Novel compound and organic light-emitting element comprising same

Abstract

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

Description

Novel compound and organic light-emitting device comprising the same

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0039153, filed March 21, 2024, and Korean Patent Application No. 10-2025-0036452, filed March 21, 2025, the entire contents of which are incorporated herein by reference.

[0003]

[0004] The present invention relates to a novel compound and an organic light-emitting device comprising the same.

[0005]

[0006] Organic light-emitting diodes (OLEDs) generally refer to the conversion of electrical energy into light energy using organic materials. Organic light-emitting devices utilizing this phenomenon boast a wide viewing angle, excellent contrast, and fast response times, and are actively researched due to their superior brightness, operating voltage, and response speed characteristics.

[0007]

[0008] Organic light-emitting devices generally have a structure including an anode, a cathode, and an organic layer between the anode and the cathode. The organic layer is often formed as a multilayer structure composed of different materials to increase the efficiency and stability of the organic light-emitting device, and may be formed, for example, of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In the structure of such an organic light-emitting device, when a voltage is applied between two electrodes, holes are injected into the organic layer from the anode and electrons are injected into the organic layer from the cathode, and when the injected holes and electrons meet, excitons are formed, and when these excitons fall back to the ground state, light is emitted.

[0009]

[0010] There is a continuous demand for the development of new materials for organic materials used in organic light-emitting devices such as the above.

[0011]

[0012] [Prior Art Literature]

[0013] [Patent Document]

[0014] (Patent Document 1) Korean Patent Publication No. 10-2000-0051826

[0015] The present invention relates to a novel organic light-emitting material and an organic light-emitting device comprising the same.

[0016]

[0017] The present invention provides a compound represented by the following chemical formula 1:

[0018] [Chemical Formula 1]

[0019]

[0020] In the above chemical formula 1,

[0021] Dn means that n hydrogens are replaced with deuterium,

[0022] n is an integer greater than or equal to 0,

[0023] A is phenyl which is unsubstituted or substituted with one or more deuterium atoms, or naphthyl which is unsubstituted or substituted with one or more deuterium atoms,

[0024] L1 and L2 are each independently a single bond, phenylene, or naphthalenediyl, and the phenylene and naphthalenediyl are each independently unsubstituted or substituted with at least one selected from the group consisting of deuterium; phenyl unsubstituted or substituted with deuterium; and naphthyl unsubstituted or substituted with deuterium;

[0025] Ar1 and Ar2 are each independently C 1-10 Alkyl-substituted phenyl, biphenylyl, terphenylyl, naphthyl, benzo[c]phenanthrenyl, chrysenyl, phenyl naphthyl, naphthylphenyl, or any one selected from the group consisting of; wherein C1-10 Phenyl substituted with alkyl is unsubstituted or substituted with deuterium; the group consisting of biphenylyl, terphenylyl, naphthyl, benzo[c]phenanthrenyl, chrysenyl, phenyl naphthyl, naphthyl phenyl and the group consisting of the following are each independently unsubstituted or substituted with deuterium and unsubstituted or substituted with deuterium C 1-10 is substituted with one or more selected from the group consisting of alkyl:

[0026] .

[0027]

[0028] In addition, the present invention provides an organic light-emitting device comprising a first electrode; a second electrode provided opposite the first electrode; and one or more organic layers provided between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound represented by the chemical formula 1.

[0029]

[0030] The compound represented by the above-described chemical formula 1 can be used as a material for an organic layer of an organic light-emitting device, and can improve efficiency, lower operating voltage, and / or lifespan characteristics in the organic light-emitting device. In particular, the compound represented by the above-described chemical formula 1 can be used as a hole injection, hole transport, hole transport assisting, luminescent, hole blocking, electron transport, and / or electron injection material.

[0031]

[0032] Figure 1 illustrates an example of an organic light-emitting device composed of a substrate (1), an anode (2), an organic layer (3), and a cathode (4).

[0033] Figure 2 illustrates an example of an organic light-emitting device composed of 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 this structure, the compound represented by the chemical formula 1 may be included in the light-emitting layer.

[0034] Hereinafter, the present invention will be described in more detail to help understand it.

[0035]

[0036] The present invention provides a compound represented by the above chemical formula 1.

[0037]

[0038] In this specification, or means a bond that connects to another substituent.

[0039]

[0040] The term "substituted or unsubstituted" as used herein means a group that is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a nitrile group; a nitro group; a hydroxy group; a carbonyl group; an ester group; an imide group; an amino group; a phosphine oxide group; an alkoxy group; an aryloxy group; an alkylthioxy group; an arylthioxy group; an alkylsulfoxy group; an arylsulfoxy group; a silyl group; a boron group; an alkyl group; a cycloalkyl group; an alkenyl group; an aryl group; an aralkyl group; an aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; a heteroarylamine group; an arylphosphine group; or a heteroaryl group containing at least one of N, O, and S atoms, or a substituted or unsubstituted group in which two or more of the above-mentioned substituents are linked. For example, the "substituent linked with two or more substituents" may be a biphenyl group. That is, a biphenyl group can be an aryl group, or can be interpreted as a substituent in which two phenyl groups are connected. For example, the term "substituted or unsubstituted" means "unsubstituted, or substituted with deuterium, halogen, C 1-10 Alkyl, C1-10 Alkoxy, C 6-20 C containing aryl and one or more heteroatoms of N, O and S 2-20 The term "substituted with one or more, for example, 1 to 5, substituents selected from the group consisting of heteroaryl" can be understood to mean "substituted with one or more, for example, 1 to 5, substituents." In addition, the term "substituted with one or more, for example, 1 to 5, substituents" in the present specification can be understood to mean "substituted with one to 5, for example, 1 to 2, or 2, substituents."

[0041]

[0042] In this specification, the number of carbon atoms in the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a substituent having the following structure, but is not limited thereto.

[0043]

[0044]

[0045] In the present specification, the ester group may have the oxygen of the ester group substituted with a straight-chain, branched-chain, or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, the substituent may have the following structural formula, but is not limited thereto.

[0046]

[0047]

[0048] In this specification, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a substituent having the following structure, but is not limited thereto.

[0049]

[0050]

[0051] In the present specification, the silyl group specifically includes, but is not limited to, a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, etc.

[0052]

[0053] In this specification, the boron group specifically includes, but is not limited to, a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, etc.

[0054]

[0055] In this specification, examples of halogen groups include fluorine, chlorine, bromine or iodine.

[0056]

[0057] In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 6. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, Examples include, but are not limited to, 2-methylpentyl, 4-methylhexyl, and 5-methylhexyl.

[0058]

[0059] In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the number of carbon atoms in the alkenyl group is 2 to 20. According to another embodiment, the number of carbon atoms in the alkenyl group is 2 to 10. According to another embodiment, the number of carbon atoms in the alkenyl group is 2 to 6. Specific examples include, but are not limited to, 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, stilbenyl, and styrenyl.

[0060]

[0061] In the present specification, the cycloalkyl group is not particularly limited, but preferably has 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, examples thereof include, but are not limited to, 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, and the like.

[0062]

[0063] In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The monocyclic aryl group may be, but is not limited to, a phenyl group, a biphenyl group, a terphenyl group, etc. The polycyclic aryl group may be, but is not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, etc.

[0064]

[0065] In the present specification, the fluorenyl group may be substituted, and two substituents may combine with each other to form a spiro structure. When the fluorenyl group is substituted, It can be, but is not limited to, the following.

[0066]

[0067] In the present specification, a heteroaryl group is a heteroaryl group containing at least one of O, N, Si, and S as a heteroatom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. According to one embodiment, the number of carbon atoms of the heteroaryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the heteroaryl group is 6 to 20. Examples of heteroaryl groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group, carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group, There are, but are not limited to, phenothiazinyl groups and dibenzofuranyl groups.

[0068]

[0069] In this specification, the aryl group among the aralkyl group, the aralkenyl group, the alkylaryl group, and the arylamine group is the same as the examples of the aryl group described above. In this specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the examples of the alkyl group described above. In this specification, the heteroaryl among the heteroarylamine may be applied to the description of the heteroaryl group described above. In this specification, the alkenyl group among the aralkenyl group is the same as the examples of the alkenyl group described above. In this specification, the description of the aryl group described above may be applied to the arylene except that it is a divalent group. In this specification, the description of the heteroaryl group described above may be applied to the heteroarylene except that it is a divalent group. In this specification, the description of the aryl group or the cycloalkyl group described above may be applied to the hydrocarbon ring except that it is not a monovalent group but is formed by combining two substituents. In this specification, the description of the heteroaryl group described above may be applied, except that the heteroaryl is not monovalent and is formed by combining two substituents.

[0070]

[0071] Preferably, A may be phenyl or naphthyl.

[0072]

[0073] Preferably, L1 and L2 are each independently a single bond, phenylene, phenylene substituted with one phenyl, phenylene substituted with two phenyls, or naphthalenediyl, wherein L1 and L2 are each independently unsubstituted or substituted with one or more deuterium atoms.

[0074] Preferably, L1 and L2 are each independently a single bond, phenylene, naphthalenediyl, or any one selected from the group consisting of: wherein the phenylene, naphthalenediyl, and the group consisting of may each be independently unsubstituted or substituted with one or more deuterium atoms:

[0075] .

[0076] More preferably, L1 and L2 may each independently be a single bond, or phenylene which is unsubstituted or substituted with deuterium.

[0077]

[0078] Preferably, Ar1 and Ar2 are each independently C 1-5 It may be any one selected from the group consisting of alkyl substituted phenyl, biphenylyl, terphenylyl, naphthyl, benzo[c]phenanthrenyl, chrysenyl, phenyl naphthyl, naphthyl phenyl, or the group consisting of; 1-10 Phenyl substituted with alkyl may be unsubstituted or substituted with deuterium; the group consisting of biphenylyl, terphenylyl, naphthyl, benzo[c]phenanthrenyl, chrysenyl, phenyl naphthyl, naphthyl phenyl and the group consisting of the following are each independently unsubstituted, deuterium and unsubstituted or deuterium substituted C 1-5 which may be substituted with one or more selected from the group consisting of alkyl:

[0079] .

[0080] Preferably, Ar1 and Ar2 may each independently be phenyl substituted with at least one selected from the group consisting of methyl, isopropyl and tert-butyl; biphenylyl; terphenylyl; naphthyl; benzo[c]phenanthrenyl; chrysenyl; phenyl naphthyl; naphthyl phenyl; or any one selected from the group consisting of the following; and wherein Ar1 and Ar2 may each independently be unsubstituted or substituted with deuterium:

[0081] .

[0082] Preferably, Ar1 and Ar2 may each independently be any one selected from the group consisting of phenyl, phenyl substituted with one methyl, phenyl substituted with two methyls, phenyl substituted with one isopropyl, phenyl substituted with two isopropyls, phenyl substituted with one tert-butyl, phenyl substituted with two tert-butyls, biphenylyl, terphenylyl, naphthyl, benzo[c]phenanthrenyl, chrysenyl, phenyl naphthyl, naphthylphenyl, or the group consisting of; wherein Ar1 and Ar2 may each independently be substituted or substituted with one or more deuterium:

[0083] .

[0084]

[0085] Representative examples of compounds represented by the above chemical formula 1 are as follows:

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123] .

[0124]

[0125] The compound represented by the above chemical formula 1 can be manufactured by, for example, a manufacturing method such as the following reaction scheme 1, and the remaining compounds can also be manufactured similarly.

[0126] [Reaction Formula 1]

[0127]

[0128] In the above reaction formula 1, D, n, A, L1, L2, Ar1 and Ar2 are as defined in the above chemical formula 1, X is halogen, and preferably X is chloro or bromo.

[0129]

[0130] Step 1 of the above reaction scheme 1 is an amine substitution reaction, which is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. Step 2 of the above reaction scheme 1 is a deuterium substitution reaction, which can be changed as known in the art. In this case, a compound in which n is 0 and is not deuterium substituted can be prepared by omitting step 2 of the above reaction scheme 1. The above preparation method can be further specified in the preparation examples described below.

[0131]

[0132] In addition, the present invention provides an organic light-emitting device comprising a compound represented by the above chemical formula 1. For example, the present invention provides an organic light-emitting device comprising a first electrode; a second electrode provided opposite the first electrode; and at least one organic layer provided between the first electrode and the second electrode, wherein at least one layer of the organic layer comprises a compound represented by the above chemical formula 1.

[0133]

[0134] The organic layer of the organic light-emitting device of the present invention may be formed as a single layer structure, but may also be formed as a multilayer structure in which two or more organic layers are laminated. For example, the organic light-emitting device of the present invention may 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 the organic layers. However, the structure of the organic light-emitting device is not limited thereto and may include a smaller number of organic layers.

[0135]

[0136] In addition, the organic layer may include a hole transport layer, a hole injection layer, a layer that simultaneously transports and injects holes, or a hole transport auxiliary layer, and the hole transport layer, the hole injection layer, the layer that simultaneously transports and injects holes, or the hole transport auxiliary layer may include a compound represented by the chemical formula 1.

[0137]

[0138] In addition, the organic light-emitting device according to the present invention may be an organic light-emitting device having a structure (normal type) in which an anode, one or more organic layers, and a cathode are sequentially laminated on a substrate. In addition, the organic light-emitting device according to the present invention may be an organic light-emitting device having a structure (inverted type) in which a cathode, one or more organic layers, and an anode are sequentially laminated on a substrate. For example, the structure of an organic light-emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

[0139]

[0140] Figure 1 illustrates an example of an organic light-emitting device composed of a substrate (1), an anode (2), an organic layer (3), and a cathode (4). In such a structure, the compound represented by the chemical formula 1 may be included in the light-emitting layer.

[0141] Figure 2 illustrates an example of an organic light-emitting device composed of 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 this structure, the compound represented by the chemical formula 1 may be included in the light-emitting layer.

[0142]

[0143] The organic light-emitting device according to the present invention can be manufactured using materials and methods known in the art, except that at least one of the organic layers includes a compound represented by the chemical formula 1. In addition, when the organic light-emitting device includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

[0144]

[0145] 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. At this time, a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation is used to deposit a metal or a conductive metal oxide or an alloy thereof on the substrate to form an anode, and then an organic layer including a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. In addition to this method, the organic light-emitting device can be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on the substrate.

[0146]

[0147] In addition, the compound represented by the above chemical formula 1 can be formed into an organic layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light-emitting device. Here, the solution coating method refers to, but is not limited to, spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc.

[0148]

[0149] In addition to this method, an organic light-emitting device can be manufactured by sequentially depositing an organic layer and an anode material from a cathode material on a substrate (WO 2003 / 012890). However, the manufacturing method is not limited to this.

[0150]

[0151] For example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

[0152]

[0153] As the anode material, a material having a high work function is generally preferred so that hole injection into the organic layer can be facilitated. Specific examples of the anode material include, but are not limited to, metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline.

[0154]

[0155] The cathode material is preferably a material having a low work function to facilitate electron injection into the organic layer. Specific examples of the cathode material include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayered materials such as LiF / Al or LiO2 / Al.

[0156]

[0157] The above-mentioned hole injection layer is a layer that injects holes from the electrode, and the hole injection material is preferably a compound that has the ability to transport holes, has an excellent hole injection effect at the anode, an excellent hole injection effect for the light-emitting layer or the light-emitting material, prevents the movement of excitons generated in the light-emitting layer to the electron injection layer or the electron injection material, and has excellent thin film forming ability. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include, but are not limited to, metal porphyrins, oligothiophenes, arylamine-based organic compounds, hexanitrilehexaazatriphenylene-based organic compounds, quinacridone-based organic compounds, perylene-based organic compounds, anthraquinones, and conductive polymers such as polyaniline and polythiophene.

[0158]

[0159] The above hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light-emitting layer. A hole transport material that can transport holes from the anode or the hole injection layer and transfer them to the light-emitting layer is suitable. Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated portions.

[0160]

[0161] The above hole transport auxiliary layer is an auxiliary layer for smooth transport of holes and prevention of luminescence leakage between the hole transport layer and the light emitting layer. By the auxiliary layer, holes are transported more smoothly from the hole transport layer to the light emitting layer, and excitons are confined within the light emitting layer, thereby preventing luminescence leakage, thereby enabling implementation of an organic electroluminescent device having excellent luminescence efficiency. Preferably, a compound represented by the above chemical formula 1 can be used as a material for the hole transport auxiliary layer.

[0162]

[0163] The above-mentioned light-emitting material is a material that can emit light in the visible light range by transporting holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining them, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include, but are not limited to, 8-hydroxy-quinoline aluminum complex (Alq3); carbazole series compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; benzoxazole, benzthiazole, and benzimidazole series compounds; poly(p-phenylenevinylene) (PPV) series polymers; spiro compounds; polyfluorene, rubrene, etc.

[0164]

[0165] The above-mentioned light-emitting layer may include a host material and a dopant material. The host material may be a condensed aromatic ring derivative or a heterocyclic compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and the heterocyclic compound may include, but is not limited to, carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, etc.

[0166]

[0167] Dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, etc. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, and periflanthene having an arylamino group, and styrylamine compounds are compounds in which at least one arylvinyl group is substituted in a substituted or unsubstituted arylamine, and one or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but are not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes, platinum complexes, etc.

[0168]

[0169] The above hole blocking layer refers to a layer formed on a light-emitting layer, preferably provided in contact with the light-emitting layer, and serves to improve the efficiency of an organic light-emitting device by controlling electron mobility and preventing excessive movement of holes to increase the probability of hole-electron coupling. The hole blocking layer includes a hole blocking material, and examples of such hole blocking materials include compounds having an electron-withdrawing group introduced therein, such as azine derivatives including triazine; triazole derivatives; oxadiazole derivatives; phenanthroline derivatives; and phosphine oxide derivatives, but are not limited thereto.

[0170]

[0171] The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light-emitting layer. As the electron transport material, a material that can easily receive electrons from the cathode and transfer them to the light-emitting layer is suitable. A material with high electron mobility is suitable. Specific examples include, but are not limited to, Al complexes of 8-hydroxyquinoline; complexes containing Alq3; organic radical compounds; and hydroxyflavone-metal complexes. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by an aluminum layer or a silver layer. Specifically, cesium, barium, calcium, ytterbium, and samarium are used, and in each case, followed by an aluminum layer or a silver layer.

[0172]

[0173] The above electron injection layer is a layer that injects electrons from an electrode, has the ability to transport electrons, has an electron injection effect from a cathode, an excellent electron injection effect for a light-emitting layer or a light-emitting material, prevents movement of excitons generated in the light-emitting layer to the hole injection layer, and is preferably a compound having excellent thin-film forming ability. Specifically, examples thereof include, but are not limited to, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and the like, derivatives thereof, metal complex compounds, and nitrogen-containing 5-membered ring derivatives.

[0174]

[0175] The above metal complex compounds include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)(o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, Bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc., but are not limited thereto.

[0176]

[0177] Meanwhile, in the present invention, the "electron injection and transport layer" is a layer that performs the roles of both the electron injection layer and the electron transport layer, and materials that perform the roles of each layer may be used alone or in combination, but are not limited thereto.

[0178]

[0179] The organic light-emitting device according to the present invention may be a bottom emission device, a top emission device, or a double-sided emission device, and in particular, may be a bottom emission device requiring relatively high luminous efficiency.

[0180]

[0181] In addition, the compound represented by the above chemical formula 1 can be included in an organic solar cell or organic transistor in addition to an organic light-emitting device.

[0182]

[0183] Hereinafter, the present invention will be described in more detail to aid understanding. However, the following examples are merely illustrative of the present invention, and the content of the present invention is not limited to the following examples.

[0184]

[0185] Manufacturing Example 1

[0186]

[0187] In a nitrogen atmosphere, compound amine1 (15 g, 35.6 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.7 g of compound 1. (Yield 72%, MS: [M+H] + = 651)

[0188]

[0189] Manufacturing Example 2

[0190]

[0191] In a nitrogen atmosphere, compound amine2 (15 g, 37.7 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.7 g of compound 2. (Yield 75%, MS: [M+H] + = 627)

[0192]

[0193] Manufacturing Example 3

[0194]

[0195] In a nitrogen atmosphere, compound amine3 (15 g, 31.7 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of compound 3. (Yield 61%, MS: [M+H] + = 703)

[0196]

[0197] Manufacturing Example 4

[0198]

[0199] In a nitrogen atmosphere, compound amine4 (15 g, 28.8 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.5 g of compound 4. (Yield 72%, MS: [M+H] + = 751)

[0200]

[0201] Manufacturing Example 5

[0202]

[0203] In a nitrogen atmosphere, compound amine 5 (15 g, 37.7 mmol), compound sub 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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.5 g of compound 5. (Yield 74%, MS: [M+H] + = 627)

[0204]

[0205] Manufacturing Example 6

[0206]

[0207] In a nitrogen atmosphere, compound amine6 (15 g, 33.5 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.7 g of compound 6. (Yield 78%, MS: [M+H] + = 677)

[0208]

[0209] Manufacturing Example 7

[0210]

[0211] In a nitrogen atmosphere, compound amine7 (15 g, 34.3 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.5 g of compound 7. (Yield 66%, MS: [M+H] + = 687)

[0212]

[0213] Manufacturing Example 8

[0214]

[0215] In a nitrogen atmosphere, compound amine8 (15 g, 34.3 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.9 g of compound 8. (Yield 74%, MS: [M+H]+ = 667)

[0216]

[0217] Manufacturing Example 9

[0218]

[0219] In a nitrogen atmosphere, compound amine9 (15 g, 30.5 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.8 g of compound 9. (Yield 63%, MS: [M+H] + = 721)

[0220]

[0221] Manufacturing Example 10

[0222]

[0223] In a nitrogen atmosphere, compound amine 10 (15 g, 46.7 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.1 g of compound 10. (Yield 79%, MS: [M+H] + = 601)

[0224]

[0225] Manufacturing Example 11

[0226]

[0227] In a nitrogen atmosphere, compound amine 11 (15 g, 33.5 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.8 g of compound 11. (Yield 61%, MS: [M+H] + = 727)

[0228]

[0229] Manufacturing Example 12

[0230]

[0231] In a nitrogen atmosphere, compound amine 12 (15 g, 33.5 mmol), compound sub 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. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.5 g of compound 12. (Yield 68%, MS: [M+H] + = 727)

[0232]

[0233] Manufacturing Example 13

[0234]

[0235] In a nitrogen atmosphere, compound amine 13 (15 g, 31.8 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.9 g of compound 13. (Yield 75%, MS: [M+H] + = 751)

[0236]

[0237] Manufacturing Example 14

[0238]

[0239] In a nitrogen atmosphere, compound amine 14 (15 g, 33.5 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.3 g of compound 14. (Yield 63%, MS: [M+H] + = 727)

[0240]

[0241] Manufacturing Example 15

[0242]

[0243] In a nitrogen atmosphere, compound amine 15 (15 g, 34.6 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.7 g of compound 15. (Yield 72%, MS: [M+H] + = 713)

[0244]

[0245] Manufacturing Example 16

[0246]

[0247] In a nitrogen atmosphere, compound amine 16 (15 g, 38.5 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.3 g of compound 16. (Yield 71%, MS: [M+H] + = 669)

[0248]

[0249] Manufacturing Example 17

[0250]

[0251] In a nitrogen atmosphere, compound amine 17 (15 g, 35.6 mmol), compound sub3 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.9 g of compound 17. (Yield 60%, MS: [M+H] + = 701)

[0252]

[0253] Manufacturing Example 18

[0254]

[0255] In a nitrogen atmosphere, compound amine 18 (15 g, 28.8 mmol), compound sub3 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.3 g of compound 18. (Yield 75%, MS: [M+H] + = 801)

[0256]

[0257] Manufacturing Example 19

[0258]

[0259] In a nitrogen atmosphere, compound amine 19 (15 g, 50.8 mmol), compound sub3 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 22.7 g of compound 19. (Yield 78%, MS: [M+H] + = 575)

[0260]

[0261] Manufacturing Example 20

[0262]

[0263] In a nitrogen atmosphere, compound amine 20 (15 g, 30.1 mmol), compound sub 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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.8 g of compound 20. (Yield 76%, MS: [M+H] + = 777)

[0264]

[0265] Manufacturing Example 21

[0266]

[0267] In a nitrogen atmosphere, compound amine 21 (15 g, 34.8 mmol), compound sub3 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.5 g of compound 21. (Yield 71%, MS: [M+H] + = 711)

[0268]

[0269] Manufacturing Example 22

[0270]

[0271] In a nitrogen atmosphere, compound amine 22 (15 g, 30.6 mmol), compound sub3 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.6 g of compound 22. (Yield 79%, MS: [M+H] + = 769)

[0272]

[0273] Manufacturing Example 23

[0274]

[0275] In a nitrogen atmosphere, compound amine 23 (15 g, 38.9 mmol), compound sub3 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.4 g of compound 23. (Yield 79%, MS: [M+H] + = 665)

[0276]

[0277] Manufacturing Example 24

[0278]

[0279] In a nitrogen atmosphere, compound amine24 (15 g, 31.7 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.6 g of compound 24_P1. (Yield 70%, MS: [M+H] + = 703)

[0280] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, 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)

[0281]

[0282] Manufacturing Example 25

[0283]

[0284] In a nitrogen atmosphere, compound amine 25 (15 g, 33.5 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.8 g of compound 25_P1. (Yield 74%, MS: [M+H] + = 677)

[0285] 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 ℃ and stirred for 10 hours to prepare a solution. After that, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 ℃ and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.3 g of compound 25 (yield 71%, MS: [M+H]+ = 698)

[0286]

[0287] Manufacturing Example 26

[0288]

[0289] In a nitrogen atmosphere, compound amine 26 (15 g, 31.8 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.6 g of compound 26_P1. (Yield 61%, MS: [M+H] + = 701)

[0290] 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. After that, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.1 g of compound 26 (yield 69%, MS: [M+H] + = 725)

[0291]

[0292] Manufacturing Example 27

[0293]

[0294] In a nitrogen atmosphere, compound amine 27 (15 g, 33.5 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.6 g of compound 27_P1. (Yield 69%, MS: [M+H] + = 677)

[0295] 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. After that, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.9 g of compound 27 (yield 67%, MS: [M+H]+ = 698)

[0296]

[0297] Manufacturing Example 28

[0298]

[0299] In a nitrogen atmosphere, compound amine 28 (15 g, 34.9 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.7 g of compound 28_P1. (Yield 64%, MS: [M+H] + = 659)

[0300] 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 ℃ and stirred for 10 hours to prepare a solution. After that, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 ℃ and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, 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 28 (yield 70%, MS: [M+H] + = 677)

[0301]

[0302] Manufacturing Example 29

[0303]

[0304] In a nitrogen atmosphere, compound amine 29 (15 g, 37.2 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.6 g of compound 29_P1. (Yield 75%, MS: [M+H] + = 633)

[0305] 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 ℃ and stirred for 10 hours to prepare a solution. After that, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 ℃ and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.5 g of compound 29 (yield 73%, MS: [M+H]+ = 648)

[0306]

[0307] Manufacturing Example 30

[0308]

[0309] In a nitrogen atmosphere, compound amine30 (15 g, 37 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.8 g of compound 30_P1. (Yield 80%, MS: [M+H] + = 635)

[0310] 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. After that, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.3 g of compound 30 (yield 61%, MS: [M+H] + = 652)

[0311]

[0312] Manufacturing Example 31

[0313]

[0314] In a nitrogen atmosphere, compound amine 31 (15 g, 31.8 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.9 g of compound 31_P1. (Yield 71%, MS: [M+H] + = 751)

[0315] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.8 g of compound 31 (yield 66%, MS: [M+H] += 774)

[0316]

[0317] Manufacturing Example 32

[0318]

[0319] In a nitrogen atmosphere, compound amine32 (15 g, 28.6 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.9 g of compound 32_P1. (Yield 69%, MS: [M+H] + = 803)

[0320] 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. After that, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.5 g of compound 32 (yield 73%, MS: [M+H] + = 824)

[0321]

[0322] Manufacturing Example 33

[0323]

[0324] In a nitrogen atmosphere, compound amine33 (15 g, 30.1 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.5 g of compound 33_P1. (Yield 75%, MS: [M+H] + = 777)

[0325] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, 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 33. (Yield 70%, MS: [M+H]+ = 801)

[0326]

[0327] Manufacturing Example 34

[0328]

[0329] In a nitrogen atmosphere, compound amine 34 (15 g, 39.5 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20 g of compound 34_P1. (Yield 77%, MS: [M+H] + = 659)

[0330] 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 ℃ and stirred for 10 hours to prepare a solution. After that, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 ℃ and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7 g of compound 34 (yield 68%, MS: [M+H] + = 676)

[0331]

[0332] Manufacturing Example 35

[0333]

[0334] In a nitrogen atmosphere, compound amine 35 (15 g, 34.6 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19.2 g of compound 35_P1. (Yield 78%, MS: [M+H] + = 713)

[0335] 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. Afterwards, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of compound 35 (yield 63%, MS: [M+H]+ = 732)

[0336]

[0337] Manufacturing Example 36

[0338]

[0339] In a nitrogen atmosphere, compound amine36 (15 g, 33.5 mmol), compound sub3 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.5 g of compound 36_P1. (Yield 68%, MS: [M+H] + = 727)

[0340] 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. Afterwards, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.6 g of compound 36 (yield 74%, MS: [M+H] + = 748)

[0341]

[0342] Manufacturing Example 37

[0343]

[0344] In a nitrogen atmosphere, compound amine37 (15 g, 35.6 mmol), compound sub3 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.9 g of compound 37_P1. (Yield 60%, MS: [M+H] + = 701)

[0345] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.4 g of compound 37 (yield 62%, MS: [M+H]+ = 719)

[0346]

[0347] Manufacturing Example 38

[0348]

[0349] In a nitrogen atmosphere, compound amine 38 (15 g, 38.1 mmol), compound sub 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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.2 g of compound 38_P1. (Yield 67%, MS: [M+H] + = 673)

[0350] 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. Afterwards, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.6 g of compound 38 (yield 74%, MS: [M+H] + = 693)

[0351]

[0352] Manufacturing Example 39

[0353]

[0354] In a nitrogen atmosphere, compound amine39 (15 g, 41.8 mmol), compound sub3 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 23 g of compound 39_P1. (Yield 77%, MS: [M+H] + = 715)

[0355] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 5 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of compound 39 (yield 64%, MS: [M+H]+ = 731)

[0356]

[0357] Manufacturing Example 40

[0358]

[0359] In a nitrogen atmosphere, compound amine 40 (15 g, 35.6 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.8 g of compound 40_P1. (Yield 64%, MS: [M+H] + = 651)

[0360] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and 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)

[0361]

[0362] Manufacturing Example 41

[0363]

[0364] In a nitrogen atmosphere, compound amine 41 (15 g, 31.8 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.7 g of compound 41_P1. (Yield 75%, MS: [M+H] + = 701)

[0365] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and 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)

[0366]

[0367] Manufacturing Example 42

[0368]

[0369] In a nitrogen atmosphere, compound amine 42 (15 g, 35.6 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.4 g of compound 42_P1. (Yield 71%, MS: [M+H] + = 651)

[0370] 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 ℃ and stirred for 10 hours to prepare a solution. After that, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 ℃ and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and 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)

[0371]

[0372] Manufacturing Example 43

[0373]

[0374] In a nitrogen atmosphere, compound amine 43 (15 g, 33.5 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.7 g of compound 43_P1. (Yield 65%, MS: [M+H] + = 677)

[0375] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.4 g of compound 43 (yield 61%, MS: [M+H]+ = 708)

[0376]

[0377] Manufacturing Example 44

[0378]

[0379] In a nitrogen atmosphere, compound amine 44 (15 g, 32.9 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.2 g of compound 44_P1. (Yield 63%, MS: [M+H] + = 685)

[0380] 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 ℃ and stirred for 10 hours to prepare a solution. After that, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 ℃ and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.6 g of compound 44 (yield 72%, MS: [M+H] + = 722)

[0381]

[0382] Manufacturing Example 45

[0383]

[0384] In a nitrogen atmosphere, compound amine 45 (15 g, 34.6 mmol), compound sub1 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.7 g of compound 45_P1. (Yield 73%, MS: [M+H] + = 663)

[0385] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and 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)

[0386]

[0387] Manufacturing Example 46

[0388]

[0389] In a nitrogen atmosphere, compound amine 46 (15 g, 35.6 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 15.2 g of compound 46_P1. (Yield 61%, MS: [M+H] + = 701)

[0390] 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. Afterwards, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and 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)

[0391]

[0392] Manufacturing Example 47

[0393]

[0394] In a nitrogen atmosphere, compound amine 47 (15 g, 31.7 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.6 g of compound 47_P1. (Yield 74%, MS: [M+H] + = 753)

[0395] 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. Afterwards, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.3 g of compound 47 (yield 70%, MS: [M+H]+ = 788)

[0396]

[0397] Manufacturing Example 48

[0398]

[0399] In a nitrogen atmosphere, compound amine 48 (15 g, 38.9 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 18.9 g of compound 48_P1. (Yield 73%, MS: [M+H] + = 665)

[0400] 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 ℃ and stirred for 10 hours to prepare a solution. After that, the mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 ℃ and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and 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)

[0401]

[0402] Manufacturing Example 49

[0403]

[0404] In a nitrogen atmosphere, compound amine 49 (15 g, 39.7 mmol), compound sub2 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.2 g of compound 49_P1. (Yield 62%, MS: [M+H] + = 657)

[0405] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, 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 49 (yield 69%, MS: [M+H]+ = 688)

[0406]

[0407] Manufacturing Example 50

[0408]

[0409] In a nitrogen atmosphere, compound amine50 (15 g, 31.8 mmol), compound sub3 (12 g, 33.4 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to 300 ml of xylene, stirred, and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. After that, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 17.4 g of compound 50_P1. (Yield 73%, MS: [M+H] + = 751)

[0410] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.4 g of compound 50 (yield 61%, MS: [M+H] + = 788)

[0411]

[0412] Manufacturing Example 51

[0413]

[0414] In a nitrogen atmosphere, compound amine 51 (15 g, 33.5 mmol), compound sub3 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 19 g of compound 51_P1. (Yield 78%, MS: [M+H] + = 727)

[0415] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, 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 51 (yield 69%, MS: [M+H]+ = 761)

[0416]

[0417] Manufacturing Example 52

[0418]

[0419] In a nitrogen atmosphere, compound amine 52 (15 g, 36.6 mmol), compound sub3 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 16.4 g of compound 52_P1. (Yield 65%, MS: [M+H] + = 689)

[0420] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.4 g of compound 52 (yield 61%, MS: [M+H] + = 724)

[0421]

[0422] Manufacturing Example 53

[0423]

[0424] In a nitrogen atmosphere, compound amine 53 (15 g, 45 mmol), compound sub3 (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 completed, cooled to room temperature, and the solvent was removed under reduced pressure. After this, the compound was completely dissolved in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 20.6 g of compound 53_P1. (Yield 75%, MS: [M+H] + = 613)

[0425] 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. Afterwards, a mixed solution of trifluoromethanesulfonic anhydride and deuterium oxide was added dropwise to the prepared mixed solution of 1,2,4-trichlorobenzene, and the mixture was heated to 140 °C and stirred while maintaining the temperature. After 10 hours of reaction, the mixture was cooled to room temperature and the organic layer and aqueous layer 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, stirred, filtered, and 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)

[0426]

[0427] Example 1-1

[0428] A glass substrate coated with a 1000 Å thick ITO (Indium Tin Oxide) thin film was placed in distilled water containing detergent and ultrasonically cleaned. The detergent was a Fischer Co. product, and the distilled water was distilled water that had been filtered twice through a Millipore Co. filter. After washing the ITO for 30 minutes, ultrasonically cleaned twice with distilled water for 10 minutes each. After washing with distilled water, ultrasonically cleaned with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transferred to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using oxygen plasma and then transferred to a vacuum deposition machine.

[0429] On the ITO transparent electrode thus prepared, the following compound HI-1 was formed as a hole injection layer with a thickness of 1100 Å, and the following compound A-1 was p-doped at a concentration of 1.5 wt%. The following compound HT-1 was vacuum-deposited on the hole injection layer to form a hole transport layer with a film thickness of 800 Å. Next, the previously prepared compound 1 was thermally vacuum-deposited as a hole transport auxiliary layer with a thickness of 100 Å. Next, the following compound BH-1 and compound BD-1 were vacuum-deposited as an emitting layer with a weight ratio of 25:1 to a thickness of 250 Å. Next, the following compound HB-1 was vacuum-deposited as a hole blocking layer with a thickness of 50 Å. Next, the following compound ET-1 and the following compound LiQ were thermally vacuum-deposited as a layer performing both electron transport and electron injection at the same time with a weight ratio of 1:1 to a thickness of 310 Å. An organic light-emitting device was manufactured by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1000 Å on the electron transport and electron injection layers to form a cathode.

[0430]

[0431] In the above process, the deposition rate of organic materials was maintained at 0.4 to 0.7 Å / sec, the lithium fluoride of the cathode was maintained at 0.3 Å / sec, and the aluminum was maintained at 2 Å / sec, and the vacuum during deposition was 2*10 -7 ~ 5*10 -6 torr, and an organic light-emitting device was manufactured.

[0432]

[0433] Examples 1-2 to 1-53

[0434] Organic light-emitting devices of Examples 1-2 to 1-53 were manufactured in the same manner as in Example 1-1, except that the compounds described in Table 1 below were used instead of Compound 1.

[0435]

[0436] Comparative Examples 1-1 to 1-6

[0437] Organic light-emitting devices of Comparative Examples 1-1 to 1-6 were manufactured in the same manner 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 as follows.

[0438]

[0439]

[0440] Experimental example

[0441] 15 mA / cm for the organic light-emitting devices manufactured in Examples 1-1 to 1-53 and Comparative Examples 1-1 to 1-6 2 When a current of , voltage and efficiency were measured and the results are shown in Table 1 below. Lifespan T95 refers to the time required for the luminance to decrease to 95% of the initial luminance (1000 nit).

[0442]

[0443] Compound Voltage (V) Efficiency (cd / A) Lifespan T95 (hr) Luminescent color Example 1-1 Compound 13.474.76191 Blue Example 1-2 Compound 23.574.73194 Blue Example 1-3 Compound 33.524.62199 Blue Example 1-4 Compound 43.504.77203 Blue Example 1-5 Compound 53.544.86198 Blue Example 1-6 Compound 63.594.78186 Blue Example 1-7 Compound 73.474.74195 Blue Example 1-8 Compound 83.544.67191 Blue Example 1-9 Compound 93.514.74203 Blue Example 1-10 Compound 103.325.06208 Blue Example 1-11 Compound 113.375.14222 Blue Example 1-12 Compound 123.344.98214 Blue Example 1-13 Compound 133.424.88203 Blue Example 1-14 Compound 143.365.02208 Blue Example 1-15 Compound 153.415.14216 Blue Example 1-16 Compound 163.394.93223 Blue Example 1-17 Compound 173.545.09218 Blue Example 1-18 Compound 183.475.02220 Blue Example 1-19 Compound 193.494.98214 Blue Example 1-20 Compound 203.505.01227 Blue Example 1-21 Compound 213.475.07224 Blue Example 1-22 Compound 223.524.93208 Blue Example 1-23 Compound 233.564.98203 Blue Example 1-24 Compound 243.504.77211 Blue Example 1-25 Compound 253.484.89213 Blue Example 1-26 Compound 263.564.90209 Blue Example 1-27 Compound 273.464.93215 Blue Example 1-28 Compound 283.514.84208 Blue Example 1-29 Compound 293.564.91227 Blue Example 1-30 Compound 303.474.77212 Blue Example 1-31 Compound 313.415.17225 Blue Example 1-32 Compound 323.445.07237 Blue Example 1-33 Compound 333.355.06244 Blue Example 1-34 Compound 343.364.97237 Blue Example 1-35 Compound 353.375.13227 Blue Example 1-36 Compound 363.515.02235 Blue Example 1-37 Compound 373.475.15244 Blue Example 1-38 Compound 383.565.00229 Blue Example 1-39 Compound 393.545.03247 Blue Example 1-40 Compound 403.494.81261 Blue Example 1-41 Compound 413.454.89257 Blue Example 1-42 Compound 423.514.90242 Blue Example 1-43 Compound 433.584.83264 Blue Example 1-44 Compound 443.534.92261 Blue Example 1-45 Compound 453.494.78253 Blue Example 1-46 Compound 463.364.77246 Blue Example 1-47 Compound 473.494.69263 Blue Example 1-48 Compound 483.364.84252 Blue Example 1-49 Compound 493.424.92261 Blue Example 1-50 Compound 503.515.05247 Blue Example 1-51 Compound 513.544.92256 Blue Example 1-52 Compound 523.614.95246 Blue Example 1-53 Compound 533.585.08253 Blue Comparative Example 1-1 Compound C-14.024.1881 Blue Comparative Example 1-2 Compound C-23.924.35153Blue Comparative Example 1-3 Compound C-33.844.49137Blue Comparative Example 1-4 Compound C-43.934.42168Blue Comparative Example 1-5 Compound C-53.864.37136Blue Comparative Example 1-6 Compound C-63.874.46142Blue.

[0444]

[0445] As can be seen in Table 1 above, it was confirmed that the organic light-emitting device using the compound of the present invention showed an improvement in driving voltage, efficiency, and lifespan compared to the organic light-emitting device of the comparative example. In addition, it was confirmed that the organic light-emitting device using the compound substituted with deuterium further increased the lifespan characteristics. It is believed that the effect of improving the characteristics of the organic light-emitting device is achieved by using the compound of the present invention in the hole transport auxiliary layer by contributing to the stability of the excitons formed in the light-emitting layer.

[0446]

[0447] [Explanation of symbols]

[0448] 1: Substrate 2: Anode

[0449] 3: Organic layer 4: Cathode

[0450] 5: Hole injection layer 6: Hole transport layer

[0451] 7: Hole transport auxiliary layer 8: Light emitting layer

[0452] 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 above chemical formula 1, Dn means that n hydrogens are replaced with deuterium, n is an integer greater than or equal to 0, A is phenyl which is unsubstituted or substituted with one or more deuterium atoms, or naphthyl which is unsubstituted or substituted with one or more deuterium atoms, L1 and L2 are each independently a single bond, phenylene, or naphthalenediyl, and the phenylene and naphthalenediyl are each independently unsubstituted or substituted with at least one selected from the group consisting of deuterium; phenyl unsubstituted or substituted with deuterium; and naphthyl unsubstituted or substituted with deuterium; Ar1 and Ar2 are each independently C 1-10 Alkyl-substituted phenyl, biphenylyl, terphenylyl, naphthyl, benzo[c]phenanthrenyl, chrysenyl, phenyl naphthyl, naphthylphenyl, or any one selected from the group consisting of; wherein C 1-10 Phenyl substituted with alkyl is unsubstituted or substituted with deuterium; the group consisting of biphenylyl, terphenylyl, naphthyl, benzo[c]phenanthrenyl, chrysenyl, phenyl naphthyl, naphthyl phenyl and the group consisting of the following are each independently unsubstituted or substituted with deuterium and unsubstituted or substituted with deuterium C 1-10 is substituted with one or more selected from the group consisting of alkyl: .

2. In paragraph 1, L1 and L2 are each independently a single bond, phenylene, naphthalenediyl, or any one selected from the group consisting of the following, wherein the phenylene, naphthalenediyl, and the group consisting of the following are each independently unsubstituted or substituted with one or more deuterium. compound: .

3. In paragraph 1, L1 and L2 are each independently a single bond, or phenylene which is unsubstituted or substituted with one or more deuteriums, compound.

4. In paragraph 1, Ar1 and Ar2 are each independently selected from the group consisting of phenyl, phenyl substituted with one methyl, phenyl substituted with two methyls, phenyl substituted with one isopropyl, phenyl substituted with two isopropyls, phenyl substituted with one tert-butyl, phenyl substituted with two tert-butyls, biphenylyl, terphenylyl, naphthyl, benzo[c]phenanthrenyl, chrysenyl, phenyl naphthyl, naphthylphenyl, or the group consisting of; wherein Ar1 and Ar2 are each independently unsubstituted or substituted with one or more deuterium, compound: .

5. In paragraph 1, The compound represented by the above chemical formula 1 is one selected from the group consisting of: compound: .

6. An organic light-emitting device comprising a first electrode; a second electrode provided opposite the first electrode; and one or more organic layers provided between the first electrode and the second electrode, wherein at least one of the organic layers comprises a compound according to any one of claims 1 to 5. Organic light emitting diode.

7. In paragraph 6, The above organic layer is a hole injection layer, a hole transport layer, or a hole transport auxiliary layer. Organic light emitting diode.

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