Compounds and organic light emitting devices comprising the same

Abstract

The present application relates to a compound represented by chemical formula 1; and an organic light emitting device, comprising: a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode, wherein one or more of the organic layers comprises the compound represented by chemical formula 1.

Description

Technical Field

[0001] Cross-Reference to Related Applications

[0002] This application claims priority based on Korean Patent Application No. 10-2021-0093022 dated July 15, 2021 and Korean Patent Application No. 10-2022-0087405 dated July 15, 2022, the entire contents of which are disclosed in the documents of the Korean patent applications and are incorporated herein by reference.

[0003] This invention relates to novel compounds and organic light-emitting devices containing the same. 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] On the other hand, in recent years, in order to save on process costs, organic light-emitting devices (OLEDs) are being developed that utilize solution processes, especially inkjet processes, to replace existing vapor deposition processes. In the early stages, attempts were made to develop OLEDs by coating all the OLED layers using solution processes, but existing technologies have limitations. Therefore, research is underway on hybrid processes where only HIL, HTL, and EML are coated using solution processes in a normal structural form, while subsequent processes utilize existing vapor deposition processes.

[0008] Therefore, the present invention provides a novel material for organic light-emitting devices, which can be used in organic light-emitting devices and also in solution processing.

[0009] Existing technical documents

[0010] Patent documents

[0011] (Patent Document 0001) Korean Patent Publication No. 10-2000-0051826 Summary of the Invention

[0012] Technical issues

[0013] This invention relates to novel compounds and organic light-emitting devices containing the same.

[0014] Solution to the problem

[0015] This invention provides compounds represented by the following chemical formula 1:

[0016] [Chemical Formula 1]

[0017]

[0018] In the above chemical formula 1,

[0019] X1 to X 10 One of them is N, and the rest are CR1.

[0020] One of R1 is a substituent represented by the following chemical formula 2, and the rest are hydrogen or deuterium.

[0021] [Chemical Formula 2]

[0022]

[0023] In the above chemical formula 2,

[0024] L1 represents C that is directly bonded, substituted, or unsubstituted. 6-60 aryl, or substituted or unsubstituted C 5-60 heteroaryl,

[0025] L2 is a directly bonded, substituted, or unsubstituted C. 6-60 aryl, or substituted or unsubstituted C 5-60 heteroaryl,

[0026] Ar1 represents substituted or unsubstituted C. 6-60 aryl, or substituted or unsubstituted C 5-60 heteroaryl, Ar2 is substituted or unsubstituted C 6-60 aryl, or substituted or unsubstituted C 5-60 Mixed aromatic compounds.

[0027] Furthermore, the present invention provides an organic light-emitting device, comprising: a first electrode, a second electrode disposed opposite to the first electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises a compound represented by the aforementioned chemical formula 1. Specifically, the organic layer comprising the aforementioned compound may be an electron-emitting layer.

[0028] Invention Effects

[0029] The compounds represented by the above-described chemical formula 1 can be used as materials for the organic layer of organic light-emitting devices, thereby achieving improved efficiency, lower driving voltage, and / or improved lifetime characteristics in organic light-emitting devices. In particular, the compounds represented by the above-described chemical formula 1 can be used as materials for hole injection, hole transport, hole injection and transport, electron suppression, luminescence, electron transport, or electron injection. Attached Figure Description

[0030] 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.

[0031] 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, a light-emitting layer 7, an electron injection and transport layer 8, and a cathode 4. Detailed Implementation

[0032] The invention will now be described in more detail to aid in understanding.

[0033] (Definition of the term)

[0034] In this instruction manual, This indicates a bond that is linked to other substituents.

[0035] In this specification, the term "substituted or unsubstituted" refers to a group selected from deuterium; halogen group; cyano 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; alkylamino; aralkylamino; heteroarylamino; arylamino; arylphosphinyl; or a substituent consisting of one or more heteroaryl groups containing N, O, and S atoms, substituted or unsubstituted, or substituted or unsubstituted by two or more substituents linked together as exemplified above. For example, "a substituent consisting of two or more substituents linked together" can be biphenyl. That is, biphenyl can be aryl, or it can be interpreted as a substituent consisting of two phenyl groups linked together.

[0036] 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 compound with the following structure, but is not limited thereto.

[0037]

[0038] 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 compound with the following structural formula, but is not limited thereto.

[0039]

[0040] 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 compound with the following structure, but is not limited thereto.

[0041]

[0042] In this specification, silanes specifically include trimethylsilane, triethylsilane, tert-butyldimethylsilane, vinyldimethylsilane, propyldimethylsilane, triphenylsilane, diphenylsilane, phenylsilane, etc., but are not limited to these.

[0043] In this specification, boron groups specifically include trimethylboronyl, triethylboronyl, tert-butyldimethylboronyl, triphenylboronyl, phenylboronyl, etc., but are not limited to these.

[0044] Examples of halogen groups in this specification include fluorine, chlorine, bromine, or iodine.

[0045] 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, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but are not limited to these.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] In this specification, a heteroaryl group is a heteroaryl 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 heteroaryl groups include xanthene, thioxanthen, thiophene, furanyl, pyrrole, imidazolyl, 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.

[0051] In this specification, the aryl groups in aralkyl, aryl-alkenyl, alkylaryl, arylamino, and arylsilyl are the same as those exemplified above. In this specification, the alkyl groups in aralkyl, alkylaryl, and alkylamino are the same as those exemplified above. In this specification, the heteroaryl groups in heteroarylamines are subject to the above descriptions of heteroaryl 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 descriptions of aryl groups apply. In this specification, heteroarylene is a divalent group; otherwise, the above descriptions of heteroaryl groups apply. In this specification, the hydrocarbon ring is not a monovalent group but is formed by the combination of two substituents; otherwise, the above descriptions of aryl or cycloalkyl groups apply. In this specification, the heterocycle is not a monovalent group but is formed by the combination of two substituents; otherwise, the above descriptions of heteroaryl groups apply.

[0052] (compound)

[0053] The present invention provides compounds represented by the above chemical formula 1.

[0054] In the above chemical formula 1, Ar1 is a substituted or unsubstituted C. 6-60 aryl, or substituted or unsubstituted C 5-60 Heteroaryl. Preferably, Ar1 can be phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, (phenyl)naphthyl, (naphthyl)phenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9'-spirodi[9H-fluoren]yl, dibenzofuranyl, dibenzothiopheneyl or 9-phenyl-carbazoyl.

[0055] In the above chemical formula 1, Ar2 is a substituted or unsubstituted C. 6-60 aryl, or substituted or unsubstituted C 5-60 Heteroaryl. Preferably, Ar2 can be phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, (phenyl)naphthyl, (naphthyl)phenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9'-spirobis[9H-fluoren]yl, dibenzofuranyl, dibenzothiopheneyl or 9-phenyl-carbazoyl.

[0056] L1 represents C that is directly bonded, substituted, or unsubstituted. 6-60 aryl, or substituted or unsubstituted C 5-60 Hypoaryl group. Preferably, L1 is directly bonded, phenylene, biphenylene, terphenylene, naphthylene, 9,9-dimethylfluorene, or 9,9-diphenylfluorene.

[0057] L2 is a directly bonded, substituted, or unsubstituted C. 6-60 aryl, or substituted or unsubstituted C 5-60Hypoaryl group. Preferably, L2 is directly bonded, phenylene, biphenylene, terphenylene, naphthylene, 9,9-dimethylfluorene, or 9,9-diphenylfluorene.

[0058] In addition, in chemical formula 1, the above-mentioned compound may have CR1, represented by chemical formula 2, attached to one of X1 to X4.

[0059] Representative examples of compounds represented by the above chemical formula 1 are shown below:

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094] In addition, the present invention provides a method for manufacturing the compound represented by the above chemical formula 1 as shown in the following reaction formula 1.

[0095] [Reaction Formula 1]

[0096]

[0097] In the above reaction formula 1, X1 to X 10 The definitions of L1, L2, Ar1, and Ar2 are the same as those for chemical formulas 1 and 2. Furthermore, in reaction formula 1, Y is a halogen, preferably chlorine.

[0098] The above reaction formula 1 is preferably carried out in the presence of a palladium catalyst and a base, and the above manufacturing method can be further specified in the synthesis examples described later.

[0099] (Organic light-emitting devices)

[0100] Furthermore, the present invention provides an organic light-emitting device comprising a compound represented by the above-described chemical formula 1. As an example, the present invention provides an organic light-emitting device comprising: a first electrode, a second electrode disposed opposite to the first electrode, and one or more organic layers disposed between the first electrode and the second electrode, wherein one or more of the organic layers comprises a compound represented by the above-described chemical formula 1.

[0101] The organic layer of the organic light-emitting device of the present invention can be formed as a single layer or as a multilayer structure with two or more organic layers stacked on top of each other. For example, the organic light-emitting device of the present invention can have a structure including a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer as organic layers. However, the structure of the organic light-emitting device is not limited to this and may include fewer organic layers.

[0102] In addition, the aforementioned organic layer may include a hole injection layer, a hole transport layer, or a layer that performs both hole injection and transport simultaneously, and the aforementioned hole injection layer, hole transport layer, or layer that performs both hole injection and transport simultaneously may contain a compound represented by the aforementioned chemical formula 1.

[0103] In addition, the aforementioned organic layer may include a light-emitting layer, which may contain a compound represented by the aforementioned chemical formula 1.

[0104] In addition, the aforementioned organic layer may include a hole-blocking layer, an electron transport layer, an electron injection layer, or a layer that simultaneously performs electron transport and electron injection. The aforementioned hole-blocking layer, electron transport layer, electron injection layer, or layer that simultaneously performs electron transport and electron injection may contain a compound represented by the aforementioned chemical formula 1.

[0105] In addition, the aforementioned organic layer may include a light-emitting layer and an electron injection and transport layer, wherein the electron injection and transport layer may contain a compound represented by the aforementioned chemical formula 1.

[0106] Furthermore, the organic light-emitting device according to the present invention can be a structure (normal type) in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. Additionally, the organic light-emitting device according to the present invention can be a reverse structure (inverted type) in which a cathode, one or more organic layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light-emitting device according to an embodiment of the present invention is illustrated below. Figure 1 and 2 .

[0107] 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.

[0108] 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, a light-emitting layer 7, an electron injection and transport layer 8, and a cathode 4. In the structure described above, the compound represented by the above chemical formula 1 may be included in the light-emitting layer.

[0109] The organic light-emitting device according to the present invention, except that one or more of the organic layers contain a compound represented by the above-described chemical formula 1, can be manufactured using materials and methods known in the art. Furthermore, when the organic light-emitting device comprises a plurality of organic layers, the organic layers can be formed from the same substance or different substances.

[0110] For example, the organic light-emitting device according to the present invention can be manufactured by sequentially stacking an anode, an organic layer, and a cathode on a substrate. This can be achieved by depositing a metal or a conductive metal oxide or alloy thereof onto the substrate using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation to form an anode, then forming an organic layer comprising a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer on the anode, and finally depositing a material suitable for use as a cathode onto the organic layer. Alternatively, the organic light-emitting device can also be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material onto the substrate.

[0111] Furthermore, the compound represented by the above chemical formula 1 can be used to form an organic layer in the manufacture of organic light-emitting devices not only by vacuum evaporation but also by solution coating. Here, solution coating refers to methods such as spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, and roller coating, but is not limited to these.

[0112] In addition to these methods, organic light-emitting devices can also be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (WO 2003 / 012890). However, the manufacturing method is not limited to these methods.

[0113] As an example, the first electrode is the anode and the second electrode is the cathode, or the first electrode is the cathode and the second electrode is the anode.

[0114] 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 compounds such as poly(3-methylthiophene), poly[3,4-(ethylidene-1,2-dioxo)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited to these.

[0115] 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.

[0116] The aforementioned hole injection layer is a layer that injects holes from the electrode. Preferably, the 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 light-emitting layer or light-emitting material, prevents excitons generated in the light-emitting layer from migrating to the electron injection layer or electron injection material, and exhibits excellent thin film formation capability. Preferably, the HOMO (highest occupied molecular orbital) of the hole injection material is between that of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injection materials include, but are not limited to, metalloporphyrins, oligothiophenes, arylamine-based organic compounds, hexanitrile hexaazabenzophenanthrene-based organic compounds, quinacridone-based organic compounds, perylene-based organic compounds, anthraquinones, and conductive compounds based on polyaniline and polythiophene.

[0117] The aforementioned hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light-emitting layer. The hole transport material is a material capable of receiving holes from the anode or hole injection layer and transferring them to the light-emitting layer; materials with high hole mobility are suitable. Specific examples include aryl amine-based organic compounds, conductive compounds, and block copolymers that simultaneously contain conjugated and non-conjugated portions, but are not limited to these.

[0118] The aforementioned luminescent material is capable of emitting light in the visible light region by receiving holes and electrons from the hole transport layer and electron transport layer, respectively, and combining them. Preferably, it is a material with high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxyquinoline aluminum complexes (Alq3); carbazole compounds; diluted styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; and benzo[…]. Compounds including azoles, benzothiazoles and benzimidazoles; poly(p-phenylenevinylene) (PPV) polymers; spiro compounds; polyfluorene, fluorene, etc., but not limited to these.

[0119] The aforementioned electron suppression layer is a layer placed between the hole transport layer and the light-emitting layer to prevent electrons injected from the cathode from recombining in the light-emitting layer and transferring to the hole transport layer. It is also called an electron blocking layer. Preferably, the electron suppression layer uses a material with lower electrophilicity compared to the electron transport layer. Preferably, it may contain a compound represented by the above-described chemical formula 1 as the electron suppression layer material.

[0120] The aforementioned luminescent layer may comprise a host material and a dopant material. As the host material, compounds represented by the aforementioned chemical formula 1 can be used. Furthermore, as a host material that can be further used, aromatic fused-ring derivatives or heterocyclic compounds can be used. Specifically, as aromatic fused-ring derivatives, there are anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentane derivatives, phenanthrene compounds, fluoranthene compounds, etc.; as heterocyclic compounds, there are carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, etc. Pyrimidine derivatives, etc., but not limited to these.

[0121] As dopant materials, there are aromatic amine derivatives, styrylamine 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 arylamine, 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.

[0122] For example, one of the following Dp-1 to Dp-38 can be cited as a dopant material of the present invention, but it is not limited thereto.

[0123]

[0124]

[0125]

[0126]

[0127] The aforementioned electron transport layer is the layer that receives electrons from the electron injection layer and transports them to the light-emitting layer. The electron transport material is one that can effectively receive electrons from the cathode and transfer them to the light-emitting layer; materials with high electron mobility are suitable. Specific examples include Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free 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, these include cesium, barium, calcium, ytterbium, and samarium, each accompanied by an aluminum or silver layer.

[0128] The aforementioned electron injection layer is a layer that injects electrons from the electrode. Preferably, compounds are those that possess electron transport capabilities, effectively inject electrons from the cathode, exhibit excellent electron injection performance for the light-emitting layer or light-emitting material, prevent excitons generated in the light-emitting layer from migrating to the hole injection layer, and possess excellent thin-film forming ability. Specifically, these 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.

[0129] 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.

[0130] On the other hand, in this invention, the "electron injection and transport layer" is a layer that fully utilizes the functions of the aforementioned electron injection layer and electron transport layer. Substances that perform the functions of each layer can be used individually or in combination, but are not limited thereto. Preferably, the substance comprising the compound represented by the aforementioned chemical formula 1 may be used as the electron injection and transport layer.

[0131] 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.

[0132] In addition, the compounds according to the present invention can be included not only in organic light-emitting devices, but also in organic solar cells or organic transistors.

[0133] The manufacture of compounds represented by the above chemical formula 1 and organic light-emitting devices containing them is specifically described in the following examples. However, the following examples are for illustrative purposes only and the scope of the invention is not limited thereto.

[0134] [Manufacturing Example]

[0135] Manufacturing Example 1

[0136]

[0137] 3-Bromo-2-chloropyridin-4-amine (15 g, 72.3 mmol) and (3-methoxynaphthyl-2-yl)boronic acid (15.3 g, 75.9 mmol) were added to tetrahydrofuran (300 ml), stirred, and refluxed. Then, potassium carbonate (30 g, 216.9 mmol) was dissolved in water (90 ml) and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol). After reacting for 4 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 14.6 g of compound Aa-1_P1. (Yield 71%, MS: [M+H)) + =285)

[0138] Compound Aa-1_P1 (10 g, 35.1 mmol) and HBF4 (6.2 g, 70.2 mmol) were added to acetonitrile (100 mL) and stirred. Then, NaNO2 (4.8 g, 70.2 mmol) was dissolved in H2O (20 mL) and slowly added at 0 °C. After reacting for 10 hours, the mixture was heated to room temperature and diluted with water (200 mL). The solution was completely dissolved 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 concentrated compound was purified by silica gel column chromatography to produce 6.6 g of compound Aa-1. (Yield 74%, MS: [M+H]) + =254)

[0139] Manufacturing Example 2

[0140]

[0141] Compound Aa-2 was prepared by the same method as in Manufacturing Example 1, except that 5-bromo-2-chloropyridin-4-amine was used instead of 3-bromo-2-chloropyridin-4-amine.

[0142] Manufacturing Example 3

[0143]

[0144] Compound Aa-3 was prepared by the same method as in Manufacturing Example 1, except that 3-bromo-5-chloropyridin-4-amine was used instead of 3-bromo-2-chloropyridin-4-amine.

[0145] Manufacturing Example 4

[0146]

[0147] Compound Ab-1 was prepared by the same method as in Manufacturing Example 1, except that 4-bromo-5-chloropyridin-3-amine was used instead of 3-bromo-2-chloropyridin-4-amine.

[0148] Manufacturing Example 5

[0149]

[0150] Compound Ab-2 was prepared by the same method as in Manufacturing Example 1, except that 4-bromo-6-chloropyridin-3-amine was used instead of 3-bromo-2-chloropyridin-4-amine.

[0151] Manufacturing Example 6

[0152]

[0153] The compound Ab-3 was prepared by the same method as in Manufacturing Example 1, except that 4-bromo-2-chloropyridin-3-amine was used instead of 3-bromo-2-chloropyridin-4-amine.

[0154] Manufacturing Example 7

[0155]

[0156] Compound Ac-1 was prepared by the same method as in Manufacturing Example 1, except that 3-bromo-4-chloropyridin-2-amine was used instead of 3-bromo-2-chloropyridin-4-amine.

[0157] Manufacturing Example 8

[0158]

[0159] Compound Ac-2 was prepared by the same method as in Manufacturing Example 1, except that 3-bromo-5-chloropyridin-2-amine was used instead of 3-bromo-2-chloropyridin-4-amine.

[0160] Manufacturing Example 9

[0161]

[0162] Compound Ac-3 was prepared by the same method as in Manufacturing Example 1, except that 3-bromo-6-chloropyridin-2-amine was used instead of 3-bromo-2-chloropyridin-4-amine.

[0163] Manufacturing Example 10

[0164]

[0165] Compound Ad-1 was prepared by the same method as in Manufacturing Example 1, except that 2-bromo-4-chloropyridin-3-amine was used instead of 3-bromo-2-chloropyridin-4-amine.

[0166] Manufacturing Example 11

[0167]

[0168] Compound Ad-2 was prepared by the same method as in Manufacturing Example 1, except that 2-bromo-5-chloropyridin-3-amine was used instead of 3-bromo-2-chloropyridin-4-amine.

[0169] Manufacturing Example 12

[0170]

[0171] The compound Ad-3 was prepared by the same method as in Manufacturing Example 1, except that 2-bromo-6-chloropyridin-3-amine was used instead of 3-bromo-2-chloropyridin-4-amine.

[0172] Manufacturing Example 13

[0173]

[0174] 6-Bromoquinoline-7-amine (15 g, 67.2 mmol) and (2-chloro-6-methoxyphenyl)boronic acid (13.2 g, 70.6 mmol) were added to tetrahydrofuran (300 ml) and stirred under reflux. Then, potassium carbonate (27.9 g, 201.7 mmol) was dissolved in water (84 ml) and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.7 mmol) was added. After reacting for 3 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 12.6 g of compound Ba-1_P1 (66% yield, MS: [M+H)). + =285).

[0175] Compound Ba-1_P1 (10 g, 35.1 mmol) and HBF4 (6.2 g, 70.2 mmol) were added to acetonitrile (100 mL) and stirred. Then, NaNO2 (4.8 g, 70.2 mmol) was dissolved in H2O (20 mL) and slowly added at 0 °C. After reacting for 10 hours, the mixture was heated to room temperature and diluted with water (200 mL). The solution was completely dissolved 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 concentrated compound was purified by silica gel column chromatography to produce 6.1 g of compound Ba-1 (68% yield, MS: [M+H)). + =254).

[0176] Manufacturing Example 14

[0177]

[0178] The compound Ba-2 was prepared by the same method as in Manufacturing Example 13, except that (5-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0179] Manufacturing Example 15

[0180]

[0181] The compound Ba-3 was prepared by the same method as in Manufacturing Example 13, except that (4-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0182] Manufacturing Example 16

[0183]

[0184] The compound Ba-4 was prepared by the same method as in Manufacturing Example 13, except that (3-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0185] Manufacturing Example 17

[0186]

[0187] Compound Bb-1 was prepared by the same method as in Manufacturing Example 13, except that 6-bromoisoquinoline-7-amine was used instead of 6-bromoquinoline-7-amine.

[0188] Manufacturing Example 18

[0189]

[0190] Compound Bb-2 was manufactured by the same method as in Manufacturing Example 13, except that 6-bromoisoquinoline-7-amine was used instead of 6-bromoquinoline-7-amine and (5-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0191] Manufacturing Example 19

[0192]

[0193] Compound Bb-3 was manufactured by the same method as in Manufacturing Example 13, except that 6-bromoisoquinoline-7-amine was used instead of 6-bromoquinoline-7-amine and (4-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0194] Manufacturing Example 20

[0195]

[0196] Compound Bb-4 was manufactured by the same method as in Manufacturing Example 13, except that 6-bromoisoquinoline-7-amine was used instead of 6-bromoquinoline-7-amine and (3-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0197] Manufacturing Example 21

[0198]

[0199] Compound Bc-1 was prepared by the same method as in Manufacturing Example 13, except that 7-bromoisoquinoline-6-amine was used instead of 6-bromoquinoline-7-amine.

[0200] Manufacturing Example 22

[0201]

[0202] Compound Bc-2 was manufactured by the same method as in Manufacturing Example 13, except that 7-bromoisoquinoline-6-amine was used instead of 6-bromoquinoline-7-amine and (5-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0203] Manufacturing Example 23

[0204]

[0205] Compound Bc-3 was manufactured by the same method as in Manufacturing Example 13, except that 7-bromoisoquinoline-6-amine was used instead of 6-bromoquinoline-7-amine and (4-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0206] Manufacturing Example 24

[0207]

[0208] Compound Bc-4 was manufactured by the same method as in Manufacturing Example 13, except that 7-bromoisoquinoline-6-amine was used instead of 6-bromoquinoline-7-amine and (3-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0209] Manufacturing Example 25

[0210]

[0211] Compound Bd-1 was prepared by the same method as in Manufacturing Example 13, except that 7-bromoquinoline-6-amine was used instead of 6-bromoquinoline-7-amine.

[0212] Manufacturing Example 26

[0213]

[0214] Compound Bd-2 was manufactured by the same method as in Manufacturing Example 13, except that 7-bromoquinoline-6-amine was used instead of 6-bromoquinoline-7-amine and (5-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0215] Manufacturing Example 27

[0216]

[0217] Compound Bd-3 was prepared by the same method as in Manufacturing Example 13, except that 7-bromoquinoline-6-amine was used instead of 6-bromoquinoline-7-amine and (4-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0218] Manufacturing Example 28

[0219]

[0220] Compound Bd-4 was prepared by the same method as in Manufacturing Example 13, except that 7-bromoquinoline-6-amine was used instead of 6-bromoquinoline-7-amine and (3-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0221] Manufacturing Example 29

[0222]

[0223] The compound Be-1 was prepared by the same method as in Manufacturing Example 13, except that 2-bromoquinoline-3-amine was used instead of 6-bromoquinoline-7-amine.

[0224] Manufacturing Example 30

[0225]

[0226] The compound Be-2 was prepared by the same method as in Manufacturing Example 13, except that 2-bromoquinoline-3-amine was used instead of 6-bromoquinoline-7-amine and (5-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0227] Manufacturing Example 31

[0228]

[0229] The compound Be-3 was prepared by the same method as in Manufacturing Example 13, except that 2-bromoquinoline-3-amine was used instead of 6-bromoquinoline-7-amine and (4-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0230] Manufacturing Example 32

[0231]

[0232] The compound Be-4 was prepared by the same method as in Manufacturing Example 13, except that 2-bromoquinoline-3-amine was used instead of 6-bromoquinoline-7-amine and (3-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0233] Manufacturing Example 33

[0234]

[0235] Compound Bf-1 was prepared by the same method as in Manufacturing Example 13, except that 3-bromoquinoline-2-amine was used instead of 6-bromoquinoline-7-amine.

[0236] Manufacturing Example 34

[0237]

[0238] Compound Bf-2 was manufactured by the same method as in Manufacturing Example 13, except that 3-bromoquinoline-2-amine was used instead of 6-bromoquinoline-7-amine and (5-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0239] Manufacturing Example 35

[0240]

[0241] Compound Bf-3 was prepared by the same method as in Manufacturing Example 13, except that 3-bromoquinoline-2-amine was used instead of 6-bromoquinoline-7-amine and (4-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0242] Manufacturing Example 36

[0243]

[0244] Compound Bf-4 was prepared by the same method as in Manufacturing Example 13, except that 3-bromoquinoline-2-amine was used instead of 6-bromoquinoline-7-amine and (3-chloro-2-methoxyphenyl)boronic acid was used instead of (2-chloro-6-methoxyphenyl)boronic acid.

[0245] Manufacturing Example 37

[0246]

[0247] 2-Bromopyridin-3-amine (15 g, 86.7 mmol) and (6-chloro-3-methoxynaphthyl-2-yl)boronic acid (21.5 g, 91 mmol) were added to tetrahydrofuran (300 ml) and stirred under reflux. Then, potassium carbonate (35.9 g, 260.1 mmol) was dissolved in water (108 ml) and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 mmol) was added. After reacting for 3 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 redissolved in chloroform, washed twice with water, and the organic layer was separated again. 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 17 g of compound Ca-1_P1 (69% yield, MS: [M+H)). + =285).

[0248] Compound Ca-1_P1 (10 g, 35.1 mmol) and HBF4 (6.2 g, 70.2 mmol) were added to acetonitrile (100 mL) and stirred. Then, NaNO2 (4.8 g, 70.2 mmol) was dissolved in H2O (20 mL) and slowly added at 0 °C. After reacting for 10 hours, the mixture was heated to room temperature and diluted with water (200 mL). The solution was completely dissolved 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 concentrated compound was purified by silica gel column chromatography to produce 6.0 g of compound Ca-1 (67% yield, MS: [M+H)). + =254).

[0249] Manufacturing Example 38

[0250]

[0251] The compound Ca-2 was prepared by the same method as in Manufacturing Example 37, except that (7-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0252] Manufacturing Example 39

[0253]

[0254] The compound Ca-3 was prepared by the same method as in Manufacturing Example 37, except that (8-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0255] Manufacturing Example 40

[0256]

[0257] The compound Ca-4 was prepared by the same method as in Manufacturing Example 37, except that (1-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0258] Manufacturing Example 41

[0259]

[0260] The compound Ca-5 was prepared by means of the same method as in manufacturing example 37, except that (4-chloro-3-methoxynaphth-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphth-2-yl)boronic acid.

[0261] Manufacturing Example 42

[0262]

[0263] The compound Ca-6 was prepared by the same method as in Manufacturing Example 37, except that (5-chloro-3-methoxynaphth-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphth-2-yl)boronic acid.

[0264] Manufacturing Example 43

[0265]

[0266] The compound Cb-1 was prepared by the same method as in manufacturing example 37, except that 3-bromopyridine-4-amine was used instead of 2-bromopyridine-3-amine.

[0267] Manufacturing Example 44

[0268]

[0269] The compound Cb-2 was prepared by the same method as in Manufacturing Example 37, except that 3-bromopyridin-4-amine was used instead of 2-bromopyridin-3-amine and (7-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0270] Manufacturing Example 45

[0271]

[0272] The compound Cb-3 was prepared by the same method as in Manufacturing Example 37, except that 3-bromopyridin-4-amine was used instead of 2-bromopyridin-3-amine and (8-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0273] Manufacturing Example 46

[0274]

[0275] The compound Cb-4 was prepared by the same method as in Manufacturing Example 37, except that 3-bromopyridin-4-amine was used instead of 2-bromopyridin-3-amine and (1-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0276] Manufacturing Example 47

[0277]

[0278] Compound Cb-5 was prepared by the same method as in Manufacturing Example 37, except that 3-bromopyridin-4-amine was used instead of 2-bromopyridin-3-amine and (4-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0279] Manufacturing Example 48

[0280]

[0281] Compound Cb-6 was prepared by the same method as in Manufacturing Example 37, except that 3-bromopyridin-4-amine was used instead of 2-bromopyridin-3-amine and (5-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0282] Manufacturing Example 49

[0283]

[0284] Compound Cc-1 was prepared by the same method as in Manufacturing Example 37, except that 4-bromopyridine-3-amine was used instead of 2-bromopyridine-3-amine.

[0285] Manufacturing Example 50

[0286]

[0287] Compound Cc-2 was manufactured by the same method as in Manufacturing Example 37, except that 4-bromopyridin-3-amine was used instead of 2-bromopyridin-3-amine and (7-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0288] Manufacturing Example 51

[0289]

[0290] The compound Cc-3 was prepared by the same method as in Manufacturing Example 37, except that 4-bromopyridin-3-amine was used instead of 2-bromopyridin-3-amine and (8-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0291] Manufacturing Example 52

[0292]

[0293] Compound Cc-4 was prepared by the same method as in Manufacturing Example 37, except that 4-bromopyridin-3-amine was used instead of 2-bromopyridin-3-amine and (1-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0294] Manufacturing Example 53

[0295]

[0296] Compound Cc-5 was prepared by the same method as in Manufacturing Example 37, except that 4-bromopyridin-3-amine was used instead of 2-bromopyridin-3-amine and (4-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0297] Manufacturing Example 54

[0298]

[0299] Compound Cc-6 was prepared by the same method as in Manufacturing Example 37, except that 4-bromopyridin-3-amine was used instead of 2-bromopyridin-3-amine and (5-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0300] Manufacturing Example 55

[0301]

[0302] The compound Cd-1 was prepared by the same method as in manufacturing example 37, except that 3-bromopyridine-2-amine was used instead of 2-bromopyridine-3-amine.

[0303] Manufacturing Example 56

[0304]

[0305] The compound Cd-2 was prepared by the same method as in Manufacturing Example 37, except that 3-bromopyridin-2-amine was used instead of 2-bromopyridin-3-amine and (7-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0306] Manufacturing Example 57

[0307]

[0308] The compound Cd-3 was prepared by the same method as in Manufacturing Example 37, except that 3-bromopyridin-2-amine was used instead of 2-bromopyridin-3-amine and (8-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0309] Manufacturing Example 58

[0310]

[0311] The compound Cd-4 was prepared by the same method as in Manufacturing Example 37, except that 3-bromopyridin-2-amine was used instead of 2-bromopyridin-3-amine and (1-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0312] Manufacturing Example 59

[0313]

[0314] The compound Cd-5 was prepared by the same method as in Manufacturing Example 37, except that 3-bromopyridin-2-amine was used instead of 2-bromopyridin-3-amine and (4-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0315] Manufacturing Example 60

[0316]

[0317] The compound Cd-6 was prepared by the same method as in Manufacturing Example 37, except that 3-bromopyridin-2-amine was used instead of 2-bromopyridin-3-amine and (5-chloro-3-methoxynaphthyl-2-yl)boronic acid was used instead of (6-chloro-3-methoxynaphthyl-2-yl)boronic acid.

[0318] Manufacturing Example 61

[0319]

[0320] 15 g (58.2 mmol) and 9.3 g (61.2 mmol) of 2-bromo-5-chloroquinoline-3-amine were added to tetrahydrofuran (300 mL), stirred, and refluxed. Then, 24.2 g (174.7 mmol) of potassium carbonate was dissolved in 72 mL of water and added. After thorough stirring, 0 g (0.3 g, 0.6 mmol) of bis(tri-tert-butylphosphine)palladium(0) was added. After reacting for 5 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 10.8 g of compound Ca-1_P1. (Yield 65%, MS: [M+H]) + =285)

[0321] Compound Da-1_P1 (10 g, 35.1 mmol) and HBF4 (6.2 g, 70.2 mmol) were added to acetonitrile (100 mL) and stirred. Then, NaNO2 (4.8 g, 70.2 mmol) was dissolved in H2O (20 mL) and slowly added at 0 °C. After reacting for 10 hours, the mixture was heated to room temperature and diluted with water (200 mL). The solution was completely dissolved 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 concentrated compound was purified by silica gel column chromatography to produce 5.4 g of compound Da-1. (Yield 61%, MS: [M+H]) + =254)

[0322] Manufacturing Example 62

[0323]

[0324] Compound Da-2 was prepared by the same method as in Manufacturing Example 61, except that 2-bromo-6-chloroquinoline-3-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0325] Manufacturing Example 63

[0326]

[0327] The compound Da-3 was prepared by the same method as in Manufacturing Example 61, except that 2-bromo-7-chloroquinoline-3-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0328] Manufacturing Example 64

[0329]

[0330] Compound Da-4 was prepared by the same method as in Manufacturing Example 61, except that 2-bromo-8-chloroquinoline-3-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0331] Manufacturing Example 65

[0332]

[0333] Compound Da-5 was prepared by the same method as in Manufacturing Example 61, except that 2-bromo-4-chloroquinoline-3-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0334] Manufacturing Example 66

[0335]

[0336] Compound Db-1 was prepared by the same method as in Manufacturing Example 61, except that 3-bromo-8-chloroquinoline-2-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0337] Manufacturing Example 67

[0338]

[0339] The compound Db-2 was prepared by the same method as in manufacturing example 61, except that 3-bromo-7-chloroquinoline-2-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0340] Manufacturing Example 68

[0341]

[0342] The compound Db-3 was prepared by the same method as in manufacturing example 61, except that 3-bromo-6-chloroquinoline-2-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0343] Manufacturing Example 69

[0344]

[0345] The compound Db-4 was otherwise manufactured by the same method as in manufacturing example 61, except that 3-bromo-5-chloroquinoline-2-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0346] Manufacturing Example 70

[0347]

[0348] The compound Db-5 was otherwise manufactured by the same method as in manufacturing example 61, except that 3-bromo-4-chloroquinoline-2-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0349] Manufacturing Example 71

[0350]

[0351] Compound Dc-1 was prepared by the same method as in Manufacturing Example 61, except that 6-bromo-2-chloroquinoline-7-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0352] Manufacturing Example 72

[0353]

[0354] Compound Dc-2 was prepared by the same method as in Manufacturing Example 61, except that 6-bromo-3-chloroquinoline-7-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0355] Manufacturing Example 73

[0356]

[0357] The compound Dc-3 was prepared by the same method as in manufacturing example 61, except that 6-bromo-4-chloroquinoline-7-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0358] Manufacturing Example 74

[0359]

[0360] Compound Dc-4 was prepared by the same method as in Manufacturing Example 61, except that 6-bromo-5-chloroquinoline-7-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0361] Manufacturing Example 75

[0362]

[0363] Compound Dc-5 was prepared by the same method as in Manufacturing Example 61, except that 6-bromo-8-chloroquinoline-7-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0364] Manufacturing Example 76

[0365]

[0366] Compound Dd-1 was prepared by the same method as in Manufacturing Example 61, except that 6-bromo-1-chloroisoquinoline-7-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0367] Manufacturing Example 77

[0368]

[0369] The compound Dd-2 was prepared by the same method as in manufacturing example 61, except that 6-bromo-3-chloroisoquinoline-7-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0370] Manufacturing Example 78

[0371]

[0372] The compound Dd-3 was prepared by the same method as in manufacturing example 61, except that 6-bromo-4-chloroisoquinoline-7-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0373] Manufacturing Example 79

[0374]

[0375] The compound Dd-4 was otherwise manufactured by the same method as in manufacturing example 61, except that 6-bromo-5-chloroisoquinoline-7-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0376] Manufacturing Example 80

[0377]

[0378] The compound Dd-5 was otherwise manufactured by the same method as in Manufacturing Example 61, except that 6-bromo-8-chloroisoquinoline-7-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0379] Manufacturing Example 81

[0380]

[0381] Compound De-1 was prepared by the same method as in Manufacturing Example 61, except that 7-bromo-4-chloroisoquinoline-6-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0382] Manufacturing Example 82

[0383]

[0384] Compound De-2 was prepared by the same method as in Manufacturing Example 61, except that 7-bromo-3-chloroisoquinoline-6-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0385] Manufacturing Example 83

[0386]

[0387] The compound De-3 was prepared by the same method as in manufacturing Example 61, except that 7-bromo-1-chloroisoquinoline-6-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0388] Manufacturing Example 84

[0389]

[0390] The compound De-4 was prepared by the same method as in manufacturing Example 61, except that 7-bromo-8-chloroisoquinoline-6-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0391] Manufacturing Example 85

[0392]

[0393] The compound De-5 was prepared by the same method as in manufacturing Example 61, except that 7-bromo-5-chloroisoquinoline-6-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0394] Manufacturing Example 86

[0395]

[0396] Compound Df-1 was prepared by the same method as in Manufacturing Example 61, except that 7-bromo-4-chloroquinoline-6-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0397] Manufacturing Example 87

[0398]

[0399] Compound Df-2 was prepared by the same method as in Manufacturing Example 61, except that 7-bromo-3-chloroquinoline-6-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0400] Manufacturing Example 88

[0401]

[0402] The compound Df-3 was otherwise manufactured by the same method as in manufacturing example 61, except that 7-bromo-2-chloroquinoline-6-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0403] Manufacturing Example 89

[0404]

[0405] The compound Df-4 was prepared by the same method as in manufacturing example 61, except that 7-bromo-8-chloroquinoline-6-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0406] Manufacturing Example 90

[0407]

[0408] The compound Df-5 was otherwise manufactured by the same method as in manufacturing example 61, except that 7-bromo-5-chloroquinoline-6-amine was used instead of 2-bromo-5-chloroquinoline-3-amine.

[0409] [Synthesis example]

[0410] Synthesis example 1

[0411]

[0412] Under a nitrogen atmosphere, compound Aa-1 (10 g, 39.4 mmol), amine 1 (15.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 14.6 g of compound 1. (Yield 63%, MS: [M+H)) + =589)

[0413] Synthesis example 2

[0414]

[0415] Under a nitrogen atmosphere, compound Aa-2 (10 g, 39.4 mmol), amine 2 (13.3 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 14.6 g of compound 2. (Yield 69%, MS: [M+H)) + =539)

[0416] Synthesis example 3

[0417]

[0418] Under a nitrogen atmosphere, compound Aa-3 (10 g, 39.4 mmol), amine 3 (23.2 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 17.8 g of compound 3. (Yield 58%, MS: [M+H)) + =779)

[0419] Synthesis example 4

[0420]

[0421] Under a nitrogen atmosphere, compound Aa-3 (10 g, 39.4 mmol), amine 4 (17.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 16.9 g of compound 4. (Yield 67%, MS: [M+H)) + =639)

[0422] Synthesis example 5

[0423]

[0424] Under a nitrogen atmosphere, compound Ab-1 (10 g, 39.4 mmol), amine 5 (17 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 17.6 g of compound 5. (Yield 71%, MS: [M+H)) + =628)

[0425] Synthesis example 6

[0426]

[0427] Under a nitrogen atmosphere, compound Ab-2 (10 g, 39.4 mmol), amine 6 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 18.9 g of compound 6. (Yield 72%, MS: [M+H)) + =665)

[0428] Synthesis Example 7

[0429]

[0430] Under a nitrogen atmosphere, compound Ab-2 (10 g, 39.4 mmol), amine 7 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 18.1 g of compound 7. (Yield 69%, MS: [M+H)) + =665)

[0431] Synthesis example 8

[0432]

[0433] Under a nitrogen atmosphere, compound Ab-2 (10 g, 39.4 mmol), amine 8 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 16.2 g of compound 8. (Yield 62%, MS: [M+H)) + =665)

[0434] Synthesis example 9

[0435]

[0436] Under a nitrogen atmosphere, compound Ab-2 (10 g, 39.4 mmol), amine 9 (14.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 14.3 g of compound 9. (Yield 64%, MS: [M+H)) + =567)

[0437] Synthesis example 10

[0438]

[0439] Under a nitrogen atmosphere, compound Ac-1 (10 g, 39.4 mmol), amine 10 (13.9 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 13.1 g of compound 10. (Yield 60%, MS: [M+H)) + =553)

[0440] Synthesis example 11

[0441]

[0442] Under a nitrogen atmosphere, compound Ac-2 (10 g, 39.4 mmol), amine 11 (17.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 15.3 g of compound 11. (Yield 61%, MS: [M+H)) + =639)

[0443] Synthesis example 12

[0444]

[0445] Under a nitrogen atmosphere, compound Ac-2 (10 g, 39.4 mmol), amine 12 (15.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 13.7 g of compound 12. (Yield 59%, MS: [M+H)) + =589)

[0446] Synthesis example 13

[0447]

[0448] Under a nitrogen atmosphere, compound Ad-2 (10 g, 39.4 mmol), amine 13 (14.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 14.6 g of compound 13. (Yield 65%, MS: [M+H)) + =569)

[0449] Synthesis example 14

[0450]

[0451] Under a nitrogen atmosphere, compound Ad-1 (10 g, 39.4 mmol), amine 14 (16.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 15 g of compound 14. (Yield 62%, MS: [M+H)) + =615)

[0452] Synthesis Example 15

[0453]

[0454] Under a nitrogen atmosphere, compound Ba-1 (10 g, 39.4 mmol), amine 15 (15.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 14.8 g of compound 15. (Yield 64%, MS: [M+H)) + =589)

[0455] Synthesis Example 16

[0456]

[0457] Under a nitrogen atmosphere, compound Ba-3 (10 g, 39.4 mmol), amine 16 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 15.4 g of compound 16. (Yield 59%, MS: [M+H)) + =665)

[0458] Synthesis Example 17

[0459]

[0460] Under a nitrogen atmosphere, compound Bb-1 (10 g, 39.4 mmol), amine 17 (14.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 15.7 g of compound 17. (Yield 70%, MS: [M+H)) + =569)

[0461] Synthesis example 18

[0462]

[0463] Under a nitrogen atmosphere, compound Bb-2 (10 g, 39.4 mmol), amine 18 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 18.6 g of compound 18. (Yield 71%, MS: [M+H)) + =665)

[0464] Synthesis example 19

[0465]

[0466] Under a nitrogen atmosphere, compound Bb-3 (10 g, 39.4 mmol), amine 19 (16.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 ml) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 17.2 g of compound 19. (Yield 71%, MS: [M+H)) + =615)

[0467] Synthesis example 20

[0468]

[0469] Under a nitrogen atmosphere, compound Bb-4 (10 g, 39.4 mmol), amine 20 (13.9 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 14.6 g of compound 20. (Yield 67%, MS: [M+H)) + =553)

[0470] Synthesis Example 21

[0471]

[0472] Under a nitrogen atmosphere, compound Bc-1 (10 g, 39.4 mmol), amine 21 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 15.2 g of compound 21. (Yield 58%, MS: [M+H)) + =665)

[0473] Synthesis example 22

[0474]

[0475] Under a nitrogen atmosphere, compound Bc-2 (10 g, 39.4 mmol), amine 22 (16.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 14.3 g of compound 22. (Yield 59%, MS: [M+H)) + =615)

[0476] Synthesis example 23

[0477]

[0478] Under a nitrogen atmosphere, compound Bc-2 (10 g, 39.4 mmol), amine 23 (17.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 16.1 g of compound 23. (Yield 64%, MS: [M+H)) + =639)

[0479] Synthesis example 24

[0480]

[0481] Under a nitrogen atmosphere, compound Bc-3 (10 g, 39.4 mmol), amine 24 (15 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 16 g of compound 24. (Yield 70%, MS: [M+H)) + =579)

[0482] Synthesis example 25

[0483]

[0484] Under a nitrogen atmosphere, compound Bd-1 (10 g, 39.4 mmol), amine 25 (15.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 16 g of compound 25. (Yield 69%, MS: [M+H)) + =589)

[0485] Synthesis Example 26

[0486]

[0487] Under a nitrogen atmosphere, compound Bd-2 (10 g, 39.4 mmol), amine 26 (17.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 15.6 g of compound 26. (Yield 62%, MS: [M+H)) + =639)

[0488] Synthesis Example 27

[0489]

[0490] Under a nitrogen atmosphere, compound Bd-3 (10 g, 39.4 mmol), amine 27 (17.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 17.9 g of compound 27. (Yield 71%, MS: [M+H)) + =639)

[0491] Synthesis example 28

[0492]

[0493] Under a nitrogen atmosphere, compound Be-2 (10 g, 39.4 mmol), amine 21 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 18.9 g of compound 28. (Yield 72%, MS: [M+H)) + =665)

[0494] Synthesis Example 29

[0495]

[0496] Under a nitrogen atmosphere, compound Be-3 (10 g, 39.4 mmol), amine 28 (19.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 18.4 g of compound 29. (Yield 68%, MS: [M+H)) + =689)

[0497] Synthesis example 30

[0498]

[0499] Under a nitrogen atmosphere, compound Be-4 (10 g, 39.4 mmol), amine 29 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 ml) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 16 g of compound 30. (Yield 61%, MS: [M+H)) + =665)

[0500] Synthesis Example 31

[0501]

[0502] Under a nitrogen atmosphere, compound Be-4 (10 g, 39.4 mmol), amine 30 (17.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 15.3 g of compound 31. (Yield 61%, MS: [M+H)) + =639)

[0503] Synthesis example 32

[0504]

[0505] Under a nitrogen atmosphere, compound Bf-1 (10 g, 39.4 mmol), amine 31 (19.6 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 16.3 g of compound 32. (Yield 60%, MS: [M+H)) + =691)

[0506] Synthesis example 33

[0507]

[0508] Under a nitrogen atmosphere, compound Bf-2 (10 g, 39.4 mmol), amine 32 (15.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 15.1 g of compound 33. (Yield 65%, MS: [M+H)) + =589)

[0509] Synthesis example 34

[0510]

[0511] Under a nitrogen atmosphere, compound Bf-4 (10 g, 39.4 mmol), amine 33 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 18.1 g of compound 34. (Yield 69%, MS: [M+H)) + =665)

[0512] Synthesis Example 35

[0513]

[0514] Under a nitrogen atmosphere, compound Ca-1 (10 g, 39.4 mmol), amine 34 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 ml) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 18.3 g of compound 35. (Yield 70%, MS: [M+H)) + =665)

[0515] Synthesis Example 36

[0516]

[0517] Under a nitrogen atmosphere, compound Ca-2 (10 g, 39.4 mmol), amine 14 (16.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 ml) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 15.3 g of compound 36. (Yield 63%, MS: [M+H)) + =615)

[0518] Synthesis Example 37

[0519]

[0520] Under a nitrogen atmosphere, compound Ca-5 (10 g, 39.4 mmol), amine 35 (17.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 17.4 g of compound 37. (Yield 69%, MS: [M+H)) + =639)

[0521] Synthesis example 38

[0522]

[0523] Under a nitrogen atmosphere, compound Cb-1 (10 g, 39.4 mmol), amine 6 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 18.1 g of compound 38. (Yield 69%, MS: [M+H)) + =665)

[0524] Synthesis Example 39

[0525]

[0526] Under a nitrogen atmosphere, compound Cb-4 (10 g, 39.4 mmol), amine 8 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 16.5 g of compound 39. (Yield 63%, MS: [M+H)) + =665)

[0527] Synthesis Example 40

[0528]

[0529] Under a nitrogen atmosphere, compound Cc-5 (10 g, 39.4 mmol), amine 7 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 15.7 g of compound 40. (Yield 60%, MS: [M+H)) + =665)

[0530] Synthesis Example 41

[0531]

[0532] Under a nitrogen atmosphere, compound Cc-5 (10 g, 39.4 mmol), amine 36 (20.6 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 ml) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 17.7 g of compound 41. (Yield 63%, MS: [M+H)) + =715)

[0533] Synthesis Example 42

[0534]

[0535] Under a nitrogen atmosphere, compound Cd-1 (10 g, 39.4 mmol), amine 37 (15.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 ml) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 16 g of compound 42. (Yield 69%, MS: [M+H)) + =589)

[0536] Synthesis Example 43

[0537]

[0538] Under a nitrogen atmosphere, compound Cd-2 (10 g, 39.4 mmol), amine 25 (15.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 14.6 g of compound 43. (Yield 63%, MS: [M+H)) + =589)

[0539] Synthesis Example 44

[0540]

[0541] Under a nitrogen atmosphere, compound Cd-3 (10 g, 39.4 mmol), amine 38 (15.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 13.7 g of compound 44. (Yield 59%, MS: [M+H)) + =589)

[0542] Synthesis Example 45

[0543]

[0544] Under a nitrogen atmosphere, compound Cd-4 (10 g, 39.4 mmol), amine 21 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 ml) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 17 g of compound 45. (Yield 65%, MS: [M+H)) + =665)

[0545] Synthesis Example 46

[0546]

[0547] Under a nitrogen atmosphere, compound Cd-6 (10 g, 39.4 mmol), amine 25 (15.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 ml) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 16.5 g of compound 46. (Yield 71%, MS: [M+H)) + =589)

[0548] Synthesis Example 47

[0549]

[0550] Under a nitrogen atmosphere, compound Da-5 (10 g, 39.4 mmol), amine 39 (17.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 15.1 g of compound 47. (Yield 60%, MS: [M+H)) + =639)

[0551] Synthesis Example 48

[0552]

[0553] Under a nitrogen atmosphere, compound Db-1 (10 g, 39.4 mmol), amine 40 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 ml) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 17.3 g of compound 48. (Yield 66%, MS: [M+H)) + =665)

[0554] Synthesis Example 49

[0555]

[0556] Under a nitrogen atmosphere, compound Db-2 (10 g, 39.4 mmol), amine 36 (20.6 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 ml) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 19.7 g of compound 49. (Yield 70%, MS: [M+H)) + =715)

[0557] Synthesis example 50

[0558]

[0559] Under a nitrogen atmosphere, compound Db-3 (10 g, 39.4 mmol), amine 41 (17.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 15.8 g of compound 50. (Yield 63%, MS: [M+H)) + =639)

[0560] Synthesis Example 51

[0561]

[0562] Under a nitrogen atmosphere, compound Db-4 (10 g, 39.4 mmol), amine 42 (17.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 14.8 g of compound 51. (Yield 59%, MS: [M+H)) + =639)

[0563] Synthesis example 52

[0564]

[0565] Under a nitrogen atmosphere, compound Dc-2 (10 g, 39.4 mmol), amine 43 (18.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 ml) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 16.5 g of compound 52. (Yield 63%, MS: [M+H)) + =665)

[0566] Synthesis example 53

[0567]

[0568] Under a nitrogen atmosphere, compound Dc-4 (10 g, 39.4 mmol), amine 44 (17.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL), stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 16.3 g of compound 53. (Yield 65%, MS: [M+H)) + =637)

[0569] Synthesis example 54

[0570]

[0571] Under a nitrogen atmosphere, compound Dd-3 (10 g, 39.4 mmol), amine 45 (17.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 15.3 g of compound 54. (Yield 61%, MS: [M+H)) + =639)

[0572] Synthesis Example 55

[0573]

[0574] Under a nitrogen atmosphere, compound Dd-5 (10 g, 39.4 mmol), amine 1 (15.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 ml) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 14.4 g of compound 55. (Yield 62%, MS: [M+H)) + =589)

[0575] Synthesis Example 56

[0576]

[0577] Under a nitrogen atmosphere, compound De-1 (10 g, 39.4 mmol), amine 30 (17.4 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 16.4 g of compound 56. (Yield 65%, MS: [M+H)) + =639)

[0578] Synthesis Example 57

[0579]

[0580] Under a nitrogen atmosphere, compound De-4 (10 g, 39.4 mmol), amine 46 (13.3 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 2 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 12.7 g of compound 57. (Yield 60%, MS: [M+H)) + =539)

[0581] Synthesis example 58

[0582]

[0583] Under a nitrogen atmosphere, compound Df-2 (10 g, 39.4 mmol), amine 47 (16.5 g, 41.4 mmol), and sodium tert-butoxide (4.9 g, 51.2 mmol) were added to xylene (200 mL) and stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then 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 concentrated compound was purified by silica gel column chromatography to give 14.8 g of compound 58. (Yield 61%, MS: [M+H)) + =615)

[0584] Experimental Example

[0585] Example 1

[0586] 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.

[0587] 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 of... A second hole transport layer is formed by vacuum evaporation of compound 1. Then, on compound 1, compound RH-1 is used as the host and compound Dp-7 is used as the dopant in a weight ratio of 98:2 by vacuum evaporation 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.

[0588]

[0589] During the above process, the evaporation rate of organic matter is maintained. / second, lithium fluoride at the cathode maintains Evaporation rate of / second, aluminum maintains A vapor deposition rate of / second is achieved, while maintaining a vacuum level of 2×10⁻⁶ during vapor deposition. -7 ~5×10 -6 This led to the creation of organic light-emitting devices.

[0590] Examples 2 to 58

[0591] In the organic light-emitting device of Example 1, compound 1 was replaced by the compound listed in Table 1 below. Otherwise, the organic light-emitting device was manufactured by the same method as in Example 1 above.

[0592] Comparative Examples 1 to 14

[0593] In the organic light-emitting device of Example 1, compound 1 was replaced by the compound listed in Table 1 below. Otherwise, the organic light-emitting device was manufactured by the same method as in Comparative Example 1 above.

[0594]

[0595] When an electric current was applied to the organic light-emitting devices manufactured in Examples 1 to 58 and Comparative Examples 1 to 14, the voltage and efficiency (15 mA / cm²) were measured. 2 The results are shown in Tables 1 to 4 below. Lifetime T95 refers to the time required for the brightness to decrease from the initial brightness (6000 nits) to 95%.

[0596] [Table 1]

[0597] Differentiation Substance Driving voltage (V) Efficiency (cd / A) Lifetime T95 (hr) Emission color Example 1 Compound 1 3.61 21.17 143 Red Example 2 Compound 2 3.65 21.42 130 Red Example 3 Compound 3 3.62 24.19 134 Red Example 4 Compound 4 3.62 20.25 140 Red Example 5 Compound 5 3.60 22.71 141 Red Example 6 Compound 6 3.59 21.18 131 Red Example 7 Compound 7 3.63 21.51 137 Red Example 8 Compound 8 3.61 19.97 129 Red Example 9 Compound 9 3.64 21.75 139 Red Example 10 Compound 10 3.65 23.77 138 Red Example 11 Compound 11 3.57 21.17 147 Red Example 12 Compound 12 3.56 21.42 167 Red Example 13 Compound 13 3.57 24.19 138 Red Example 14 Compound 14 3.53 20.25 158 Red Example 15 Compound 15 3.53 22.71 150 Red Example 16 Compound 16 3.57 21.18 167 Red Example 17 Compound 17 3.61 21.51 142 Red Example 18 Compound 18 3.55 19.97 150 Red Example 19 Compound 19 3.58 21.75 146 Red Example 20 Compound 20 3.52 23.77 146 Red

[0598] [Table 2]

[0599] Differentiation Substance Driving voltage (V) Efficiency (cd / A) Lifetime T95 (hr) Emission color Example 21 Compound 21 3.61 20.90 183 Red Example 22 Compound 22 3.65 21.41 171 Red Example 23 Compound 23 3.62 21.25 185 Red Example 24 Compound 24 3.62 20.65 181 Red Example 25 Compound 25 3.60 20.92 176 Red Example 26 Compound 26 3.59 20.70 173 Red Example 27 Compound 27 3.63 21.57 184 Red Example 28 Compound 28 3.61 20.82 165 Red Example 29 Compound 29 3.64 21.09 185 Red Example 30 Compound 30 3.65 21.35 163 Red Example 31 Compound 31 3.77 19.72 133 Red Example 32 Compound 32 3.72 19.43 128 Red Example 33 Compound 33 3.67 19.39 131 Red Example 34 Compound 34 3.75 19.77 136 Red Example 35 Compound 35 3.69 19.91 129 Red Example 36 Compound 36 3.67 18.06 134 Red Example 37 Compound 37 3.68 18.97 139 Red Example 38 Compound 38 3.71 18.99 130 Red Example 39 Compound 39 3.75 19.74 129 Red Example 40 Compound 40 3.65 19.37 129 Red

[0600] [Table 3]

[0601] Differentiation Substance Driving voltage (V) Efficiency (cd / A) Lifetime T95 (hr) Emission color Example 41 Compound 41 3.64 21.21 175 Red Example 42 Compound 42 3.64 20.29 170 Red Example 43 Compound 43 3.65 21.47 184 Red Example 44 Compound 44 3.62 21.40 166 Red Example 45 Compound 45 3.64 21.63 172 Red Example 46 Compound 46 3.60 21.62 185 Red Example 47 Compound 47 3.75 18.62 141 Red Example 48 Compound 48 3.66 18.34 132 Red Example 49 Compound 49 3.71 18.32 130 Red Example 50 Compound 50 3.73 18.57 143 Red Example 51 Compound 51 3.71 18.47 138 Red Example 52 Compound 52 3.68 19.73 143 Red Example 53 Compound 53 3.70 19.56 142 Red Example 54 Compound 54 3.78 18.89 141 Red Example 55 Compound 55 3.69 18.20 130 Red Example 56 Compound 56 3.69 18.37 128 Red Example 57 Compound 57 3.66 21.39 182 Red Example 58 Compound 58 3.63 21.27 163 Red

[0602] [Table 4]

[0603] Differentiation Substance Driving voltage (V) Efficiency (cd / A) Lifetime T95 (hr) Emission color Comparative Example 1 C-1 3.99 16.63 97 Red Comparative Example 2 C-2 3.88 16.86 92 Red Comparative Example 3 C-3 3.89 16.99 96 Red Comparative Example 4 C-4 3.93 16.69 74 Red Comparative Example 5 C-5 3.94 16.63 96 Red Comparative Example 6 C-6 4.16 15.02 72 Red Comparative Example 7 C-7 4.08 15.19 98 Red Comparative Example 8 C-8 4.15 15.00 87 Red Comparative Example 9 C-9 4.13 15.21 73 Red Comparative Example 10 C-10 4.14 14.77 95 Red Comparative Example 11 C-11 4.07 16.12 88 Red Comparative Example 12 C-12 4.23 14.13 53 Red Comparative Example 13 C-13 4.29 11.77 29 Red Comparative Example 14 C-14 4.21 13.24 47 Red

[0604] When current was applied to the organic light-emitting devices (OLEDs) fabricated according to Examples 1 to 58 and Comparative Examples 1 to 14, the results shown in Tables 1 to 4 were obtained. The red OLED of Example 1 used a conventionally widely used material, a structure in which Dp-7 was used as the dopant for the red light-emitting layer. Comparative Examples 1 to 14 used C-1 to C-14 instead of Compound 1 to fabricate OLEDs. From the results in Tables 1 to 4, it can be seen that when the compound of the present invention is used as the second hole transport layer, the driving voltage is significantly reduced compared to the comparative example materials, and the efficiency is also improved, thus achieving good energy transfer from the host to the red dopant. Furthermore, it can be seen that while maintaining high efficiency, lifetime characteristics can also be significantly improved. This can be attributed to the higher stability of the compound of the present invention for electrons and holes compared to the comparative example compounds. In conclusion, it can be confirmed that using the compound of the present invention as the second hole transport layer can improve the driving voltage, luminous efficiency, and lifetime characteristics of the OLED.

[0605] [Symbol Explanation]

[0606] 1: Substrate 2: Anode

[0607] 3: Light-emitting layer 4: Cathode

[0608] 5: Hole injection layer; 6: Hole transport layer

[0609] 7: Light-emitting layer; 8: Electron injection and transport layer.

Claims

1. A compound represented by the following chemical formula 1: ， In the chemical formula 1, X1 to X 10 One of them is N, and the rest are CR1. One of R1 is a substituent represented by the following chemical formula 2, and the rest are hydrogen or deuterium. ， In the chemical formula 2, L1 represents C that is directly bonded, substituted, or unsubstituted. 6-60 Alpha-aryl L2 is a directly bonded, substituted, or unsubstituted C. 6-60 Alpha-aryl Ar1 represents substituted or unsubstituted C. 6-60 aryl, or substituted or unsubstituted C 5-60 Mixed aromatics, Ar2 is C with or without substitution. 6-60 aryl, or substituted or unsubstituted C 5-60 heteroaryl, and "Substituted or unsubstituted" means substituted with one or more substituents selected from phenyl, naphthyl, methyl, biphenyl, phenanthryl, phenylnaphthyl, naphthylphenyl, dibenzofuranyl, and dibenzothiophene.

2. The compound according to claim 1, wherein, L1 can be directly bonded, phenylene, biphenylene, terphenylene, naphthylene, 9,9-dimethylfluorene, or 9,9-diphenylfluorene.

3. The compound according to claim 1, wherein, L2 can be directly bonded, phenylene, biphenylene, terphenylene, naphthylene, 9,9-dimethylfluorene, or 9,9-diphenylfluorene.

4. The compound according to claim 1, wherein, Ar1 is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, phenylnaphthyl, naphthylphenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9'-spirodi[9H-fluoren]yl, dibenzofuranyl, dibenzothiopheneyl or 9-phenyl-carbazoyl.

5. The compound according to claim 1, wherein, Ar2 is phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, phenylnaphthyl, naphthylphenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9'-spirodi[9H-fluoren]yl, dibenzofuranyl, dibenzothiopheneyl or 9-phenyl-carbazoyl.

6. The compound according to claim 1, wherein, In the chemical formula 1, CR1, represented by chemical formula 2, is attached to one of X1 to X4.

7. The compound according to claim 1, wherein, The compound represented by the chemical formula 1 is selected from any one of the following: 。 8. An organic light-emitting device, wherein, include: A first electrode, a second electrode disposed opposite to the first electrode, and an organic layer disposed between the first electrode and the second electrode, the organic layer comprising the compound of any one of claims 1 to 7.

9. The organic light-emitting device according to claim 8, wherein, The organic layer containing the compound is an electron-emitting layer.

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