Novel compound and organic light-emitting device comprising same

Abstract

The present invention relates to a novel organic light-emitting material and an organic light-emitting device comprising the same.

Description

Technical Field

[0001] Cross-reference with related applications

[0002] This application claims priority based on Korean Patent Application No. 10-2024-0039153 dated March 21, 2024 and Korean Patent Application No. 10-2025-0036452 dated March 21, 2025, the entire contents disclosed in those Korean patent applications being incorporated into this specification.

[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, they form excitons, which emit light when they re-enter the ground state.

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

[0007] Existing technical documents

[0008] Patent documents

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

[0010] Technical issues

[0011] This invention relates to novel organic light-emitting materials and organic light-emitting devices containing the same.

[0012] Solution to the problem

[0013] This invention provides compounds represented by the following chemical formula 1:

[0014] [Chemical Formula 1]

[0015]

[0016] In the above chemical formula 1,

[0017] Dn represents n hydrogen atoms replaced by deuterium.

[0018] n is an integer greater than or equal to 0.

[0019] A is a phenyl group that is either unsubstituted or substituted with one or more deuterium groups, or a naphthyl group that is either unsubstituted or substituted with one or more deuterium groups.

[0020] L1 and L2 are each independently a single bond, a phenylene group, or a naphthyl group, wherein the aforementioned phenylene group and naphthyl group are each independently unsubstituted or substituted by one or more of a group selected from deuterium, an unsubstituted or deuterated phenyl group, and an unsubstituted or deuterated naphthyl group.

[0021] Ar1 and Ar2 are each independently of C 1-10 Alkyl-substituted phenyl, biphenyl, terphenyl, naphthyl, benzo[c]phenanthrene, phenylnaphthyl, naphthylphenyl, or any one of the following groups, wherein the above is C 1-10 Alkyl-substituted phenyl groups are either unsubstituted or deuterated, and the aforementioned biphenyl, terphenyl, naphthyl, benzo[c]phenanthrene, phenylnaphthyl, naphthylphenyl, and the following groups are each independently unsubstituted or selected from deuterium and unsubstituted or deuterated C groups. 1-10 Any one or more substitutions in the alkyl group:

[0022]

[0023] In addition, 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 chemical formula 1.

[0024] Invention Effects

[0025] 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 transport assistance, light emission, hole blocking, electron transport, and / or electron injection. Attached Figure Description

[0026] Figure 1The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, an organic layer 3, and a cathode 4.

[0027] Figure 2 The illustration shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a hole transport auxiliary layer 7, a light-emitting layer 8, a hole blocking layer 9, an electron transport and injection layer 10, 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. Detailed Implementation

[0028] The invention will now be described in more detail to aid in understanding.

[0029] The present invention provides compounds represented by the above chemical formula 1.

[0030] In this instruction manual, or This indicates a bond that is linked to other substituents.

[0031] In this specification, the term "substituted or unsubstituted" refers to a group selected from deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thio group ( ); aryl thio ( ); alkylsulfonyl ( ); arylsulfonyl ( ); silyl; boronyl; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; arylenyl; 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. As an example, the term "substituted or unsubstituted" can be understood as "unsubstituted or selected from deuterium; halogen; C 1-10 Alkyl; C 1-10 Alkoxy; C 6-20 aryl; and C containing one or more heteroatoms of N, O and S. 2-20 The phrase "replaced by one or more substituents" in this specification can be understood as, for example, "replaced by one to five substituents" or "replaced by one or two substituents."

[0032] 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 substituent with the following structures, but is not limited thereto.

[0033]

[0034] In this specification, the oxygen atom in the ester group may 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 may be a substituent of the structure described below, but is not limited thereto.

[0035]

[0036] 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 substituent with the following structures, but is not limited to them.

[0037]

[0038] In this specification, silanes specifically include trimethylsilane, triethylsilane, tert-butyldimethylsilane, vinyldimethylsilane, propyldimethylsilane, triphenylsilane, diphenylsilane, phenylsilane, etc., but are not limited to these.

[0039] In this specification, the boron group specifically includes trimethylboryl, triethylboryl, tert-butyldimethylboryl, triphenylboryl, phenylboryl, etc., but is not limited to these.

[0040] Examples of halogen groups in this specification include fluorine, chlorine, bromine, or iodine.

[0041] 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-dimethylpropyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but are not limited to these.

[0042] 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.

[0043] In this specification, the cycloalkyl group is not particularly limited, but it 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.

[0044] In this specification, the aryl group is not particularly limited, but it is preferably composed of 6 to 60 carbon atoms, and can be either a monocyclic aryl or a 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, peryl, thionyl, fluoreneyl, etc., but is not limited to these.

[0045] 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 be used to... Etc. But it is not limited to this.

[0046] In this specification, a heteroaryl group is a heteroaryl group containing one or more of O, N, Si, and S as heteroatoms. The number of carbon atoms is not particularly limited, but is preferably 2 to 60. According to one embodiment, the heteroaryl group has 6 to 30 carbon atoms. According to another embodiment, the heteroaryl group has 6 to 20 carbon atoms. Examples of heteroaryl groups include 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.

[0047] In this specification, the aryl groups in aralkyl, aryl-alkenyl, alkylaryl, and arylamine are the same as those exemplified above. In this specification, the alkyl groups in aralkyl, alkylaryl, and alkylamine are the same as those exemplified above. In this specification, the heteroaryl groups in heteroarylamines are subject to the above description of 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 description of aryl groups applies. In this specification, heteroarylene is a divalent group; otherwise, the above description of heteroaryl groups applies. In this specification, the hydrocarbon ring is not a monovalent group but is formed by the combination of two substituents; otherwise, the above description of aryl or cycloalkyl groups applies. In this specification, heteroaryl is not a monovalent group but is formed by the combination of two substituents; otherwise, the above description of heteroaryl groups applies.

[0048] Preferably, A can be phenyl or naphthyl.

[0049] Preferably, L1 and L2 are each independently a single bond, a phenylene, a phenylene substituted with one phenyl group, a phenylene substituted with two phenyl groups, or a naphthyl group, and L1 and L2 may each be unsubstituted or substituted with one or more deuterium groups.

[0050] Preferably, L1 and L2 are each independently selected from single bonds, phenylene, naphthyl, or any of the following groups, and the aforementioned phenylene, naphthyl, and the following groups can each be independently unsubstituted or substituted with one or more deuterium groups:

[0051] .

[0052] More preferably, L1 and L2 can each independently be a single bond, or an unsubstituted or deuterated phenylene.

[0053] Preferably, Ar1 and Ar2 can each be independently selected from C 1-5 Alkyl-substituted phenyl, biphenyl, terphenyl, naphthyl, benzo[c]phenanthrene, phenylnaphthyl, naphthylphenyl, or any one of the following groups, wherein the above is C 1-10 Alkyl-substituted phenyl groups may be unsubstituted or deuterated. The aforementioned biphenyl, terphenyl, naphthyl, benzo[c]phenanthrene, phenylnaphthyl, naphthylphenyl, and the following groups may each be unsubstituted, selected from deuterium, and unsubstituted or deuterated C- groups. 1-5 Any one or more substitutions in the alkyl group,

[0054] .

[0055] Preferably, Ar1 and Ar2 can each independently be a phenyl group selected from one or more substituted groups selected from methyl, isopropyl, and tert-butyl; biphenyl; terphenyl; naphthyl; benzo[c]phenanthrene; hydroxyl; phenylnaphthyl; naphthylphenyl; or any of the following groups, wherein Ar1 and Ar2 can each independently be unsubstituted or deuterated.

[0056] .

[0057] Preferably, Ar1 and Ar2 can each independently be selected from phenyl, phenyl substituted with one methyl group, phenyl substituted with two methyl groups, phenyl substituted with one isopropyl group, phenyl substituted with two isopropyl groups, phenyl substituted with one tert-butyl group, phenyl substituted with two tert-butyl groups, biphenyl, terphenyl, naphthyl, benzo[c]phenanthryl, hydroxyl, phenylnaphthyl, naphthylphenyl, or any of the following groups, wherein Ar1 and Ar2 can each independently be unsubstituted or substituted with one or more deuterium groups.

[0058] .

[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]

[0095]

[0096]

[0097] 。

[0098] As an example, the compound represented by the above chemical formula 1 can be manufactured by the manufacturing method shown in reaction formula 1 below, and other compounds can be manufactured in a similar manner.

[0099] [Reaction Formula 1]

[0100]

[0101] In the above reaction formula 1, D, n, A, L1, L2, Ar1 and Ar2 are defined as in the above chemical formula 1, and X is a halogen, preferably chlorine or bromine.

[0102] In reaction formula 1 above, step 1 is an amine substitution reaction, preferably carried out in the presence of a palladium catalyst and a base. The reactive group used for the amine substitution reaction can be modified according to techniques known in the art. In reaction formula 1 above, step 2 is a deuterium substitution reaction, which can be modified according to techniques known in the art. In this case, the compound with n=0 that is not substituted by deuterium can omit step 2 in reaction formula 1 for manufacturing. The above manufacturing method can be further specified in the manufacturing examples described later.

[0103] 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.

[0104] 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 hole transport auxiliary layer, a light-emitting layer, a hole blocking layer, an electron transport and injection layer, etc., as organic layers. However, the structure of the organic light-emitting device is not limited to this, and may include fewer organic layers.

[0105] In addition, the aforementioned organic layer may include a hole transport layer, a hole injection layer, a layer that performs both hole transport and hole injection, or a hole transport auxiliary layer. The aforementioned hole transport layer, hole injection layer, layer that performs both hole transport and hole injection, or hole transport auxiliary 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 Figure 2 middle.

[0107] Figure 1 The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, an organic layer 3, 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.

[0108] Figure 2 The illustration shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a hole transport auxiliary layer 7, a light-emitting layer 8, a hole blocking layer 9, an electron transport and injection layer 10, 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 a first electrode, an organic layer, and a second electrode 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 polymers 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 polymers 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 substance capable of receiving holes from the anode or hole injection layer and transferring them to the light-emitting layer; substances with high hole mobility are suitable. Specific examples include aryl amine-based organic compounds, conductive polymers, and block copolymers that simultaneously contain conjugated and non-conjugated portions, but are not limited to these.

[0118] The aforementioned hole transport auxiliary layer is an auxiliary layer between the hole transport layer and the light-emitting layer, used to facilitate hole transport and prevent light leakage. Through this auxiliary layer, holes are transported more smoothly from the hole transport layer to the light-emitting layer, while excitons are bound within the light-emitting layer, thereby preventing light leakage. Therefore, an organic electroluminescent device with excellent luminous efficiency can be realized. Preferably, a compound represented by the aforementioned chemical formula 1 can be used as the material for the hole transport auxiliary layer.

[0119] The aforementioned luminescent material is capable of receiving holes and electrons from the hole transport layer and electron transport layer, respectively, and combining them to emit light in the visible light region. Preferably, it is a material with high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxyquinoline aluminum complex (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.

[0120] The aforementioned luminescent layer may comprise a host material and a dopant material. The host material may be an aromatic fused-ring derivative or a heterocyclic compound. Specifically, aromatic fused-ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentane derivatives, phenanthrene compounds, and fluoranthene compounds; heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder-type furan compounds. ), pyrimidine derivatives, etc., but not limited to these.

[0121] As dopant materials, there are aromatic amine derivatives, styrene amine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives are aromatic fused-ring derivatives having substituted or unsubstituted aryl amino groups, such as pyrene, anthracene, benzo[a]pyrene, etc., having aryl amino groups. Styrene amine compounds are compounds in which at least one aryl vinyl group is substituted on a substituted or unsubstituted aryl amine, and is substituted or unsubstituted by one or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino groups. Specifically, there are styrene amines, styrene diamines, styrene triamines, styrene tetraamines, 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] The aforementioned hole-blocking layer refers to a layer formed on the light-emitting layer, preferably in contact with it, which improves the probability of hole-electron binding by adjusting electron mobility and preventing excessive hole migration, thereby improving the efficiency of the organic light-emitting device. The hole-blocking layer contains a hole-blocking material; examples of such materials include azazine derivatives containing triazine; triazole derivatives; Compounds containing electron-withdrawing groups, such as diazole derivatives, phenanthrene-rhein derivatives, and phosphine oxide derivatives, are included, but are not limited to these.

[0123] 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 are cesium, barium, calcium, ytterbium, and samarium, each accompanied by an aluminum or silver layer.

[0124] 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 material, prevent excitons generated in the light-emitting layer from migrating to the hole injection layer, and demonstrate excellent thin-film formation ability. Specifically, these include fluorenone, anthraquinone dimethyl ether, biphenylquinone, thiamethoxam dioxide, etc. azole, Diazoles, triazoles, imidazoles, perylenetetracarboxylic acids, fluorenemethane, anthrones, and their derivatives, metal coordination compounds, and nitrogen-containing five-membered ring derivatives, but not limited to these.

[0125] 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.

[0126] On the other hand, in this invention, the “electron injection and transport layer” is a layer that functions as both the electron injection layer and the electron transport layer, and can be a substance that functions as each of the above layers, either alone or in combination, but is not limited thereto.

[0127] 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.

[0128] In addition, the compound represented by the above chemical formula 1 can be included not only in organic light-emitting devices, but also in organic solar cells or organic transistors.

[0129] The present invention will now be described in more detail to aid in understanding. However, the following embodiments are merely illustrative of the invention, and the scope of the invention is not limited to these embodiments.

[0130] Manufacturing Example 1

[0131]

[0132] Under a nitrogen atmosphere, amine 1 (15 g, 35.6 mmol), sub compound 1 (11.6 g, 37.4 mmol), and sodium tert-butoxide (4.4 g, 46.3 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 16.7 g of compound 1. (Yield 72%, MS: [M+H]) + =651)

[0133] Manufacturing Example 2

[0134]

[0135] Under a nitrogen atmosphere, amine 2 (15 g, 37.7 mmol), compound 1 (12.3 g, 39.6 mmol), and sodium tert-butoxide (4.7 g, 49.1 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 17.7 g of compound 2. (Yield 75%, MS: [M+H)) + =627)

[0136] Manufacturing Example 3

[0137]

[0138] Under a nitrogen atmosphere, amine 3 (15 g, 31.7 mmol), compound 1 (10.3 g, 33.3 mmol), and sodium tert-butoxide (4 g, 41.2 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 13.6 g of compound 3. (Yield 61%, MS: [M+H)) + =703)

[0139] Manufacturing Example 4

[0140]

[0141] Under a nitrogen atmosphere, amine 4 (15 g, 28.8 mmol), compound 1 (9.3 g, 30.2 mmol), and sodium tert-butoxide (3.6 g, 37.4 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 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 15.5 g of compound 4. (Yield 72%, MS: [M+H]) + =751)

[0142] Manufacturing Example 5

[0143]

[0144] Under a nitrogen atmosphere, amine 5 (15 g, 37.7 mmol), compound 1 (12.3 g, 39.6 mmol), and sodium tert-butoxide (4.7 g, 49.1 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 17.5 g of compound 5. (Yield 74%, MS: [M+H]) + =627)

[0145] Manufacturing Example 6

[0146]

[0147] Under a nitrogen atmosphere, amine 6 (15 g, 33.5 mmol), compound 1 (10.9 g, 35.2 mmol), and sodium tert-butoxide (4.2 g, 43.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 17.7 g of compound 6. (Yield 78%, MS: [M+H]) + =677)

[0148] Manufacturing Example 7

[0149]

[0150] Under a nitrogen atmosphere, amine 7 (15 g, 34.3 mmol), compound 1 (11.1 g, 36 mmol), and sodium tert-butoxide (4.3 g, 44.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 15.5 g of compound 7. (Yield 66%, MS: [M+H)) + =687)

[0151] Manufacturing Example 8

[0152]

[0153] Under a nitrogen atmosphere, compound amine 8 (15 g, 34.3 mmol), compound 1 (11.1 g, 36 mmol), and sodium tert-butoxide (4.3 g, 44.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 16.9 g of compound 8. (Yield 74%, MS: [M+H)) + =667)

[0154] Manufacturing Example 9

[0155]

[0156] Under a nitrogen atmosphere, amine 9 (15 g, 30.5 mmol), compound 1 (9.9 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 obtain 13.8 g of compound 9. (Yield 63%, MS: [M+H)) + =721)

[0157] Manufacturing Example 10

[0158]

[0159] Under a nitrogen atmosphere, compound amine 10 (15 g, 46.7 mmol), compound 2 (17.6 g, 49 mmol), and sodium tert-butoxide (5.8 g, 60.7 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 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 22.1 g of compound 10. (Yield 79%, MS: [M+H)) + =601)

[0160] Manufacturing Example 11

[0161]

[0162] Under a nitrogen atmosphere, amine 11 (15 g, 33.5 mmol), compound 2 (12.6 g, 35.2 mmol), and sodium tert-butoxide (4.2 g, 43.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 obtain 14.8 g of compound 11. (Yield 61%, MS: [M+H)) + =727)

[0163] Manufacturing Example 12

[0164]

[0165] Under a nitrogen atmosphere, amine 12 (15 g, 33.5 mmol), compound 2 (12.6 g, 35.2 mmol), and sodium tert-butoxide (4.2 g, 43.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 obtain 16.5 g of compound 12. (Yield 68%, MS: [M+H)) + =727)

[0166] Manufacturing Example 13

[0167]

[0168] Under a nitrogen atmosphere, compound amine 13 (15 g, 31.8 mmol), compound 2 (12 g, 33.4 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 13. (Yield 75%, MS: [M+H)) + =751)

[0169] Manufacturing Example 14

[0170]

[0171] Under a nitrogen atmosphere, amine 14 (15 g, 33.5 mmol), compound 2 (12.6 g, 35.2 mmol), and sodium tert-butoxide (4.2 g, 43.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 14. (Yield 63%, MS: [M+H)) + =727)

[0172] Manufacturing Example 15

[0173]

[0174] Under a nitrogen atmosphere, compound amine 15 (15 g, 34.6 mmol), compound 2 (13 g, 36.3 mmol), and sodium tert-butoxide (4.3 g, 45 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 17.7 g of compound 15. (Yield 72%, MS: [M+H]) + =713)

[0175] Manufacturing Example 16

[0176]

[0177] Under a nitrogen atmosphere, compound amine 16 (15 g, 38.5 mmol), compound 2 (14.5 g, 40.4 mmol), and sodium tert-butoxide (4.8 g, 50 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 18.3 g of compound 16. (Yield 71%, MS: [M+H]) + =669)

[0178] Manufacturing Example 17

[0179]

[0180] Under a nitrogen atmosphere, amine 17 (15 g, 35.6 mmol), compound 3 (13.4 g, 37.4 mmol), and sodium tert-butoxide (4.4 g, 46.3 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 14.9 g of compound 17. (Yield 60%, MS: [M+H)) + =701)

[0181] Manufacturing Example 18

[0182]

[0183] Under a nitrogen atmosphere, compound amine 18 (15 g, 28.8 mmol), compound 3 (10.8 g, 30.2 mmol), and sodium tert-butoxide (3.6 g, 37.4 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 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 17.3 g of compound 18 (75% yield, MS: [M+H)). + =801)

[0184] Manufacturing Example 19

[0185]

[0186] Under a nitrogen atmosphere, compound amine 19 (15 g, 50.8 mmol), compound 3 (19.2 g, 53.3 mmol), and sodium tert-butoxide (6.3 g, 66 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 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 obtain 22.7 g of compound 19. (Yield 78%, MS: [M+H]) + =575)

[0187] Manufacturing Example 20

[0188]

[0189] Under a nitrogen atmosphere, amine 20 (15 g, 30.1 mmol), compound 3 (11.4 g, 31.6 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 17.8 g of compound 20 (yield 76%, MS: [M+H]+=777).

[0190] Manufacturing Example 21

[0191]

[0192] Under a nitrogen atmosphere, amine 21 (15 g, 34.8 mmol), compound 3 (13.1 g, 36.5 mmol), and sodium tert-butoxide (4.3 g, 45.2 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 obtain 17.5 g of compound 21. (Yield 71%, MS: [M+H)) + =711)

[0193] Manufacturing Example 22

[0194]

[0195] Under a nitrogen atmosphere, amine 22 (15 g, 30.6 mmol), compound 3 (11.6 g, 32.2 mmol), and sodium tert-butoxide (3.8 g, 39.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 obtain 18.6 g of compound 22. (Yield 79%, MS: [M+H]) + =769)

[0196] Manufacturing Example 23

[0197]

[0198] Under a nitrogen atmosphere, amine 23 (15 g, 38.9 mmol), compound 3 (14.7 g, 40.8 mmol), and sodium tert-butoxide (4.9 g, 50.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 20.4 g of compound 23. (Yield 79%, MS: [M+H)) + =665)

[0199] Manufacturing Example 24

[0200]

[0201] Under a nitrogen atmosphere, compound amine 24 (15 g, 31.7 mmol), compound 1 (10.3 g, 33.3 mmol), and sodium tert-butoxide (4 g, 41.2 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 15.6 g of compound 24_P1. (Yield 70%, MS: [M+H]) + =703)

[0202] Compound 24_P1 (10 g, 14.2 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (10.3 g, 512.9 mmol) was added to trifluoromethanesulfonic anhydride (24.1 g, 85.5 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, 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 obtain 7.2 g of compound 24 (yield 70%, MS: [M+H)). + =725)

[0203] Manufacturing Example 25

[0204]

[0205] Under a nitrogen atmosphere, compound amine 25 (15 g, 33.5 mmol), compound 1 (10.9 g, 35.2 mmol), and sodium tert-butoxide (4.2 g, 43.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 16.8 g of compound 25_P1. (Yield 74%, MS: [M+H]) + =677)

[0206] Compound 25_P1 (10 g, 14.8 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (10.7 g, 532.6 mmol) was added to trifluoromethanesulfonic anhydride (25 g, 88.8 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.3 g of compound 25. (Yield 71%, MS: [M+H]) + =698)

[0207] Manufacturing Example 26

[0208]

[0209] Under a nitrogen atmosphere, compound amine 26 (15 g, 31.8 mmol), compound 1 (10.3 g, 33.4 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 13.6 g of compound 26_P1. (Yield 61%, MS: [M+H]) + =701)

[0210] Compound 26_P1 (10 g, 14.3 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (10.3 g, 514.4 mmol) was added to trifluoromethanesulfonic anhydride (24.2 g, 85.7 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.1 g of compound 26. (Yield 69%, MS: [M+H]) + =725)

[0211] Manufacturing Example 27

[0212]

[0213] Under a nitrogen atmosphere, compound amine 27 (15 g, 33.5 mmol), compound 1 (10.9 g, 35.2 mmol), and sodium tert-butoxide (4.2 g, 43.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 27_P1. (Yield 69%, MS: [M+H]) + =677)

[0214] Compound 27_P1 (10 g, 14.8 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (10.7 g, 532.6 mmol) was added to trifluoromethanesulfonic anhydride (25 g, 88.8 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.9 g of compound 27. (Yield 67%, MS: [M+H]) + =698)

[0215] Manufacturing Example 28

[0216]

[0217] Under a nitrogen atmosphere, compound amine 28 (15 g, 34.9 mmol), compound 1 (11.3 g, 36.7 mmol), and sodium tert-butoxide (4.4 g, 45.4 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 14.7 g of compound 28_P1. (Yield 64%, MS: [M+H)) + =659)

[0218] Compound 28_P1 (10 g, 15.2 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11 g, 547.2 mmol) was added to trifluoromethanesulfonic anhydride (25.7 g, 91.2 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.2 g of compound 28. (Yield 70%, MS: [M+H]+=677)

[0219] Manufacturing Example 29

[0220]

[0221] Under a nitrogen atmosphere, compound amine 29 (15 g, 37.2 mmol), compound 1 (12.1 g, 39 mmol), and sodium tert-butoxide (4.6 g, 48.3 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 29_P1. (Yield 75%, MS: [M+H)) + =633)

[0222] Compound 29_P1 (10 g, 15.8 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11.4 g, 569.7 mmol) was added to trifluoromethanesulfonic anhydride (26.8 g, 95 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.5 g of compound 29. (Yield 73%, MS: [M+H])+ =648)

[0223] Manufacturing Example 30

[0224]

[0225] Under a nitrogen atmosphere, compound amine 30 (15 g, 37 mmol), compound 1 (12 g, 38.8 mmol), and sodium tert-butoxide (4.6 g, 48.1 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 18.8 g of compound 30_P1. (Yield 80%, MS: [M+H]) + =635)

[0226] Compound 30_P1 (10 g, 15.8 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11.4 g, 567.9 mmol) was added to trifluoromethanesulfonic anhydride (26.7 g, 94.7 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.3 g of compound 30. (Yield 61%, MS: [M+H]) + =652)

[0227] Manufacturing Example 31

[0228]

[0229] Under a nitrogen atmosphere, compound amine 31 (15 g, 31.8 mmol), compound substance 2 (12 g, 33.4 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 16.9 g of compound 31_P1. (Yield 71%, MS: [M+H]) + =751)

[0230] Compound 31_P1 (10 g, 13.3 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (9.6 g, 480 mmol) was added to trifluoromethanesulfonic anhydride (22.6 g, 80 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.8 g of compound 31. (Yield 66%, MS: [M+H]) + =774)

[0231] Manufacturing Example 32

[0232]

[0233] Under a nitrogen atmosphere, amine 32 (15 g, 28.6 mmol), compound 2 (10.8 g, 30.1 mmol), and sodium tert-butoxide (3.6 g, 37.2 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 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 15.9 g of compound 32_P1. (Yield 69%, MS: [M+H]) + =803)

[0234] Compound 32_P1 (10 g, 12.5 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (9 g, 448.9 mmol) was added to trifluoromethanesulfonic anhydride (21.1 g, 74.8 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.5 g of compound 32. (Yield 73%, MS: [M+H]) + =824)

[0235] Manufacturing Example 33

[0236]

[0237] Under a nitrogen atmosphere, amine 33 (15 g, 30.1 mmol), compound 2 (11.4 g, 31.6 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 17.5 g of compound 33_P1. (Yield 75%, MS: [M+H]) + =777)

[0238] Compound 33_P1 (10 g, 12.9 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (9.3 g, 463.9 mmol) was added to trifluoromethanesulfonic anhydride (21.8 g, 77.3 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.2 g of compound 33. (Yield 70%, MS: [M+H]) + =801)

[0239] Manufacturing Example 34

[0240]

[0241] Under a nitrogen atmosphere, amine 34 (15 g, 39.5 mmol), compound 2 (14.9 g, 41.5 mmol), and sodium tert-butoxide (4.9 g, 51.4 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 20 g of compound 34_P1. (Yield 77%, MS: [M+H]) + =659)

[0242] Compound 34_P1 (10 g, 15.2 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (11 g, 547.2 mmol) was added to trifluoromethanesulfonic anhydride (25.7 g, 91.2 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7 g of compound 34. (Yield 68%, MS: [M+H]) + =676)

[0243] Manufacturing Example 35

[0244]

[0245] Under a nitrogen atmosphere, compound amine 35 (15 g, 34.6 mmol), compound substance 2 (13 g, 36.3 mmol), and sodium tert-butoxide (4.3 g, 45 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 19.2 g of compound 35_P1. (Yield 78%, MS: [M+H]) + =713)

[0246] Compound 35_P1 (10 g, 14 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (10.1 g, 505.6 mmol) was added to trifluoromethanesulfonic anhydride (23.8 g, 84.3 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.5 g of compound 35. (Yield 63%, MS: [M+H]) + =732)

[0247] Manufacturing Example 36

[0248]

[0249] Under a nitrogen atmosphere, amine 36 (15 g, 33.5 mmol), substance 3 (12.6 g, 35.2 mmol), and sodium tert-butoxide (4.2 g, 43.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 36_P1. (Yield 68%, MS: [M+H]) + =727)

[0250] Compound 36_P1 (10 g, 13.8 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (9.9 g, 495.9 mmol) was added to trifluoromethanesulfonic anhydride (23.3 g, 82.7 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.6 g of compound 36. (Yield 74%, MS: [M+H]) + =748)

[0251] Manufacturing Example 37

[0252]

[0253] Under a nitrogen atmosphere, compound amine 37 (15 g, 35.6 mmol), compound substance 3 (13.4 g, 37.4 mmol), and sodium tert-butoxide (4.4 g, 46.3 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 14.9 g of compound 37_P1. (Yield 60%, MS: [M+H]) + =701)

[0254] Compound 37_P1 (10 g, 14.3 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (10.3 g, 514.4 mmol) was added to trifluoromethanesulfonic anhydride (24.2 g, 85.7 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.4 g of compound 37. (Yield 62%, MS: [M+H]) + =719)

[0255] Manufacturing Example 38

[0256]

[0257] Under a nitrogen atmosphere, amine 38 (15 g, 38.1 mmol), substance 3 (14.4 g, 40 mmol), and sodium tert-butoxide (4.8 g, 49.5 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 38_P1. (Yield 67%, MS: [M+H]) + =673)

[0258] Compound 38_P1 (10 g, 14.9 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (10.7 g, 535.7 mmol) was added to trifluoromethanesulfonic anhydride (25.2 g, 89.3 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.6 g of compound 38. (Yield 74%, MS: [M+H]) + =693)

[0259] Manufacturing Example 39

[0260]

[0261] Under a nitrogen atmosphere, amine 39 (15 g, 41.8 mmol), substance 3 (15.8 g, 43.8 mmol), and sodium tert-butoxide (5.2 g, 54.3 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 23 g of compound 39_P1. (Yield 77%, MS: [M+H]) + =715)

[0262] Compound 39_P1 (10 g, 14 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (10.1 g, 504.2 mmol) was added to trifluoromethanesulfonic anhydride (23.7 g, 84 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.5 g of compound 39. (Yield 64%, MS: [M+H]) + =731)

[0263] Manufacturing Example 40

[0264]

[0265] Under a nitrogen atmosphere, compound amine 40 (15 g, 35.6 mmol), compound 1 (11.6 g, 37.4 mmol), and sodium tert-butoxide (4.4 g, 46.3 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 obtain 14.8 g of compound 40_P1. (Yield 64%, MS: [M+H]) + =651)

[0266] Compound 40_P1 (10 g, 15.4 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.9 g, 692.5 mmol) was added to trifluoromethanesulfonic anhydride (43.4 g, 153.9 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.1 g of compound 40. (Yield 68%, MS: [M+H]) + =680)

[0267] Manufacturing Example 41

[0268]

[0269] Under a nitrogen atmosphere, compound amine 41 (15 g, 31.8 mmol), compound 1 (10.3 g, 33.4 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 16.7 g of compound 41_P1. (Yield 75%, MS: [M+H]) + =701)

[0270] Compound 41_P1 (10 g, 14.3 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 642.9 mmol) was added to trifluoromethanesulfonic anhydride (40.3 g, 142.9 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.4 g of compound 41. (Yield 71%, MS: [M+H]) + =734)

[0271] Manufacturing Example 42

[0272]

[0273] Under a nitrogen atmosphere, amine 42 (15 g, 35.6 mmol), compound 1 (11.6 g, 37.4 mmol), and sodium tert-butoxide (4.4 g, 46.3 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 42_P1. (Yield 71%, MS: [M+H]) + =651)

[0274] Compound 42_P1 (10 g, 15.4 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.9 g, 692.5 mmol) was added to trifluoromethanesulfonic anhydride (43.4 g, 153.9 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.9 g of compound 42. (Yield 66%, MS: [M+H]) + =681)

[0275] Manufacturing Example 43

[0276]

[0277] Under a nitrogen atmosphere, amine 43 (15 g, 33.5 mmol), compound 1 (10.9 g, 35.2 mmol), and sodium tert-butoxide (4.2 g, 43.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 14.7 g of compound 43_P1. (Yield 65%, MS: [M+H]) + =677)

[0278] Compound 43_P1 (10 g, 14.8 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.3 g, 665.8 mmol) was added to trifluoromethanesulfonic anhydride (41.7 g, 148 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.4 g of compound 43. (Yield 61%, MS: [M+H]) + =708)

[0279] Manufacturing Example 44

[0280]

[0281] Under a nitrogen atmosphere, amine 44 (15 g, 32.9 mmol), compound 1 (10.7 g, 34.6 mmol), and sodium tert-butoxide (4.1 g, 42.8 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 14.2 g of compound 44_P1. (Yield 63%, MS: [M+H)) + =685)

[0282] Compound 44_P1 (10 g, 14.6 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.2 g, 658 mmol) was added to trifluoromethanesulfonic anhydride (41.3 g, 146.2 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.6 g of compound 44. (Yield 72%, MS: [M+H]) + =722)

[0283] Manufacturing Example 45

[0284]

[0285] Under a nitrogen atmosphere, compound amine 45 (15 g, 34.6 mmol), compound 1 (11.2 g, 36.3 mmol), and sodium tert-butoxide (4.3 g, 45 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 16.7 g of compound 45_P1. (Yield 73%, MS: [M+H]) + =663)

[0286] Compound 45_P1 (10 g, 15.1 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.6 g, 679.8 mmol) was added to trifluoromethanesulfonic anhydride (42.6 g, 151.1 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.7 g of compound 45. (Yield 73%, MS: [M+H]) + =701)

[0287] Manufacturing Example 46

[0288]

[0289] Under a nitrogen atmosphere, compound amine 46 (15 g, 35.6 mmol), compound substance 2 (13.4 g, 37.4 mmol), and sodium tert-butoxide (4.4 g, 46.3 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 compound 46_P1 at 15.2 mmol. (Yield 61%, MS: [M+H]) + =701)

[0290] Compound 46_P1 (10 g, 14.3 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.9 g, 642.9 mmol) was added to trifluoromethanesulfonic anhydride (40.3 g, 142.9 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.3 g of compound 46. (Yield 70%, MS: [M+H]) + =733)

[0291] Manufacturing Example 47

[0292]

[0293] Under a nitrogen atmosphere, compound amine 47 (15 g, 31.7 mmol), compound substance 2 (11.9 g, 33.3 mmol), and sodium tert-butoxide (4 g, 41.2 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 17.6 g of compound 47_P1. (Yield 74%, MS: [M+H]) + =753)

[0294] Compound 47_P1 (10 g, 13.3 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12 g, 598.5 mmol) was added to trifluoromethanesulfonic anhydride (37.5 g, 133 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.3 g of compound 47. (Yield 70%, MS: [M+H]) + =788)

[0295] Manufacturing Example 48

[0296]

[0297] Under a nitrogen atmosphere, compound amine 48 (15 g, 38.9 mmol), compound substance 2 (14.7 g, 40.8 mmol), and sodium tert-butoxide (4.9 g, 50.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 18.9 g of compound 48_P1. (Yield 73%, MS: [M+H]) + =665)

[0298] Compound 48_P1 (10 g, 15.1 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.6 g, 677.8 mmol) was added to trifluoromethanesulfonic anhydride (42.5 g, 150.6 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.8 g of compound 48. (Yield 64%, MS: [M+H]) + =702)

[0299] Manufacturing Example 49

[0300]

[0301] Under a nitrogen atmosphere, compound amine 49 (15 g, 39.7 mmol), compound substance 2 (15 g, 41.7 mmol), and sodium tert-butoxide (5 g, 51.7 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 16.2 g of compound 49_P1. (Yield 62%, MS: [M+H]) + =657)

[0302] Compound 49_P1 (10 g, 15.2 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.7 g, 686.1 mmol) was added to trifluoromethanesulfonic anhydride (43 g, 152.5 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.2 g of compound 49. (Yield 69%, MS: [M+H]) + =688)

[0303] Manufacturing Example 50

[0304]

[0305] Under a nitrogen atmosphere, compound amine 50 (15 g, 31.8 mmol), compound substance 3 (12 g, 33.4 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 17.4 g of compound 50_P1. (Yield 73%, MS: [M+H]) + =751)

[0306] Compound 50_P1 (10 g, 13.3 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12 g, 600 mmol) was added to trifluoromethanesulfonic anhydride (37.6 g, 133.3 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.4 g of compound 50. (Yield 61%, MS: [M+H]) + =788)

[0307] Manufacturing Example 51

[0308]

[0309] Under a nitrogen atmosphere, amine 51 (15 g, 33.5 mmol), compound 3 (12.6 g, 35.2 mmol), and sodium tert-butoxide (4.2 g, 43.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 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 19 g of compound 51_P1. (Yield 78%, MS: [M+H]) + =727)

[0310] Compound 51_P1 (10 g, 13.8 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (12.4 g, 619.9 mmol) was added to trifluoromethanesulfonic anhydride (38.9 g, 137.8 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.2 g of compound 51. (Yield 69%, MS: [M+H]) + =761)

[0311] Manufacturing Example 52

[0312]

[0313] Under a nitrogen atmosphere, amine 52 (15 g, 36.6 mmol), compound 3 (13.8 g, 38.5 mmol), and sodium tert-butoxide (4.6 g, 47.6 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 16.4 g of compound 52_P1. (Yield 65%, MS: [M+H)) + =689)

[0314] Compound 52_P1 (10 g, 14.5 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (13.1 g, 654.1 mmol) was added to trifluoromethanesulfonic anhydride (41 g, 145.4 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.4 g of compound 52. (Yield 61%, MS: [M+H]) + =724)

[0315] Manufacturing Example 53

[0316]

[0317] Under a nitrogen atmosphere, compound amine 53 (15 g, 45 mmol), compound substance 3 (17 g, 47.2 mmol), and sodium tert-butoxide (5.6 g, 58.5 mmol) were added to 300 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 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 20.6 g of compound 53_P1. (Yield 75%, MS: [M+H]) + =613)

[0318] Compound 53_P1 (10 g, 16.3 mmol) was added to 200 mL of 1,2,4-trichlorobenzene and stirred at room temperature. In another container, deuterium oxide (14.7 g, 735.5 mmol) was added to trifluoromethanesulfonic anhydride (46.1 g, 163.4 mmol) at 0 °C and stirred for 10 hours to prepare a solution. Then, a mixture of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared 1,2,4-trichlorobenzene solution, and the temperature was raised to 140 °C and maintained with stirring. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then neutralized with an aqueous potassium carbonate solution. After washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.8 g of compound 53. (Yield 74%, MS: [M+H]) + =644)

[0319] Example 1-1

[0320] A glass substrate coated with a 1000 Å thick ITO (Indium Tin Oxide) film was immersed in distilled water containing detergent and ultrasonically washed. 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 ultrasonic washing was repeated twice with distilled water for 10 minutes each time. 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.

[0321] On the prepared ITO transparent electrode, as a hole injection layer, compound HI-1 is formed to a thickness of 1100 Å, and compound A-1 is p-doped at a concentration of 1.5 wt%. Compound HT-1 is then vacuum-deposited onto the hole injection layer to form a hole transport layer with a thickness of 800 Å. Next, as a hole transport auxiliary layer, compound 1 is thermally vacuum-deposited to a thickness of 100 Å. Next, as a light-emitting layer, compounds BH-1 and BD-1 are vacuum-deposited at a weight ratio of 25:1 to a thickness of 250 Å. Next, as a hole blocking layer, compound HB-1 is vacuum-deposited to a thickness of 50 Å. Finally, as a layer for simultaneous electron transport and electron injection, compounds ET-1 and LiQ are thermally vacuum-deposited at a weight ratio of 1:1 to a thickness of 310 Å. On the aforementioned electron transport and electron injection layers, lithium fluoride (LiF) with a thickness of 12 Å and aluminum with a thickness of 1000 Å were sequentially vapor-deposited to form a cathode, thereby fabricating an organic light-emitting device.

[0322]

[0323] During the above process, the evaporation rate of organic materials was maintained at 0.4~0.7 Å / s, the evaporation rate of lithium fluoride cathode was maintained at 0.3 Å / s, and the evaporation rate of aluminum was maintained at 2 Å / s. During evaporation, the vacuum level was maintained at 2. 0 -7 ~5 10 -6 This led to the creation of organic light-emitting devices.

[0324] Examples 1-2 to 1-53

[0325] Organic light-emitting devices of Examples 1-2 to 1-53 were manufactured by the same method as in Examples 1-1 above, except that the compounds listed in Table 1 below were used instead of Compound 1.

[0326] Comparative Examples 1-1 to 1-6

[0327] Organic light-emitting devices of Comparative Examples 1-1 to 1-6 were manufactured using the same method as in Example 1-1, except that compounds C-1 to C-6 and the comparative example compounds described in Table 1 were used instead of compound 1. The structures of compounds C-1 to C-6 are shown below.

[0328]

[0329] Experimental Example

[0330] An application of 15 mA / cm² was made to the organic light-emitting devices manufactured in Examples 1-1 to 1-53 and Comparative Examples 1-1 to 1-6. 2 When the current was applied, the voltage and efficiency were measured, and the results are shown in Table 1 below. Lifetime T95 refers to the time required for the brightness to decrease from the initial brightness (1000 nits) to 95%.

[0331]

[0332]

[0333] As can be confirmed from Table 1 above, the organic light-emitting device using the compounds of the present invention shows improved performance in terms of driving voltage, efficiency, and lifetime compared to the organic light-emitting device of the comparative examples. Furthermore, it can be confirmed that the lifetime characteristics of the organic light-emitting device using the deuterium-substituted compounds are further improved. It is determined that by using the compounds of the present invention in the hole transport auxiliary layer, the stability of excitons formed within the light-emitting layer is improved, thereby demonstrating an effect on improving the characteristics of the organic light-emitting device.

[0334] [Symbol Explanation]

[0335] 1: Substrate 2: Anode

[0336] 3: Organic layer 4: Cathode

[0337] 5: Hole injection layer; 6: Hole transport layer

[0338] 7: Hole transport auxiliary layer; 8: Emissive layer

[0339] 9: Hole blocking layer; 10: Electron transport and injection layer.

Claims

1. A compound represented by the following Chemical Formula 1: [Chemical Formula 1] In the Chemical Formula 1, Dn represents n hydrogens are substituted with deuteriums, n is an integer of 0 or more, A is a phenyl group which is unsubstituted or substituted with one or more deuteriums, or a naphthyl group which is unsubstituted or substituted with one or more deuteriums, L1 and L2 are each independently a single bond, a phenylene group, or a naphthalene diyl group, each of the phenylene group and the naphthalene diyl group being independently unsubstituted or substituted with any one or more selected from the group consisting of deuterium, a phenyl group which is unsubstituted or substituted with deuterium, and a naphthyl group which is unsubstituted or substituted with deuterium, Ar1and Ar2are each independently selected from phenyl, biphenyl, terphenyl, naphthyl, benz[c]phenanthryl, chrysenyl, phenylnaphthyl, naphthylphenyl, or any of the following groups, and each of said phenyl, biphenyl, terphenyl, naphthyl, benz[c]phenanthryl, chrysenyl, phenylnaphthyl, naphthylphenyl, and following groups is independently unsubstituted or substituted with any one or more of the following groups: 1-10 alkyl, and each of said phenyl, biphenyl, terphenyl, naphthyl, benz[c]phenanthryl, chrysenyl, phenylnaphthyl, naphthylphenyl, and following groups is independently unsubstituted or substituted with any one or more of the following groups: 1-10 alkyl, and each of said phenyl, biphenyl, terphenyl, naphthyl, benz[c]phenanthryl, chrysenyl, phenylnaphthyl, naphthylphenyl, and following groups is independently unsubstituted or substituted with any one or more of the following groups: 1-10 alkyl, and each of said phenyl, biphenyl, terphenyl, naphthyl, benz[c]phenanthryl, chrysenyl, phenylnaphthyl, naphthylphenyl, and following groups is independently unsubstituted or substituted with any one or more of the following groups: 。 2. The compound of claim 1, wherein, L1 and L2 are each independently selected from the group consisting of a single bond, a phenylene group, a naphthalene diyl group, or any one of the following groups, and each of the phenylene group, the naphthalene diyl group, and the following groups being independently unsubstituted or substituted with one or more deuteriums: 。 3. The compound of claim 1, wherein, L1 and L2 are each independently a single bond, or a phenylene group which is unsubstituted or substituted with one or more deuteriums.

4. The compound of claim 1, wherein, Ar1 and Ar2 are each independently selected from the group consisting of a phenyl group, a phenyl group substituted with 1 methyl group, a phenyl group substituted with 2 methyl groups, a phenyl group substituted with 1 isopropyl group, a phenyl group substituted with 2 isopropyl groups, a phenyl group substituted with 1 tert-butyl group, a phenyl group substituted with 2 tert-butyl groups, a biphenyl group, a terphenyl group, a naphthyl group, a benzo[c]phenanthryl group, a fluorenyl group, a phenylnaphthyl group, a naphthylphenyl group, and any one of the following groups, and each of the Ar1 and Ar2 being independently unsubstituted or substituted with one or more deuteriums: 。 5. The compound of claim 1, wherein, The compound represented by the Chemical Formula 1 is selected from any one of the following compounds: 。 6. An organic light emitting device, wherein, including: 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, one or more of the organic layers containing the compound according to any one of claims 1 to 5.

7. The organic light emitting device according to claim 6, wherein, The organic layer is a hole injection layer, a hole transport layer, or a hole transport auxiliary layer.

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