Organic light emitting device

Abstract

The present invention provides an organic light emitting device.

Description

Technical Field

[0001] Cross-reference with related applications

[0002] This application claims priority based on Korean Patent Application No. 10-2020-0078700 dated June 26, 2020 and Korean Patent Application No. 10-2021-0083735 dated June 28, 2021, the entire contents of which are disclosed in the documents of the Korean patent applications and are incorporated in this specification.

[0003] This invention relates to organic light-emitting devices. Background Technology

[0004] Organic light emission typically refers to the phenomenon of converting electrical energy into light energy using organic materials. Organic light-emitting devices (OLEDs) utilizing organic light emission exhibit wide viewing angles, excellent contrast ratios, fast response times, and superior brightness, driving voltage, and response speed characteristics, thus attracting extensive research.

[0005] Organic light-emitting devices (OLEDs) typically have a structure comprising an anode and a cathode, and an organic layer located between the anode and cathode. To improve the efficiency and stability of OLEDs, the organic layer is often formed by a multilayer structure composed of different materials, such as a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In such an OLED structure, if a voltage is applied between the two electrodes, holes are injected into the organic layer from the anode, and electrons are injected into the organic layer from the cathode. When the injected holes and electrons meet, an exciton is formed. When this exciton re-enters the ground state, it emits light.

[0006] For organic materials used in organic light-emitting devices as described above, there is a continuous need to develop new materials.

[0007] Existing technical documents

[0008] Patent documents

[0009] (Patent Document 1) Korean Patent Publication No. 10-2000-0051826 Summary of the Invention

[0010] Technical issues

[0011] This invention relates to organic light-emitting devices with improved driving voltage, efficiency, and lifetime.

[0012] Solution to the problem

[0013] To address the aforementioned issues, the present invention provides the following organic light-emitting device:

[0014] An organic light-emitting device, comprising:

[0015] Anode, cathode, and the light-emitting layer between the anode and cathode.

[0016] The aforementioned luminescent layer comprises a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2a or 2b:

[0017] [Chemical Formula 1]

[0018]

[0019] In the above chemical formula 1,

[0020] L1 to L3 are each independently a single bond, or a substituted or unsubstituted C bond. 6-60 Alpha-aryl

[0021] Ar1 and Ar2 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms of N, O and S. 2-60 Mixed aromatics,

[0022] R1 is either hydrogen or deuterium; or two adjacent R1s combine to form an unsubstituted or deuterium-substituted benzene ring, with the remaining R1s being either hydrogen or deuterium.

[0023] R2 is either hydrogen or deuterium; or two adjacent R2s combine to form an unsubstituted or deuterium-substituted benzene ring, with the remaining R2s being either hydrogen or deuterium.

[0024] [Chemical Formula 2a]

[0025]

[0026] In the above chemical formula 2a,

[0027] A' is a naphthalene ring fused with an adjacent ring.

[0028] X' is O or S.

[0029] L' 11 and L' 21 Each is an independent single bond; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more of N, O and S. 2-60 heteroaryl,

[0030] L' 12 L' 13 L' 22 and L' 23 Each is independently a single bond, or a substituted or unsubstituted C.6-60 Alpha-aryl

[0031] Ar' 11 Ar' 12 Ar' 21 and Ar' 22 Each is independently either substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more of N, O, and S. 2-60 Mixed aromatics,

[0032] R' represents hydrogen; deuterium; halogen; cyano group; substituted or unsubstituted C. 1-60 Alkyl; substituted or unsubstituted C 1-60 Alkoxy; substituted or unsubstituted C 2-60 Alkenyl; substituted or unsubstituted C 2-60 Alkyne group; substituted or unsubstituted C 3-60 Cycloalkyl; substituted or unsubstituted C 6-60 aryl; substituted or unsubstituted C containing one or more selected from N, O and S 2-60 Mixed aromatics,

[0033] m' is an integer from 0 to 6.

[0034] [Chemical Formula 2b]

[0035]

[0036] In the above chemical formula 2b,

[0037] A" represents a naphthalene ring fused with an adjacent ring.

[0038] X" represents O or S.

[0039] L" 11 and L" 21 Each is an independent single bond; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more of N, O and S. 2-60 heteroaryl,

[0040] L" 12 、L" 13 、L" 22 and L" 23 Each is independently a single bond, or a substituted or unsubstituted C. 6-60 Alpha-aryl

[0041] Ar" 11 Ar" 12 Ar" 21 and Ar" 22 Each is independently either substituted or unsubstituted C6-60 aryl; or substituted or unsubstituted C containing one or more of N, O, and S. 2-60 Mixed aromatics,

[0042] R represents hydrogen; deuterium; halogen; cyano group; substituted or unsubstituted C. 1-60 Alkyl; substituted or unsubstituted C 1-60 Alkoxy; substituted or unsubstituted C 2-60 Alkenyl; substituted or unsubstituted C 2-60 Alkyne group; substituted or unsubstituted C 3-60 Cycloalkyl; substituted or unsubstituted C 6-60 aryl; substituted or unsubstituted C containing one or more selected from N, O and S 2-60 Mixed aromatics,

[0043] m" is an integer from 0 to 6.

[0044] Invention Effects

[0045] The aforementioned organic light-emitting devices exhibit excellent driving voltage, efficiency, and lifetime. Attached Figure Description

[0046] Figure 1 The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.

[0047] Figure 2 The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4. Detailed Implementation

[0048] The invention will now be described in more detail to aid in understanding.

[0049] In this instruction manual, The symbol indicates a bond that is linked to other substituents; D represents deuterium, and Ph represents phenyl.

[0050] In this specification, the term "substituted or unsubstituted" refers to a group selected from deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thio group. aryl thiols alkylsulfonyl arylsulfonyl Silyl; boronyl; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; arylene; alkylaryl; alkylamine; aralkylamine; heteroarylamine; arylamine; arylphosphinyl; or a heterocyclic group containing one or more N, O, and S atoms, either substituted or unsubstituted, or substituted or unsubstituted by a substituent formed by linking two or more substituents as exemplified above. For example, "a substituent formed by linking two or more substituents" can be biphenyl. That is, biphenyl can be aryl, or it can be interpreted as a substituent formed by linking two phenyl groups.

[0051] In this specification, the number of carbon atoms in the carbonyl group is not particularly limited, but it is preferred to have 1 to 40 carbon atoms. Specifically, it can be a group having the following structure, but is not limited thereto.

[0052]

[0053] In this specification, the oxygen in the ester group can be replaced by a straight-chain, branched, or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, it can be a group having the following structure, but is not limited thereto.

[0054]

[0055] In this specification, the number of carbon atoms in the imide group is not particularly limited, but it is preferred to have 1 to 25 carbon atoms. Specifically, it can be a group having the following structure, but is not limited thereto.

[0056]

[0057] In this specification, silanes specifically include trimethylsilane, triethylsilane, tert-butyldimethylsilane, vinyldimethylsilane, propyldimethylsilane, triphenylsilane, diphenylsilane, phenylsilane, etc., but are not limited to these.

[0058] In this specification, boron groups specifically include dimethylboron, diethylboron, tert-butylmethylboron, diphenylboron, phenylboron, etc., but are not limited to these.

[0059] Examples of halogen groups in this specification include fluorine, chlorine, bromine, or iodine.

[0060] In this specification, the alkyl group can be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to yet another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, n-octyl, isooctyl, tert-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 are not limited to these.

[0061] In this specification, the alkenyl group can be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to yet another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, styryl, styryl, etc., but are not limited to these.

[0062] In this specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group with 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., are used, but are not limited to these.

[0063] In this specification, the aryl group is not particularly limited, but is preferably an aryl group with 6 to 60 carbon atoms, and can be a monocyclic aryl or polycyclic aryl. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to another embodiment, the aryl group has 6 to 20 carbon atoms. Regarding the aforementioned aryl group, as a monocyclic aryl group, it can be phenyl, biphenyl, terphenyl, etc., but is not limited to these. As the aforementioned polycyclic aryl group, it can be naphthyl, anthraceneyl, phenanthryl, pyrene, perylene, etc. It includes bases, fluorenes, etc., but is not limited to these.

[0064] In this specification, the fluorene group can be substituted, and two substituents can combine with each other to form a spirostructure. When the fluorene group is substituted as described above, it can become... Etc. But it is not limited to this.

[0065] In this specification, a heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as heteroelements. The number of carbon atoms is not particularly limited, but is preferably 2 to 60. Examples of heterocyclic groups include thiophene, furanyl, pyrrole, imidazole, and thiazolyl. azole group, Diazolyl, Triazolyl, Pyridyl, Bipyridyl, Pyrimidinyl, Triazinyl, Acridineyl, Pyridazinyl, Quinolinyl, Quinazolinyl, Quinoxalinyl, Phtharazineyl, Pyridopyrimidinyl, Pyridopyrazinyl, Pyrazenopyrazinyl, Isoquinolinyl, Indoleyl, Carbazoleyl, Benzo[] Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazole, benzothiophene, dibenzothiophene, benzofuranyl, phenanthroline, iso Azolyl, thiadiazolyl, phenthiazinyl, and dibenzofuranyl groups, but not limited to these.

[0066] In this specification, the aryl groups in aralkyl, aryl-alkenyl, alkylaryl, and arylamine are the same as those exemplified above. In this specification, the alkyl groups in aralkyl, alkylaryl, and alkylamine are the same as those exemplified above. In this specification, the heteroaryl groups in heteroarylamines are subject to the above description of heterocyclic groups. In this specification, the alkenyl groups in aryl-alkenyl are the same as those exemplified above. In this specification, arylene is a divalent group; otherwise, the above description of aryl groups applies. In this specification, heteroarylene is a divalent group; otherwise, the above description of heterocyclic groups applies. In this specification, the hydrocarbon ring is not a monovalent group but is formed by the combination of two substituents; otherwise, the above description of aryl or cycloalkyl groups applies.

[0067] In this specification, the term "deuterated or deuterated" means that at least one available hydrogen atom in each chemical formula is replaced by deuterium. Specifically, in the definition of each chemical formula or substituent, deuteration means that at least one of the positions in the molecule where hydrogen can bind can be replaced by deuterium; more specifically, at least 10% of the available hydrogen atom is replaced by deuterium. As an example, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or 100% of the chemical formula is deuterated.

[0068] On the other hand, an organic light-emitting device according to one embodiment includes: an anode, a cathode disposed opposite to the anode, and a light-emitting layer disposed between the anode and the cathode, wherein the light-emitting layer comprises a first compound represented by the above chemical formula 1 and a second compound represented by the above chemical formula 2.

[0069] The organic light-emitting device according to the present invention contains two compounds with specific structures as host materials in the light-emitting layer, thereby improving the efficiency, driving voltage and / or lifetime characteristics of the organic light-emitting device.

[0070] The present invention will now be described in detail according to its constituent parts.

[0071] Anode and cathode

[0072] The anode and cathode used in this invention refer to electrodes used in organic light-emitting devices.

[0073] As the aforementioned anode material, a material with a high work function is preferred in order to facilitate the injection of holes into the organic layer. Specific examples of the aforementioned anode materials include metals such as vanadium, chromium, copper, zinc, and gold, or their alloys; 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 SnO2:Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylidene-1,2-dioxo)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited to these.

[0074] As the cathode material described above, a material with a low work function is generally preferred in order to facilitate the injection of electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or their alloys; multilayer structures such as LiF / Al or LiO2 / Al, etc., but are not limited to these.

[0075] Hole injection layer

[0076] The organic light-emitting device according to the present invention may include a hole injection layer between the anode and the hole transport layer described later, as needed.

[0077] The aforementioned hole injection layer is a layer located on the anode and injecting holes from the anode, comprising a hole injection material. Preferably, this hole injection material is a compound that possesses the ability to transport holes, the effect of injecting holes from the anode, excellent hole injection performance for the luminescent layer or luminescent material, prevents excitons generated in the luminescent layer from migrating to the electron injection layer or electron injection material, and exhibits excellent thin film formation capability. In particular, it is suitable that the HOMO (highest occupied molecular orbital) of the hole injection material is between that of the anolyte and the HOMO of the surrounding organic layer.

[0078] Specific examples of the aforementioned hole-injection materials include metalloporphyrins, oligothiophenes, arylamine-based organic compounds, hexanitrile hexaazabenzophenanthrene-based organic compounds, quinacridone-based organic compounds, perylene-based organic compounds, anthraquinones, and conductive polymers based on polyaniline and polythiophene, but are not limited to these.

[0079] Hole transport layer

[0080] The organic light-emitting device according to the present invention may include a hole transport layer on the anode (or on the hole injection layer if a hole injection layer is present) as needed.

[0081] The aforementioned hole transport layer is a layer that receives holes from the anode or a hole injection layer formed on the anode and transports the holes to the light-emitting layer, and includes a hole transport material. The aforementioned hole transport material is a substance capable of receiving holes from the anode or hole injection layer and transferring them to the light-emitting layer; substances with high hole mobility are suitable. Specific examples include arylamine-based organic compounds, conductive polymers, and block copolymers containing both conjugated and non-conjugated portions, but are not limited to these.

[0082] Electron blocking layer

[0083] The organic light-emitting device according to the present invention may include an electron blocking layer between the hole transport layer and the light-emitting layer as needed.

[0084] The aforementioned electron blocking layer refers to a layer formed on the aforementioned hole transport layer, preferably disposed in contact with the light-emitting layer, which improves the efficiency of the organic light-emitting device by adjusting the hole mobility to prevent excessive electron migration and thereby increasing the probability of hole-electron binding. The aforementioned electron blocking layer contains an electron blocking material; examples of such electron blocking materials include aryl amine-based organic compounds, but it is not limited to these.

[0085] Emissive layer

[0086] The organic light-emitting device according to the present invention includes a light-emitting layer between the anode and the cathode, wherein the light-emitting layer comprises the first compound and the second compound as host materials. Specifically, the first compound functions as an N-type host material with superior electron transport capability compared to hole transport capability, and the second compound functions as a P-type host material with superior hole transport capability compared to electron transport capability, thereby appropriately maintaining the hole-to-electron ratio within the light-emitting layer. Therefore, excitons emit light uniformly throughout the entire light-emitting layer, thereby simultaneously improving the luminous efficiency and lifetime characteristics of the organic light-emitting device.

[0087] The first compound and the second compound described above will be explained in turn below.

[0088] (First compound)

[0089] The aforementioned first compound is represented by the aforementioned chemical formula 1. Specifically, the aforementioned first compound is a compound in which a triazine group is attached to the N atom of a carbazole core via a linking group L3, characterized in that the compound has no substituents other than hydrogen / deuterium on the carbazole core. In particular, compared with compounds in which the carbazole core is substituted with substituents other than hydrogen / deuterium, such as aryl or heteroaryl groups, the aforementioned first compound exhibits superior electron transport capability, thereby efficiently transferring electrons to the dopant material, thereby increasing the electron-hole recombination probability in the luminescent layer.

[0090] In the above chemical formula 1, it can be

[0091] R1 and R2 are each independently hydrogen or deuterium; or

[0092] In R1, two adjacent rings combine to form an unsubstituted or deuterated benzene ring, while the remaining rings are independently hydrogen or deuterated; in R2, each ring is independently hydrogen or deuterated; or

[0093] R1 is independently either hydrogen or deuterium; two adjacent R2 rings combine to form an unsubstituted or deuterium-substituted benzene ring; the remaining R2 rings are independently either hydrogen or deuterium; or

[0094] In R1, two adjacent rings combine to form an unsubstituted or deuterated benzene ring, while the remaining rings are independently hydrogen or deuterated. In R2, two adjacent rings combine to form an unsubstituted or deuterated benzene ring, while the remaining rings are independently hydrogen or deuterated.

[0095] More specifically, the first compound described above can be represented by any one of the following chemical formulas 1-1 to 1-10:

[0096]

[0097]

[0098] In the above chemical formulas 1-1 to 1-10,

[0099] L1 to L3, Ar1 and Ar2 are defined in the same way as in the above chemical formula 1.

[0100] Furthermore, in the aforementioned chemical formula 1, L1 and L2 can each independently be a single bond, or an unsubstituted or deuterated C bond. 6-20 Alpha-aryl.

[0101] More specifically, L1 and L2 can each independently be a single bond, a phenylene group, or a naphthylene group.

[0102] More specifically, L1 and L2 can each be a single bond or selected from any of the following groups:

[0103]

[0104] In the above chemical formulas, the dashed lines indicate the bonding positions.

[0105] For example, both L1 and L2 can be single bonds; or one of L1 and L2 can be a single bond, and the other can be any one of the following groups:

[0106]

[0107] In the above chemical formulas, the dashed lines indicate the bonding positions.

[0108] Furthermore, L1 and L2 mentioned above can be the same as each other or different from each other.

[0109] Furthermore, in the aforementioned chemical formula 1, L3 can specifically be a single bond, or an unsubstituted C bond, or a C bond substituted with one or more deuterium atoms. 6-20 Alpha-aryl.

[0110] More specifically, the L3 mentioned above can be a single bond, phenylene, biphenyl dimethyl, or naphthylene.

[0111] More specifically, the L3 mentioned above can be a single bond, or selected from any of the following groups:

[0112]

[0113] In the above chemical formulas, the dashed lines indicate the bonding positions.

[0114] Furthermore, in the aforementioned chemical formula 1, Ar1 and Ar2 can each independently be unsubstituted or substituted with one or more deuterium atoms. 6-20 Aryl; or unsubstituted or selected from deuterium, C 1-10 Alkyl and C6-20 A C-type aryl group containing any one of the heteroatoms N, O, and S, substituted by one or more substituents. 2-20 Mixed aromatic compounds.

[0115] Specifically, Ar1 and Ar2 are each independently phenyl, biphenyl, terphenyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, phenanthryl, dibenzofuranyl, dibenzothiophene, carbazole, benzonaphthiofuranyl, or benzonaphthiophene.

[0116] Ar1 and Ar2 can each be independently unsubstituted or selected from deuterium and C. 1-10 Alkyl and C 6-20 One or more substituents of the aryl group are substituted; more specifically, Ar1 and Ar2 may be independently unsubstituted or substituted with one or more substituents selected from deuterium, methyl and phenyl.

[0117] More specifically, Ar1 and Ar2 can each independently be phenyl, biphenyl, terphenyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, phenanthryl, dibenzofuranyl, dibenzothiophene, 9-phenylcarbazoyl, benzonaphthiofuranyl, or benzonaphthiophene.

[0118] More specifically, Ar1 and Ar2 can each independently be selected from any of the following groups:

[0119]

[0120]

[0121] In the above chemical formulas,

[0122] X is O or S.

[0123] The dashed line indicates the joint position.

[0124] For example, one of Ar1 and Ar2 can be phenyl, biphenyl, or naphthyl, and the other can be phenyl, biphenyl, terphenyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, or phenanthryl.

[0125] As another example, one of Ar1 and Ar2 can be phenyl, biphenyl, terphenyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl or phenanthryl, and the other can be dibenzofuranyl, dibenzothiophenyl, 9-phenylcarbazoyl, benzonaphthiophenyl, or benzonaphthiophenyl.

[0126] As another example, Ar1 and Ar2 could each be independently dibenzofuranyl, dibenzothiophenyl, 9-phenylcarbazoyl, benzonaphthofuranyl, or benzonaphthothiophenyl.

[0127] Furthermore, Ar1 and Ar2 mentioned above can be the same as or different from each other.

[0128] A representative example of the first compound represented by the above chemical formula 1 is shown below:

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[0223] On the other hand, as an example, the compound represented by the above chemical formula 1 can be manufactured by the manufacturing method shown in the following reaction formula 1.

[0224] [Reaction Formula 1]

[0225]

[0226] In the above reaction formula 1, Ar1, Ar2, L1 to L3, R1 and R2 are defined as in the above chemical formula 1, and Z1 is a halogen, preferably chlorine or bromine.

[0227] The above-described reaction formula 1 is an amine substitution reaction, preferably carried out in the presence of a palladium catalyst and a base. The reactive group used in the amine substitution reaction can be modified according to techniques known in the art. As an example, the above manufacturing method can be further specified in the synthetic examples described later.

[0228] (Second compound)

[0229] The second compound is represented by the aforementioned chemical formula 2a or 2b. Specifically, the second compound has an amino group bonded to a specific position on the benzo[a]naphthofuranyl or benzo[a]naphthothiopheneyl core. This second compound, being a compound with a dibenzofuranyl or dibenzothiopheneyl core, can more efficiently transfer holes to the dopant material compared to compounds where the amino group is bonded to a different position relative to the core. Therefore, it can, together with the first compound, which has excellent electron transport capabilities, increase the recombination probability of holes and electrons within the luminescent layer.

[0230] More specifically, the aforementioned chemical formula 2a is represented by any one of the following chemical formulas 2a-1 to 2a-3.

[0231] The above chemical formula 2b can be represented by any one of the following chemical formulas 2b-1 to 2b-3:

[0232]

[0233] In the above chemical formulas 2a-1 to 2a-3 and chemical formulas 2b-1 to 2b-3,

[0234] X'、L' 11 To L' 13 L' 21 To L' 23 Ar' 11 Ar' 12 Ar' 21 Ar' 22 、R'、m'、X"、L" 11 To L" 13 、L" 21 To L" 23 Ar" 11 Ar" 12 Ar" 21 Ar" 22 R" and m" are defined in the same way as in the above chemical formulas 2a and 2b.

[0235] In addition, L' 11 L' 21 、L" 11 and L" 21 Each can be a single bond, or a C bond that is either unsubstituted or substituted by one or more deuterium atoms.6-20 Alpha-aryl.

[0236] More specifically, L' 11 L' 21 、L" 11 and L" 21 Each can be independently a single bond or a phenylene group; more specifically, L' 11 L' 21 、L" 11 and L" 21 Each can be a single key.

[0237] In addition, L' 12 L' 13 L' 22 L' 23 、L" 12 、L" 13 、L" 22 and L" 23 Each can be a single bond, or a C bond that is either unsubstituted or substituted by one or more deuterium atoms. 6-20 Alpha-aryl.

[0238] More specifically, L' 12 L' 13 L' 22 L' 23 、L" 12 、L" 13 、L" 22 and L" 23 Each can be a single bond, phenylene, biphenyl dimethyl, or naphthylene.

[0239] More specifically, the aforementioned L' 12 L' 13 L' 22 L' 23 、L" 12 、L" 13 、L" 22 and L" 23 Each can be a single bond or selected from any of the following groups:

[0240]

[0241] In the above chemical formulas, the dashed lines indicate the bonding positions.

[0242] At this time, L' 12 and L' 13 and L' 22 and L' 23 They can be the same as or different from each other; in addition, L" 12 and L" 13 and L"22 and L" 23 They can be the same as or different from each other.

[0243] In addition, L' 12 and L' 22 and L' 13 and L' 23 They can be the same as or different from each other; in addition, L" 12 and L" 22 and L" 13 and L" 23 They can be the same as or different from each other.

[0244] Additionally, Ar' 11 Ar' 12 Ar' 21 Ar' 22 Ar" 11 Ar" 12 Ar" 21 and Ar" 22 Each can be substituted or unsubstituted C independently. 6-20 aryl; or substituted or unsubstituted C containing any one of N, O, and S heteroatoms. 2-20 Mixed aromatic compounds.

[0245] More specifically, Ar' 11 Ar' 12 Ar' 21 Ar' 22 Ar" 11 Ar" 12 Ar" 21 and Ar" 22 Each can be independently phenyl, biphenyl, terphenyl, naphthyl, (phenyl)naphthyl, (naphthyl)phenyl, dibenzofuranyl, or dibenzothiophene.

[0246] Among them, Ar' 11 Ar' 12 Ar' 21 Ar' 22 Ar" 11 Ar" 12 Ar" 21 and Ar" 22 Each can be independent and unreplaced, or selected from deuterium and C. 1-10 Alkyl and C 6-20 One or more substituents of the aryl group are substituted. More specifically, Ar' 11 Ar' 12 Ar' 21 Ar' 22 Ar" 11 Ar"12 Ar" 21 and Ar" 22 Each can be independently unsubstituted; or substituted with one or more substituents selected from deuterium, methyl, and phenyl.

[0247] More specifically, Ar' 11 Ar' 12 Ar' 21 Ar' 22 Ar" 11 Ar" 12 Ar" 21 and Ar" 22 Each can be independently selected from any of the following groups:

[0248]

[0249] In the above chemical formulas, the dashed lines indicate the bonding positions.

[0250] At this time, Ar' 11 and Ar' 12 and Ar" 11 and Ar" 12 They can be the same as or different from each other; in addition, Ar' 21 and Ar' 22 and Ar" 21 and Ar" 22 They can be the same as or different from each other.

[0251] Additionally, Ar' 11 and Ar' 21 and Ar' 12 and Ar' 22 They can be the same or different from each other, Ar" 11 and Ar" 21 and Ar" 12 and Ar" 22 They can be the same as or different from each other.

[0252] As an example, in the above chemical formula 2a, -L' 12 -Ar' 11 and -L' 13 -Ar' 12 They can have the same or different structures, and in addition, -L' 22 -Ar' 21 and -L' 23 -Ar' 22 They can have the same or different structures.

[0253] Additionally, in the above chemical formula 2a, it could be -L' 12 -Ar'11 and -L' 22 -Ar' 21 Having the same structure, -L' 13 -Ar' 12 and -L' 23 -Ar' 22 They have the same structure as each other. Furthermore, it can be -L'. 12 -Ar' 11 -L' 13 -Ar' 12 、-L' 22 -Ar' 21 and -L' 23 -Ar' 22 They all have the same structure, or each has a different structure.

[0254] As another example, in the above chemical formula 2b, -L" 12 -Ar" 11 and -L" 13 -Ar" 12 They can have the same or different structures, and in addition, -L" 22 -Ar" 21 and -L" 23 -Ar" 22 They can have the same or different structures.

[0255] Additionally, in the above chemical formula 2b, it can be -L". 12 -Ar" 11 and -L" 22 -Ar" 21 Having the same structure as each other, -L" 13 -Ar" 12 and -L" 23 -Ar" 22 They have the same structure as each other. Furthermore, it can be -L". 12 -Ar" 11 、-L" 13 -Ar" 12 、-L" 22 -Ar" 21 and -L" 23 -Ar" 22 They all have the same structure, or each has a different structure.

[0256] In addition, both R' and R" can be hydrogen, in which case both m' and m" are 6.

[0257] Representative examples of the second compound mentioned above are shown below:

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282] On the other hand, as an example, the second compound described above can be manufactured by the manufacturing method shown in reaction formula 2 below.

[0283] [Reaction 2]

[0284]

[0285] In reaction formula 2 above, A, X', L' 11 To L' 13 L' 21 To L' 23 Ar' 11 Ar' 12 Ar' 21 Ar' 22 R' and m' are defined as in chemical formula 2a above, Z 21 and Z 22 Each is an independent halogen, preferably, Z 21 and Z 22 Each can be chlorine or bromine independently.

[0286] The above reaction formula 2 is an amine substitution reaction, preferably carried out in the presence of a palladium catalyst and a base. The reactive group used for the amine substitution reaction can be changed according to the techniques known in this art.

[0287] On the other hand, in reaction formula 2 above, the second compound is produced through a two-step amine substitution reaction. However, if the amino group bound to the parent nucleus has the same structure, the second compound can also be produced through a one-step amine substitution reaction. The above-described manufacturing method can be further specified in the synthetic examples described later.

[0288] Furthermore, the first compound and the second compound may be included in the light-emitting layer in a weight ratio of 1:99 to 99:1. In this case, in order to properly maintain the ratio of holes to electrons in the light-emitting layer, it is more preferable to include the first compound and the second compound in a weight ratio of 30:70 to 70:30.

[0289] On the other hand, in addition to the two main materials mentioned above, the light-emitting layer may also contain dopant materials.

[0290] There are no particular restrictions on the dopant materials mentioned above, as long as they are used in organic light-emitting devices. Examples include aromatic amine derivatives, styrene amine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives are aromatic fused-ring derivatives with substituted or unsubstituted aryl amino groups, such as pyrene, anthracene, etc. Diindrone pyrene, etc., styrylamine compounds are compounds in which at least one aryl vinyl group is substituted onto a substituted or unsubstituted aryl amine, and is substituted or unsubstituted by one or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino groups. Specifically, there are styrylamines, styryldiamines, styryltriamines, styryltetraamines, etc., but they are not limited to these. In addition, as metal complexes, there are iridium complexes, platinum complexes, etc., but they are not limited to these.

[0291] More specifically, compounds with the following structures can be cited as examples of the dopant materials mentioned above, but are not limited to these:

[0292]

[0293]

[0294]

[0295]

[0296] Cavity barrier

[0297] The organic light-emitting device according to the present invention can include a hole-blocking layer between the light-emitting layer and the electron transport layer (described later) as needed. The hole-blocking layer refers to a layer formed on the light-emitting layer, preferably in contact with it, which improves the probability of hole-electron binding by adjusting electron mobility and preventing excessive hole migration, thereby improving the efficiency of the organic light-emitting device. The hole-blocking layer contains a hole-blocking material; examples of such a hole-blocking material include azine derivatives, triazole derivatives, etc. Compounds containing electron-withdrawing groups, such as diazole derivatives, phenanthrene-rhein derivatives, and phosphine oxide derivatives, are included, but are not limited to these.

[0298] Electron transport layer

[0299] The organic light-emitting device according to the present invention may include an electron transport layer on the light-emitting layer (or on the hole blocking layer if a hole blocking layer is formed) as needed.

[0300] The aforementioned electron transport layer serves to receive electrons from the cathode or an electron injection layer formed on the cathode and transport them to the light-emitting layer. This electron transport layer contains an electron transport material that is capable of effectively receiving electrons from the cathode and transferring them to the light-emitting layer; materials with high electron mobility are suitable.

[0301] Specific examples of the aforementioned electron transport materials include Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic radical compounds, hydroxyflavonoid-metal complexes, etc., but are not limited to these. The electron transport layer can be used with any desired cathode material as used in the prior art. In particular, examples of suitable cathode materials are common materials with low work functions and accompanied by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium, and samarium are all accompanied by an aluminum or silver layer in each case.

[0302] Electron injection layer

[0303] The organic light-emitting device according to the present invention may include an electron injection layer on the light-emitting layer (or on the electron transport layer if an electron transport layer is present) as needed.

[0304] The aforementioned electron injection layer is a layer that injects electrons from the electrode. Preferably, the following compounds are used: compounds that have the ability to transport electrons, have the effect of injecting electrons from the cathode, have excellent electron injection effect on the light-emitting layer or light-emitting material, prevent excitons generated in the light-emitting layer from migrating to the hole injection layer, and have excellent thin film forming ability.

[0305] Specific examples of substances that can be used in the aforementioned electron-injection layer include fluorenone, anthraquinone dimethyl ether, biphenylquinone, thiamethoxam dioxide, etc. azole, Diazoles, triazoles, imidazoles, perylenetetracarboxylic acid, fluorenemethane, anthrones, and their derivatives, metal coordination compounds, and nitrogen-containing five-membered ring derivatives, but not limited to these.

[0306] Examples of the aforementioned metal coordination compounds include lithium 8-hydroxyquinoline, bis(8-hydroxyquinoline)zinc, bis(8-hydroxyquinoline)copper, bis(8-hydroxyquinoline)manganese, tris(8-hydroxyquinoline)aluminum, tris(2-methyl-8-hydroxyquinoline)aluminum, tris(8-hydroxyquinoline)gallium, bis(10-hydroxybenzo[h]quinoline)beryllium, bis(10-hydroxybenzo[h]quinoline)zinc, bis(2-methyl-8-quinoline)gallium chloride, bis(2-methyl-8-quinoline)(o-cresol)gallium, bis(2-methyl-8-quinoline)(1-naphthol)aluminum, and bis(2-methyl-8-quinoline)(2-naphthol)gallium, but are not limited to these.

[0307] Organic light-emitting devices

[0308] The structure of the organic light-emitting device according to the present invention is illustrated in... Figure 1 and Figure 2 .

[0309] Figure 1The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In the structure described above, the first compound and the second compound may be included in the light-emitting layer.

[0310] Figure 2 The illustration shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4. In the structure described above, the first compound and the second compound may be included in the light-emitting layer.

[0311] The organic light-emitting device according to the present invention can be manufactured by sequentially stacking the above-described structures. It can be manufactured as follows: using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation, a metal or a conductive metal oxide or alloy thereof is deposited on a substrate to form an anode, then the aforementioned layers are formed on the anode, and subsequently a material suitable for use as a cathode is deposited on it. Besides this method, the organic light-emitting device can also be manufactured by sequentially depositing the cathode material onto the anode material on the substrate in the reverse order of the above-described structures (WO 2003 / 012890). Furthermore, not only vacuum evaporation but also solution coating can be used to form the light-emitting layer from the substrate and the dopant. Here, solution coating refers to, but is not limited to, spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, roll coating, etc.

[0312] On the other hand, the organic light-emitting device according to the present invention can be a bottom-emission device, a top-emission device, or a bidirectional light-emitting device, and in particular, it can be a bottom-emission device that requires relatively high luminous efficiency.

[0313] Preferred embodiments are presented below to aid in understanding the present invention. However, these embodiments are merely illustrative and the scope of the invention is not limited to them.

[0314] Manufacturing Example 1

[0315] Manufacturing of compound Aa

[0316]

[0317] Under a nitrogen atmosphere, (1-hydroxynaphthalen-2-yl)boronicacid (10 g, 53.2 mmol) and 5-bromo-1-chloro-2-fluoro-3-iodobenzene (17.8 g, 53.2 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (22.1 g, 159.6 mmol) was dissolved in 66 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated by distillation of the organic layer. The compound was redissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.3 g of the compound with the chemical formula A-a_P-1. (Yield 77%, MS: [M+H)) + =351)

[0318] Under a nitrogen atmosphere, 10 g (28.4 mmol) of compound A-a_P-1 and 11.8 g (85.3 mmol) were added to 200 mL of DMAc, and the mixture was stirred and refluxed. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic solvent was distilled under reduced pressure. The mixture was redissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.8 g of compound Aa. (Yield 72%, MS: [M+H]) + =331)

[0319] Manufacturing Example 2

[0320] Manufacturing of compound Ab

[0321]

[0322] Compound Ab was prepared by the same method as in Preparation Example 1, except that 1-bromo-5-chloro-3-fluoro-2-iodobenzene was used instead of 5-bromo-1-chloro-2-fluoro-3-iodobenzene.

[0323] Manufacturing Example 3

[0324] Manufacturing of compound Ac

[0325]

[0326] Compound Ac was prepared by means of the same method as in Manufacturing Example 1, except that (3-hydroxynaphthalen-2-yl)boronic acid was used instead of (1-hydroxynaphthalen-2-yl)boronic acid.

[0327] Manufacturing Example 4

[0328] Manufacturing of compound Ad

[0329]

[0330] Compound Ad was manufactured by the same method as in Manufacturing Example 1, except that (3-hydroxynaphth-2-yl)boronic acid was used instead of (1-hydroxynaphth-2-yl)boronic acid and 1-bromo-5-chloro-3-fluoro-2-iodobenzene was used instead of 5-bromo-1-chloro-2-fluoro-3-iodobenzene.

[0331] Manufacturing Example 5

[0332] Manufacturing of compound Ae

[0333]

[0334] Compound Ae was prepared by the same method as in Manufacturing Example 1, except that (2-hydroxynaphthalen-1-yl)boronic acid was used instead of (1-hydroxynaphthalen-2-yl)boronic acid.

[0335] Manufacturing Example 6

[0336] Manufacturing of compound Af

[0337]

[0338] Compound Af was manufactured by the same method as in Manufacturing Example 1, except that (2-hydroxynaphth-1-yl)boronic acid was used instead of (1-hydroxynaphth-2-yl)boronic acid and 1-bromo-5-chloro-3-fluoro-2-iodobenzene was used instead of 5-bromo-1-chloro-2-fluoro-3-iodobenzene.

[0339] Manufacturing Example 7

[0340] Manufacturing of compound Ba

[0341]

[0342] Under a nitrogen atmosphere, (1-(methylthio)naphthalen-2-yl)boronic acid (10 g, 45.9 mmol) and 1-bromo-3-chloro-5-iodobenzene (16 g, 50.4 mmol) were added to 200 mL of THF, stirred, and refluxed. Then, potassium carbonate (19 g, 137.6 mmol) was dissolved in 57 mL of water and added, stirred thoroughly, followed by bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol). After reacting for 12 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.1 g of the chemical formula B-a_P-2. (Yield 73%, MS: [M+H)) + =363)

[0343] Under a nitrogen atmosphere, 10 g (27.5 mmol) of B-a_P-2 and 1 g (30.2 mmol) of hydrogen peroxide were added to 200 mL of acetic acid, and the mixture was stirred and refluxed. After 3 hours, the reaction mixture was poured into water to allow crystals to settle, and then filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 7.4 g of B-a_P-1. (Yield 71%, MS: [M+H)) + =379)

[0344] Under a nitrogen atmosphere, 10 g (26.3 mmol) of compound B-a_P-1 was added to 200 mL of H₂SO₄ and stirred. After 2 hours, when the reaction was complete, the reactants were poured into water to allow the crystals to settle, and then filtered. The filtered solid was redissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 7.1 g of compound Ba. (Yield 78%, MS: [M+H)) + =347)

[0345] Manufacturing Example 8

[0346] Manufacturing of compound Bb

[0347]

[0348] Compound Bb was prepared by the same method as in Preparation Example 7, except that 2-bromo-4-chloro-1-iodobenzene was used instead of 1-bromo-3-chloro-5-iodobenzene.

[0349] Manufacturing Example 9

[0350] Manufacturing of compound Bc

[0351]

[0352] Compound Bc was prepared by the same method as in Manufacturing Example 7, except that (3-(methylthio)naphthalen-2-yl)boronic acid was used instead of (1-(methylthio)naphthalen-2-yl)boronic acid.

[0353] Manufacturing Example 10

[0354] Manufacturing of compound Bd

[0355]

[0356] Compound Bd was manufactured by the same method as in Manufacturing Example 7, except that (3-(methylthio)naphth-2-yl)boronic acid was used instead of (1-(methylthio)naphth-2-yl)boronic acid, and 2-bromo-4-chloro-1-iodobenzene was used instead of 1-bromo-3-chloro-5-iodobenzene.

[0357] Manufacturing Example 11

[0358] Manufacturing of compound Be

[0359]

[0360] The compound Be was prepared by means of the same method as in Example 7, except that (2-(methylthio)naphthalen-1-yl)boronic acid was used instead of (1-(methylthio)naphthalen-2-yl)boronic acid.

[0361] Manufacturing Example 12

[0362] Manufacturing of compound Bf

[0363]

[0364] Compound Bf was prepared by the same method as in Manufacturing Example 7, except that (2-(methylthio)naphth-1-yl)boronic acid was used instead of (1-(methylthio)naphth-2-yl)boronic acid, and 2-bromo-4-chloro-1-iodobenzene was used instead of 1-bromo-3-chloro-5-iodobenzene.

[0365] Synthesis example 1-1

[0366]

[0367] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), substance 1 (25.6 g, 62.8 mmol), and potassium phosphate (K3PO4) (38.1 g, 179.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0)(Pd(t-Bu3P)2) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature, and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 17.7 g of compound 1-1 (yield 55%, MS: [M+H)). + =539).

[0368] Synthesis example 1-2

[0369]

[0370] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), substance 2 (25.6 g, 62.8 mmol), and potassium phosphate (38.1 g, 179.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 19 g of compounds 1-2 (yield 59%, MS: [M+H)). + =539).

[0371] Synthesis Example 1-3

[0372]

[0373] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), substance 3 (27.2 g, 62.8 mmol), and potassium phosphate (38.1 g, 179.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 18.5 g of compounds 1-3 (yield 55%, MS: [M+H)). + =564).

[0374] Synthesis Example 1-4

[0375]

[0376] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), substance 4 (30.4 g, 62.8 mmol), and potassium phosphate (38.1 g, 179.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 20.9 g of compounds 1-4 (yield 57%, MS: [M+H)). + =615).

[0377] Synthesis Example 1-5

[0378]

[0379] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), substance 5 (29.5 g, 62.8 mmol), and sodium tert-butoxide (NaOtBu) (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(O) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 23.3 g of compounds 1-5 (65% yield, MS: [M+H)). + =601).

[0380] Synthesis Example 1-6

[0381]

[0382] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), substance 6 (29.5 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 20.5 g of compounds 1-6 (yield 57%, MS: [M+H)). + =601).

[0383] Synthesis Example 1-7

[0384]

[0385] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), substance 7 (27.2 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 19.2 g of compounds 1-7 (yield 57%, MS: [M+H)). + =565).

[0386] Synthesis Example 1-8

[0387]

[0388] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), substance 8 (32.7 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 26.4 g of compounds 1-8 (68% yield, MS: [M+H)). + =651).

[0389] Synthesis Example 1-9

[0390]

[0391] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), substance 9 (30.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 24.6 g of compounds 1-9 (yield 67%, MS: [M+H)). + =615).

[0392] Synthesis Example 1-10

[0393]

[0394] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), substance 10 (30.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 23.5 g of compound 1-10 (yield 64%, MS: [M+H)). + =615).

[0395] Synthesis Example 1-11

[0396]

[0397] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound 11 (27.2 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 17.5 g of compound 1-11 (yield 52%, MS: [M+H)). + =565).

[0398] Synthesis Example 1-12

[0399]

[0400] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound 12 (27.9 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 18.2 g of compound 1-12 (yield 53%, MS: [M+H)). + =575).

[0401] Synthesis Example 1-13

[0402]

[0403] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound 13 (29.5 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 19.4 g of compound 1-13 (yield 54%, MS: [M+H)). + =601).

[0404] Synthesis Example 1-14

[0405]

[0406] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), substance 14 (35.1 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 28.4 g of compound 1-14 (69% yield, MS: [M+H)). + =690).

[0407] Synthesis Example 1-15

[0408]

[0409] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound 15 (31 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 26.1 g of compound 1-15 (70% yield, MS: [M+H)). + =625).

[0410] Synthesis Example 1-16

[0411]

[0412] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound 16 (31.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 22.2 g of compound 1-16 (yield 59%, MS: [M+H)). + =631).

[0413] Synthesis Example 1-17

[0414]

[0415] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), substance 17 (26.4 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 18.1 g of compound 1-17 (yield 55%, MS: [M+H)). + =551).

[0416] Synthesis Example 1-18

[0417]

[0418] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound 18 (32 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 24.5 g of compound 1-18 (64% yield, MS: [M+H)). + =641).

[0419] Synthesis Example 1-19

[0420]

[0421] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), compound 19 (31.1 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 25.1 g of compound 1-19 (67% yield, MS: [M+H)). + =627).

[0422] Synthesis Example 1-20

[0423]

[0424] Under a nitrogen atmosphere, 9H-carbazole (10 g, 59.8 mmol), substance 20 (33 g, 62.8 mmol), and sodium tert-butoxide (7.5 g, 77.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.6 g, 1.2 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 20 g of compound 1-20 (yield 51%, MS: [M+H)). + =657).

[0425] Synthesis example 1-21

[0426]

[0427] Under a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), substance 21 (18.1 g, 48.3 mmol), and potassium phosphate (29.3 g, 138.1 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 14.3 g of compound 1-21 (yield 56%, MS: [M+H)). + =555).

[0428] Synthesis example 1-22

[0429]

[0430] Under a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), substance 7 (21 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 14.7 g of compound 1-22 (yield 52%, MS: [M+H)). + =615).

[0431] Synthesis example 1-23

[0432]

[0433] Under a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), substance 22 (26.9 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 22 g of compounds 1-23 (65% yield, MS: [M+H)). + =737).

[0434] Synthesis Example 1-24

[0435]

[0436] Under a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), substance 23 (16.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 12.1 g of compound 1-24 (50% yield, MS: [M+H)). + =525).

[0437] Synthesis Example 1-25

[0438]

[0439] Under a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), substance 24 (16.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 12.5 g of compound 1-25 (yield 52%, MS: [M+H)). + =525).

[0440] Synthesis example 1-26

[0441]

[0442] Under a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), substance 25 (25.1 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 20.3 g of compound 1-26 (63% yield, MS: [M+H)). + =701).

[0443] Synthesis Example 1-27

[0444]

[0445] Under a nitrogen atmosphere, 7H-benzo[c]carbazole (10 g, 46 mmol), substance 26 (25.4 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 18.2 g of compound 1-27 (yield 56%, MS: [M+H)). + =707).

[0446] Synthesis example 1-28

[0447]

[0448] Under a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), substance 27 (17.8 g, 48.3 mmol), and potassium phosphate (29.3 g, 138.1 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(O) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 16.9 g of compound 1-28 (67% yield, MS: [M+H)). + =549).

[0449] Synthesis example 1-29

[0450]

[0451] Under a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), substance 28 (20.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 19.3 g of compound 1-29 (70% yield, MS: [M+H)). + =601).

[0452] Synthesis Example 1-30

[0453]

[0454] Under a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), substance 29 (21.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 17.7 g of compound 1-30 (61% yield, MS: [M+H)). + =631).

[0455] Synthesis example 1-31

[0456]

[0457] Under a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), substance 30 (24.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 20 g of compound 1-31 (63% yield, MS: [M+H)). + =690).

[0458] Synthesis example 1-32

[0459]

[0460] Under a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), substance 31 (25.1 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 21.3 g of compound 1-32 (66% yield, MS: [M+H)). + =701).

[0461] Synthesis example 1-33

[0462]

[0463] Under a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), substance 32 (19 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 14 g of compound 1-33 (yield 53%, MS: [M+H)). + =575).

[0464] Synthesis example 1-34

[0465]

[0466] Under a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), substance 33 (22.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 15.3 g of compound 1-34 (yield 51%, MS: [M+H)). + =651).

[0467] Synthesis example 1-35

[0468]

[0469] Under a nitrogen atmosphere, 5H-benzo[b]carbazole (10 g, 46 mmol), substance 17 (20.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 18.2 g of compound 1-35 (66% yield, MS: [M+H)). + =601).

[0470] Synthesis example 1-36

[0471]

[0472] Under a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), substance 34 (22.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(O) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 15 g of compound 1-36 (50% yield, MS: [M+H)). + =651).

[0473] Synthesis example 1-37

[0474]

[0475] Under a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), substance 35 (21.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 20.3 g of compound 1-37 (70% yield, MS: [M+H)). + =631).

[0476] Synthesis example 1-38

[0477]

[0478] Under a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), substance 36 (27.1 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 20.4 g of compound 1-38 (60% yield, MS: [M+H)). + =741).

[0479] Synthesis example 1-39

[0480]

[0481] Under a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), substance 37 (25.4 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 17.9 g of compound 1-39 (yield 55%, MS: [M+H)). + =707).

[0482] Synthesis Example 1-40

[0483]

[0484] Under a nitrogen atmosphere, 11H-benzo[a]carbazole (10 g, 46 mmol), substance 38 (24.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The resulting product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 15.9 g of compound 1-40 (50% yield, MS: [M+H)). + =691).

[0485] Synthesis example 1-41

[0486]

[0487] Under a nitrogen atmosphere, 7H-dibenzo[b,g]carbazole (10 g, 37.4 mmol), substance 39 (14.7 g, 39.3 mmol), and potassium phosphate (23.8 g, 112.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(O) (0.4 g, 0.7 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 11.5 g of compound 1-41 (yield 51%, MS: [M+H)). + =605).

[0488] Synthesis example 1-42

[0489]

[0490] Under a nitrogen atmosphere, 7H-dibenzo[b,g]carbazole (10 g, 37.4 mmol), substance 40 (19 g, 39.3 mmol), and sodium tert-butoxide (4.7 g, 48.6 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 13.9 g of compound 1-42 (yield 52%, MS: [M+H)). + =715).

[0491] Synthesis example 1-43

[0492]

[0493] Under a nitrogen atmosphere, 10 g (37.4 mmol) of 6H-dibenzo[b,h]carbazole, 14.1 g (39.3 mmol) of substance 41, and 23.8 g (112.2 mmol) of potassium phosphate were added to 200 mL of xylene, and the mixture was stirred and refluxed. Bis(tri-tert-butylphosphine)palladium(O) (0.4 g, 0.7 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 13.6 g of compound 1-43 (62% yield, MS: [M+H)). + =589).

[0494] Synthesis example 1-44

[0495]

[0496] Under a nitrogen atmosphere, 10 g (37.4 mmol) of 6H-dibenzo[b,h]carbazole, 19.6 g (39.3 mmol) of substance 42, and 4.7 g (48.6 mmol) of sodium tert-butoxide were added to 200 mL of xylene, and the mixture was stirred and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added to the resulting mixture. After 2 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 19.1 g of compound 1-44 (70% yield, MS: [M+H)). + =731).

[0497] Synthesis example 1-45

[0498]

[0499] Under a nitrogen atmosphere, 13H-dibenzo[a,h]carbazole (10 g, 37.4 mmol), substance 43 (16 g, 39.3 mmol), and potassium phosphate (23.8 g, 112.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 14.1 g of compound 1-45 (59% yield, MS: [M+H)). + =639).

[0500] Synthesis example 1-46

[0501]

[0502] Under a nitrogen atmosphere, 13H-dibenzo[a,h]carbazole (10 g, 37.4 mmol), substance 44 (17.7 g, 39.3 mmol), and sodium tert-butoxide (4.7 g, 48.6 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 13.7 g of compound 1-46 (yield 54%, MS: [M+H)). + =681).

[0503] Synthesis Example 1-47

[0504]

[0505] Under a nitrogen atmosphere, 10 g (37.4 mmol) of 7H-dibenzo[c,g]carbazole, 14.1 g (39.3 mmol) of substance 45, and 23.8 g (112.2 mmol) of potassium phosphate were added to 200 mL of xylene, and the mixture was stirred and refluxed. Bis(tri-tert-butylphosphine)palladium(O) (0.4 g, 0.7 mmol) was added to the resulting mixture. After 3 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 12.1 g of compound 1-47 (55% yield, MS: [M+H)). + =589).

[0506] Synthesis example 2-1

[0507]

[0508] Under a nitrogen atmosphere, compound Aa (10 g, 30.2 mmol), amine 1 (8.7 g, 31.7 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 8.6 g of compound Aa-1 (yield 54%, MS: [M+H)). + =526).

[0509] Under a nitrogen atmosphere, compound Aa-1 (10 g, 19 mmol), amine 2 (3.3 g, 19.4 mmol), and sodium tert-butoxide (2.4 g, 24.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 7 g of compound 2-1 (yield 56%, MS: [M+H)). +=659).

[0510] Synthesis example 2-2

[0511]

[0512] Under a nitrogen atmosphere, compound Aa (10 g, 30.2 mmol), amine 3 (9.4 g, 31.7 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 9.7 g of compound Aa-2 (yield 59%, MS: [M+H)). + =546).

[0513] Under a nitrogen atmosphere, compound Aa-2 (10 g, 18.3 mmol), amine 4 (4.1 g, 18.7 mmol), and sodium tert-butoxide (2.3 g, 23.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 7.6 g of compound 2-2 (yield 57%, MS: [M+H)). + =729).

[0514] Synthesis example 2-3

[0515]

[0516] Under a nitrogen atmosphere, compound Aa (10 g, 30.2 mmol), amine 5 (9.4 g, 31.7 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 9.2 g of compound Aa-3 (yield 56%, MS: [M+H)). + =546).

[0517] Under a nitrogen atmosphere, compound Aa-3 (10 g, 18.3 mmol), amine 3 (5.5 g, 18.7 mmol), and sodium tert-butoxide (2.3 g, 23.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 10 g of compound 2-3 (yield 68%, MS: [M+H)). + =805).

[0518] Synthesis example 2-4

[0519]

[0520] Under a nitrogen atmosphere, compound Aa (10 g, 30.2 mmol), amine 6 (10.2 g, 31.7 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 9.6 g of compound Aa-4 (yield 56%, MS: [M+H)). + =572).

[0521] Under a nitrogen atmosphere, compound Aa-4 (10 g, 17.5 mmol), amine 2 (3 g, 17.8 mmol), and sodium tert-butoxide (2.2 g, 22.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 8.2 g of compound 2-4 (67% yield, MS: [M+H)). + =705).

[0522] Synthesis Example 2-5

[0523]

[0524] Under a nitrogen atmosphere, compound Aa (10 g, 30.2 mmol), amine 7 (11.6 g, 31.7 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature, and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 10.2 g of compound Aa-5 (yield 55%, MS: [M+H)). + =616).

[0525] Under a nitrogen atmosphere, compound Aa-5 (10 g, 16.2 mmol), amine 2 (2.8 g, 16.6 mmol), and sodium tert-butoxide (2 g, 21.1 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 8.1 g of compound 2-5 (yield 67%, MS: [M+H)). + =749).

[0526] Synthesis Example 2-6

[0527]

[0528] Under a nitrogen atmosphere, compound Ab (10 g, 30.2 mmol), amine 8 (9.4 g, 31.7 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 9 g of compound Ab-1 (yield 55%, MS: [M+H)). + =546).

[0529] Under a nitrogen atmosphere, compound Ab-1 (10 g, 18.3 mmol), amine 9 (4.6 g, 18.7 mmol), and sodium tert-butoxide (2.3 g, 23.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 8.1 g of compound 2-6 (yield 59%, MS: [M+H)). + =755).

[0530] Synthesis Example 2-7

[0531]

[0532] Under a nitrogen atmosphere, compound Ab (10 g, 30.2 mmol), amine 9 (15.5 g, 63.3 mmol), and sodium tert-butoxide (7.2 g, 75.4 mmol) were added to 300 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 11.3 g of compound 2-7 (yield 53%, MS: [M+H)). + =705).

[0533] Synthesis example 2-8

[0534]

[0535] Under a nitrogen atmosphere, compound Ac (10 g, 30.2 mmol), amine 10 (16.4 g, 63.3 mmol), and sodium tert-butoxide (7.2 g, 75.4 mmol) were added to 300 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature, and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 12.1 g of compound 2-8 (55% yield, MS: [M+H)). + =733).

[0536] Synthesis example 2-9

[0537]

[0538] Under a nitrogen atmosphere, compound Ac (10 g, 30.2 mmol), amine 2 (5.4 g, 31.7 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 6.4 g of compound Ac-1 (yield 51%, MS: [M+H)). + =420).

[0539] Under a nitrogen atmosphere, compound Ac-1 (10 g, 23.8 mmol), amine 11 (8.5 g, 24.3 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature, and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 9.4 g of compound 2-9 (yield 54%, MS: [M+H)). + =733).

[0540] Synthesis example 2-10

[0541]

[0542] Under a nitrogen atmosphere, compound Ad (10 g, 30.2 mmol), amine 4 (6.9 g, 31.7 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 7.4 g of compound Ad-1 (yield 52%, MS: [M+H)). + =470).

[0543] Under a nitrogen atmosphere, compound Ad-1 (10 g, 21.3 mmol), amine 12 (6.4 g, 21.7 mmol), and sodium tert-butoxide (2.7 g, 27.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 10.8 g of compound 2-10 (70% yield, MS: [M+H)). + =729).

[0544] Synthesis example 2-11

[0545]

[0546] Under a nitrogen atmosphere, compound Ad (10 g, 30.2 mmol), amine 9 (7.8 g, 31.7 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 7.9 g of compound Ad-2 (yield 53%, MS: [M+H)). + =496).

[0547] Under a nitrogen atmosphere, compound Ad-2 (10 g, 20.2 mmol), amine 13 (5.3 g, 20.6 mmol), and sodium tert-butoxide (2.5 g, 26.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 9.7 g of compound 2-11 (67% yield, MS: [M+H)). + =719).

[0548] Synthesis example 2-12

[0549]

[0550] Under a nitrogen atmosphere, compound Ad (10 g, 30.2 mmol), amine 9 (15.5 g, 63.3 mmol), and sodium tert-butoxide (7.2 g, 75.4 mmol) were added to 300 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 11.9 g of compound 2-12 (yield 56%, MS: [M+H)). + =705).

[0551] Synthesis example 2-13

[0552]

[0553] Under a nitrogen atmosphere, compound Ae (10 g, 30.2 mmol), amine 14 (10.2 g, 31.7 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 9.8 g of compound Ae-1 (yield 57%, MS: [M+H)). + =572).

[0554] Under a nitrogen atmosphere, compound Ae-1 (10 g, 17.5 mmol), amine 9 (4.4 g, 17.8 mmol), and sodium tert-butoxide (2.2 g, 22.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature, and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 7.1 g of compound 2-13 (yield 52%, MS: [M+H)). + =781).

[0555] Synthesis example 2-14

[0556]

[0557] Under a nitrogen atmosphere, compound Af (10 g, 30.2 mmol), amine 2 (10.7 g, 63.3 mmol), and sodium tert-butoxide (7.2 g, 75.4 mmol) were added to 300 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 11.3 g of compound 2-14 (68% yield, MS: [M+H)). + =553).

[0558] Synthesis example 2-15

[0559]

[0560] Under a nitrogen atmosphere, compound Af (10 g, 30.2 mmol), amine 4 (6.9 g, 31.7 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 8.8 g of compound Af-1 (yield 62%, MS: [M+H)). + =470).

[0561] Under a nitrogen atmosphere, compound Af-1 (10 g, 21.3 mmol), amine 15 (6.4 g, 21.7 mmol), and sodium tert-butoxide (2.7 g, 27.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 10.4 g of compound 2-15 (67% yield, MS: [M+H)). + =729).

[0562] Synthesis example 2-16

[0563]

[0564] Under a nitrogen atmosphere, compound Af (10 g, 30.2 mmol), amine 2 (5.4 g, 31.7 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 6.8 g of compound Af-2 (yield 54%, MS: [M+H)). + =420).

[0565] Under a nitrogen atmosphere, compound Af-2 (10 g, 23.8 mmol), amine 16 (8.5 g, 24.3 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature, and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 12.2 g of compound 2-16 (70% yield, MS: [M+H)). + =735).

[0566] Synthesis example 2-17

[0567]

[0568] Under a nitrogen atmosphere, compound Ba (10 g, 28.8 mmol), amine 2 (10.2 g, 60.4 mmol), and sodium tert-butoxide (6.9 g, 71.9 mmol) were added to 300 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 9.5 g of compound 2-17 (yield 58%, MS: [M+H)). + =569).

[0569] Synthesis example 2-18

[0570]

[0571] Under a nitrogen atmosphere, compound Ba (10 g, 28.8 mmol), amine 17 (7.4 g, 30.2 mmol), and sodium tert-butoxide (3.6 g, 37.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature, and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 9 g of compound Ba-1 (61% yield, MS: [M+H)). + =512).

[0572] Under a nitrogen atmosphere, compound Ba-1 (10 g, 19.5 mmol), amine 9 (4.9 g, 19.9 mmol), and sodium tert-butoxide (2.4 g, 25.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature, and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 7.5 g of compound 2-18 (yield 53%, MS: [M+H)). + =721).

[0573] Synthesis example 2-19

[0574]

[0575] Under a nitrogen atmosphere, compound Ba (10 g, 28.8 mmol), amine 18 (14.8 g, 60.4 mmol), and sodium tert-butoxide (6.9 g, 71.9 mmol) were added to 300 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 13.3 g of compound 2-19 (64% yield, MS: [M+H)). + =721).

[0576] Synthesis example 2-20

[0577]

[0578] Under a nitrogen atmosphere, compound Ba (10 g, 28.8 mmol), amine 8 (8.9 g, 30.2 mmol), and sodium tert-butoxide (3.6 g, 37.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 10.3 g of compound Ba-2 (64% yield, MS: [M+H)). + =562).

[0579] Under a nitrogen atmosphere, compound Ba-2 (10 g, 17.8 mmol), amine 9 (4.5 g, 18.1 mmol), and sodium tert-butoxide (2.2 g, 23.1 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 6.9 g of compound 2-20 (50% yield, MS: [M+H)). + =771).

[0580] Synthesis example 2-21

[0581]

[0582] Under a nitrogen atmosphere, compound Bb (10 g, 28.8 mmol), amine 19 (10.1 g, 30.2 mmol), and sodium tert-butoxide (3.6 g, 37.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 9.2 g of compound Bb-1 (yield 53%, MS: [M+H)). + =602).

[0583] Under a nitrogen atmosphere, compound Bb-1 (10 g, 16.6 mmol), amine 2 (2.9 g, 16.9 mmol), and sodium tert-butoxide (2.1 g, 21.6 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 8 g of compound 2-21 (66% yield, MS: [M+H)). + =735).

[0584] Synthesis example 2-22

[0585]

[0586] Under a nitrogen atmosphere, compound Bb (10 g, 28.8 mmol), amine 15 (8.9 g, 30.2 mmol), and sodium tert-butoxide (3.6 g, 37.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 10.7 g of compound Bb-2 (66% yield, MS: [M+H)). + =562).

[0587] Under a nitrogen atmosphere, compound Bb-2 (10 g, 17.8 mmol), amine 20 (5.4 g, 18.1 mmol), and sodium tert-butoxide (2.2 g, 23.1 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 8.9 g of compound 2-22 (61% yield, MS: [M+H)). + =821).

[0588] Synthesis example 2-23

[0589]

[0590] Under a nitrogen atmosphere, compound Bc (10 g, 28.8 mmol), amine 9 (7.4 g, 30.2 mmol), and sodium tert-butoxide (3.6 g, 37.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 10 g of compound Bc-1 (yield 68%, MS: [M+H)). + =512).

[0591] Under a nitrogen atmosphere, compound Bc-1 (10 g, 19.5 mmol), amine 10 (5.2 g, 19.9 mmol), and sodium tert-butoxide (2.4 g, 25.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 9.3 g of compound 2-23 (65% yield, MS: [M+H)). + =735).

[0592] Synthesis example 2-24

[0593]

[0594] Under a nitrogen atmosphere, compound Bc (10 g, 28.8 mmol), amine 17 (14.8 g, 60.4 mmol), and sodium tert-butoxide (6.9 g, 71.9 mmol) were added to 300 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 12.6 g of compound 2-24 (61% yield, MS: [M+H)). + =721).

[0595] Synthesis example 2-25

[0596]

[0597] Under a nitrogen atmosphere, compound Bc (10 g, 28.8 mmol), amine 20 (8.9 g, 30.2 mmol), and sodium tert-butoxide (3.6 g, 37.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 9.2 g of compound Bc-2 (yield 57%, MS: [M+H)). + =562).

[0598] Under a nitrogen atmosphere, compound Bc-2 (10 g, 17.8 mmol), amine 4 (4 g, 18.1 mmol), and sodium tert-butoxide (2.2 g, 23.1 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 7.5 g of compound 2-25 (yield 57%, MS: [M+H)). + =745).

[0599] Synthesis example 2-26

[0600]

[0601] Under a nitrogen atmosphere, compound Bd (10 g, 28.8 mmol), amine 21 (15.7 g, 60.4 mmol), and sodium tert-butoxide (6.9 g, 71.9 mmol) were added to 300 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 11.6 g of compound 2-26 (yield 54%, MS: [M+H)). + =749).

[0602] Synthesis example 2-27

[0603]

[0604] Under a nitrogen atmosphere, compound Bd (10 g, 28.8 mmol), amine 6 (9.7 g, 30.2 mmol), and sodium tert-butoxide (3.6 g, 37.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature, and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 10.5 g of compound Bd-1 (yield 62%, MS: [M+H)). + =588).

[0605] Under a nitrogen atmosphere, compound Bd-1 (10 g, 17 mmol), amine 2 (2.9 g, 17.3 mmol), and sodium tert-butoxide (2.1 g, 22.1 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature, and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 7.1 g of compound 2-27 (58% yield, MS: [M+H)). + =721).

[0606] Synthesis example 2-28

[0607]

[0608] Under a nitrogen atmosphere, compound Be (10 g, 28.8 mmol), amine 2 (5.1 g, 30.2 mmol), and sodium tert-butoxide (3.6 g, 37.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 6.9 g of compound Be-1 (yield 55%, MS: [M+H)). + =436).

[0609] Under a nitrogen atmosphere, compound Be-1 (10 g, 22.9 mmol), amine 22 (6.4 g, 23.4 mmol), and sodium tert-butoxide (2.9 g, 29.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 10.5 g of compound 2-28 (68% yield, MS: [M+H)). + =675).

[0610] Synthesis example 2-29

[0611]

[0612] Under a nitrogen atmosphere, compound Be (10 g, 28.8 mmol), amine 23 (10.6 g, 30.2 mmol), and sodium tert-butoxide (3.6 g, 37.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 11.3 g of compound Be-2 (64% yield, MS: [M+H)). + =616).

[0613] Under a nitrogen atmosphere, compound Be-2 (10 g, 16.2 mmol), amine 2 (2.8 g, 16.6 mmol), and sodium tert-butoxide (2 g, 21.1 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 8.3 g of compound 2-29 (68% yield, MS: [M+H)). + =749).

[0614] Synthesis example 2-30

[0615]

[0616] Under a nitrogen atmosphere, compound Be (10 g, 28.8 mmol), amine 4 (6.6 g, 30.2 mmol), and sodium tert-butoxide (3.6 g, 37.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 7.4 g of compound Be-3 (yield 53%, MS: [M+H)). + =486).

[0617] Under a nitrogen atmosphere, compound Be-3 (10 g, 20.6 mmol), amine 5 (6.2 g, 21 mmol), and sodium tert-butoxide (2.6 g, 26.7 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature, and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 10.6 g of compound 2-30 (69% yield, MS: [M+H)). + =745).

[0618] Synthesis example 2-31

[0619]

[0620] Under a nitrogen atmosphere, compound Bf (10 g, 28.8 mmol), amine 2 (5.1 g, 30.2 mmol), and sodium tert-butoxide (3.6 g, 37.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 8.6 g of compound Bn-1 (69% yield, MS: [M+H)). + =436).

[0621] Under a nitrogen atmosphere, compound Bf-1 (10 g, 22.9 mmol), amine 24 (6.9 g, 23.4 mmol), and sodium tert-butoxide (2.9 g, 29.8 mmol) were added to 200 mL of xylene, stirred, and refluxed. Bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added to the resulting mixture. After 5 hours, when the reaction was complete, the reactants were cooled to room temperature and the solvent was removed under reduced pressure. The product was completely dissolved again in chloroform, washed twice with water, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrate obtained was purified by silica gel column chromatography to give 8.1 g of compound 2-31 (yield 51%, MS: [M+H)). + =695).

[0622] Example 1

[0623] ITO (indium tin oxide) is used as A glass substrate coated with a thin film of ITO was immersed in distilled water containing detergent and washed using ultrasound. The detergent used was from Fischer Co., and the distilled water was filtered twice using a filter manufactured by Millipore Co. After washing the ITO for 30 minutes, the process was repeated twice with distilled water for 10 minutes of ultrasonic washing. Following the distilled water washing, the substrate was ultrasonically washed with a solvent of isopropanol, acetone, and methanol, dried, and then transferred to a plasma cleaner. Additionally, the substrate was cleaned with oxygen plasma for 5 minutes before being transferred to a vacuum evaporation machine.

[0624] On the prepared ITO transparent electrode, as a hole injection layer, the following HI-1 compound is applied... The thickness is formed by p-doping the A-1 compound at a concentration of 1.5%. The HT-1 compound is then vacuum-deposited onto the hole-implanted layer to form a film thickness. The hole transport layer. Next, on the aforementioned hole transport layer, at a film thickness... An electron blocking layer was formed by vacuum evaporation of the following EB-1 compound. Then, on the electron blocking layer, compound 1-1 (the first main component) manufactured in synthesis example 1-1, compound 2-4 (the second main component) manufactured in synthesis example 2-4, and the following Dp-7 compound (the dopant) were vacuum evaporated in a weight ratio of 49:49:2 to form... A red luminescent layer of a certain thickness. On the aforementioned luminescent layer, a film thickness of... A hole-blocking layer was formed by vacuum evaporation of the HB-1 compound described below. Next, the ET-1 compound and the LiQ compound described below were vacuum evaporated onto the hole-blocking layer in a 2:1 weight ratio, thereby achieving... The thickness forms an electron injection and transport layer. On this electron injection and transport layer, lithium fluoride (LiF) is sequentially applied... The thickness, using aluminum The cathode is formed by vapor deposition of a certain thickness.

[0625]

[0626] During the above process, the evaporation rate of organic matter is maintained. Lithium fluoride maintenance of the cathode The evaporation rate of aluminum maintains The evaporation rate was such that the vacuum level was maintained at 2×10⁻⁶ during evaporation. -7 ~5×10 -6 This led to the creation of organic light-emitting devices.

[0627] Examples 2 to 205

[0628] In the organic light-emitting device of Example 1, the first and second host compounds described in Tables 1 to 6 below were used instead of the first and second host compounds, and the organic light-emitting device was otherwise manufactured by the same method as in Example 1 above.

[0629] Comparative Examples 1 to 30

[0630] In the organic light-emitting device of Example 1, the first and second subjects (compounds B-1 to B-3) and the second subject described in Table 7 below were used instead of the first and second subjects. Otherwise, the organic light-emitting device was manufactured by the same method as in Example 1 above.

[0631] Comparative Examples 31 to 63

[0632] In the organic light-emitting device of Example 1, the first and second subjects (compounds C-1 to C-3) described in Table 8 below were used instead of the first and second subjects. Otherwise, the organic light-emitting device was manufactured by the same method as in Example 1 above.

[0633] On the other hand, compounds B-1 to B-3 and compounds C-1 to C-3 used in the above comparative examples are as follows:

[0634]

[0635] Experimental Example

[0636] When a current was applied to the organic light-emitting devices manufactured in the above embodiments and comparative examples, the driving voltage and efficiency were measured respectively, and the results are shown in Tables 1 to 8 below (15 mA / cm). 2 (Benchmark). Furthermore, lifetime T95 refers to the time required for the brightness to decrease from its initial brightness (6000 nits) to 95%.

[0637] [Table 1]

[0638]

[0639]

[0640] [Table 2]

[0641]

[0642]

[0643] [Table 3]

[0644]

[0645]

[0646] [Table 4]

[0647]

[0648]

[0649] [Table 5]

[0650]

[0651]

[0652] [Table 6]

[0653]

[0654] [Table 7]

[0655]

[0656] [Table 8]

[0657]

[0658] The organic light-emitting device of the embodiment in which a red light-emitting layer is formed by co-evaporation of the first compound of chemical formula 1 and the second compound of chemical formula 2 according to the present invention has a reduced driving voltage and improved efficiency and lifetime characteristics compared with the organic light-emitting devices of Comparative Examples 1 to 30, which form a red light-emitting layer by co-evaporation of compounds B-1 to B-3 and the second compound of the present invention, and the organic light-emitting devices of Comparative Examples 31 to 63, which form a red light-emitting layer by co-evaporation of compounds C-1 to C-3 and the first compound of the present invention.

[0659] Therefore, it can be seen that by combining the first compound of Formula 1 and the second compound of Formula 2 as the host, energy transfer from the host to the red dopant within the red emitting layer is well achieved. Furthermore, the organic light-emitting device of the above embodiment maintains high efficiency and exhibits significantly improved lifetime characteristics compared to the comparative example. This is because by using the combination of the first compound of Formula 1 and the second compound of Formula 2, a stable balance of electrons and holes is formed within the emitting layer, thus allowing electrons and holes to combine and uniformly form excitons throughout the emitting layer.

[0660] In summary, it can be confirmed that when the combination of the first compound of Chemical Formula 1 and the second compound of Chemical Formula 2 of the present invention is used as the main body of the red light-emitting layer, the driving voltage, luminous efficiency and lifetime characteristics of the organic light-emitting device can be improved. Considering that the luminous efficiency and lifetime characteristics of organic light-emitting devices are usually trade-offs, it can be considered that the organic light-emitting device of the embodiment shows significantly improved device characteristics compared with the comparative example device.

[0661] [Symbol Explanation]

[0662] 1: Substrate 2: Anode

[0663] 3: Light-emitting layer 4: Cathode

[0664] 5: Hole injection layer; 6: Hole transport layer

[0665] 7: Electron blocking layer; 8: Hole blocking layer

[0666] 9: Electron injection and transport layer.

Claims

1. An organic light-emitting device, wherein, include: Anode, cathode, and light-emitting layer between the anode and the cathode, The luminescent layer comprises a first compound represented by chemical formula 1 and a second compound represented by chemical formula 2a or 2b: Chemical Formula 1 In the chemical formula 1, L1 to L2 are each independently a single bond, or C 6-60 Alpha-aryl L3 can be a single bond, phenylene, biphenyl dimethyl, or naphthylene. Ar1 and Ar2 are each independently unsubstituted or selected from deuterium and C. 1-10 Alkyl and C 6-20 C with one or more substituents in the aryl group 6-60 Aryl; or unsubstituted or selected from deuterium, C 1-10 Alkyl and C 6-20 A C-type compound containing one or more heteroatoms of N, O, and S, substituted by one or more substituents in the aryl group. 2-60 Mixed aromatics, R1 is either hydrogen or deuterium; or two adjacent R1s combine to form an unsubstituted or deuterium-substituted benzene ring, with the remaining R1s being either hydrogen or deuterium. R2 is either hydrogen or deuterium; or two adjacent R2s combine to form an unsubstituted or deuterium-substituted benzene ring, with the remaining R2s being either hydrogen or deuterium. Chemical formula 2a In the chemical formula 2a, A' is a naphthalene ring fused with an adjacent ring. X' is O or S. L' 11 and L' 21 Each is an independent single key. L' 12 L' 13 L' 22 and L' 23 Each can be independently a single bond, phenylene, biphenyl diyl, or naphthylene. Ar' 11 Ar' 12 Ar' 21 and Ar' 22 Each of these can be independently phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, dibenzofuranyl, or dibenzothiopheneyl, and Ar' 11 Ar' 12 Ar' 21 and Ar' 22 Each independently remained unreplaced, or was selected from deuterium and C. 1-10 Alkyl and C 6-20 One or more substituents of the aryl group are substituted. R' represents hydrogen; deuterium; or C. 1-10 alkyl, m' is an integer from 0 to 6. Chemical formula 2b In the chemical formula 2b, A" represents a naphthalene ring fused with an adjacent ring. X" represents O or S. L" 11 and L" 21 Each is an independent single key. L" 12 、L" 13 、L" 22 and L" 23 Each can be independently a single bond, phenylene, biphenyl diyl, or naphthylene. Ar" 11 Ar" 12 Ar" 21 and Ar" 22 Each of these can be independently phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, dibenzofuranyl, or dibenzothiopheneyl, and Ar" 11 Ar" 12 Ar" 21 and Ar" 22 Each independently remained unreplaced, or was selected from deuterium and C. 1-10 Alkyl and C 6-20 One or more substituents of the aryl group are substituted. R represents hydrogen; deuterium; or C. 1-10 alkyl, m" is an integer from 0 to 6.

2. The organic light-emitting device according to claim 1, wherein, The first compound is represented by any one of the following chemical formulas 1-1 to 1-10: In the 1-1 to 1-10, L1 to L3, Ar1 and Ar2 are the same as defined in claim 1.

3. The organic light-emitting device according to claim 1, wherein, L1 and L2 are each independently a single bond, a phenylene group, or a naphthylene group.

4. The organic light-emitting device according to claim 1, wherein, Ar1 and Ar2 are each independently phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenanthryl, dibenzofuranyl, dibenzothiophene, carbazole, benzonaphthiofuranyl, or benzonaphthiophene. Among them, Ar1 and Ar2 are independently not replaced, or are selected from deuterium and C. 1-10 Alkyl and C 6-20 One or more substituents of the aryl group are substituted.

5. The organic light-emitting device according to claim 4, wherein, Ar1 and Ar2 are each independently selected from any of the following groups: In each of the aforementioned chemical formulas, X is O or S. The dashed line indicates the joint position.

6. The organic light-emitting device according to claim 1, wherein, The first compound is selected from any one of the following compounds: 。 7. The organic light-emitting device according to claim 1, wherein, The chemical formula 2a is represented by any one of the following chemical formulas 2a-1 to 2a-3. The chemical formula 2b is represented by any one of the following chemical formulas 2b-1 to 2b-3: In the chemical formulas 2a-1 to 2a-3 and 2b-1 to 2b-3, X'、L' 11 To L' 13 L' 21 To L' 23 Ar' 11 Ar' 12 Ar' 21 Ar' 22 、R'、m'、X"、L" 11 To L" 13 、L" 21 To L" 23 Ar" 11 Ar" 12 Ar" 21 Ar" 22 R" and m" are the same as defined in claim 1.

8. The organic light-emitting device according to claim 1, wherein, Ar' 11 Ar' 12 Ar' 21 Ar' 22 Ar" 11 Ar" 12 Ar" 21 and Ar" 22 Each is independently selected from any of the following groups: In each of the aforementioned chemical formulas, The dashed line indicates the joint position.

9. The organic light-emitting device according to claim 1, wherein, Both R' and R" are hydrogen.

10. The organic light-emitting device according to claim 1, wherein, The second compound is selected from any one of the following compounds: 。

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