Organic light emitting device

Abstract

The present disclosure provides organic light emitting devices.

Description

Technical Field

[0001] Cross-references to related applications

[0002] This application claims the benefit of Korean Patent Application No. 10-2020-0137751, filed on October 22, 2020, and Korean Patent Application No. 10-2021-0142117, filed on October 22, 2021, the disclosures of which are incorporated herein by reference in their entirety.

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

[0004] Organic light emission generally refers to the phenomenon of converting electrical energy into light energy using organic materials. Organic light-emitting devices (OLEDs) utilizing organic light emission exhibit characteristics such as wide viewing angle, excellent contrast ratio, fast response time, and superior brightness, driving voltage, and response speed, and have therefore been the subject of much research.

[0005] Organic light-emitting devices (OLEDs) typically have a structure comprising an anode, a cathode, and an organic material layer between the anode and cathode. The organic material layer often has a multilayer structure containing different materials to improve the efficiency and stability of the OLED. For example, the organic material layer can be formed from a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In the structure of an OLED, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic material layer, and electrons are injected from the cathode into the organic material layer. When the injected holes and electrons meet, excitons are formed, and light is emitted when the excitons return to the ground state.

[0006] There is a continued need to develop new organic materials for use in organic light-emitting devices as described above.

[0007] [Existing Technical Documents]

[0008] (Patent Document 0001) Korean Unexamined Patent Publication No. 10-2000-0051826 Summary of the Invention

[0009] Technical issues

[0010] This disclosure relates to organic light-emitting devices with improved drive voltage, efficiency, and lifetime.

[0011] Technical solution

[0012] In this public disclosure,

[0013] An organic light-emitting device is provided, the organic light-emitting device comprising:

[0014] Anode; cathode; and the light-emitting layer between the anode and cathode.

[0015] The luminescent layer comprises a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2:

[0016] [Chemical Formula 1]

[0017]

[0018] In chemical formula 1,

[0019] L is a single bond; or C is either substituted or unsubstituted. 6-60 Alpha-aryl

[0020] Ar1 and Ar2 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing at least one of N, O and S. 2-60 heteroaryl, and

[0021] Ar3 represents hydrogen; deuterium; and substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing at least one of N, O and S. 2-60 Mixed aromatics,

[0022] [Chemical Formula 2]

[0023]

[0024] In chemical formula 2,

[0025] A′ is a naphthalene ring fused with an adjacent ring and that is either unsubstituted or deuterated.

[0026] L′1 and L′2 are each independent single bonds; substituted or unsubstituted C 6-60 Aromatic; or substituted or unsubstituted C containing at least one of N, O, and S. 2-60 Hybrid aryl,

[0027] L′3 is C with or without substitution. 6-60 Aromatic; or substituted or unsubstituted C containing at least one of N, O and S. 2-60 Hybrid aryl, and

[0028] Ar′1 and Ar′2 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing at least one heteroatom selected from N, O, and S. 2-60 Mixed aromatic compounds.

[0029] Beneficial effects

[0030] The aforementioned organic light-emitting devices have improved driving voltage, efficiency, and lifetime. Attached Figure Description

[0031] Figure 1 An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.

[0032] Figure 2 An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 3, an electron transport layer 7, an electron injection layer 8, and a cathode 4.

[0033] Figure 3 An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 9, a light-emitting layer 3, a hole blocking layer 10, an electron injection and transport layer 11, and a cathode 4. Detailed Implementation

[0034] In the following sections, embodiments of the present disclosure will be described in more detail to facilitate understanding of the invention.

[0035] As used in this article, symbols This refers to a bond that is connected to another substituent.

[0036] As used herein, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from: deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thio group; aryl thio group; alkyl sulfonyl group; aryl sulfonyl group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; arylenyl group; alkylamino group; aralkylamino group; heteroarylamino group; arylamino group; arylphosphine group; and heterocyclic group containing at least one of N, O, and S atoms, or unsubstituted or substituted with two or more substituents linked together from the substituents exemplified above. For example, "substituents linked together from two or more substituents" can be biphenyl. That is, biphenyl can be aryl, or it can also be interpreted as a substituent in which two phenyl groups are linked together.

[0037] In this disclosure, the number of carbon atoms in the carbonyl group is not particularly limited, but is preferably from 1 to 40. Specifically, the carbonyl group can be a group having the following structural formula, but is not limited thereto.

[0038]

[0039] In this disclosure, the ester group may have a structure in which the oxygen atom of the ester group is substituted by a straight-chain, branched, or cyclic alkyl group having 1 to 25 carbon atoms, or by an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a group having the following structural formulas, but is not limited thereto.

[0040]

[0041] In this disclosure, the number of carbon atoms in the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the imide group can be a group having the following structural formula, but is not limited thereto.

[0042]

[0043] In this disclosure, silane specifically includes, but is not limited to, trimethylsilane, triethylsilane, tert-butyldimethylsilane, vinyldimethylsilane, propyldimethylsilane, triphenylsilane, diphenylsilane, phenylsilane, etc.

[0044] In this disclosure, boron group specifically includes, but is not limited to, trimethylboronyl, triethylboronyl, tert-butyldimethylboronyl, triphenylboronyl, phenylboronyl, etc.

[0045] Examples of halogen groups in this disclosure include fluorine, chlorine, bromine, or iodine.

[0046] In this disclosure, the alkyl group can be straight-chain or branched, and its carbon number is not particularly limited, but is preferably from 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbons. According to another embodiment, the alkyl group has 1 to 10 carbons. According to yet another embodiment, the alkyl group has 1 to 6 carbons. Specific examples of alkyl groups include, but are not limited to, 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.

[0047] In this disclosure, the alkenyl group can be straight-chain or branched, and its carbon number is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbons. According to another embodiment, the alkenyl group has 2 to 10 carbons. According to yet another embodiment, the alkenyl group has 2 to 6 carbons. Specific examples include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, styryl, styryl, etc.

[0048] In this disclosure, the cycloalkyl group is not particularly limited, but it is preferably composed of 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 yet another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc.

[0049] In this disclosure, the aryl group is not particularly limited, but it is preferably composed of 6 to 60 carbon atoms, and can be either a monocyclic aryl or a polycyclic aryl. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to another embodiment, the aryl group has 6 to 20 carbon atoms. Monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, etc. Polycyclic aryl groups include naphthyl, anthraceneyl, phenanthryl, pyrene, perylene, etc. It includes, but is not limited to, methyl, fluorene, etc.

[0050] In this disclosure, the fluorene group can be substituted, and the two substituents can bond together to form a spirocyclic structure. When the fluorene group is substituted, a spirocyclic structure can be formed. However, the structure is not limited to this.

[0051] In this disclosure, the heterocyclic group is a heterocyclic group containing at least one heteroatom selected from O, N, Si, and S as a heteroelement, and its carbon number is not particularly limited, but is preferably 2 to 60. Examples of heterocyclic groups include thiophene, furanyl, pyrrole, imidazolyl, thiazolyl, and others. 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, phenanthrolinel, iso Azolyl, thiadiazolyl, phenthiazinyl, dibenzofuranyl, etc., but not limited to these.

[0052] In this disclosure, the aryl group in aralkyl, arylene, alkylaryl, and arylamine is the same as the aforementioned examples of aryl. In this disclosure, the alkyl group in aralkyl, alkylaryl, and alkylamine is the same as the aforementioned examples of alkyl. In this disclosure, the heteroaryl group in heteroarylamine can be described using the aforementioned description of heterocyclic groups. In this disclosure, the alkenyl group in arylene is the same as the aforementioned examples of alkenyl. In this disclosure, the aforementioned description of aryl can be applied, except that the arylene group is a divalent group. In this disclosure, the aforementioned description of heterocyclic groups can be applied, except that the heteroarylene group is a divalent group. In this disclosure, the aforementioned description of aryl or cycloalkyl can be applied, except that the hydrocarbon ring is not a monovalent group but is formed by the combination of two substituents. In this disclosure, the aforementioned description of heterocyclic groups can be applied, except that the heterocycle is not a monovalent group but is formed by the combination of two substituents.

[0053] The invention will be described in detail below for each configuration.

[0054] Anode and cathode

[0055] The anode and cathode used in this disclosure refer to the electrodes used in organic light-emitting devices.

[0056] As an anode material, materials with a high work function are generally preferred to allow holes to be smoothly injected into the organic material layer. Specific examples of anode materials include: metals, such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides, such as ZnO:Al or SnO2:Sb; conductive polymers, such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxo)thiophene] (PEDOT), polypyrrole, and polyaniline; and so on, but are not limited thereto.

[0057] As cathode materials, materials with low work functions are generally preferred, allowing electrons to be easily injected into the organic material layer. Specific examples of cathode materials include: metals, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer materials, such as LiF / Al or LiO2 / Al; and so on, but are not limited to these.

[0058] Emissive layer

[0059] The luminescent layer used in this disclosure refers to a layer that emits light in the visible light region by combining holes and electrons transported from the anode and cathode. Typically, the luminescent layer comprises a host material and a dopant material. In this disclosure, compounds represented by Chemical Formula 1 and compounds represented by Chemical Formula 2 are used as the host material.

[0060] Based on the bonding positions of dibenzofuran and triazine, chemical formula 1 can be represented by the following chemical formula 1-1:

[0061] [Chemical Formula 1-1]

[0062]

[0063] In chemical formula 1-1, L and Ar1 to Ar3 are as defined in chemical formula 1.

[0064] Furthermore, based on the bonding positions of Ar3, chemical formula 1-1 can be represented by the following chemical formula 1-1-a:

[0065] [Chemical formula 1-1-a]

[0066]

[0067] In chemical formula 1-1-a, L and Ar1 to Ar3 are as defined in chemical formula 1.

[0068] Preferably, L is a single bond; or C is substituted or unsubstituted. 6-20 Aryl, Ar1, and Ar2 are each independently substituted or unsubstituted C. 6-20 aryl; or substituted or unsubstituted C containing at least one of N, O and S. 2-20 heteroaryl groups, and Ar3 being substituted or unsubstituted C. 6-20 aryl; or substituted or unsubstituted C containing at least one of N, O and S. 2-20 Mixed aromatic compounds.

[0069] Preferably, L is a single bond; phenylene; or naphthyldiyl.

[0070] Preferably, Ar1 and Ar2 are each independently phenyl; biphenyl; terphenyl; naphthyl; phenanthryl; phenylnaphthyl; naphthylphenyl; dibenzofuranyl; or dibenzothiophene.

[0071] Preferably, Ar3 is phenyl; biphenyl; terphenyl; naphthyl; phenanthrene; phenylnaphthyl; naphthylphenyl; triphenylene; dibenzofuranyl; dibenzothiophene; benzonaphthiophene; or benzonaphthiophene.

[0072] Preferably, Ar3 is biphenyl; terphenyl; naphthyl; phenanthrene; phenylnaphthyl; naphthylphenyl; triphenylene; benzonaphthuronyl; benzonaphthiophene; or fluoranthracene.

[0073] Preferably, Ar1 to Ar3 can each be independently substituted or unsubstituted C. 6-20 Aryl.

[0074] Preferably, Ar1 and Ar2 can each be independently triphenyl; naphthyl; phenanthryl; phenylnaphthyl; or naphthylphenyl.

[0075] Preferably, Ar3 is biphenyl; terphenyl; naphthyl; phenanthrene; phenylnaphthyl; naphthylphenyl; or triphenylene.

[0076] Preferably, when chemical formula 1 is a compound represented by chemical formula 1-1-a, Ar3 is naphthyl.

[0077] Representative examples of compounds represented by chemical formula 1 are as follows:

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[0169] The mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer. The organic layer was then distilled. It was then dissolved in chloroform and washed twice with water. The organic layer was subsequently separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-2 (yield 66%, MS: [M+H]+=626).

[0170] Preparation Examples 1-3

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[0214] The compound represented by chemical formula 1 can be prepared by, for example, the preparation method shown in reaction scheme 1 below.

[0215] [Reaction Scheme 1]

[0216]

[0217] In reaction scheme 1, the substituents other than X1 and X2 are defined as described above. X1 and X2 are each independently a halogen, and more preferably bromine or chlorine.

[0218] Reaction scheme 1 is a Suzuki coupling reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactants used for the Suzuki coupling reaction can be modified as is known in the art. The method for preparing the compound represented by chemical formula 1 can be described in more detail in the preparation examples below.

[0219] Chemical formula 2 can be represented by any of the following chemical formulas 2-1 to 2-3:

[0220] [Chemical Formula 2-1]

[0221]

[0222] [Chemical Formula 2-2]

[0223]

[0224] [Chemical Formula 2-3]

[0225]

[0226] In chemical formulas 2-1 to 2-3,

[0227] Ar′1, Ar′2 and L′1 to L′3 are as defined in chemical formula 2.

[0228] One or more hydrogen atoms in chemical formula 2 can be substituted with deuterium.

[0229] Preferably, L′3 is substituted or unsubstituted C. 6-20 Aromatic; or substituted or unsubstituted C containing at least one of N, O and S. 2-20 Hybrid aryl. More preferably, L′3 is selected from any of the following structural formulas:

[0230]

[0231] Preferably, L′1 and L′2 are each independently a single bond; or substituted or unsubstituted C 6-20 Arylene. More preferably, L′1 and L′2 are each independently a single bond; or phenylene.

[0232] Preferably, Ar′1 and Ar′2 are each independently substituted or unsubstituted C. 6-20 aryl; or substituted or unsubstituted C containing at least one of N, O and S. 2-20 Mixed aromatic compounds.

[0233] Preferably, Ar′1 and Ar′2 are each independently phenyl; biphenyl; terphenyl; naphthyl; phenanthryl; dibenzofuranyl; dibenzothiophene; or benzonaphthofuranyl.

[0234] Representative examples of compounds represented by chemical formula 2 are as follows:

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[0269] The compound represented by chemical formula 2 can be prepared by, for example, the preparation method shown in reaction scheme 2 below.

[0270] [Reaction Scheme 2]

[0271]

[0272] In reaction scheme 2, the substituents other than X′1 and X′2 are defined in the same way as described above. X′1 and X′2 are each independently a halogen, and more preferably bromine or chlorine.

[0273] Reaction scheme 2 is an amine substitution reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactants used for the amine substitution reaction can be modified as is known in the art. The preparation method can be described in more detail in the preparation examples below.

[0274] In the luminescent layer, the weight ratio of the compound represented by chemical formula 1 to the compound represented by chemical formula 2 is 1:99 to 99:1, 5:95 to 95:5, or 10:90 to 90:10.

[0275] There are no particular limitations on the dopant material, as long as it is a material used in organic light-emitting devices. For example, dopant materials include aromatic amine derivatives, styrene amine compounds, boron complexes, fluoranthene compounds, metal complexes, etc. Specifically, aromatic amine derivatives are fused aromatic ring derivatives with aryl amino groups, whether substituted or unsubstituted, and examples include pyrene, anthracene, etc., which have aryl amino groups. Diindrone pyrene, etc. Styrene amine compounds are compounds in which at least one aryl vinyl group is substituted in a substituted or unsubstituted aryl amine, wherein one or two or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino groups are substituted or unsubstituted. Specific examples include, but are not limited to, styrene amines, styrene diamines, styrene triamines, styrene tetraamines, etc. Furthermore, metal complexes include, but are not limited to, iridium complexes, platinum complexes, etc.

[0276] Specific examples of doped materials include, but are not limited to, the following compounds:

[0277]

[0278]

[0279]

[0280] Hole transport layer

[0281] Organic light-emitting devices according to this disclosure may include a hole transport layer between the light-emitting layer and the anode.

[0282] The hole transport layer is the layer that receives holes from the hole injection layer and transports them to the light-emitting layer. Suitable hole transport materials are those with high hole mobility, capable of receiving holes from the anode or hole injection layer and transferring them to the light-emitting layer.

[0283] Specific examples of hole transport materials include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers containing both conjugated and non-conjugated portions.

[0284] Hole injection layer

[0285] If necessary, the organic light-emitting device according to this disclosure may also include a hole injection layer between the anode and the hole transport layer.

[0286] The hole injection layer is a layer used to inject holes from the electrode, and the hole injection material is preferably a compound that can transport holes, thus having the effect of injecting holes into the anode and excellent hole injection effect on the light-emitting layer or light-emitting material, preventing excitons generated in the light-emitting layer from moving to the electron injection layer or electron injection material, and having excellent ability to form thin films. Preferably, the HOMO (highest occupied molecular orbital) of the hole injection material is between that of the work function of the anode material and the HOMO of the surrounding organic material layer.

[0287] Specific examples of hole injection materials include, but are not limited to, metalloporphyrins, oligothiophenes, arylamine-based organic materials, hexanitrile hexaazabenzophenanthrene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinones, conductive polymers based on polyaniline and polythiophene.

[0288] Electron blocking layer

[0289] If necessary, the organic light-emitting device according to this disclosure may include an electron blocking layer between the hole transport layer and the light-emitting layer.

[0290] The electron blocking layer prevents electrons injected from the cathode from transferring to the hole transport layer and recombinating in the light-emitting layer; it is also known as the electron suppression layer. Materials with lower electron affinity than the electron transport layer are preferred for the electron blocking layer.

[0291] Electron transport layer

[0292] Organic light-emitting devices according to this disclosure may include an electron transport layer between the light-emitting layer and the cathode.

[0293] An electron transport layer is a layer that receives electrons from the cathode or an electron injection layer formed on the cathode and transports them to the light-emitting layer, while also suppressing the transport of holes in the light-emitting layer. Suitable electron transport materials are those that can effectively receive electrons from the cathode and transport them to the light-emitting layer, and that possess high electron mobility.

[0294] Specific examples of electron transport materials include Al complexes of 8-hydroxyquinoline; complexes containing Alq3; organic radical compounds; hydroxyflavonoid-metal complexes; and so on, but are not limited to these. The electron transport layer can be used with any desired cathode material as used in the relevant field. In particular, suitable examples of cathode materials are typically materials with low work functions followed by an aluminum or silver layer. Specific examples include cesium, barium, calcium, ytterbium, and samarium, each followed by an aluminum or silver layer.

[0295] Electron injection layer

[0296] If necessary, the organic light-emitting device according to this disclosure may also include an electron injection layer between the electron transport layer and the cathode.

[0297] The electron injection layer is a layer that injects electrons from the electrode, and the electron injection material is preferably a compound that can transport electrons, has the effect of injecting electrons from the cathode and has an excellent effect of injecting electrons into the light-emitting layer or light-emitting material, prevents excitons generated by the light-emitting layer from moving to the hole injection layer, and is also excellent in terms of the ability to form a thin film.

[0298] Specific examples of materials that can be used as electron injection layers include fluorenone, anthraquinone dimethyl ether, biphenylquinone, thiamethoxam dioxide, etc. azole, Diazoles, triazoles, imidazoles, perylenetetracarboxylic acid, fluorenemethane, anthrones and their derivatives; metal complexes; nitrogen-containing 5-membered ring derivatives; and so on, but not limited to these.

[0299] Examples of metal complex compounds include, but are not limited to, lithium 8-hydroxyquinoline, bis(8-hydroxyquinoline)zinc, bis(8-hydroxyquinoline)copper, bis(8-hydroxyquinoline)manganese, tris(8-hydroxyquinoline)aluminum, tris(2-methyl-8-hydroxyquinoline)aluminum, tris(8-hydroxyquinoline)gallium, bis(10-hydroxybenzo[h]quinoline)beryllium, bis(10-hydroxybenzo[h]quinoline)zinc, bis(2-methyl-8-quinoline)chlorogallium, bis(2-methyl-8-quinoline)(o-cresol)gallium, bis(2-methyl-8-quinoline)(1-naphthol)aluminum, and bis(2-methyl-8-quinoline)(2-naphthol)gallium.

[0300] According to one embodiment of this disclosure, electron transport materials and electron injection materials can be deposited simultaneously to form an electron injection and transport layer as a single layer.

[0301] Cavity barrier

[0302] If necessary, the organic light-emitting device according to this disclosure includes a hole-blocking layer between the electron transport layer and the light-emitting layer.

[0303] The hole blocking layer prevents holes injected from the anode from transferring to the electron transport layer without recombinizing in the light-emitting layer, and preferably uses materials with high ionization energy for the hole blocking layer.

[0304] Organic light-emitting devices

[0305] The structure of the organic light-emitting device according to this disclosure is shown in Figure 1 middle. Figure 1 An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. Figure 2An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 3, an electron transport layer 7, an electron injection layer 8, and a cathode 4. Figure 3 An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 9, a light-emitting layer 3, a hole blocking layer 10, an electron injection and transport layer 11, and a cathode 4.

[0306] The organic light-emitting device according to this disclosure can be manufactured by sequentially laminating the above-described components. In this case, the organic light-emitting device can be manufactured by depositing a metal, a conductive metal oxide or an alloy thereof on a substrate using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation to form an anode, forming the aforementioned layers on the anode, and then depositing a material that can be used as a cathode thereon.

[0307] Besides this method, organic light-emitting devices can also be fabricated by depositing the aforementioned components on a substrate in reverse order, from cathode material to anode material (WO 2003 / 012890). Furthermore, the light-emitting layer can be formed using a substrate and dopant via solution coating and vacuum deposition. In this document, solution coating refers to, but is not limited to, spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, and roll coating.

[0308] Furthermore, depending on the materials used, the organic light-emitting device according to this disclosure can be a front-emitting, rear-emitting, or dual-emitting type.

[0309] The fabrication of organic light-emitting devices will be described in detail in the following embodiments. However, these embodiments are presented for illustrative purposes only and are not intended to limit the scope of this disclosure.

[0310] [Preparation Example]

[0311] Preparation Example 1-1

[0312]

[0313] Compound 1-A (15 g, 60.9 mmol) and Trz1 (19.3 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (16.8 g, 121.7 mmol) was then dissolved in 50 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.9 g of sub1-A-1 (71% yield, MS: [M+H]+ = 484).

[0314] Under a nitrogen atmosphere, sub1-A-1 (15 g, 31 mmol) and sub1 (6.1 g, 31 mmol) were added to 300 mL of THF, and the mixture was stirred and refluxed. Potassium carbonate (8.6 g, 62 mmol) was then dissolved in 26 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-1 (66% yield, MS: [M+H]+=602).

[0315] Preparation Examples 1-2

[0316]

[0317] Compound 1-A (15 g, 60.9 mmol) and Trz2 (16.3 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5 g sub1-A-2 (74% yield, MS: [M+H]+ = 434).

[0318] Sub1-A-2 (15 g, 34.6 mmol) and sub2 (9.4 g, 34.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (9.6 g, 69.1 mmol) was then dissolved in 29 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-2 (66% yield, MS: [M+H]+ = 626).

[0319] Preparation Examples 1-3

[0320]

[0321] Compound 1-A (15 g, 60.9 mmol) and Trz3 (19.3 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.2 g of sub1-A-3 (79% yield, MS: [M+H]+ = 484).

[0322] Sub1-A-3 (15 g, 31 mmol) and sub3 (7.1 g, 31 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (8.6 g, 62 mmol) was then dissolved in 26 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-3 (yield 66%, MS: [M+H]+ = 632).

[0323] Preparation Examples 1-4

[0324]

[0325] Compound 1-A (15 g, 60.9 mmol) and Trz4 (27 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of sub1-A-4 (70% yield, MS: [M+H]+ = 610).

[0326] Under a nitrogen atmosphere, sub1-A-4 (15 g, 24.6 mmol) and sub4 (5.6 g, 24.6 mmol) were added to 300 mL of THF, and the mixture was stirred and refluxed. Potassium carbonate (6.8 g, 49.2 mmol) was then dissolved in 20 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of compound 1-4 (60% yield, MS: [M+H]+ = 758).

[0327] Preparation Examples 1-5

[0328]

[0329] Compound 1-B (15 g, 60.9 mmol) and Trz5 (24 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2 g of sub1-B-1 (77% yield, MS: [M+H]+ = 560).

[0330] Sub1-B-1 (15 g, 26.8 mmol) and sub5 (3.3 g, 26.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (7.4 g, 53.6 mmol) was then dissolved in 22 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-5 (80% yield, MS: [M+H]+ = 602).

[0331] Preparation Examples 1-6

[0332]

[0333] Compound 1-B (15 g, 60.9 mmol) and Trz3 (19.3 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.2 g sub1-B-2 (62% yield, MS: [M+H]+ = 484).

[0334] Sub1-B-2 (15 g, 31 mmol) and sub6 (7.6 g, 31 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (8.6 g, 62 mmol) was then dissolved in 26 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compounds were purified by silica gel column chromatography to prepare 15.3 g of compounds 1-6 (76% yield, MS: [M+H]+ = 650).

[0335] Preparation Examples 1-7

[0336]

[0337] Compound 1-B (15 g, 60.9 mmol) and Trz2 (16.3 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of sub1-B-3 (79% yield, MS: [M+H]+ = 434).

[0338] Sub1-B-3 (15 g, 34.6 mmol) and sub7 (8.6 g, 34.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (9.6 g, 69.1 mmol) was then dissolved in 29 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compounds were purified by silica gel column chromatography to prepare 15.4 g of compounds 1-7 (74% yield, MS: [M+H]+ = 602).

[0339] Preparation Examples 1-8

[0340]

[0341] Sub1-B-2 (15 g, 31 mmol) and sub8 (8.1 g, 31 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (8.6 g, 62 mmol) was then dissolved in 26 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.5 g of compound 1-8 (75% yield, MS: [M+H]+ = 666).

[0342] Preparation Examples 1-9

[0343]

[0344] Compound 1-B (15 g, 60.9 mmol) and Trz6 (22.4 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.7 g of sub1-B-4 (73% yield, MS: [M+H]+ = 534).

[0345] Sub1-B-4 (15 g, 28.1 mmol) and sub9 (6 g, 28.1 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (7.8 g, 56.2 mmol) was then dissolved in 23 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compounds were purified by silica gel column chromatography to prepare 11.6 g of compounds 1-9 (62% yield, MS: [M+H]+ = 666).

[0346] Preparation Examples 1-10

[0347]

[0348] Compound 1-B (15 g, 60.9 mmol) and Trz7 (28.6 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.6 g sub1-B-5 (74% yield, MS: [M+H]+ = 636).

[0349] Under a nitrogen atmosphere, sub1-B-5 (15 g, 23.6 mmol) and sub5 (2.9 g, 23.6 mmol) were added to 300 mL of THF, and the mixture was stirred and refluxed. Potassium carbonate (6.5 g, 47.2 mmol) was then dissolved in 20 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4 g of compound 1-5 (65% yield, MS: [M+H]+ = 678).

[0350] Preparation Examples 1-11

[0351]

[0352] Compound 1-B (15 g, 60.9 mmol) and Trz8 (21.8 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.1 g of sub1-B-6 (63% yield, MS: [M+H]+ = 524).

[0353] Sub1-B-6 (15 g, 28.6 mmol) and sub10 (4.9 g, 28.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (7.9 g, 57.3 mmol) was then dissolved in 24 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of compound 1-11 (65% yield, MS: [M+H]+ = 616).

[0354] Preparation Examples 1-12

[0355]

[0356] Compound 1-C (15 g, 60.9 mmol) and Trz3 (19.3 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g of sub1-C-1 (60% yield, MS: [M+H]+ = 484).

[0357] Sub1-C-1 (15 g, 31 mmol) and sub10 (5.3 g, 31 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (8.6 g, 62 mmol) was then dissolved in 26 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then reconstituted in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-12 (72% yield, MS: [M+H]+ = 576).

[0358] Preparation Examples 1-13

[0359]

[0360] Compound 1-C (15 g, 60.9 mmol) and Trz9 (24 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.5 g of sub1-C-2 (69% yield, MS: [M+H]+ = 560).

[0361] Sub1-C-2 (15 g, 26.8 mmol) and sub10 (4.6 g, 26.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (7.4 g, 53.6 mmol) was then dissolved in 22 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound 1-13 (80% yield, MS: [M+H]+ = 652).

[0362] Preparation Examples 1-14

[0363]

[0364] Compound 1-C (15 g, 60.9 mmol) and Trz10 (20.9 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.5 g of sub1-C-3 (66% yield, MS: [M+H]+ = 510).

[0365] Sub1-C-3 (15 g, 29.4 mmol) and sub11 (7.3 g, 29.4 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (8.1 g, 58.8 mmol) was then dissolved in 24 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3 g of compound 1-14 (77% yield, MS: [M+H]+ = 678).

[0366] Preparation Examples 1-15

[0367]

[0368] Compound 1-C (15 g, 60.9 mmol) and Trz2 (16.3 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7 g sub1-C-4 (71% yield, MS: [M+H]+ = 434).

[0369] Sub1-C-4 (15 g, 37.1 mmol) and sub12 (9.7 g, 37.1 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (10.3 g, 74.3 mmol) was then dissolved in 31 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of compound 1-15 (64% yield, MS: [M+H]+ = 616).

[0370] Preparation Examples 1-16

[0371]

[0372] Sub1-C-2 (15 g, 26.8 mmol) and sub13 (7.4 g, 26.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (7.4 g, 53.6 mmol) was then dissolved in 22 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.2 g of compound 1-16 (80% yield, MS: [M+H]+ = 758).

[0373] Preparation Examples 1-17

[0374]

[0375] Sub1-C-4 (15 g, 34.6 mmol) and sub14 (7.7 g, 34.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (9.6 g, 69.1 mmol) was then dissolved in 29 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-17 (62% yield, MS: [M+H]+ = 576).

[0376] Preparation Examples 1-18

[0377]

[0378] Sub1-C-1 (15 g, 31 mmol) and sub9 (6.6 g, 31 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (8.6 g, 62 mmol) was then dissolved in 26 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of compound 1-18 (63% yield, MS: [M+H]+=616).

[0379] Preparation Examples 1-19

[0380]

[0381] Compound 1-C (15 g, 60.9 mmol) and Trz11 (22.4 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.4 g sub1-C-5 (69% yield, MS: [M+H]+ = 534).

[0382] Sub1-C-5 (15 g, 28.1 mmol) and sub15 (6 g, 28.1 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (7.8 g, 56.2 mmol) was then dissolved in 23 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-19 (71% yield, MS: [M+H]+ = 666).

[0383] Preparation Examples 1-20

[0384]

[0385] Compound 1-C (15 g, 60.9 mmol) and Trz12 (21.8 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21 g of sub1-C-6 (66% yield, MS: [M+H]+ = 524).

[0386] Sub1-C-6 (15 g, 28.6 mmol) and sub10 (4.9 g, 28.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (11.9 g, 85.9 mmol) was then dissolved in 36 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-20 (70% yield, MS: [M+H]+ = 616).

[0387] Preparation Examples 1-21

[0388]

[0389] Compound 1-C (15 g, 60.9 mmol) and Trz13 (24 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2 g of sub1-C-7 (77% yield, MS: [M+H]+ = 560).

[0390] Sub1-C-7 (15 g, 26.8 mmol) and sub5 (3.3 g, 26.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (11.1 g, 80.3 mmol) was then dissolved in 33 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5 g of compound 1-21 (65% yield, MS: [M+H]+=602).

[0391] Preparation Examples 1-22

[0392]

[0393] Compound 1-D (15 g, 60.9 mmol) and Trz14 (19.3 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.9 g of sub1-D-1 (67% yield, MS: [M+H]+ = 586).

[0394] Sub1-D-1 (15 g, 25.6 mmol) and sub5 (3.1 g, 25.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (10.6 g, 76.8 mmol) was then dissolved in 32 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.3 g of compound 1-22 (64% yield, MS: [M+H]+ = 628).

[0395] Preparation Examples 1-23

[0396]

[0397] Compound 1-D (15 g, 60.9 mmol) and Trz2 (16.3 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20 g of sub1-D-2 (76% yield, MS: [M+H]+ = 434).

[0398] Sub1-D-2 (15 g, 34.6 mmol) and sub16 (9.1 g, 34.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14.3 g, 103.7 mmol) was then dissolved in 43 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound 1-23 (66% yield, MS: [M+H]+ = 616).

[0399] Preparation Examples 1-24

[0400]

[0401] Compound 1-D (15 g, 60.9 mmol) and Trz10 (20.9 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of sub1-D-3 (67% yield, MS: [M+H]+ = 510).

[0402] Sub1-D-3 (15 g, 29.4 mmol) and sub17 (7.7 g, 29.4 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12.2 g, 88.2 mmol) was then dissolved in 37 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound 1-24 (yield 61%, MS: [M+H]+ = 692).

[0403] Preparation Examples 1-25

[0404]

[0405] Compound 1-D (15 g, 60.9 mmol) and Trz15 (21.8 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.3 g sub1-D-4 (67% yield, MS: [M+H]+ = 524).

[0406] Sub1-D-4 (15 g, 28.6 mmol) and sub10 (4.9 g, 28.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (11.9 g, 85.9 mmol) was then dissolved in 36 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.7 g of compound 1-25 (61% yield, MS: [M+H]+ = 616).

[0407] Preparation Examples 1-26

[0408]

[0409] Sub1-D-3 (15 g, 29.4 mmol) and sub18 (6.2 g, 29.4 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12.2 g, 88.2 mmol) was then dissolved in 37 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-26 (76% yield, MS: [M+H]+ = 642).

[0410] Preparation Examples 1-27

[0411]

[0412] Compound 1-D (15 g, 60.9 mmol) and Trz16 (27 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.1 g sub1-D-5 (73% yield, MS: [M+H]+ = 610).

[0413] Sub1-D-5 (15 g, 24.6 mmol) and sub9 (5.2 g, 24.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (10.2 g, 73.8 mmol) was then dissolved in 31 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-27 (70% yield, MS: [M+H]+ = 742).

[0414] Preparation Examples 1-28

[0415]

[0416] Compound 1-D (15 g, 60.9 mmol) and Trz13 (24 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of sub1-D-6 (61% yield, MS: [M+H]+ = 560).

[0417] Sub1-D-6 (15 g, 26.8 mmol) and sub10 (4.6 g, 26.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (11.1 g, 80.3 mmol) was then dissolved in 33 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-28 (70% yield, MS: [M+H]+ = 652).

[0418] Preparation Examples 1-29

[0419]

[0420] Compound 1-E (15 g, 60.9 mmol) and Trz2 (16.3 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.1 g sub1-E-1 (65% yield, MS: [M+H]+ = 434).

[0421] Sub1-E-1 (15 g, 34.6 mmol) and sub2 (9.4 g, 34.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14.3 g, 103.7 mmol) was then dissolved in 43 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5 g of compound 1-29 (67% yield, MS: [M+H]+ = 626).

[0422] Preparation Examples 1-30

[0423]

[0424] Compound 1-E (15 g, 60.9 mmol) and Trz9 (24 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.9 g sub1-E-2 (79% yield, MS: [M+H]+ = 560).

[0425] Sub1-E-2 (15 g, 26.8 mmol) and sub19 (7 g, 26.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (11.1 g, 80.3 mmol) was then dissolved in 33 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.9 g of compound 1-30 (80% yield, MS: [M+H]+ = 742).

[0426] Preparation Examples 1-31

[0427]

[0428] Compound 1-E (15 g, 60.9 mmol) and Trz17 (22.4 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.3 g sub1-E-3 (78% yield, MS: [M+H]+ = 534).

[0429] Sub1-E-3 (15 g, 28.1 mmol) and sub20 (7.8 g, 28.1 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (11.6 g, 84.3 mmol) was then dissolved in 35 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8 g of compound 1-31 (72% yield, MS: [M+H]+=732).

[0430] Preparation Examples 1-32

[0431]

[0432] Sub1-E-1 (15 g, 34.6 mmol) and sub21 (7.7 g, 34.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14.3 g, 103.7 mmol) was then dissolved in 43 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-32 (65% yield, MS: [M+H]+ = 576).

[0433] Preparation Examples 1-33

[0434]

[0435] Compound 1-E (15 g, 60.9 mmol) and Trz15 (21.8 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.5 g sub1-E-4 (80% yield, MS: [M+H]+ = 524).

[0436] Sub1-E-4 (15 g, 28.6 mmol) and sub10 (4.9 g, 28.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (11.9 g, 85.9 mmol) was then dissolved in 36 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of compound 1-33 (60% yield, MS: [M+H]+ = 616).

[0437] Preparation Examples 1-34

[0438]

[0439] Compound 1-E (15 g, 60.9 mmol) and Trz3 (19.3 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(O) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g sub1-E-5 (60% yield, MS: [M+H]+ = 484).

[0440] Sub1-E-5 (15 g, 31 mmol) and sub9 (6.6 g, 31 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12.9 g, 93 mmol) was then dissolved in 39 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of compound 1-34 (60% yield, MS: [M+H]+ = 616).

[0441] Preparation Examples 1-35

[0442]

[0443] Compound 1-E (15 g, 60.9 mmol) and Trz10 (20.9 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7 g of sub1-E-6 (70% yield, MS: [M+H]+ = 510).

[0444] Sub1-E-6 (15 g, 29.4 mmol) and sub22 (7.7 g, 29.4 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12.2 g, 88.2 mmol) was then dissolved in 37 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of compound 1-35 (72% yield, MS: [M+H]+ = 692).

[0445] Preparation Examples 1-36

[0446]

[0447] Sub1-E-5 (15 g, 31 mmol) and sub23 (8.1 g, 31 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12.9 g, 93 mmol) was then dissolved in 39 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound 1-36 (60% yield, MS: [M+H]+=666).

[0448] Preparation Examples 1-37

[0449]

[0450] Sub1-E-5 (15 g, 31 mmol) and sub10 (5.3 g, 31 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12.9 g, 93 mmol) was then dissolved in 39 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of compound 1-37 (79% yield, MS: [M+H]+ = 576).

[0451] Preparation Examples 1-38

[0452]

[0453] Compound 1-E (15 g, 60.9 mmol) and Trz18 (27 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.1 g sub1-E-7 (65% yield, MS: [M+H]+ = 610).

[0454] Sub1-E-7 (15 g, 24.6 mmol) and sub5 (3 g, 24.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (10.2 g, 73.8 mmol) was then dissolved in 31 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1 g of compound 1-38 (63% yield, MS: [M+H]+ = 652).

[0455] Preparation Examples 1-39

[0456]

[0457] Compound 1-E (15 g, 60.9 mmol) and Trz13 (24 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2 g sub1-E-8 (77% yield, MS: [M+H]+ = 560).

[0458] Sub1-E-8 (15 g, 26.8 mmol) and sub5 (3.3 g, 26.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (11.1 g, 80.3 mmol) was then dissolved in 33 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9 g of compound 1-39 (68% yield, MS: [M+H]+=602).

[0459] Preparation Examples 1-40

[0460]

[0461] Compound 1-F (15 g, 60.9 mmol) and Trz2 (16.3 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.2 g sub1-F-1 (73% yield, MS: [M+H]+ = 434).

[0462] Sub1-F-1 (15 g, 34.6 mmol) and sub6 (8.5 g, 34.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14.3 g, 103.7 mmol) was then dissolved in 43 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of compound 1-40 (71% yield, MS: [M+H]+ = 600).

[0463] Preparation Examples 1-41

[0464]

[0465] Compound 1-F (15 g, 60.9 mmol) and Trz10 (20.9 g, 60.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1 g of sub1-F-2 (68% yield, MS: [M+H]+ = 510).

[0466] Sub1-F-2 (15 g, 29.4 mmol) and sub1 (5.8 g, 29.4 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12.2 g, 88.2 mmol) was then dissolved in 37 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 1-41 (77% yield, MS: [M+H]+ = 628).

[0467] Preparation Examples 1-42

[0468]

[0469] Trz7 (15 g, 31.9 mmol) and sub9 (6.8 g, 31.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (13.2 g, 95.8 mmol) was then dissolved in 40 mL of water and added to the mixture. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of compound 1-42 (79% yield, MS: [M+H]+=602).

[0470] Preparation Examples 1-43

[0471]

[0472] Trz16 (15 g, 33.8 mmol) and sub9 (7.2 g, 33.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 mL of water and added to the mixture. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound 1-43 (77% yield, MS: [M+H]+ = 576).

[0473] Preparation Examples 1-44

[0474]

[0475] Trz4 (15 g, 33.8 mmol) and sub9 (7.2 g, 33.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 mL of water and added to the mixture. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 1-44 (73% yield, MS: [M+H]+ = 576).

[0476] Preparation Examples 1-45

[0477]

[0478] Trz1' (15 g, 35.7 mmol) and sub9 (7.6 g, 35.7 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14.8 g, 107.2 mmol) was then dissolved in 44 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-45 (62% yield, MS: [M+H]+=552).

[0479] Preparation Examples 1-46

[0480]

[0481] Trz19 (15 g, 33.8 mmol) and sub9 (7.2 g, 33.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 mL of water and added to the mixture. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of compound 1-46 (70% yield, MS: [M+H]+ = 576).

[0482] Preparation Examples 1-47

[0483]

[0484] Trz20 (15 g, 35.9 mmol) and sub9 (7.6 g, 35.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14.9 g, 107.7 mmol) was then dissolved in 45 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound 1-47 (76% yield, MS: [M+H]+ = 550).

[0485] Preparation Examples 1-48

[0486]

[0487] Trz3 (15 g, 47.2 mmol) and sub24 (9.7 g, 47.2 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (19.6 g, 141.6 mmol) was then dissolved in 59 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of sub1-G-1 (62% yield, MS: [M+H]+ = 444).

[0488] Sub1-G-1 (15 g, 33.8 mmol) and sub9 (7.2 g, 33.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of compound 1-48 (78% yield, MS: [M+H]+ = 576).

[0489] Preparation Examples 1-49

[0490]

[0491] Trz15 (15 g, 41.9 mmol) and sub25 (8.7 g, 41.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (17.4 g, 125.8 mmol) was then dissolved in 52 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6 g of sub1-G-2 (62% yield, MS: [M+H]+ = 484).

[0492] Sub1-G-2 (15 g, 31 mmol) and sub9 (6.6 g, 31 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12.9 g, 93 mmol) was then dissolved in 39 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound 1-49 (72% yield, MS: [M+H]+ = 616).

[0493] Preparation Examples 1-50

[0494]

[0495] Trz21 (15 g, 36.8 mmol) and sub26 (5.8 g, 36.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (15.2 g, 110.3 mmol) was then dissolved in 46 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of sub1-G-3 (72% yield, MS: [M+H]+ = 484).

[0496] Sub1-G-3 (15 g, 31 mmol) and sub9 (6.6 g, 31 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12.9 g, 93 mmol) was then dissolved in 39 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of compound 1-50 (69% yield, MS: [M+H]+ = 616).

[0497] Preparation Examples 1-51

[0498]

[0499] Trz16 (15 g, 33.8 mmol) and sub27 (5.3 g, 33.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of sub1-G-4 (76% yield, MS: [M+H]+ = 520).

[0500] Sub1-G-4 (15 g, 28.8 mmol) and sub9 (6.1 g, 28.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12 g, 86.5 mmol) was then dissolved in 36 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-51 (71% yield, MS: [M+H]+ = 652).

[0501] Preparation Examples 1-52

[0502]

[0503] Trz22 (15 g, 36.8 mmol) and sub28 (5.8 g, 36.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (15.2 g, 110.3 mmol) was then dissolved in 46 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of sub1-G-5 (72% yield, MS: [M+H]+ = 484).

[0504] Sub1-G-5 (15 g, 31 mmol) and sub9 (6.6 g, 31 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12.9 g, 93 mmol) was then dissolved in 39 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of compound 1-52 (68% yield, MS: [M+H]+ = 616).

[0505] Preparation Examples 1-53

[0506]

[0507] Trz23 (15 g, 34.6 mmol) and sub27 (5.4 g, 34.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14.3 g, 103.7 mmol) was then dissolved in 43 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3 g of sub1-G-6 (64% yield, MS: [M+H]+ = 510).

[0508] Sub1-G-6 (15 g, 31 mmol) and sub9 (6.6 g, 31 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12.9 g, 93 mmol) was then dissolved in 39 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of compound 1-53 (68% yield, MS: [M+H]+=616).

[0509] Preparation Examples 1-54

[0510]

[0511] Sub1-G-1 (15 g, 33.8 mmol) and compound 1-E (8.3 g, 33.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 mL of water and added to the mixture. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 8 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of sub1-E-9 (70% yield, MS: [M+H]+ = 610).

[0512] Sub1-E-9 (15 g, 24.6 mmol) and sub5 (3 g, 24.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (10.2 g, 73.8 mmol) was then dissolved in 31 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-54 (76% yield, MS: [M+H]+ = 652).

[0513] Preparation Examples 1-55

[0514]

[0515] Trz2 (15 g, 56 mmol) and sub24 (11.6 g, 56 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (23.2 g, 168.1 mmol) was then dissolved in 70 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6 g of sub1-G-7 (71% yield, MS: [M+H]+ = 394).

[0516] Sub1-G-7 (15 g, 38.1 mmol) and compound 1-B (9.4 g, 38.1 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (15.8 g, 114.3 mmol) was then dissolved in 47 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of sub1-B-7 (65% yield, MS: [M+H]+ = 560).

[0517] Sub1-B-7 (15 g, 26.8 mmol) and sub5 (3.3 g, 26.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (11.1 g, 80.3 mmol) was then dissolved in 33 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-55 (80% yield, MS: [M+H]+=602).

[0518] Preparation Examples 1-56

[0519]

[0520] Trz24 (15 g, 38.1 mmol) and compound sub25 (9.4 g, 38.1 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (15.8 g, 114.3 mmol) was then dissolved in 47 mL of water and added to the mixture. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound sub1-G-8 (65% yield, MS: [M+H]+ = 560).

[0521] Compounds sub1-G-8 (15 g, 30 mmol) and sub9 (6.4 g, 30 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12.4 g, 90 mmol) was then dissolved in 37 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound 1-56 (71% yield, MS: [M+H]+ = 632).

[0522] Preparation Examples 1-57

[0523]

[0524] Trz25 (15 g, 41.9 mmol) and sub24 (8.7 g, 41.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (17.4 g, 125.8 mmol) was then dissolved in 52 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of sub1-G-9 (61% yield, MS: [M+H]+ = 484).

[0525] Sub1-G-9 (15 g, 31 mmol) and compound 1-F (7.6 g, 31 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12.9 g, 93 mmol) was then dissolved in 39 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then reconstituted in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of sub1-F-3 (62% yield, MS: [M+H]+ = 650).

[0526] Sub1-F-3 (15 g, 23.1 mmol) and sub5 (2.8 g, 23.1 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (9.6 g, 69.2 mmol) was then dissolved in 29 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-57 (80% yield, MS: [M+H]+ = 692).

[0527] Preparation Examples 1-58

[0528]

[0529] Trz26 (15 g, 33.8 mmol) and sub26 (5.3 g, 33.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then reconstituted in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10⁻⁵ g of sub1-G-10 (60% yield, MS: [M+H]⁺ = 520).

[0530] Sub1-G-10 (15 g, 28.8 mmol) and compound 1-D (7.1 g, 28.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12 g, 86.5 mmol) was then dissolved in 36 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of sub1-D-7 (76% yield, MS: [M+H]+ = 686).

[0531] Sub1-D-7 (15 g, 21.9 mmol) and sub5 (2.7 g, 21.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (9.1 g, 65.6 mmol) was then dissolved in 27 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9 g of compound 1-58 (62% yield, MS: [M+H]+ = 728).

[0532] Preparation Examples 1-59

[0533]

[0534] Trz15 (15 g, 41.9 mmol) and compound sub24 (8.7 g, 41.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (17.4 g, 125.8 mmol) was then dissolved in 52 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 11 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound sub1-G-11 (61% yield, MS: [M+H]+ = 484).

[0535] Sub1-G-11 (15 g, 28.8 mmol) and compound 1-F (7.1 g, 28.8 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (12 g, 86.5 mmol) was then dissolved in 36 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound sub1-F-4 (76% yield, MS: [M+H]+ = 686).

[0536] Sub1-F-4 (15 g, 23.1 mmol) and sub5 (2.8 g, 23.1 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (9.6 g, 69.2 mmol) was then dissolved in 29 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1 g of compound 1-59 (76% yield, MS: [M+H]+ = 692).

[0537] Preparation Examples 1-60

[0538]

[0539] Trz12 (15 g, 41.9 mmol) and sub28 (6.6 g, 41.9 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (17.4 g, 125.8 mmol) was then dissolved in 52 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then redissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1 g of sub1-G-12 (61% yield, MS: [M+H]+ = 434).

[0540] Sub1-G-12 (15 g, 34.6 mmol) and compound 1-D (8.5 g, 34.6 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14.3 g, 103.7 mmol) was then dissolved in 43 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 9 hours of reaction, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then dissolved in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of sub1-D-8 (79% yield, MS: [M+H]+ = 500).

[0541] Sub-1-D-8 (15 g, 25 mmol) and sub-10 (4.3 g, 25 mmol) were added to 300 mL of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (10.4 g, 75 mmol) was then dissolved in 31 mL of water and added to the solution. The mixture was then stirred thoroughly, and bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer was separated from the aqueous layer and distilled. The organic layer was then reconstituted in chloroform and washed twice with water. The organic layer was then separated, treated with anhydrous magnesium sulfate, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-60 (77% yield, MS: [M+H]+ = 692).

[0542] Preparation Example 2-1

[0543]

[0544] Compound A (10 g, 46 mmol), sub2-1 (9.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.7 g of subA-1 (yield 58%, MS: [M+H]+ = 328).

[0545] Under a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), amine 1 (10.7 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1 g of compound 2-1 (yield 53%, MS: [M+H]+ = 627).

[0546] Preparation Example 2-2

[0547]

[0548] Under a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), amine 2 (11.1 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1 g of compound 2-2 (yield 52%, MS: [M+H]+ = 637).

[0549] Preparation Examples 2-3

[0550]

[0551] Under a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), amine 3 (14.5 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of compound 2-3 (yield 65%, MS: [M+H]+ = 743).

[0552] Preparation Examples 2-4

[0553]

[0554] Under a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), amine 4 (11.2 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1 g of compound 2-4 (yield 62%, MS: [M+H]+ = 641).

[0555] Preparation Examples 2-5

[0556]

[0557] Compound A (10 g, 46 mmol), sub2-2 (12.9 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1 g of subA-2 (60% yield, MS: [M+H]+ = 404).

[0558] Under a nitrogen atmosphere, subA-2 (10 g, 37.4 mmol), amine 5 (12.6 g, 39.2 mmol), and sodium tert-butoxide (4.7 g, 48.6 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.7 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7 g of compound 2-5 (yield 61%, MS: [M+H]+ = 689).

[0559] Preparation Examples 2-6

[0560]

[0561] Compound A (10 g, 46 mmol), sub2-3 (11.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.7 g of subA-3 (yield 56%, MS: [M+H]+ = 378).

[0562] Under a nitrogen atmosphere, subA-3 (10 g, 26.5 mmol), amine 6 (6.8 g, 27.8 mmol), and sodium tert-butoxide (3.3 g, 34.4 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.1 g of compound 2-6 (yield 52%, MS: [M+H]+ = 587).

[0563] Preparation Examples 2-7

[0564]

[0565] Compound A (10 g, 46 mmol), sub2-4 (15.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of subA-4 (70% yield, MS: [M+H]+ = 454).

[0566] Under a nitrogen atmosphere, subA-4 (10 g, 22 mmol), amine 6 (5.7 g, 23.1 mmol), and sodium tert-butoxide (2.8 g, 28.6 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.9 g of compound 2-7 (yield 54%, MS: [M+H]+ = 663).

[0567] Preparation Examples 2-8

[0568]

[0569] Compound A (10 g, 46 mmol), sub2-5 (11.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.7 g of subA-5 (50% yield, MS: [M+H]+ = 378).

[0570] Under a nitrogen atmosphere, subA-5 (10 g, 26.5 mmol), amine 7 (9.8 g, 27.8 mmol), and sodium tert-butoxide (3.3 g, 34.4 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7 g of compound 2-8 (yield 64%, MS: [M+H]+ = 693).

[0571] Preparation Examples 2-9

[0572]

[0573] Compound A (10 g, 46 mmol), sub2-6 (11.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.7 g of subA-6 (50% yield, MS: [M+H]+ = 378).

[0574] Under a nitrogen atmosphere, subA-6 (10 g, 26.5 mmol), amine 8 (8.9 g, 27.8 mmol), and sodium tert-butoxide (3.3 g, 34.4 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.5 g of compound 2-9 (yield 54%, MS: [M+H]+ = 663).

[0575] Preparation Example 2-10

[0576]

[0577] Compound A (10 g, 46 mmol), sub2-7 (11.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1 g of subA-7 (64% yield, MS: [M+H]+ = 378).

[0578] Under a nitrogen atmosphere, subA-7 (10 g, 26.5 mmol), amine 8 (8.9 g, 27.8 mmol), and sodium tert-butoxide (3.3 g, 34.4 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.7 g of compound 2-10 (yield 61%, MS: [M+H]+=663).

[0579] Preparation Example 2-11

[0580]

[0581] Compound A (10 g, 46 mmol), sub2-8 (13.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of subA-8 (68% yield, MS: [M+H]+ = 418).

[0582] Under a nitrogen atmosphere, subA-8 (10 g, 23.9 mmol), amine 6 (6.2 g, 25.1 mmol), and sodium tert-butoxide (3 g, 31.1 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.9 g of compound 2-11 (yield 53%, MS: [M+H]+ = 627).

[0583] Preparation Example 2-12

[0584]

[0585] Compound A (10 g, 46 mmol), sub2-9 (13.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of subA-9 (68% yield, MS: [M+H]+ = 418).

[0586] Under a nitrogen atmosphere, subA-9 (10 g, 23.9 mmol), amine 6 (6.2 g, 25.1 mmol), and sodium tert-butoxide (3 g, 31.1 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.4 g of compound 2-12 (yield 63%, MS: [M+H]+ = 627).

[0587] Preparation Example 2-13

[0588]

[0589] Compound B (10 g, 46 mmol), sub2-1 (9.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.7 g of subB-1 (yield 58%, MS: [M+H]+ = 328).

[0590] Under a nitrogen atmosphere, subB-1 (10 g, 30.5 mmol), amine 9 (10.3 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 2-13 (69% yield, MS: [M+H]+=613).

[0591] Preparation Example 2-14

[0592]

[0593] Under a nitrogen atmosphere, subB-1 (10 g, 30.5 mmol), amine 10 (14 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6 g of compound 2-14 (yield 57%, MS: [M+H]+ = 727).

[0594] Preparation Example 2-15

[0595]

[0596] Under a nitrogen atmosphere, subB-1 (10 g, 30.5 mmol), amine 11 (11.9 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound 2-15 (66% yield, MS: [M+H]+ = 668).

[0597] Preparation Example 2-16

[0598]

[0599] Under a nitrogen atmosphere, subB-1 (10 g, 30.5 mmol), amine 12 (11.7 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of compound 2-16 (60% yield, MS: [M+H]+ = 657).

[0600] Preparation Example 2-17

[0601]

[0602] Compound B (10 g, 46 mmol), sub2-5 (11.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9 g of subB-2 (yield 57%, MS: [M+H]+ = 378).

[0603] Under a nitrogen atmosphere, subB-2 (10 g, 26.5 mmol), amine 6 (6.8 g, 27.8 mmol), and sodium tert-butoxide (3.3 g, 34.4 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.7 g of compound 2-17 (yield 56%, MS: [M+H]+=587).

[0604] Preparation Example 2-18

[0605]

[0606] Under a nitrogen atmosphere, subB-2 (10 g, 26.5 mmol), amine 13 (8.2 g, 27.8 mmol), and sodium tert-butoxide (3.3 g, 34.4 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.9 g of compound 2-18 (yield 53%, MS: [M+H]+ = 637).

[0607] Preparation Example 2-19

[0608]

[0609] Compound B (10 g, 46 mmol), sub2-10 (15.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1 g of subB-3 (yield 58%, MS: [M+H]+ = 454).

[0610] Under a nitrogen atmosphere, subB-3 (10 g, 22 mmol), amine 14 (6.8 g, 23.1 mmol), and sodium tert-butoxide (2.8 g, 28.6 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of compound 2-19 (69% yield, MS: [M+H]+ = 713).

[0611] Preparation Example 2-20

[0612]

[0613] Compound B (10 g, 46 mmol), sub2-11 (11.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.2 g of subB-4 (yield 59%, MS: [M+H]+ = 378).

[0614] Under a nitrogen atmosphere, subB-4 (10 g, 26.5 mmol), amine 15 (9.8 g, 27.8 mmol), and sodium tert-butoxide (3.3 g, 34.4 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of compound 2-20 (yield 62%, MS: [M+H]+ = 693).

[0615] Preparation Example 2-21

[0616]

[0617] Compound B (10 g, 46 mmol), sub2-7 (11.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.5 g of subB-5 (yield 55%, MS: [M+H]+ = 378).

[0618] Under a nitrogen atmosphere, subB-5 (10 g, 26.5 mmol), amine 16 (10.3 g, 27.8 mmol), and sodium tert-butoxide (3.3 g, 34.4 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of compound 2-21 (70% yield, MS: [M+H]+=713).

[0619] Preparation Example 2-22

[0620]

[0621] Compound B (10 g, 46 mmol), sub2-12 (15.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of subB-6 (70% yield, MS: [M+H]+ = 454).

[0622] Under a nitrogen atmosphere, subB-6 (10 g, 22 mmol), amine 6 (5.7 g, 23.1 mmol), and sodium tert-butoxide (2.8 g, 28.6 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1 g of compound 2-22 (69% yield, MS: [M+H]+ = 665).

[0623] Preparation Example 2-23

[0624]

[0625] Compound B (10 g, 46 mmol), sub2-13 (13.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of subB-7 (70% yield, MS: [M+H]+ = 418).

[0626] Under a nitrogen atmosphere, subB-7 (10 g, 23.9 mmol), amine 6 (6.2 g, 25.1 mmol), and sodium tert-butoxide (3 g, 31.1 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10 g of compound 2-23 (yield 67%, MS: [M+H]+=627).

[0627] Preparation Examples 2-24

[0628]

[0629] Compound B (10 g, 46 mmol), sub2-14 (13.6 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1 g of subB-8 (63% yield, MS: [M+H]+ = 418).

[0630] Under a nitrogen atmosphere, subB-8 (10 g, 23.9 mmol), amine 6 (6.2 g, 25.1 mmol), and sodium tert-butoxide (3 g, 31.1 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9 g of compound 2-24 (66% yield, MS: [M+H]+ = 627).

[0631] Preparation Example 2-25

[0632]

[0633] Compound C (10 g, 46 mmol), sub2-1 (9.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.8 g of subC-1 (65% yield, MS: [M+H]+ = 328).

[0634] Under a nitrogen atmosphere, subC-1 (10 g, 30.5 mmol), amine 7 (11.3 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 2-25 (yield 66%, MS: [M+H]+ = 643).

[0635] Preparation Example 2-26

[0636]

[0637] Under a nitrogen atmosphere, subC-1 (10 g, 30.5 mmol), amine 17 (13.7 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of compound 2-26 (67% yield, MS: [M+H]+ = 719).

[0638] Preparation Example 2-27

[0639]

[0640] Under a nitrogen atmosphere, subC-1 (10 g, 30.5 mmol), amine 18 (10.7 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of compound 2-27 (63% yield, MS: [M+H]+=627).

[0641] Preparation Example 2-28

[0642]

[0643] Under a nitrogen atmosphere, subC-1 (10 g, 30.5 mmol), amine 19 (12.3 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of compound 2-28 (yield 64%, MS: [M+H]+=677).

[0644] Preparation Example 2-29

[0645]

[0646] Under a nitrogen atmosphere, subC-1 (10 g, 30.5 mmol), amine 20 (12.9 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of compound 2-29 (69% yield, MS: [M+H]+=693).

[0647] Preparation Examples 2-30

[0648]

[0649] Under a nitrogen atmosphere, subC-1 (10 g, 30.5 mmol), amine 21 (12.7 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of compound 2-30 (65% yield, MS: [M+H]+ = 689).

[0650] Preparation Example 2-31

[0651]

[0652] Under a nitrogen atmosphere, subC-l (10 g, 30.5 mmol), amine 22 (11.2 g, 32 mmol), and sodium tert-butoxide (3.8 g, 39.7 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.2 g of compound 2-31 (yield 52%, MS: [M+H]+ = 641).

[0653] Preparation Example 2-32

[0654]

[0655] Compound C (10 g, 46 mmol), sub2-2 (12.9 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7 g of subC-2 (63% yield, MS: [M+H]+ = 404).

[0656] Under a nitrogen atmosphere, subC-2 (10 g, 24.8 mmol), amine 13 (7.7 g, 26 mmol), and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.2 g of compound 2-32 (yield 62%, MS: [M+H]+=663).

[0657] Preparation Examples 2-33

[0658]

[0659] Compound C (10 g, 46 mmol), sub2-3 (11.7 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9 g of subC-3 (yield 63%, MS: [M+H]+ = 378).

[0660] Under a nitrogen atmosphere, subC-3 (10 g, 24.8 mmol), amine 23 (8.7 g, 26 mmol), and sodium tert-butoxide (3.1 g, 32.2 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of compound 2-33 (yield 54%, MS: [M+H]+ = 677).

[0661] Preparation Examples 2-34

[0662]

[0663] Compound C (10 g, 46 mmol), sub2-15 (15.3 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of subC-4 (65% yield, MS: [M+H]+ = 454).

[0664] Under a nitrogen atmosphere, subC-4 (10 g, 22 mmol), amine 5 (7.4 g, 23.1 mmol), and sodium tert-butoxide (2.8 g, 28.6 mmol) were added to 200 mL of xylene, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.2 g of compound 2-34 (63% yield, MS: [M+H]+ = 739).

[0665] Preparation Examples 2-35

[0666]

[0667] Compound C (10 g, 46 mmol), sub2-16 (12.9 g, 48.3 mmol), and sodium tert-butoxide (5.7 g, 59.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.5 g, 0.9 mmol) was added. After 2 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4 g of subC-5 (50% yield, MS: [M+H]+ = 454).

[0668] SubC-5 (10 g, 22 mmol), amine 6 (5.7 g, 23.1 mmol), and sodium tert-butoxide (2.8 g, 28.6 mmol) were added to 200 mL of xylene under a nitrogen atmosphere. The mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, and the solvent was removed by cooling to room temperature under reduced pressure. The compound was then completely dissolved in chloroform and washed twice with water. Subsequently, the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.5 g of compound 2-35 (yield 58%, MS: [M+H]+ = 663).

[0669] [Example]

[0670] Example 1

[0671] It is coated with a thickness of The glass substrate with ITO (indium tin oxide) as the thin film was immersed in distilled water containing a cleaning agent and ultrasonically cleaned. A product manufactured by Fischer Co. was used as the cleaning agent, and distilled water filtered twice using a filter manufactured by Millipore Co. was used as the distilled water. After cleaning the ITO for 30 minutes, ultrasonic cleaning was repeated twice for 10 minutes each time with distilled water. After cleaning with distilled water, the substrate was ultrasonically cleaned with isopropanol, acetone, and methanol solvents, 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 deposition unit.

[0672] A hole injection layer was formed on the prepared ITO transparent electrode using the following compound HI-1 until... The thickness was determined, and compound A-1 was p-doped at a concentration of 1.5%. Then, compound HT-1 was vacuum-deposited onto the hole-injection layer to... The thickness is increased to form a hole transport layer. Subsequently, the following compound EB-1 is vacuum-deposited onto the hole transport layer. The thickness was used as an electron blocking layer. Then, compounds 1-2, 2-1, and Dp-7 were vacuum deposited on the EB-1 deposition film at a weight ratio of 49:49:2. The thickness is increased to form a red luminescent layer. This is achieved by vacuum deposition of the following compound HB-1 onto the luminescent layer. The thickness is used to form a hole-blocking layer. Then, compounds ET-1 and LiQ are vacuum-deposited on the hole-blocking layer at a weight ratio of 2:1. The thickness is adjusted to form the electron injection and transport layers. Lithium fluoride (LiF) and aluminum are sequentially deposited on the electron injection and transport layers, respectively. and The thickness is used to form the cathode.

[0673]

[0674] In the above process, the deposition rate of organic materials is maintained at to Maintain the deposition rate of lithium fluoride on the cathode at and maintaining the aluminum deposition rate In addition, the vacuum level during deposition was maintained at 2×10⁻⁶. -7 Up to 5×10 -6 This allows for the fabrication of organic light-emitting devices.

[0675] Examples 1 to 145

[0676] Organic light-emitting devices were manufactured in the same manner as in Example 1, except that compounds 1-2 and 2-1 were replaced with the compounds shown in Table 1.

[0677] Comparative Examples 1 to 60

[0678] Organic light-emitting devices were fabricated in the same manner as in Example 1, except that compounds 1-2 and 2-1 were used instead of those shown in Table 2.

[0679] Comparative Examples 61 to 124

[0680] Organic light-emitting devices were fabricated in the same manner as in Example 1, except that compounds 1-2 and 2-1 were replaced with the compounds shown in Table 3.

[0681] The compounds B-1 to B-12 and compounds C-1 to C-8 used in Comparative Examples 1 to 124 are as follows.

[0682]

[0683]

[0684] Experimental Example

[0685] By applying 15 mA / cm² to the organic light-emitting devices prepared in Examples 1 to 145 and Comparative Examples 1 to 124 above... 2 Current is used to measure drive voltage, efficiency, and lifespan. Lifespan T95 refers to the time (in hours) until the initial brightness (6000 nits) decreases to 95%.

[0686] The results are shown in Tables 1 to 3 below.

[0687] [Table 1]

[0688]

[0689]

[0690]

[0691]

[0692]

[0693]

[0694]

[0695]

[0696]

[0697]

[0698] [Table 2]

[0699]

[0700]

[0701]

[0702]

[0703] [Table 3]

[0704]

[0705]

[0706]

[0707] Referring to Tables 1 to 3, it was determined that, compared with Comparative Examples 1 to 124, the organic light-emitting devices of Examples 1 to 145, in which the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 are co-deposited as the main body of the red light-emitting layer, have a lower driving voltage and increased efficiency and lifetime.

[0708] Based on these results, it can be determined that the combination of the compound of chemical formula 1 and the compound of chemical formula 2 is more effective in transferring energy to the dopant in the light-emitting layer compared with the combination of the comparative examples.

[0709] [Explanation of reference numerals in the attached figures]

[0710] 1: Substrate 2: Anode

[0711] 3: Light-emitting layer 4: Cathode

[0712] 5: Hole injection layer; 6: Hole transport layer

[0713] 7: Electron transport layer; 8: Electron injection layer

[0714] 9: Electron blocking layer 10: Hole blocking layer

[0715] 11: Electron Injection and Transport Layer

Claims

1. An organic light-emitting device, comprising: anode; cathode; And the light-emitting layer between the anode and the cathode, The light-emitting layer comprises a compound represented by the following chemical formula 1-1 and a compound represented by the following chemical formula 2: ， In chemical formula 1-1, L represents a single bond; or a phenylene group. Ar1 and Ar2 are each independently of C 6-10 Aryl-substituted or unsubstituted C 6-60 aryl; or unsubstituted C containing at least one of N, O, and S. 2-60 heteroaryl, and Ar3 is derived from C 6-10 Aryl-substituted or unsubstituted C 6-60 aryl; or unsubstituted C containing at least one of N, O, and S. 2-60 Mixed aromatics, ， In chemical formula 2, A' represents an unsubstituted naphthalene ring fused with an adjacent ring. L'1 and L'2 are each independent single bonds; unreplaced C 6-60 Aromatic; or unsubstituted C containing at least one of N, O, and S. 2-60 Hybrid aryl, L'3 is unsubstituted C 6-60 Aromatic; or unsubstituted C containing at least one of N, O, and S. 2-60 Hybrid aryl, and Ar'1 and Ar'2 are each independently unsubstituted C 6-60 aryl; or unsubstituted C containing at least one heteroatom selected from N, O, and S. 2-60 Mixed aromatic compounds.

2. The organic light-emitting device according to claim 1, Ar1 and Ar2 are each independently phenyl; biphenyl; terphenyl; naphthyl; phenanthryl; phenylnaphthyl; naphthylphenyl; dibenzofuranyl; or dibenzothiophene.

3. The organic light-emitting device according to claim 1, Ar3 is phenyl; biphenyl; terphenyl; naphthyl; phenanthryl; phenylnaphthyl; naphthylphenyl; triphenylene; dibenzofuranyl; dibenzothiophene; benzonaphthiophene; or fluoranthyl.

4. The organic light-emitting device according to claim 1, The compound represented by chemical formula 1 is selected from any of the following compounds: 。 5. The organic light-emitting device according to claim 1, Chemical formula 2 is represented by any one of the following chemical formulas 2-1 to 2-3: ， In chemical formulas 2-1 to 2-3 Ar1', Ar'2 and L'1 to L'3 as defined in claim 1.

6. The organic light-emitting device according to claim 1, Where L'3 is selected from any of the following structural formulas: 。 7. The organic light-emitting device according to claim 1, L'1 and L'2 are each independently a single bond; or phenylene.

8. The organic light-emitting device according to claim 1, Ar'1 and Ar'2 are each independently phenyl; biphenyl; terphenyl; naphthyl; phenanthryl; dibenzofuranyl; dibenzothiophene; or benzonaphthofuranyl.

9. The organic light-emitting device according to claim 1, The compound represented by chemical formula 2 is selected from any of the following compounds: 。

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