol), potassium acetate (11.8g, 120.5mmol), 1,4-dioxane (150ml) in a reaction flask, the mixture was heated to 120°C for 5 hours , The resulting product is cooled to room temperature, and extracted with distilled water and dichloromethane, 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 Then the target compound 5-87-2 (12.7g, 78%) was obtained.

Preparation of compound 5-87-1

Take compound 5-87-2 (14g, 34.6mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (11.2g, 41.5mmol), Pd(PPh ₃ ) ₄ (2g , 1.7mmol), potassium carbonate (14.3g, 103.8mmol), toluene (120ml), ethanol (20ml) and water (20ml) in a reaction flask, the mixture is heated to 120 ℃ for 8 hours, the resulting product is cooled to At room temperature, it was extracted with distilled water and dichloromethane, and then the extract was dissolved in dichloromethane. The resulting solution was filtered with silica gel, diatomaceous earth and magnesium silicate, and the filtrate was recrystallized with dichloromethane and methanol to obtain the target compound 5- 87-1 (14.1g, 80%).

Preparation of compound 5-87

Take compound 5-87-1 (4.9g, 9.582mmol), (2-cyanophenyl)boronic acid (2.1g, 14.37mmol), tris(dibenzylideneacetone) two palladium (Pd ₂ (dba) ₃ , 0.61 g, 0.67mmol), potassium phosphate (6.1g, 28.7mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (Xphos, 0.91g, 1.91mmol), toluene (60ml) and water (10ml) in a reaction flask, the mixture was replaced with nitrogen, the resulting product was refluxed for 12 hours, and then extracted with distilled water and dichloromethane, the organic layer was dried with magnesium sulfate, and the rotary evaporator The solvent was removed, and the resulting product was purified by column (dichloromethane: hexane=1:1) to obtain the target compound 5-87 (4.0 g, 73%).

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

Preparation of compound 5-99-1

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

Preparation of compound 5-99

Take compound 5-99-1 (6g, 9.582mmol), (2-cyanophenyl)boronic acid (2.1g, 14.37mmol), Pd ₂ (dba) ₃ (0.61g, 0.67mmol), potassium phosphate (6.1g, 28.7mmol), Xphos (0.91g, 1.91mmol), toluene (60ml) and water (10ml) in a reaction flask, the mixture was replaced with nitrogen, the resulting product was refluxed for 12 hours, and then extracted with distilled water and dichloromethane , The organic layer was dried with magnesium sulfate, the solvent was removed with a rotary evaporator, and the resulting product was purified by column (dichloromethane:hexane=1:1) to obtain the target compound 5-99 (4.1g, 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 (15g, 52.93mmol), 1-bromo-3-chloro-5-fluorobenzene (22.1g, 105.8 mmol), sodium hydride (1.9g, 79.4mmol), DMF (200ml) in a reaction flask, the mixture was heated to 120 ℃ 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, the resulting solution was filtered with silica gel and magnesium silicate (florisil), and the solvent was removed to obtain the target compound 5-203-3 (19g, 76%).

Preparation of compound 5-203-2

Take compound 5-203-3 (19g, 40.18mmol), double pinacol borate (13.26g, 52.24mmol), PdCl ₂ (dppf) (0.8g, 1.21mmol), potassium acetate (11.8g, 120.5 mmol), 1,4-dioxane (150ml) in a reaction flask, the mixture was heated to 120 ℃ for 5 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, and then the extract with The methylene chloride was dissolved, the resulting solution was filtered with silica gel, diatomaceous earth and magnesium silicate, and the solvent was removed to obtain the target compound 5-203-2 (18g, 76%).

Preparation of compound 5-203-1

Take compound 5-203-2 (18g, 34.6mmol), 2-chloro-4,6-diphenylpyrimidine (11.0g, 41.5mmol), Pd(PPh ₃ ) ₄ (2g, 1.7mmol), potassium carbonate ( 14.3g, 103.8mmol), toluene (120ml), ethanol (20ml) and water (20ml) in a reaction flask, the mixture was heated to 120 ℃ for 8 hours, the resulting product was cooled to room temperature, and distilled water and two Extract with methyl chloride, then dissolve the extract with dichloromethane, filter the resulting solution with silica gel, diatomaceous earth and magnesium silicate, and recrystallize the filtrate with dichloromethane and methanol to obtain the target compound 5-203-1 (15g, 78%) ).

Preparation of compound 5-203

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

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

Take compound 5-99-1 (5g, 7.98mmol), (3-cyanophenyl) boric acid (1.5g, 10.38mmol), Pd ₂ (dba) ₃ (0.36g, 0.39mmol), potassium phosphate (5.2g, 23.9mmol), Sphos (0.33g, 0.79mmol), toluene (60ml) and water (10ml) in a reaction flask, the mixture was replaced with nitrogen, the resulting product was refluxed for 12 hours, and then extracted with distilled water and dichloromethane , The organic layer was dried with magnesium sulfate, the solvent was removed with a rotary evaporator, and the resulting product was purified by column (dichloromethane:hexane=1:1) to obtain the target compound 5-260 (3.5g, 64%) ).

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

Preparation of compound 5-262-3

Take 11,11-dimethyl-5,11-dihydroindeno[2,1-b]carbazole (15g, 53mmol), 1-bromo-3-chloro-5-fluorobenzene (24.3g, 106.01mmol) ), sodium hydride (3.1g, 79.54mmol), DMF (200ml) in a reaction flask, the mixture was heated to 120 ℃ 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, the resulting solution was filtered with silica gel and magnesium silicate, and the solvent was removed to obtain the target compound 5-262-3 (17g, 71%).

Preparation of compound 5-262-2

Take compound 5-262-3 (17g, 40.25mmol), double pinacolato diboron (bis(pinacolato) diboron, 15.2g, 60.81mmol), PdCl ₂ (dppf) (1.4g, 2.01mmol), acetic acid Put potassium (11.8g, 120.7mmol) and 1,4-dioxane (150ml) in a reaction flask, heat the mixture to 120°C for 5 hours, cool the resulting product to room temperature, and use distilled water and dichloromethane After extraction, 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 to obtain the target compound 5-262-2 (16g, 72%).

Preparation of compound 5-262-1

Take compound 5-262-2 (16g, 34.68mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (19.4g, 52.02mmol), Pd(PPh ₃ ) ₄ (2.6 g, 1.7mmol), potassium carbonate (14.3g, 109.8mmol), toluene (120ml), ethanol (20ml) and water (20ml) in a reaction flask, heat the mixture to 120°C for 8 hours, and cool the resulting product Bring to room temperature and extract with distilled water and dichloromethane. Then the extract is dissolved in dichloromethane. The resulting solution is filtered with silica gel, diatomaceous earth and magnesium silicate. The filtrate is recrystallized with dichloromethane and methanol to obtain the target compound 5. -262-1 (16g, 75%).

Preparation of compound 5-262

Take compound 5-262-1 (6g, 9.648mmol), (3-cyanophenyl)boronic acid (2.1g, 14.42mmol), Pd ₂ (dba) ₃ (0.44g, 0.48mmol), potassium phosphate (6.1g, 28.9mmol), Sphos (0.39g, 0.94mmol), toluene (60ml) and water (10ml) in a reaction flask, the mixture was replaced with nitrogen, the resulting product was refluxed for 12 hours, and then extracted with distilled water and dichloromethane , The organic layer was dried with magnesium sulfate, the solvent was removed with a rotary evaporator, and the resulting product was purified by column (dichloromethane: hexane=1:1) to obtain the target compound 5-262 (4.6g, 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 (15g, 53mmol), 1-bromo-3-chloro-5-fluorobenzene (24.3g, 106.01mmol) ), sodium hydride (3.1g, 79.54mmol), DMF (200ml) in a reaction flask, the mixture was heated to 120 ℃ 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, and the resulting solution was filtered with silica gel and magnesium silicate (florisil), and the solvent was removed to obtain the target compound 5-264-3 (19g, 78%).

Preparation of compound 5-264-2

Take compound 5-264-3 (19g, 40.25mmol), double pinacol borate (15.2g, 60.81mmol), PdCl ₂ (dppf) (1.4g, 2.01mmol), potassium acetate (11.8g, 120.7 mmol), 1,4-dioxane (150ml) in a reaction flask, the mixture was heated to 120 ℃ for 5 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, and then the extract with The methylene chloride was dissolved, the resulting solution was filtered with silica gel, diatomaceous earth and magnesium silicate, and the solvent was removed to obtain the target compound 5-264-2 (18g, 73%).

Preparation of compound 5-264-1

Take compound 5-264-2 (18g, 34.68mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (19.4g, 52.02mmol), Pd(PPh ₃ ) ₄ (2.6 g, 1.7mmol), potassium carbonate (14.3g, 109.8mmol), toluene (120ml), ethanol (20ml) and water (20ml) in a reaction flask, heat the mixture to 120°C for 8 hours, and cool the resulting product Bring to room temperature and extract with distilled water and dichloromethane. Then the extract is dissolved in dichloromethane. The resulting solution is filtered with silica gel, diatomaceous earth and magnesium silicate. The filtrate is recrystallized with dichloromethane and methanol to obtain the target compound 5. -264-1 (16g, 74%).

Preparation of compound 5-264

Take compound 5-264-1 (6g, 9.64mmol), (3-cyanophenyl)boronic acid (2.1g, 14.42mmol), Pd ₂ (dba) ₃ (0.44g, 0.48mmol), potassium phosphate (6.1g, 28.9mmol), Sphos (0.39g, 0.94mmol), toluene (60ml) and water (10ml) in a reaction flask, the mixture was replaced with nitrogen, the resulting product was refluxed for 12 hours, and then extracted with distilled water and dichloromethane , The organic layer was dried with magnesium sulfate, the solvent was removed with a rotary evaporator, and the resulting product was purified by column (dichloromethane:hexane=1:1) to obtain the target compound 5-264 (4.6g, 75%) ).

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

Preparation of compound 5-267-3

Take 5H-benzo[4,5]thieno[3,2-c]carbazole (15g, 54.94mmol), 1-bromo-3-chloro-5-fluorobenzene (22.9g, 109.89mmol), sodium hydride (3.2g, 82.41mmol), DMF (200ml) in the reaction flask, The mixture was heated to 120°C and reacted 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, and the resulting solution was filtered with silica gel and magnesium silicate (florisil). After removing the solvent, the target compound 5-267-3 (17 g, 76%) was obtained.

Preparation of compound 5-267-2

Take compound 5-267-3 (17g, 41.12mmol), double pinacol borate (15.6g, 61.68mmol), PdCl ₂ (dppf) (1.5g, 2.056mmol), potassium acetate (12.08g, 123.3 mmol), 1,4-dioxane (150ml) in a reaction flask, the mixture was heated to 120 ℃ for 5 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, and then the extract with The methylene chloride was dissolved, and the resulting solution was made of silica gel, diatomaceous earth and magnesium silicate (filtered and removed the solvent to obtain the target compound 5-267-2 (19g, 76%).

Preparation of compound 5-267-1

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

Preparation of compound 5-267

Take compound 5-267-1 (5.9g, 9.64mmol), (3-cyanophenyl) boric acid (2.1g, 14.42mmol), Pd ₂ (dba) ₃ (0.44g, 0.48mmol), potassium phosphate (6.1g) , 28.9mmol), Sphos (0.39g, 0.94mmol), toluene (60ml) and water (10ml) in a reaction flask, the mixture was replaced with nitrogen, the resulting product was refluxed for 12 hours, followed by distilled water and dichloromethane After extraction, the organic layer was dried with magnesium sulfate, the solvent was removed with a rotary evaporator, and the resulting product was purified by column (dichloromethane:hexane=1:1) to obtain the target compound 5-267 (4.9g, 75 %).

[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 mmol), DMF (200ml) in a reaction flask, the mixture was heated to 120 ℃ 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 produce The solution was filtered with silica gel and magnesium silicate (florisil), and the solvent was removed to obtain the target compound 5-271-3 (18g, 73%).

Preparation of compound 5-271-2

Take compound 5-271-3 (18g, 42.6mmol), double pinacol borate (15.6g, 63.90mmol), PdCl ₂ (dppf) (1.5g, 2.13mmol), potassium acetate (12.08g, 127.9 mmol), 1,4-dioxane (150ml) in a reaction flask, the mixture was heated to 120 ℃ for 5 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, and then the extract with The methylene chloride was dissolved, and the resulting solution was filtered with silica gel, diatomaceous earth and magnesium silicate (florisil), and the solvent was removed to obtain the target compound 5-271-2 (17g, 78%).

Preparation of compound 5-271-1

Take compound 5-271-2 (17g, 36.51mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (19.4g, 73.02mmol), Pd(PPh ₃ ) ₄ (2.6 g, 1.7mmol), potassium carbonate (14.3g, 106.0mmol), toluene (120ml), ethanol (20ml) and water (20ml) in a reaction flask, heat the mixture to 120°C for 8 hours, and cool the resulting product Bring to room temperature and extract with distilled water and dichloromethane, then dissolve the extract with dichloromethane, the resulting solution is silica gel, diatomaceous earth and magnesium silicate (filtered, the filtrate is recrystallized with dichloromethane and methanol to obtain the target compound 5-271-1 (18g, 71%).

Preparation of compound 5-271

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

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

Take compound 5-99-1 (5g, 7.98mmol), (4-cyanophenyl) boric acid (1.5g, 10.38mmol), Pd ₂ (dba) ₃ (0.36g, 0.39mmol), potassium phosphate (5.2g, 23.9mmol), Sphos (0.33g, 0.79mmol), toluene (60ml) and water (10ml) in a reaction flask, the mixture was replaced with nitrogen, the resulting product was refluxed for 12 hours, and then extracted with distilled water and dichloromethane , The organic layer was dried with magnesium sulfate, the solvent was removed with a rotary evaporator, and the resulting product was purified by column (dichloromethane: hexane=1:1) to obtain the target compound 5-416 (4.1g, 73%) ).

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

Preparation of compound 5-421-3

Take 12H-benzo[4,5]thieno[3,2-a]carbazole (15g, 54.94mmol), 1-bromo-3-chloro-5-fluorobenzene (22.9g, 109.89mmol), sodium hydride (3.2g, 82.41mmol), DMF (200ml) in a reaction flask, the mixture was heated to 120 ℃ for 8 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, and then the extract with two The methyl chloride is dissolved, the resulting solution is filtered with silica gel and magnesium silicate (florisil), and the solvent is removed to obtain the target compound 5-421-3 (17g, 76%).

Preparation of compound 5-421-2

Take compound 5-421-3 (17g, 41.12mmol), double pinacol borate (15.6g, 61.68mmol), PdCl ₂ (dppf) (1.5g, 2.056mmol), potassium acetate (12.08g, 123.3 mmol), 1,4-dioxane (150ml) in a reaction flask, the mixture was heated to 120 ℃ for 5 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, and then the extract with The methylene chloride was dissolved, the resulting solution was filtered with silica gel, diatomaceous earth and magnesium silicate, and the solvent was removed to obtain the target compound 5-421-2 (19g, 76%).

Preparation of compound 5-421-1

Take compound 5-421-2 (19g, 35.36mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (14.1g, 53.04mmol), Pd(PPh ₃ ) ₄ (2g , 1.7mmol), potassium carbonate (14.3g, 106.0mmol), toluene (120ml), ethanol (20ml) and water (20ml) in a reaction flask, the mixture is heated to 120 ℃ for 8 hours, the resulting product is cooled to At room temperature, it was extracted with distilled water and dichloromethane, and then the extract was dissolved in dichloromethane. The resulting solution was filtered with silica gel, diatomaceous earth and magnesium silicate, and the filtrate was recrystallized with dichloromethane and methanol to obtain the target compound 5- 421-1 (15g, 77%).

Preparation of compound 5-421

Take compound 5-421-1 (5g, 8.13mmol), (4-cyanophenyl) boric acid (1.7g, 12.19mmol), Pd ₂ (dba) ₃ (0.36g, 0.40mmol), potassium phosphate (5.8g, 24.39mmol), Sphos (0.33g, 0.79mmol), toluene (60ml) and water (10ml) in a reaction flask, the mixture was replaced with nitrogen, the resulting product was refluxed for 12 hours, and then extracted with distilled water and dichloromethane , The organic layer was dried with magnesium sulfate, and the solvent was removed with a rotary evaporator, and the resulting product was purified by column (dichloromethane: hexane=1:1) to obtain the target compound 5-421 (4.5g, 78%) ).

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

Take compound 5-267-1 (5g, 8.13mmol), (4-cyanophenyl) boric acid (1.7g, 12.19mmol), Pd ₂ (dba) ₃ (0.36g, 0.40mmol), potassium phosphate (5.8g, 24.39mmol), Sphos (0.33g, 0.79mmol), toluene (60ml) and water (10ml) in a reaction flask, the mixture was replaced with nitrogen, the resulting product was refluxed for 12 hours, and then extracted with distilled water and dichloromethane , The organic layer was dried with magnesium sulfate, and the solvent was removed by a rotary evaporator, and the resulting product was purified by column (dichloromethane: hexane=1:1) to obtain the target compound 5-422 (4.3g, 72%) ).

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

Preparation of compound 5-450-3

Take 2-phenyl-9H-carbazole (12.8g, 52.89mmol), 1-bromo-3-chloro-5-fluorobenzene (22.1g, 105.8mmol), sodium hydride (1.9g, 79.40mmol), DMF ( 200ml) in a reaction flask, heat the mixture to 120°C for 8 hours, cool the resulting product to room temperature, and extract with distilled water and dichloromethane, then dissolve the extract with dichloromethane, and the resulting solution with silica gel and The magnesium silicate was filtered and the solvent was removed to obtain the target compound 5-450-3 (17.2 g, 74%).

Preparation of compound 5-450-2

Take compound 5-450-3 (17.3g, 40.09mmol), double pinacol borate (13.26g, 52.24mmol), PdCl ₂ (dppf) (0.8g, 1.205mmol), potassium acetate (11.8g, 120.5mmol), 1,4-dioxane (150ml) in a reaction flask, the mixture was heated to 120 ℃ for 5 hours, the resulting product was cooled to room temperature, and extracted with distilled water and dichloromethane, and then the extract Dissolve with dichloromethane, filter the resulting solution with silica gel, diatomaceous earth and magnesium silicate, and remove the solvent to obtain the target compound 5-450-2 (14.8g, 74%).

Preparation of compound 5-450-1

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

Preparation of compound 5-450

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

[Comparative Preparation Example 1] Preparation of Reference 5

Reference 5-1 Preparation

Take compound H (30g, 61.40mmol), (9-phenyl-9H-carbazol-3-yl)boronic acid (17.63g, 61.40mmol), Pd(PPh ₃ ) ₄ (3.1g, 3.55mmol), potassium carbonate (25.46g, 184.2mmol), 1,4-dioxane (300ml) and water (60ml) in a reaction flask, the mixture was heated to 120℃ for 12 hours, the resulting product was cooled to room temperature, and distilled water And dichloromethane extraction, then the extract was dissolved in dichloromethane, the resulting solution was filtered with silica gel, diatomaceous earth and magnesium silicate and the solvent was removed, the target compound reference 5-1 (17.9g, 60%).

Preparation of Reference 5

Take compound reference 5-1 (6g, 12.28mmol), (9-phenyl-9H-carbazol-3-yl)boronic acid (7.08g, 24.57mmol), Pd(PPh ₃ ) ₄ (0.71g, 0.61mmol) , Potassium carbonate (5.09g, 36.84mmol), cesium fluoride (3.7g, 24.57mmol), toluene (60ml), ethanol (10ml) and water (60ml) in a reaction flask, the mixture is heated to 100 ℃ for 12 hours , The resulting product is cooled to room temperature, and extracted with distilled water and dichloromethane, 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, The target compound reference 5 (1g, 63%) was obtained by column chromatography.

The compound was prepared by the same method as the preparation example, and its synthetic determination results are listed in Table 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) Manufacturing of organic light-emitting devices

A glass substrate with an indium tin oxide (ITO) coating with a thickness of 1500Å is ultrasonically cleaned with distilled water, and then the glass substrate is ultrasonically cleaned and dried with solvents such as acetone, methanol and isopropanol, and then in a UV washing machine UVO treatment was carried out with UV for 5 minutes, after which the substrate was transferred to a plasma washing machine (PT) for plasma treatment. Perform work function and remove indium tin oxide (ITO) for plasma treatment in the state, thereby transferring to thermal deposition equipment 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 Perform thermal vacuum lamination on the transport layer to form a light-emitting layer with a thickness of 400Å. For the light-emitting layer, use the compound described in the following table as the host and doped with 7% tris(2-phenylpyridine)iridium (Ir(ppy) ) ₃ ) As a phosphorescent dopant, then, BCP with a thickness of 60Å is deposited as a hole barrier layer, and Alq ₃ with a thickness of 200Å is deposited on it as an electron transport layer, and finally, a lithium fluoride (LiF) with a thickness of 10Å ) Is deposited on the electron transport layer to form an electron injection layer, and aluminum (Al) with a thickness of 1200 Å is deposited on the electron injection layer to form a negative electrode, thereby manufacturing an organic light-emitting device.

At the same time, all the organic compounds needed to manufacture OLEDs are vacuum sublimated and purified at 10 ^-6 to 10 ^-8 torr, and then used in OLED manufacturing.

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

For the organic light-emitting device manufactured as described above, the electroluminescence (EL) characteristics were 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 service life measuring device (M6000) measures T ₉₀ . The characteristics of the organic light emitting device of the present invention are shown in Table 8 and Table 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 No. 2 position of dibenzofuran was substituted with carbazole-N, the service life was poor , Because the oxygen of dibenzofuran in the para position can be activated by nitrogen as an electron donating group to weaken the resonance effect, which deteriorates the stability of the molecule. In the case of reference 4, it is determined that when the 4th position of dibenzofuran is an electron-withdrawing heteroaryl group, the service life will be reduced, because the oxygen atom of dibenzofuran provides electrons to make electron injection along the LUMO unstable . Reference 5 has a molecular structure similar to the present invention, However, it is determined that when the 2 and 4 positions of dibenzofuran are replaced with the carbazole in the 3 position at the same time, the service life will be reduced. The reason is the same as that of reference 1, reference 2 and reference 3.

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

The organic light-emitting device of the present invention includes 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. Therefore, the organic light-emitting device of the present invention is consistent with the prior art Compared with the organic light-emitting device composed of a single compound as the host compound, it has a better service life.

In particular, the pn-type host of the present invention has the advantage of adjusting the ratio of the host to increase the light-emitting characteristics, and this advantage is achieved by appropriately combining a p-type host with good hole mobility and an n-type host with good electron mobility. The result reached.

100‧‧‧Substrate

200‧‧‧Positive electrode

300‧‧‧Organic material layer

301‧‧‧hole injection layer

302‧‧‧Electric hole transfer layer

303‧‧‧Light-emitting layer

304‧‧‧electric hole barrier

305‧‧‧Electron transport layer

306‧‧‧Electron 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 the 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; deuterium; 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 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 R, R', R" are the same or different from each other and are independently hydrogen; deuterium; -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 , And m, n, o, p, q, r, s, t, and u are each independently an integer of 0-4. The heterocyclic compound described in item 1 of the scope of the patent application, wherein R1-R9 of formulas 1 to 3 are each independently hydrogen or deuterium. The heterocyclic compound described in item 1 of the scope of the patent application, wherein chemical formulas 1 to 3 are represented by any of the following compounds:

An organic light emitting device, comprising: a positive electrode; a negative electrode; and an organic material layer having one or more layers arranged between the positive electrode and the negative electrode, wherein one or more layers of the organic material layer include the scope of the patent application The heterocyclic compound described in any one of items 1 to 3. The organic light-emitting device according to claim 4, wherein the organic material layer includes at least one of a hole blocking layer, an electron injection layer, and an electron transport layer, and the hole blocking layer, the electron At least one of the injection layer and the electron transport layer contains the heterocyclic compound. The organic light-emitting device according to claim 4, wherein the organic material layer includes a light-emitting layer, and the light-emitting layer includes the heterocyclic compound. The organic light-emitting device according to claim 4, wherein the organic material layer includes one or more of a hole injection layer, a hole transfer layer, and a layer that simultaneously injects and transfers holes, and in the layer One layer contains the heterocyclic compound. The organic light-emitting device according to claim 4, wherein the organic material layer including the heterocyclic compound further includes a compound represented by the following chemical formula 4 or 5:

Wherein in the chemical formula 4, L1 and L2 are the same or different from each other, and each independently is a bond or a substituted or unsubstituted C ₆ -C ₆₀ arylene group, and Ar7 is a substituted or unsubstituted C ₆ -C ₆₀ group containing at least one N The substituted C ₂ -C ₆₀ heteroaryl group, Ar8 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; deuterium; 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 The amine group, or two or more adjacent groups are bonded to each other to form a group consisting of substituted or unsubstituted aliphatic or aromatic hydrocarbon rings, R, R'and R" are the same or different from each other, And each independently is hydrogen; deuterium; -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, 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, R17, R18 and R35 are the same or different from each other, and are each independently selected from hydrogen; deuterium; 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 Alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ heteroaryl substituted amine group, or two or more adjacent groups are bonded to each other to form 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; deuterium; 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 alkane Oxy; 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 The group consisting of substituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ heteroaryl substituted amine groups, R31-R34 are the same or different from each other, and are each independently selected from hydrogen; deuterium; 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 alkyl, substituted or unsubstituted C ₆ -C ₆₀ aryl or C ₂ -C ₆₀ heteroaryl substituted amine group, or two or more adjacent groups are bonded to each other to form a A group of substituted or unsubstituted hydrocarbon rings or heterocycles, at least one of R22-R26 is -CN , And the rest are each independently selected from hydrogen; deuterium; halogen; -CN; substituted or unsubstituted C ₁ -C ₆₀ alkyl; substituted or unsubstituted C ₂ -C ₆₀ alkenyl; substituted or unsubstituted A substituted C ₂ -C ₆₀ alkynyl group; a substituted or unsubstituted C ₁ -C ₆₀ alkoxy group; a substituted or unsubstituted C ₃ -C ₆₀ cycloalkyl group; a 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 substituted amine group, or Two or more adjacent groups are bonded to each other to form a group consisting of substituted or unsubstituted aliphatic or aromatic hydrocarbon rings, R, R'and R" are the same or different from each other, and each independently is hydrogen ; Deuterium; -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 Group; or substituted or unsubstituted C ₂ -C ₆₀ heteroaryl. The organic light-emitting device described in item 8 of the scope of patent application, wherein the compound represented by Chemical Formula 4 is represented by any one of the following compounds:

The organic light-emitting device described in item 8 of the scope of patent application, 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 the heterocyclic compound as a host material for the light-emitting layer; and the compound represented by Chemical Formula 4 or 5.

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