Novel compounds and organic light-emitting devices comprising the same

Abstract

The present invention provides novel compounds and organic light emitting devices comprising the same.

Description

Technical Field

[0001] Cross-reference with related applications

[0002] This application claims priority based on Korean Patent Application No. 10-2021-0155895 dated November 12, 2021 and Korean Patent Application No. 10-2022-0148773 dated November 9, 2022, the entire contents disclosed in those Korean patent applications being incorporated into this specification.

[0003] This invention relates to novel compounds and organic light-emitting devices containing the same. Background Technology

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

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

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

[0007] Existing technical documents

[0008] Patent documents

[0009] (Patent Document 0001) Korean Patent Publication No. 10-2000-0051826 Summary of the Invention

[0010] Technical issues

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

[0012] Solution to the problem

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

[0014] [Chemical Formula 1]

[0015]

[0016] In the above chemical formula 1,

[0017] Y is either O or S.

[0018] Each of X is independently either N or CR1, and at least one of X is N.

[0019] R1 is hydrogen; deuterium; substituted or unsubstituted C. 1-60 Alkyl; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Mixed aromatics,

[0020] R2 can be either hydrogen or deuterium independently.

[0021] L can be a single bond, or a substituted or unsubstituted C bond. 6-60 Alpha-aryl

[0022] Ar1 and Ar2 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Mixed aromatics,

[0023] n1 is an integer from 0 to 5.

[0024] In addition, the present invention provides an organic light-emitting device, comprising: a first electrode, a second electrode disposed opposite to the first electrode, and an organic layer of one or more disposed between the first electrode and the second electrode, wherein one or more of the organic layers comprises a compound represented by the above chemical formula 1.

[0025] Invention Effects

[0026] The compounds represented by the above-described chemical formula 1 can be used as materials for the organic layer of organic light-emitting devices, thereby achieving improved efficiency, lower driving voltage, and / or improved lifetime characteristics in organic light-emitting devices. In particular, the compounds represented by the above-described chemical formula 1 can be used as materials for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection. Attached Figure Description

[0027] Figure 1 The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.

[0028] Figure 2The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4. Detailed Implementation

[0029] The invention will now be described in more detail to aid in understanding.

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

[0031] In this specification, the term "substituted or unsubstituted" refers to a group selected from deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thio group. aryl thiols alkylsulfonyl arylsulfonyl Silyl; boronyl; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; arylene; alkylaryl; alkylamino; aralkylamino; heteroarylamino; arylamino; arylphosphinyl; or a substituent formed by connecting two or more of the above-exemplified substituents, either substituted or unsubstituted. For example, "a substituent formed by connecting two or more substituents" can be biphenyl. That is, biphenyl can be aryl, or it can be interpreted as a substituent formed by connecting two phenyl groups.

[0032] In this specification, the number of carbon atoms in the carbonyl group is not particularly limited, but it is preferred to have 1 to 40 carbon atoms. Specifically, it can be a substituent with the following structures, but is not limited thereto.

[0033]

[0034] In this specification, the oxygen in the ester group can be replaced by a straight-chain, branched, or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, it can be a substituent of the following structural formula, but is not limited thereto.

[0035]

[0036] In this specification, the number of carbon atoms in the imide group is not particularly limited, but it is preferred to have 1 to 25 carbon atoms. Specifically, it can be a substituent with the following structure, but is not limited thereto.

[0037]

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

[0039] In this specification, boron groups specifically include trimethylboronyl, triethylboronyl, tert-butyldimethylboronyl, triphenylboronyl, phenylboronyl, etc., but are not limited to these.

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

[0041] In this specification, the alkyl group can be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to yet another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but are not limited to these.

[0042] In this specification, the alkenyl group can be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to yet another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, styryl, styryl, etc., but are not limited to these.

[0043] In this specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group with 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., are used, but are not limited to these.

[0044] In this specification, the aryl group is not particularly limited, but is preferably an aryl group with 6 to 60 carbon atoms, and can be a monocyclic aryl or polycyclic aryl. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to another embodiment, the aryl group has 6 to 20 carbon atoms. Regarding the aforementioned aryl group, as a monocyclic aryl group, it can be phenyl, biphenyl, terphenyl, etc., but is not limited to these. As the aforementioned polycyclic aryl group, it can be naphthyl, anthraceneyl, phenanthryl, pyrene, perylene, etc. It includes bases, fluorenes, etc., but is not limited to these.

[0045] In this specification, the fluorene group can be substituted, and two substituents can combine with each other to form a spirostructure. When the fluorene group is substituted as described above, it can be used to...

[0046] Etc. But it is not limited to this.

[0047] In this specification, a heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as heteroelements. The number of carbon atoms is not particularly limited, but is preferably 2 to 60. Examples of heterocyclic groups include thiophene, furanyl, pyrrole, imidazole, and thiazolyl. azole group, Diazolyl, Triazolyl, Pyridyl, Bipyridyl, Pyrimidinyl, Triazinyl, Acridineyl, Pyridazinyl, Quinolinyl, Quinazolinyl, Quinoxalinyl, Phtharazineyl, Pyridopyrimidinyl, Pyridopyrazinyl, Pyrazenopyrazinyl, Isoquinolinyl, Indoleyl, Carbazoleyl, Benzo[] Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazole, benzothiophene, dibenzothiophene, benzofuranyl, phenanthroline, iso Azolyl, thiadiazolyl, phenthiazinyl, and dibenzofuranyl groups, but not limited to these.

[0048] In this specification, the aryl groups in aralkyl, aryl-alkenyl, alkylaryl, and arylamine are the same as those exemplified above. In this specification, the alkyl groups in aralkyl, alkylaryl, and alkylamine are the same as those exemplified above. In this specification, the heteroaryl groups in heteroarylamines are subject to the above description of heterocyclic groups. In this specification, the alkenyl groups in aryl-alkenyl are the same as those exemplified above. In this specification, arylene is a divalent group; otherwise, the above description of aryl groups applies. In this specification, heteroarylene is a divalent group; otherwise, the above description of heterocyclic groups applies. In this specification, the hydrocarbon ring is not a monovalent group but is formed by the combination of two substituents; otherwise, the above description of aryl or cycloalkyl groups applies. In this specification, the heterocycle is not a monovalent group but is formed by the combination of two substituents; otherwise, the above description of heterocyclic groups applies.

[0049] (compound)

[0050] The present invention provides compounds represented by the above chemical formula 1.

[0051] Preferably, the above chemical formula 1 is represented by any one of the following chemical formulas 1-1 to 1-6:

[0052] [Chemical Formula 1-1]

[0053]

[0054] [Chemical Formula 1-2]

[0055]

[0056] [Chemical Formulas 1-3]

[0057]

[0058] [Chemical Formulas 1-4]

[0059]

[0060] [Chemical Formulas 1-5]

[0061]

[0062] [Chemical Formulas 1-6]

[0063]

[0064] In the above chemical formulas 1-1 to 1-6,

[0065] Y, X, R2, L, Ar1, Ar2, and n1 are defined in the same way as in Formula 1.

[0066] Preferably, one of X is N.

[0067] Preferably, the above chemical formula 1 is represented by any one of the following chemical formulas 2-1 to 2-16:

[0068]

[0069]

[0070] In the above chemical formulas 2-1 to 2-16,

[0071] Y, R2, L, Ar1, Ar2, and n1 are defined the same as above.

[0072] X is N.

[0073] Preferably, R1 is hydrogen or deuterium.

[0074] Preferably, L is a single bond, phenylene, naphthylene, or biphenyl dimethyl, wherein the phenylene, naphthylene, or biphenyl dimethyl is not substituted or is substituted by one or more deuterium groups.

[0075] Preferably, L is a single bond or selected from any of the following groups:

[0076]

[0077] Preferably, Ar1 and Ar2 are each independently phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, phenylnaphthyl, naphthylphenyl, dibenzofuranyl, dibenzothiopheneyl, 9-phenyl-carbazoyl, carbazo-9-yl, benzophenanthryl, or The base, Ar1 and Ar2 mentioned above, are not substituted or are substituted by more than one deuterium.

[0078] Representative examples of compounds represented by the above chemical formula 1 are shown below:

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101] In addition, the present invention provides a method for manufacturing the compound represented by the above chemical formula 1 as shown in the following reaction formula 1.

[0102] [Reaction Formula 1]

[0103]

[0104] In the above reaction formula 1, except for Y, everything else is the same as defined above. Y is a halogen, preferably bromine or chlorine.

[0105] The above reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups used in the above reaction can be modified according to techniques known in the art. The above manufacturing method can be further specified in the manufacturing examples described later.

[0106] (Organic light-emitting devices)

[0107] Furthermore, the present invention provides an organic light-emitting device comprising a compound represented by the above-described chemical formula 1. As an example, the present invention provides an organic light-emitting device comprising: a first electrode, a second electrode disposed opposite to the first electrode, and one or more organic layers disposed between the first electrode and the second electrode, wherein one or more of the organic layers comprises a compound represented by the above-described chemical formula 1.

[0108] The organic layer of the organic light-emitting device of the present invention can be formed as a single layer or as a multilayer structure with two or more organic layers stacked on top of each other. For example, the organic light-emitting device of the present invention can have a structure including a hole injection layer, a hole transport layer, an electron suppression layer, a light-emitting layer, an electron transport layer, and an electron injection layer as organic layers. However, the structure of the organic light-emitting device is not limited to this and may include fewer organic layers.

[0109] In addition, the aforementioned organic layer may include a hole injection layer, a hole transport layer, or a layer that performs both hole injection and transport simultaneously, and the aforementioned hole injection layer, hole transport layer, or layer that performs both hole injection and transport simultaneously may contain a compound represented by the aforementioned chemical formula 1.

[0110] Furthermore, the aforementioned organic layer may include a light-emitting layer, which may contain a compound represented by the aforementioned chemical formula 1. In particular, the compound according to the present invention can be used as a dopant in the light-emitting layer.

[0111] In addition, the aforementioned organic layer may include an electron transport layer, an electron injection layer, or a layer that performs both electron transport and electron injection simultaneously, and the aforementioned electron transport layer, electron injection layer, or layer that performs both electron transport and electron injection simultaneously may contain a compound represented by the aforementioned chemical formula 1.

[0112] Furthermore, the organic light-emitting device according to the present invention can be a structure (normal type) in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. Additionally, the organic light-emitting device according to the present invention can be a reverse structure (inverted type) in which a cathode, one or more organic layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light-emitting device according to an embodiment of the present invention is illustrated below. Figure 1 and 2 .

[0113] Figure 1 The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In the structure described above, the compound represented by the above chemical formula 1 may be included in the light-emitting layer.

[0114] Figure 2 The illustration shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4. In the structure described above, the compound represented by the above-described chemical formula 1 may be included in the light-emitting layer.

[0115] The organic light-emitting device according to the present invention, except that one or more of the organic layers contain a compound represented by the above-described chemical formula 1, can be manufactured using materials and methods known in the art. Furthermore, when the organic light-emitting device comprises a plurality of organic layers, the organic layers can be formed from the same substance or different substances.

[0116] For example, the organic light-emitting device according to the present invention can be manufactured by sequentially stacking a first electrode, an organic layer, and a second electrode on a substrate. This can be achieved by: depositing a metal or a conductive metal oxide or alloy thereof onto the substrate using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation to form an anode; then forming an organic layer comprising a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer on the anode; and finally depositing a material suitable for use as a cathode onto the organic layer. Alternatively, the organic light-emitting device can also be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material onto the substrate.

[0117] Furthermore, the compound represented by the above chemical formula 1 can be used to form an organic layer in the manufacture of organic light-emitting devices not only by vacuum evaporation but also by solution coating. Here, solution coating refers to methods such as spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, and roller coating, but is not limited to these.

[0118] In addition to these methods, organic light-emitting devices can also be manufactured by sequentially depositing a cathode material, an organic layer, and an anode material on a substrate (WO 2003 / 012890). However, the manufacturing method is not limited to these methods.

[0119] As an example, the first electrode is the anode and the second electrode is the cathode, or the first electrode is the cathode and the second electrode is the anode.

[0120] As the aforementioned anode material, a material with a high work function is preferred in order to facilitate the injection of holes into the organic layer. Specific examples of the aforementioned anode materials include metals such as vanadium, chromium, copper, zinc, and gold, or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylidene-1,2-dioxo)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited to these.

[0121] As the cathode material described above, a material with a low work function is generally preferred in order to facilitate the injection of electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or their alloys; multilayer structures such as LiF / Al or LiO2 / Al, etc., but are not limited to these.

[0122] The aforementioned hole injection layer is a layer that injects holes from the electrode. Preferably, the hole injection material is a compound that possesses the ability to transport holes, the effect of injecting holes from the anode, excellent hole injection performance for the light-emitting layer or light-emitting material, prevents excitons generated in the light-emitting layer from migrating to the electron injection layer or electron injection material, and exhibits excellent thin film formation capability. Preferably, the HOMO (highest occupied molecular orbital) of the hole injection material is between that of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injection materials include, but are not limited to, metalloporphyrins, oligothiophenes, arylamine-based organic compounds, hexanitrile hexaazabenzophenanthrene-based organic compounds, quinacridone-based organic compounds, perylene-based organic compounds, anthraquinones, and conductive polymers based on polyaniline and polythiophene.

[0123] The aforementioned hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light-emitting layer. The hole transport material is a substance capable of receiving holes from the anode or hole injection layer and transferring them to the light-emitting layer; substances with high hole mobility are suitable. Specific examples include aryl amine-based organic compounds, conductive polymers, and block copolymers that simultaneously contain conjugated and non-conjugated portions, but are not limited to these.

[0124] The aforementioned luminescent material is capable of receiving holes and electrons from the hole transport layer and electron transport layer, respectively, and combining them to emit light in the visible light region. Preferably, it is a material with high quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxyquinoline aluminum complex (Alq3); carbazole compounds; diluted styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; and benzo[…]. Compounds of the azole, benzothiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV) polymers; spirocyclic compounds; polyfluorene, fluorene, etc., but not limited to these.

[0125] The aforementioned luminescent layer may comprise a host material and a dopant material. The host material may be an aromatic fused-ring derivative or a heterocyclic compound. Specifically, aromatic fused-ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentane derivatives, phenanthrene compounds, and fluoranthene compounds; heterocyclic compounds include carbazole derivatives, dibenzofuran derivatives, and ladder-type furan compounds. Pyrimidine derivatives, etc., but not limited to these.

[0126] As dopant materials, there are aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives are aromatic fused-ring derivatives with substituted or unsubstituted aryl amino groups, such as pyrene, anthracene, etc. Diindrone pyrene, etc., styrylamine compounds are compounds in which at least one aryl vinyl group is substituted onto a substituted or unsubstituted arylamine, and is substituted or unsubstituted by one or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino groups. Specifically, there are styrylamines, styryldiamines, styryltriamines, styryltetraamines, etc., but they are not limited to these. In addition, as metal complexes, there are iridium complexes, platinum complexes, etc., but they are not limited to these.

[0127] The aforementioned electron transport layer is the layer that receives electrons from the electron injection layer and transports them to the light-emitting layer. The electron transport material is one that can effectively receive electrons from the cathode and transfer them to the light-emitting layer; materials with high electron mobility are suitable. Specific examples include Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavonoid-metal complexes, etc., but are not limited to these. The electron transport layer can be used with any desired cathode material as used in the prior art. In particular, examples of suitable cathode materials are common materials with low work functions and accompanied by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium, and samarium are all accompanied by an aluminum or silver layer.

[0128] The aforementioned electron injection layer is a layer that injects electrons from the electrode. Preferably, compounds are those that possess electron transport capabilities, effectively inject electrons from the cathode, exhibit excellent electron injection performance for the light-emitting layer or light-emitting material, prevent excitons generated in the light-emitting layer from migrating to the hole injection layer, and possess excellent thin-film forming ability. Specifically, these include fluorenone, anthraquinone dimethyl ether, biphenylquinone, thiamethoxam dioxide, etc. azole, Diazoles, triazoles, imidazoles, perylenetetracarboxylic acid, fluorenemethane, anthrones, and their derivatives, metal coordination compounds, and nitrogen-containing five-membered ring derivatives, but not limited to these.

[0129] Examples of the aforementioned metal coordination compounds include lithium 8-hydroxyquinoline, bis(8-hydroxyquinoline)zinc, bis(8-hydroxyquinoline)copper, bis(8-hydroxyquinoline)manganese, tris(8-hydroxyquinoline)aluminum, tris(2-methyl-8-hydroxyquinoline)aluminum, tris(8-hydroxyquinoline)gallium, bis(10-hydroxybenzo[h]quinoline)beryllium, bis(10-hydroxybenzo[h]quinoline)zinc, bis(2-methyl-8-hydroxyquinoline)gallium chloride, bis(2-methyl-8-hydroxyquinoline)(o-cresol)gallium, bis(2-methyl-8-hydroxyquinoline)(1-naphthol)aluminum, and bis(2-methyl-8-hydroxyquinoline)(2-naphthol)gallium, but are not limited to these.

[0130] Depending on the materials used, the organic light-emitting device according to the present invention can be a top-emitting type, a bottom-emitting type, or a bidirectional-emitting type.

[0131] In addition, the compounds according to the present invention can be included not only in organic light-emitting devices, but also in organic solar cells or organic transistors.

[0132] The manufacture of compounds represented by the above chemical formula 1 and organic light-emitting devices containing them is specifically described in the following examples. However, the following examples are for illustrative purposes only and the scope of the invention is not limited thereto.

[0133] [Example]

[0134] Manufacturing Example 1

[0135]

[0136] 4-bromopyridin-3-amine (15 g, 86.7 mmol) and (3-chloro-1-methoxynaphthalen-2-yl)boronic acid (21.5 g, 91 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (35.9 g, 260.1 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.7 g of compound A-1-3_P1. (Yield 72%, MS: [M+H)) + =285)

[0137] Compound A-1-3_P1 (15 g, 52.7 mmol) and HBF4 (9.3 g, 105.4 mmol) were added to 150 mL of acetonitrile and stirred. Then, NaNO2 (14.6 g, 105.4 mmol) was dissolved in 30 mL of water and slowly added at 0 °C. After reacting for 10 hours, the mixture was heated to room temperature and diluted with 300 mL of water. The solution was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 7.6 g of compound A-1-3_P2. (Yield 57%, MS: [M+H]) + =254)

[0138] Compound A-1-3_P2 (15 g, 59.1 mmol) and bis(pinacolato)diboron (16.5 g, 65 mmol) were mixed in 300 ml of 1,4-dioxanone solution. The mixture was refluxed and stirred in 1,4-dioxane. Potassium acetate (8.7 g, 88.7 mmol) was then added, and after thorough stirring, bis(dibenzylideneacetone)palladium(0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.5 mmol) were added. The reaction was allowed to proceed for 6 hours. After cooling to room temperature, the organic layer was separated using chloroform and water, and then distilled. The organic layer was redissolved in chloroform, washed twice with water, separated again, and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.5 g of compound A-1-3. (Yield 76%, MS: [M+H]) + =346)

[0139] Manufacturing Example 2

[0140]

[0141] 2-Bromopyridin-3-amine (15 g, 86.7 mmol) and (4-chloro-1-methoxynaphthalen-2-yl)boronic acid (21.5 g, 91 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (35.9 g, 260.1 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.7 g of compound A-2-1_P1. (Yield 68%, MS: [M+H]) + =285)

[0142] Compound A-2-1_P1 (15 g, 52.7 mmol) and HBF4 (9.3 g, 105.4 mmol) were added to 150 mL of acetonitrile and stirred. Then, NaNO2 (14.6 g, 105.4 mmol) was dissolved in 30 mL of water and slowly added at 0 °C. After reacting for 8 hours, the mixture was heated to room temperature and diluted with 300 mL of water. The solution was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 7.3 g of compound A-2-1_P2. (Yield 55%, MS: [M+H]) + =254)

[0143] Compound A-2-1_P2 (15 g, 59.1 mmol) and bis(pinacol)diboron (16.5 g, 65 mmol) were mixed in 300 ml of 1,4-dioxanone solution. The mixture was refluxed in alkane and stirred. Then, potassium acetate (8.7 g, 88.7 mmol) was added, and after thorough stirring, bis(dibenzylacetone)palladium(0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.5 mmol) were added. The reaction was allowed to proceed for 10 hours, cooled to room temperature, and the organic layer was separated using chloroform and water, followed by distillation. The organic layer was redissolved in chloroform, washed twice with water, separated again, and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.9 g of compound A-2-1. (Yield 73%, MS: [M+H]) + =346)

[0144] Manufacturing Example 3

[0145]

[0146] 3-bromopyridin-4-amine (15 g, 86.7 mmol) and (5-chloro-1-methoxynaphthalen-2-yl)boronic acid (21.5 g, 91 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (35.9 g, 260.1 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18.5 g of compound A-3-2_P1. (Yield 75%, MS: [M+H]) + =285)

[0147] Compound A-3-2_P1 (15 g, 52.7 mmol) and HBF4 (9.3 g, 105.4 mmol) were added to 150 mL of acetonitrile and stirred. Then, NaNO2 (14.6 g, 105.4 mmol) was dissolved in 30 mL of water and slowly added at 0 °C. After reacting for 9 hours, the mixture was heated to room temperature and diluted with 300 mL of water. The solution was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 7.9 g of compound A-3-2_P2 (yield 59%, MS: [M+H)). + =254)

[0148] Compound A-3-2_P2 (15 g, 59.1 mmol) and bis(pinacol)diboron (16.5 g, 65 mmol) were mixed in 300 ml of 1,4-dioxanone solution. The mixture was refluxed in alkane and stirred. Then, potassium acetate (8.7 g, 88.7 mmol) was added, and after thorough stirring, bis(dibenzylacetone)palladium(O) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.5 mmol) were added. The reaction was allowed to proceed for 5 hours, cooled to room temperature, and the organic layer was separated using chloroform and water, followed by distillation. The organic layer was redissolved in chloroform, washed twice with water, separated again, and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.5 g of compound A-3-2. (Yield 71%, MS: [M+H]) + =346)

[0149] Manufacturing Example 4

[0150]

[0151] 4-Bromopyridin-3-amine (15 g, 86.7 mmol) and (6-chloro-1-methoxynaphthalen-2-yl)boronic acid (21.5 g, 91 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (35.9 g, 260.1 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 mmol). After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.5 g of compound A-4-3_P1. (Yield 67%, MS: [M+H]) + =285)

[0152] Compound A-4-3_P1 (15 g, 52.7 mmol) and HBF4 (9.3 g, 105.4 mmol) were added to 150 mL of acetonitrile and stirred. Then, NaNO2 (14.6 g, 105.4 mmol) was dissolved in 30 mL of water and slowly added at 0 °C. After reacting for 8 hours, the mixture was heated to room temperature and diluted with 300 mL of water. The solution was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.1 g of compound A-4-3_P2. (Yield 68%, MS: [M+H]) + =254)

[0153] Compound A-4-3_P2 (15 g, 59.1 mmol) and bis(pinacol)diboron (16.5 g, 65 mmol) were mixed in 300 ml of 1,4-dioxanone solution. The mixture was refluxed in alkane and stirred. Then, potassium acetate (8.7 g, 88.7 mmol) was added, and after thorough stirring, bis(dibenzylacetone)palladium(O) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.5 mmol) were added. The reaction was allowed to proceed for 7 hours, cooled to room temperature, and the organic layer was separated using chloroform and water, followed by distillation. The organic layer was redissolved in chloroform, washed twice with water, separated again, and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.7 g of compound A-4-3. (Yield 72%, MS: [M+H]) + =346)

[0154] Manufacturing Example 5

[0155]

[0156] 3-bromopyridin-2-amine (15 g, 86.7 mmol) and (7-chloro-1-methoxynaphthalen-2-yl)boronic acid (21.5 g, 91 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (35.9 g, 260.1 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.3 g of compound A-5-4_P1. (Yield 62%, MS: [M+H]) + =285)

[0157] Compound A-5-4_P1 (15 g, 52.7 mmol) and HBF4 (9.3 g, 105.4 mmol) were added to 150 mL of acetonitrile and stirred. Then, NaNO2 (14.6 g, 105.4 mmol) was dissolved in 30 mL of water and slowly added at 0 °C. After reacting for 8 hours, the mixture was heated to room temperature and diluted with 300 mL of water. The solution was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.7 g of compound A-5-4_P2. (Yield 65%, MS: [M+H]) + =254)

[0158] Compound A-5-4_P2 (15 g, 59.1 mmol) and bis(pinacol)diboron (16.5 g, 65 mmol) were mixed in 300 ml of 1,4-dioxanone solution. The mixture was refluxed in alkane and stirred. Then, potassium acetate (8.7 g, 88.7 mmol) was added, and after thorough stirring, bis(dibenzylacetone)palladium(0) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.5 mmol) were added. The reaction was allowed to proceed for 10 hours, cooled to room temperature, and the organic layer was separated using chloroform and water, followed by distillation. The organic layer was redissolved in chloroform, washed twice with water, separated again, and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.1 g of compound A-5-4. (Yield 69%, MS: [M+H]) + =346)

[0159] Manufacturing Example 6

[0160]

[0161] 3-Bromopyridin-4-amine (15 g, 86.7 mmol) and (8-chloro-1-methoxynaphthalen-2-yl)boronic acid (21.5 g, 91 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (35.9 g, 260.1 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.9 mmol). After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.5 g of compound A-6-2_P1. (Yield 67%, MS: [M+H)) + =285)

[0162] Compound A-6-2_P1 (15 g, 52.7 mmol) and HBF4 (9.3 g, 105.4 mmol) were added to 150 mL of acetonitrile and stirred. Then, NaNO2 (14.6 g, 105.4 mmol) was dissolved in 30 mL of water and slowly added at 0 °C. After reacting for 10 hours, the mixture was heated to room temperature and diluted with 300 mL of water. The solution was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 7.5 g of compound A-6-2_P2. (Yield 56%, MS: [M+H]) + =254)

[0163] Compound A-6-2_P2 (15 g, 59.1 mmol) and bis(pinacol)diboron (16.5 g, 65 mmol) were mixed in 300 ml of 1,4-dioxanone solution. The mixture was refluxed in alkane and stirred. Then, potassium acetate (8.7 g, 88.7 mmol) was added, and after thorough stirring, bis(dibenzylacetone)palladium(O) (1 g, 1.8 mmol) and tricyclohexylphosphine (1 g, 3.5 mmol) were added. The reaction was allowed to proceed for 8 hours, cooled to room temperature, and the organic layer was separated using chloroform and water, followed by distillation. The organic layer was redissolved in chloroform, washed twice with water, separated again, and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.1 g of compound A-6-2. (Yield 74%, MS: [M+H)) + =346)

[0164] Manufacturing Example 7

[0165]

[0166] 2-Bromopyridine (15 g, 94.9 mmol) and (3-chloro-1-(methylthio)naphthalen-2-yl)boronic acid (25.2 g, 99.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (39.4 g, 284.8 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19.8 g of compound B-1-1_P1. (Yield 73%, MS: [M+H]) + =286)

[0167] Compound B-1-1_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 3 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9 g of compound B-1-1_P2. (Yield 57%, MS: [M+H)) + =302)

[0168] Compound B-1-1_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 3 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 5.2 g of compound B-1-1_P3. (Yield 41%, MS: [M+H)) + =254)

[0169] Compound B-1-1_P3 (15 g, 55.6 mmol) and bis(pinacol)diboron (15.5 g, 61.2 mmol) were mixed in 300 ml of 1,4-dioxanone solution. The mixture was refluxed in alkane and stirred. Then, potassium acetate (8.2 g, 83.4 mmol) was added, and after thorough stirring, bis(dibenzylacetone)palladium(0) (1 g, 1.7 mmol) and tricyclohexylphosphine (0.9 g, 3.3 mmol) were added. The reaction was allowed to proceed for 5 hours, cooled to room temperature, and the organic layer was separated using chloroform and water, followed by distillation. The organic layer was redissolved in chloroform, washed twice with water, separated again, and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.2 g of compound B-1-1. (Yield 61%, MS: [M+H]) + =362)

[0170] Manufacturing Example 8

[0171]

[0172] 3-bromopyridine (15 g, 94.9 mmol) and (4-chloro-1-(methylthio)naphthalen-2-yl)boronic acid (25.2 g, 99.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (39.4 g, 284.8 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.9 g of compound B-2-4_P1. (Yield 66%, MS: [M+H]) + =286)

[0173] Compound B-2-4_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 4 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.1 g of compound B-2-4_P2. (Yield 51%, MS: [M+H]) + =302)

[0174] Compound B-2-4_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.5 g of compound B-2-4_P3. (Yield 52%, MS: [M+H)) + =254)

[0175] Compound B-2-4_P3 (15 g, 55.6 mmol) and bis(pinacol)diboron (15.5 g, 61.2 mmol) were mixed in 300 ml of 1,4-dioxanone solution. The mixture was refluxed in alkane and stirred. Then, potassium acetate (8.2 g, 83.4 mmol) was added, and after thorough stirring, bis(dibenzylacetone)palladium(0) (1 g, 1.7 mmol) and tricyclohexylphosphine (0.9 g, 3.3 mmol) were added. The reaction was allowed to proceed for 5 hours, cooled to room temperature, and the organic layer was separated using chloroform and water, followed by distillation. The organic layer was redissolved in chloroform, washed twice with water, separated again, and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.9 g of compound B-2-4. (Yield 64%, MS: [M+H]) + =362)

[0176] Manufacturing Example 9

[0177]

[0178] 3-Bromopyridine (15 g, 94.9 mmol) and (5-chloro-1-(methylthio)naphthalen-2-yl)boronic acid (25.2 g, 99.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (39.4 g, 284.8 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol). After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18.4 g of compound B-3-4_P1. (Yield 68%, MS: [M+H]) +=286)

[0179] Compound B-3-4_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9 g of compound B-3-4_P2. (Yield 57%, MS: [M+H)) + =302)

[0180] Compound B-3-4_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 5.4 g of compound B-3-4_P3. (Yield 43%, MS: [M+H)) + =254)

[0181] Compound B-3-4_P3 (15 g, 55.6 mmol) and bis(pinacol)diboron (15.5 g, 61.2 mmol) were mixed in 300 ml of 1,4-dioxanone solution. The mixture was refluxed in alkane and stirred. Then, potassium acetate (8.2 g, 83.4 mmol) was added, and after thorough stirring, bis(dibenzylacetone)palladium(0) (1 g, 1.7 mmol) and tricyclohexylphosphine (0.9 g, 3.3 mmol) were added. The reaction was allowed to proceed for 10 hours, cooled to room temperature, and the organic layer was separated using chloroform and water, followed by distillation. The organic layer was redissolved in chloroform, washed twice with water, separated again, and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.2 g of compound B-3-4. (Yield 61%, MS: [M+H]) + =362)

[0182] Manufacturing Example 10

[0183]

[0184] 3-Bromopyridine (15 g, 94.9 mmol) and (6-chloro-1-(methylthio)naphthalen-2-yl)boronic acid (25.2 g, 99.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (39.4 g, 284.8 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.2 g of compound B-4-2_P1. (Yield 60%, MS: [M+H]) + =286)

[0185] Compound B-4-2_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 2 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.4 g of compound B-4-2_P2. (Yield 53%, MS: [M+H]) + =302)

[0186] Compound B-4-2_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, and the reactants were poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 5 g of compound B-4-2_P3. (Yield 40%, MS: [M+H)) + =254)

[0187] Compound B-4-2_P3 (15 g, 55.6 mmol) and bis(pinacol)diboron (15.5 g, 61.2 mmol) were mixed in 300 ml of 1,4-dioxanone solution. The mixture was refluxed in alkane and stirred. Then, potassium acetate (8.2 g, 83.4 mmol) was added, and after thorough stirring, bis(dibenzylacetone)palladium(0) (1 g, 1.7 mmol) and tricyclohexylphosphine (0.9 g, 3.3 mmol) were added. The reaction was allowed to proceed for 7 hours, cooled to room temperature, and the organic layer was separated using chloroform and water, followed by distillation. The organic layer was redissolved in chloroform, washed twice with water, separated again, and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.9 g of compound B-4-2. (Yield 69%, MS: [M+H]) + =362)

[0188] Manufacturing Example 11

[0189]

[0190] 2-Bromopyridine (15 g, 94.9 mmol) and (7-chloro-1-(methylthio)naphthalen-2-yl)boronic acid (25.2 g, 99.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (39.4 g, 284.8 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol). After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.9 g of compound B-5-1_P1. (Yield 66%, MS: [M+H]) + =286)

[0191] Compound B-5-1_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 4 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 8.8 g of compound B-5-1_P2. (Yield 56%, MS: [M+H]) + =302)

[0192] Compound B-5-1_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 4 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.5 g of compound B-5-1_P3. (Yield 52%, MS: [M+H)) + =254)

[0193] Compound B-5-1_P3 (15 g, 55.6 mmol) and bis(pinacol)diboron (15.5 g, 61.2 mmol) were mixed in 300 ml of 1,4-dioxanone solution. The mixture was refluxed in alkane and stirred. Then, potassium acetate (8.2 g, 83.4 mmol) was added, and after thorough stirring, bis(dibenzylacetone)palladium(0) (1 g, 1.7 mmol) and tricyclohexylphosphine (0.9 g, 3.3 mmol) were added. The reaction was allowed to proceed for 9 hours, cooled to room temperature, and the organic layer was separated using chloroform and water, followed by distillation. The organic layer was redissolved in chloroform, washed twice with water, separated again, and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12 g of compound B-5-1. (Yield 60%, MS: [M+H)) + =362)

[0194] Manufacturing Example 12

[0195]

[0196] 4-bromopyridine (15 g, 94.9 mmol) and (8-chloro-1-(methylthio)naphthalen-2-yl)boronic acid (25.2 g, 99.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (39.4 g, 284.8 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.2 g of compound B-6-3_P1. (Yield 60%, MS: [M+H]) +=286)

[0197] Compound B-6-3_P1 (15 g, 52.5 mmol) and hydrogen peroxide (2.7 g, 78.7 mmol) were added to 300 mL of acetic acid, stirred, and refluxed. After reacting for 5 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.2 g of compound B-6-3_P2. (Yield 58%, MS: [M+H]) + =302)

[0198] Compound B-6-3_P2 (15 g, 49.7 mmol) was added to 300 mL of sulfuric acid, stirred, and refluxed. After reacting for 2 hours, the mixture was cooled to room temperature, and the reaction mixture was poured into 600 mL of water to allow crystals to settle. The mixture was then filtered. The filtered solid was dissolved in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 6.9 g of compound B-6-3_P3. (Yield 55%, MS: [M+H)) + =254)

[0199] Compound B-6-3_P3 (15 g, 55.6 mmol) and bis(pinacol)diboron (15.5 g, 61.2 mmol) were mixed in 300 ml of 1,4-dioxanone solution. The mixture was refluxed in alkane and stirred. Then, potassium acetate (8.2 g, 83.4 mmol) was added, and after thorough stirring, bis(dibenzylacetone)palladium(0) (1 g, 1.7 mmol) and tricyclohexylphosphine (0.9 g, 3.3 mmol) were added. The reaction was allowed to proceed for 7 hours, cooled to room temperature, and the organic layer was separated using chloroform and water, followed by distillation. The organic layer was redissolved in chloroform, washed twice with water, separated again, and anhydrous magnesium sulfate was added. After stirring, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.5 g of compound B-6-3. (Yield 72%, MS: [M+H]) + =362)

[0200] Synthesis example 1

[0201]

[0202] Trz1 (15 g, 35.9 mmol) and compound A-6-4 (13 g, 37.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.6 g of compound 1. (Yield 68%, MS: [M+H)) + =601)

[0203] Synthesis example 2

[0204]

[0205] Trz2 (15 g, 35.4 mmol) and compound A-5-4 (12.8 g, 37.2 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.7 g, 106.2 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15 g of compound 2. (Yield 70%, MS: [M+H)) + =607)

[0206] Synthesis example 3

[0207]

[0208] Trz3 (15 g, 38.1 mmol) and compound A-4-4 (13.8 g, 40 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.9 g of compound 3. (Yield 77%, MS: [M+H)) + =577)

[0209] Synthesis example 4

[0210]

[0211] Trz4 (15 g, 41.9 mmol) and compound A-3-4 (15.2 g, 44 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.2 g of compound 4. (Yield 76%, MS: [M+H)) + =541)

[0212] Synthesis example 5

[0213]

[0214] Trz5 (15 g, 40.8 mmol) and compound A-3-4 (14.8 g, 42.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (16.9 g, 122.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.1 g of compound 5. (Yield 63%, MS: [M+H)) + =551)

[0215] Synthesis example 6

[0216]

[0217] Trz6 (15 g, 33.8 mmol) and compound A-6-3 (12.2 g, 35.5 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.3 g of compound 6. (Yield 63%, MS: [M+H)) + =627)

[0218] Synthesis Example 7

[0219]

[0220] Trz7 (15 g, 35.9 mmol) and compound A-5-3 (13 g, 37.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.2 g of compound 7. (Yield 66%, MS: [M+H)) + =601)

[0221] Synthesis example 8

[0222]

[0223] Trz8 (15 g, 41.9 mmol) and compound A-5-3 (15.2 g, 44 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.1 g of compound 8. (Yield 71%, MS: [M+H)) + =541)

[0224] Synthesis example 9

[0225]

[0226] Trz9 (15 g, 33.8 mmol) and compound A-4-3 (12.2 g, 35.5 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14 g of compound 9. (Yield 66%, MS: [M+H)) + =627)

[0227] Synthesis example 10

[0228]

[0229] Trz10 (15 g, 33.8 mmol) and compound A-4-3 (12.2 g, 35.5 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14 g of compound 10. (Yield 66%, MS: [M+H)) + =627)

[0230] Synthesis example 11

[0231]

[0232] Trz11 (15 g, 35.7 mmol) and compound A-3-3 (12.9 g, 37.5 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.9 g of compound 11. (Yield 60%, MS: [M+H)) + =603)

[0233] Synthesis example 12

[0234]

[0235] Trz12 (15 g, 34.6 mmol) and compound A-3-3 (12.6 g, 36.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.4 g, 103.9 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.3 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13 g of compound 12. (Yield 61%, MS: [M+H)) + =616)

[0236] Synthesis example 13

[0237]

[0238] Trz13 (15 g, 43.6 mmol) and compound A-6-2 (15.8 g, 45.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (18.1 g, 130.9 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.5 g of compound 13. (Yield 63%, MS: [M+H)) + =527)

[0239] Synthesis example 14

[0240]

[0241] Trz14 (15 g, 35.9 mmol) and compound A-5-2 (13 g, 37.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.9 g of compound 14. (Yield 60%, MS: [M+H)) + =601)

[0242] Synthesis Example 15

[0243]

[0244] Trz15 (15 g, 35.9 mmol) and compound A-4-2 (13 g, 37.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.9 g of compound 15. (Yield 69%, MS: [M+H)) + =601)

[0245] Synthesis example 16

[0246]

[0247] Trz16 (15 g, 38.1 mmol) and compound A-3-2 (13.8 g, 40 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.8 g of compound 16. (Yield 72%, MS: [M+H]) + =577)

[0248] Synthesis Example 17

[0249]

[0250] Trz17 (15 g, 35.9 mmol) and compound A-3-2 (13 g, 37.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.2 g of compound 17. (Yield 80%, MS: [M+H)) + =601)

[0251] Synthesis Example 18

[0252]

[0253] Trz18 (15 g, 38.1 mmol) and compound A-6-1 (13.8 g, 40 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.9 g of compound 18. (Yield 68%, MS: [M+H)) + =577)

[0254] Synthesis example 19

[0255]

[0256] Trz19 (15 g, 34.6 mmol) and compound A-5-1 (12.6 g, 36.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.4 g, 103.9 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.8 g of compound 19. (Yield 79%, MS: [M+H)) + =616)

[0257] Synthesis example 20

[0258]

[0259] Trz20 (15 g, 36.8 mmol) and compound A-4-1 (13.3 g, 38.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.5 g of compound 20. (Yield 62%, MS: [M+H)) + =591)

[0260] Synthesis Example 21

[0261]

[0262] Trz21 (15 g, 36.8 mmol) and compound A-3-1 (13.3 g, 38.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.5 g of compound 21. (Yield 76%, MS: [M+H)) + =591)

[0263] Synthesis example 22

[0264]

[0265] Trz22 (15 g, 35.9 mmol) and compound A-3-1 (13 g, 37.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.9 g of compound 22. (Yield 74%, MS: [M+H]) + =601)

[0266] Synthesis example 23

[0267]

[0268] Trz23 (15 g, 31 mmol) and compound B-6-4 (11.8 g, 32.5 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) was dissolved in 100 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.4 g of compound 23. (Yield 73%, MS: [M+H]) + =683)

[0269] Synthesis example 24

[0270]

[0271] Trz24 (15 g, 43.6 mmol) and compound B-5-4 (16.5 g, 45.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (18.1 g, 130.9 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.8 g of compound 24. (Yield 71%, MS: [M+H)) + =543)

[0272] Synthesis example 25

[0273]

[0274] Trz25 (15 g, 31.1 mmol) and compound B-4-4 (11.8 g, 32.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.9 g, 93.2 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.3 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15 g of compound 25. (Yield 71%, MS: [M+H)) + =682)

[0275] Synthesis Example 26

[0276]

[0277] Trz26 (15 g, 41.9 mmol) and compound B-3-4 (15.9 g, 44 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.9 g of compound 26. (Yield 68%, MS: [M+H]) + =557)

[0278] Synthesis Example 27

[0279]

[0280] Trz18 (15 g, 38.1 mmol) and compound B-3-4 (14.4 g, 40 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.8 g of compound 27. (Yield 61%, MS: [M+H)) + =593)

[0281] Synthesis example 28

[0282]

[0283] Trz14 (15 g, 35.9 mmol) and compound B-6-3 (13.6 g, 37.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.3 g of compound 28. (Yield 78%, MS: [M+H)) + =617)

[0284] Synthesis Example 29

[0285]

[0286] Trz27 (15 g, 38.1 mmol) and compound B-5-3 (14.4 g, 40 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18 g of compound 29. (Yield 80%, MS: [M+H)) + =593)

[0287] Synthesis example 30

[0288]

[0289] Trz15 (15 g, 35.9 mmol) and compound B-5-3 (13.6 g, 37.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.9 g of compound 30. (Yield 63%, MS: [M+H)) + =617)

[0290] Synthesis Example 31

[0291]

[0292] Trz28 (15 g, 40.1 mmol) and compound B-5-3 (15.2 g, 42.1 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (16.6 g, 120.4 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.2 g of compound 31. (Yield 75%, MS: [M+H)) + =573)

[0293] Synthesis example 32

[0294]

[0295] Trz22 (15 g, 35.9 mmol) and compound B-4-3 (13.6 g, 37.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15 g of compound 32. (Yield 68%, MS: [M+H)) + =617)

[0296] Synthesis example 33

[0297]

[0298] Trz21 (15 g, 36.8 mmol) and compound B-3-3 (14 g, 38.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.3 g of compound 33. (Yield 73%, MS: [M+H)) + =607)

[0299] Synthesis example 34

[0300]

[0301] Trz29 (15 g, 38.1 mmol) and compound B-3-3 (14.4 g, 40 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.5 g of compound 34. (Yield 60%, MS: [M+H)) + =593)

[0302] Synthesis Example 35

[0303]

[0304] Trz30 (15 g, 40.8 mmol) and compound B-6-2 (15.5 g, 42.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (16.9 g, 122.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.4 g of compound 35. (Yield 71%, MS: [M+H)) + =567)

[0305] Synthesis example 36

[0306]

[0307] Trz31 (15 g, 34.6 mmol) and compound B-5-2 (13.1 g, 36.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.4 g, 103.9 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16 g of compound 36. (Yield 71%, MS: [M+H)) + =652)

[0308] Synthesis Example 37

[0309]

[0310] Trz3 (15 g, 38.1 mmol) and compound B-4-2 (14.4 g, 40 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14 g of compound 37. (Yield 62%, MS: [M+H)) + =593)

[0311] Synthesis example 38

[0312]

[0313] Trz32 (15 g, 33.8 mmol) and compound B-4-2 (12.8 g, 35.5 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.1 g of compound 38. (Yield 65%, MS: [M+H)) + =643)

[0314] Synthesis Example 39

[0315]

[0316] Trz21 (15 g, 36.8 mmol) and compound B-3-2 (14 g, 38.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.4 g of compound 39. (Yield 60%, MS: [M+H]) + =607)

[0317] Synthesis Example 40

[0318]

[0319] Trz33 (15 g, 38.1 mmol) and compound B-6-1 (14.4 g, 40 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.5 g of compound 40. (Yield 60%, MS: [M+H)) + =593)

[0320] Synthesis Example 41

[0321]

[0322] Trz17 (15 g, 35.9 mmol) and compound B-5-1 (13.6 g, 37.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.4 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.7 g of compound 41. (Yield 71%, MS: [M+H)) + =617)

[0323] Synthesis Example 42

[0324]

[0325] Trz34 (15 g, 33.3 mmol) and compound B-4-1 (12.6 g, 35 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (13.8 g, 100 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.7 g of compound 42. (Yield 68%, MS: [M+H)) + =649)

[0326] Synthesis Example 43

[0327]

[0328] Trz11 (15 g, 35.7 mmol) and compound B-4-1 (13.6 g, 37.5 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(O) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.5 g of compound 43. (Yield 70%, MS: [M+H)) + =619)

[0329] Synthesis Example 44

[0330]

[0331] Trz3 (15 g, 38.1 mmol) and compound B-3-1 (14.4 g, 40 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 100 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18 g of compound 44. (Yield 80%, MS: [M+H)) + =593)

[0332] [Example]

[0333] Example 1

[0334] ITO (indium tin oxide) is used as A glass substrate coated with a thin film of ITO was immersed in distilled water containing detergent and washed using ultrasound. The detergent used was from Fischer Co., and the distilled water was filtered twice using a filter manufactured by Millipore Co. After washing the ITO for 30 minutes, the process was repeated twice with distilled water for 10 minutes of ultrasonic washing. Following the distilled water washing, the substrate was ultrasonically washed with a solvent of isopropanol, acetone, and methanol, dried, and then transferred to a plasma cleaner. Additionally, the substrate was cleaned with oxygen plasma for 5 minutes before being transferred to a vacuum evaporation machine.

[0335] On the prepared ITO transparent electrode, as a hole injection layer, the following HI-1 compound is applied... The thickness is formed by p-doping the following A-1 compound at a concentration of 1.5%. On the hole implantation layer, the following HT-1 compound is vacuum-deposited to form a film thickness of [missing information]. The hole transport layer. Next, on the aforementioned hole transport layer, at a film thickness of... An electron blocking layer was formed by vacuum evaporation of the following EB-1 compound. Next, on the EB-1 evaporated film, compound 1 (the main component) and compound Dp-7 (the dopant) were vacuum evaporated at a weight ratio of 98:2 to form... A red luminescent layer of a certain thickness. On the aforementioned luminescent layer, a film thickness of... A hole-blocking layer was formed by vacuum evaporation of the HB-1 compound described below. Next, the ET-1 compound and the LiQ compound described below were vacuum evaporated onto the hole-blocking layer in a 2:1 weight ratio, thereby achieving... The thickness forms an electron injection and transport layer. On this electron injection and transport layer, lithium fluoride (LiF) is sequentially applied... The thickness, using aluminum The cathode is formed by vapor deposition of a certain thickness.

[0336]

[0337] During the above process, the evaporation rate of organic matter is maintained. Lithium fluoride maintenance of the cathode The evaporation rate of aluminum maintains The evaporation rate was such that the vacuum level was maintained at 2×10⁻⁶ during evaporation. -7 ~5×10 -6 This led to the creation of organic light-emitting devices.

[0338] Examples 2 to 44

[0339] In Example 1 above, an organic light-emitting device was manufactured by the same method as in Example 1 above, except that the compounds described in Table 1 below were used.

[0340] Comparative Examples 1 to 13

[0341] In Example 1 above, an organic light-emitting device was manufactured using the same method as in Example 1, except that the compounds listed in Table 1 below were used. The compounds B-1 to B-13 in Table 1 below are shown below.

[0342]

[0343] When an electric current was applied to the organic light-emitting devices manufactured in Examples 1 to 44 and Comparative Examples 1 to 13, the voltage and efficiency (15 mA / cm²) were measured. 2 The results are shown in Table 1 below. Lifetime T95 refers to the time required for the brightness to decrease from the initial brightness (6000 nits) to 95%.

[0344] [Table 1]

[0345]

[0346]

[0347] When current was applied to the organic light-emitting devices fabricated in Examples 1 to 44 and Comparative Examples 1 to 13, the results shown in Table 1 were obtained. The red organic light-emitting device of Example 1 used a material that has been widely used in the past, and has a structure that uses compound EB-1 as an electron blocking layer and Dp-7 as a red dopant.

[0348] When the compounds of the present invention are used in the red emitting layer, compared with the comparative example compounds, a decrease in driving voltage and an increase in efficiency and lifetime are observed. This indicates that when the compounds of the present invention are used as the host, energy transfer to the red dopant within the red emitting layer is well achieved compared with the comparative example compounds. This can be attributed to the more stable equilibrium within the emitting layer compared with the comparative example compounds, allowing electrons and holes to combine and form excitons.

[0349] In summary, it can be confirmed that using the compounds of the present invention as the host of the red emitting layer can improve the driving voltage, luminous efficiency, and lifetime characteristics of organic light-emitting devices.

[0350] [Symbol Explanation]

[0351] 1: Substrate 2: Anode

[0352] 3: Light-emitting layer 4: Cathode

[0353] 5: Hole injection layer; 6: Hole transport layer

[0354] 7: Electron blocking layer; 8: Hole blocking layer

[0355] 9: Electron injection and transport layer.

Claims

1. A compound represented by the following Chemical Formula 1: [Chemical Formula 1] ， In the Chemical Formula 1, Y is O or S, X is each independently N or CR1, and one of X is N, R1 is hydrogen or deuterium, R2 is each independently hydrogen or deuterium, L is each independently a single bond, phenylene, naphthylene, or biphenyldiyl, the phenylene, naphthylene, and biphenyldiyl being unsubstituted or substituted with one or more deuterium, Ar1 and Ar2 are each independently phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, phenylnaphthyl, naphthylphenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenyl-carbazolyl, carbazol-9-yl, or phenanthryl, the Ar1 and Ar2 being unsubstituted or substituted with one or more deuterium, n1 is an integer of 0 to 5.

2. The compound of claim 1, wherein, The Chemical Formula 1 is represented by any one selected from the following Chemical Formulas 1-1 to 1-6: [Chemical Formula 1-1] ， [Chemical Formula 1-2] ， [Chemical Formula 1-3] ， [Chemical Formula 1-4] ， [Chemical Formula 1-5] ， [Chemical Formula 1-6] ， In the Chemical Formulas 1-1 to 1-6, Y, X, R2, L, Ar1, Ar2, and n1 are the same as defined in claim 1.

3. The compound of claim 1, wherein, The Chemical Formula 1 is represented by any one of the following Chemical Formulas 2-1 to 2-16: ， In the Chemical Formulas 2-1 to 2-16, Y, R2, L, Ar1, Ar2, and n1 are the same as defined in claim 1, X is N.

4. The compound of claim 1, wherein, L is a single bond or selected from any one of the following: 。 5. The compound of claim 1, wherein, The phenanthryl is a chrysenyl.

6. A compound which is any one selected from the following compounds: 。 7. An organic light emitting device, wherein, including: a first electrode, a second electrode disposed opposite to the first electrode, and one or more organic layers disposed between the first electrode and the second electrode, one or more of the organic layers containing the compound according to any one of claims 1 to 6.

8. The organic light emitting device according to claim 7, wherein, The organic layer containing the compound is a light-emitting layer.

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