Organic light emitting device

Abstract

The present application provides an organic light emitting device with improved driving voltage, efficiency and lifespan.

Description

Technical Field

[0001] Cross-reference with related applications

[0002] This application claims priority based on Korean Patent Application No. 10-2020-0057863 dated May 14, 2020 and Korean Patent Application No. 10-2021-0062251 dated May 13, 2021, the entire contents of which are disclosed in the documents of the Korean patent applications and are incorporated herein by reference.

[0003] This invention relates to organic light-emitting devices with improved driving voltage, efficiency, and lifetime. Background Technology

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

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

[0006] For the organic light-emitting devices described above, there is a continuous demand for the development of organic light-emitting devices with improved driving voltage, efficiency, and lifetime.

[0007] Existing technical documents

[0008] Patent documents

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

[0010] Technical issues

[0011] This invention relates to organic light-emitting devices with improved driving voltage, efficiency, and lifetime.

[0012] Solution to the problem

[0013] The present invention provides the following organic light-emitting device:

[0014] An organic light-emitting device, comprising:

[0015] Anode, cathode, and the light-emitting layer between the anode and cathode.

[0016] The aforementioned luminescent layer comprises a compound represented by chemical formula 1 and a compound represented by chemical formula 2:

[0017] [Chemical Formula 1]

[0018]

[0019] In the above chemical formula 1,

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

[0021] L1 to L3 are each independently a single bond, or a substituted or unsubstituted C bond. 6-60 Alpha-aryl

[0022] R1 is hydrogen; deuterium; substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing one or more of N, O, and S. 2-60 Mixed aromatics,

[0023] a is an integer from 0 to 7.

[0024] [Chemical Formula 2]

[0025]

[0026] In the above chemical formula 2,

[0027] Ar3 and Ar4 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing one or more of N, O, and S. 2-60 Mixed aromatics,

[0028] L4 through L6 are each independently a single bond, or a substituted or unsubstituted C bond. 6-60 Alpha-aryl.

[0029] Invention Effects

[0030] The above-mentioned organic light-emitting device can achieve improved efficiency, lower driving voltage, and / or improved lifetime characteristics by including the compound represented by the above-mentioned chemical formula 1 and the compound represented by the above-mentioned chemical formula 2 in the light-emitting layer. Attached Figure Description

[0031] Figure 1 The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.

[0032] Figure 2 The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron transport layer 9, an electron injection layer 10, and a cathode 4. Detailed Implementation

[0033] The invention will now be described in more detail to aid in understanding.

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

[0035] In this specification, the term "substituted or unsubstituted" refers to a group selected from deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thio group. aryl thiols alkylsulfonyl arylsulfonyl Silyl; boronyl; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; arylene; alkylaryl; alkylamino; aralkylamino; heteroarylamino; arylamino; arylphosphinyl; or a heterocyclic group containing one or more of the N, O, and S atoms, substituted or unsubstituted, or substituted or unsubstituted by two or more of the substituents exemplified above. For example, "a substituent formed by two or more substituents" can be biphenyl. That is, biphenyl can be aryl, or it can be interpreted as a substituent formed by two phenyl groups linked together.

[0036] In this specification, the number of carbon atoms in the carbonyl group is not particularly limited, but it is preferred to have 1 to 40 carbon atoms. Specifically, it can be a substituent with the following structures, but is not limited thereto.

[0037]

[0038] In this specification, the oxygen atom in the ester group may be replaced by a straight-chain, branched, or cyclic alkyl group having 1 to 25 carbon atoms; or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a substituent of the following structural formula, but is not limited thereto.

[0039]

[0040] In this specification, the number of carbon atoms in the imide group is not particularly limited, but it is preferred to have 1 to 25 carbon atoms. Specifically, it can be a substituent with the following structure, but is not limited thereto.

[0041]

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

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

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

[0045] In this specification, the alkyl group can be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to yet another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc., but are not limited to these.

[0046] In this specification, the alkenyl group can be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to yet another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, styryl, styryl, etc., but are not limited to these.

[0047] In this specification, the cycloalkyl group is not particularly limited, but is preferably a cycloalkyl group with 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., are used, but are not limited to these.

[0048] In this specification, the aryl group is not particularly limited, but is preferably an aryl group with 6 to 60 carbon atoms, and can be a monocyclic aryl or polycyclic aryl. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to another embodiment, the aryl group has 6 to 20 carbon atoms. Regarding the aforementioned aryl group, as a monocyclic aryl group, it can be phenyl, biphenyl, terphenyl, etc., but is not limited to these. As the aforementioned polycyclic aryl group, it can be naphthyl, anthraceneyl, phenanthryl, pyrene, perylene, etc. It includes bases, fluorenes, etc., but is not limited to these.

[0049] In this specification, the fluorene group can be substituted, and two substituents can combine with each other to form a spirostructure. When the fluorene group is substituted as described above, it can become... Etc. But it is not limited to this.

[0050] In this specification, a heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as heteroelements. The number of carbon atoms is not particularly limited, but is preferably 2 to 60. Examples of heterocyclic groups include thiophene, furanyl, pyrrole, imidazole, and thiazolyl. azole group, Diazolyl, Triazolyl, Pyridyl, Bipyridyl, Pyrimidinyl, Triazinyl, Acridineyl, Pyridazinyl, Quinolinyl, Quinazolinyl, Quinoxalinyl, Phtharazineyl, Pyridopyrimidinyl, Pyridopyrazinyl, Pyrazenopyrazinyl, Isoquinolinyl, Indoleyl, Carbazoleyl, Benzo[] Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazole, benzothiophene, dibenzothiophene, benzofuranyl, phenanthroline, iso Azolyl, thiadiazolyl, phenthiazinyl, and dibenzofuranyl groups, but not limited to these.

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

[0052] The present invention will now be described in detail according to its constituent parts.

[0053] Anode and cathode

[0054] The anode and cathode used in this invention refer to electrodes used in organic light-emitting devices.

[0055] As the aforementioned anode material, a material with a high work function is preferred in order to facilitate the injection of holes into the organic layer. Specific examples of the aforementioned anode materials include metals such as vanadium, chromium, copper, zinc, and gold, or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylidene-1,2-dioxo)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited to these.

[0056] As the cathode material described above, a material with a low work function is generally preferred in order to facilitate the injection of electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or their alloys; multilayer structures such as LiF / Al or LiO2 / Al, etc., but are not limited to these.

[0057] Hole injection layer

[0058] The organic light-emitting device according to the present invention may further include a hole injection layer on the anode as needed.

[0059] The aforementioned hole injection layer is a layer that injects holes from the electrode. Preferably, the hole injection material is a compound that possesses the ability to transport holes, the effect of injecting holes from the anode, excellent hole injection performance for the light-emitting layer or light-emitting material, prevents excitons generated in the light-emitting layer from migrating to the electron injection layer or electron injection material, and exhibits excellent thin film formation capability. Furthermore, it is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between that of the anode material and the HOMO of the surrounding organic layer.

[0060] Specific examples of hole-injection materials include, but are not limited to, metalloporphyrins, oligothiophenes, arylamines, hexanitrile hexaazabenzophenanthrenes, quinacridones, perylenes, anthraquinones, and conductive polymers based on polyaniline and polythiophene.

[0061] Hole transport layer

[0062] The organic light-emitting device according to the present invention may include a hole transport layer on the anode (or on the hole injection layer if a hole injection layer is present) as needed.

[0063] The aforementioned hole transport layer is a layer that receives holes from the anode or hole injection layer and transports the holes to the light-emitting layer. The hole transport material is a material that can receive holes from the anode or hole injection layer and transfer them to the light-emitting layer. Materials with high hole mobility are suitable.

[0064] Specific examples of the aforementioned hole transport substances include arylamine organic compounds, conductive polymers, and block copolymers that simultaneously contain conjugated and non-conjugated portions, but are not limited to these.

[0065] Electron blocking layer

[0066] The organic light-emitting device according to the present invention may include an electron blocking layer on the hole transport layer as needed.

[0067] The aforementioned electron blocking layer is a layer placed between the hole transport layer and the light-emitting layer to prevent electrons injected from the cathode from recombining in the light-emitting layer and transferring to the hole transport layer. It is also called an electron blocking layer or electron suppression layer. The electron blocking layer is preferably made of a material with lower electrophilicity compared to the electron transport layer.

[0068] Emissive layer

[0069] The light-emitting layer used in this invention refers to a layer capable of emitting visible light by combining holes and electrons received from the anode and cathode. Typically, the light-emitting layer comprises a host material and a dopant material; in this invention, it comprises compounds represented by Chemical Formula 1 and Chemical Formula 2 as the host material.

[0070] Preferably, the compound represented by the above chemical formula 1 can be represented by any one of the following chemical formulas 1-1 to 1-3:

[0071] [Chemical Formula 1-1]

[0072]

[0073] [Chemical Formula 1-2]

[0074]

[0075] [Chemical Formulas 1-3]

[0076]

[0077] In the above chemical formulas 1-1 to 1-3,

[0078] Ar1, Ar2, L1 to L3 and R1 are defined in the same way as in Formula 1.

[0079] Preferably, Ar1 and Ar2 can each be independently substituted or unsubstituted C. 6-20 aryl; or substituted or unsubstituted C containing one or more of N, O, and S. 2-20 Mixed aromatics,

[0080] More preferably, Ar1 and Ar2 can each be independently phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, dibenzofuranyl, or dibenzothiophene.

[0081] Most preferably, Ar1 and Ar2 can each be independently selected from any of the following groups:

[0082]

[0083] Preferably, L1 to L3 can each be a single bond, or a substituted or unsubstituted C bond. 6-20 Alpha-aryl

[0084] More preferably, L1 to L3 can each independently be a single bond, a phenylene group, a biphenylene group, or a naphthylene group.

[0085] Most preferably, L1 to L3 can each be a single bond independently, or be selected from any of the following groups:

[0086]

[0087] Preferably, R1 can be hydrogen; deuterium; substituted or unsubstituted C, each independently. 6-20 aryl; or substituted or unsubstituted C containing one or more of N, O, and S. 2-20 Mixed aromatics,

[0088] More preferably, R1 can be hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, triphenylene, naphthylphenyl, phenylnaphthyl, fluoranthyl, dibenzofuranyl, dibenzothiophene, benzonaphthiophene, or benzonaphthiophene.

[0089] Preferably, a can be 0 or 1. More preferably, a can be 1.

[0090] Preferably, at least one of Ar1, Ar2 and R1 can be naphthyl, phenylnaphthyl, naphthylphenyl, phenanthryl, fluoranthyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthiophenyl, or benzonaphthiophenyl.

[0091] More preferably, at least one of Ar1, Ar2 and R1 can be naphthyl, phenylnaphthyl, naphthylphenyl, fluoranthyl, dibenzofuranyl, benzonaphthylfuranyl, or benzonaphthiophenyl.

[0092] Representative examples of compounds represented by the above chemical formula 1 are shown below:

[0093]

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[0248] As an example, the compound represented by the above chemical formula 1 can be manufactured by the manufacturing method shown in the following reaction formula 1, and other compounds can also be manufactured by a similar method.

[0249] [Reaction Formula 1]

[0250]

[0251] In the above reaction formula 1, Ar1, Ar2, L1 to L3, R1 and a are defined as in the above chemical formula 1, and X1 is a halogen, preferably chlorine or bromine.

[0252] The above-described reaction formula 1 is a Suzuki coupling reaction, preferably carried out in the presence of a palladium catalyst and a base. The reactive group used in the Suzuki coupling reaction can be modified according to techniques known in the art. The above manufacturing method can be further specified in the manufacturing examples described later.

[0253] Preferably, Ar3 and Ar4 can each be independently substituted or unsubstituted C. 6-20 aryl; or substituted or unsubstituted C containing one or more of N, O, and S. 2-20 Mixed aromatics,

[0254] More preferably, Ar3 and Ar4 can each independently be phenyl, biphenyl, terphenyl, tetraphenyl, naphthyl, phenanthryl, naphthylphenyl, phenylnaphthyl, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, carbazole, phenylcarbazole, dibenzofuranyl, dibenzothiopheneyl, or benzonaphthiofuranyl.

[0255] Most preferably, Ar3 and Ar4 can each be independently selected from any of the following groups:

[0256]

[0257]

[0258] Preferably, L4 to L6 can each be a single bond, or a substituted or unsubstituted C bond. 6-20 Alpha-aryl

[0259] More preferably, L4 to L6 can each independently be a single bond, a phenylene group, a biphenylene group, a naphthylene group, or a dimethylfluorene group.

[0260] Most preferably, L4 to L6 can each be a single bond independently, or be selected from any of the following groups:

[0261]

[0262] Representative examples of compounds represented by the above chemical formula 2 are shown below:

[0263]

[0264]

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[0280]

[0281] As an example, the compound represented by the above chemical formula 2 can be manufactured by the manufacturing method shown in reaction formula 2 below, and other compounds can also be manufactured by a similar method.

[0282] [Reaction 2]

[0283]

[0284] In the above reaction formula 2, Ar3, Ar4 and L4 to L6 are defined as in the above chemical formula 2, and X2 is a halogen, preferably chlorine or bromine.

[0285] Reaction formula 2 described above is an amine substitution reaction, preferably carried out in the presence of a palladium catalyst and a base. The reactive group used in the amine substitution reaction can be modified according to techniques known in the art. The above manufacturing method can be further specified in the manufacturing examples described later.

[0286] Preferably, in the light-emitting layer, the weight ratio of the compound represented by the above chemical formula 1 to the compound represented by the above chemical formula 2 is 10:90 to 90:10, more preferably 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40.

[0287] On the other hand, in addition to the host material, the aforementioned light-emitting layer may further include dopants. There are no particular limitations on the dopant materials, as long as they are substances used in organic light-emitting devices. Examples include aromatic amine derivatives, styrene amine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives are aromatic fused-ring derivatives having substituted or unsubstituted aryl amino groups, such as pyrene, anthracene, etc., which have aryl amino groups. Diindrone pyrene, etc., styrylamine compounds are compounds in which at least one aryl vinyl group is substituted onto a substituted or unsubstituted arylamine, and is substituted or unsubstituted by one or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino groups. Specifically, there are styrylamines, styryldiamines, styryltriamines, styryltetraamines, etc., but they are not limited to these. In addition, as metal complexes, there are iridium complexes, platinum complexes, etc., but they are not limited to these.

[0288] Hole blocking layer

[0289] The organic light-emitting device according to the present invention may include a hole blocking layer on the light-emitting layer as needed.

[0290] The aforementioned hole blocking layer is a layer placed between the electron transport layer and the light-emitting layer to prevent holes injected from the anode from recombining in the light-emitting layer and transferring to the electron transport layer. It is also called a hole suppression layer or hole blocking layer. Materials with high ionization energy are preferably used in the hole blocking layer.

[0291] Electron transport layer

[0292] The organic light-emitting device according to the present invention may include an electron transport layer on the light-emitting layer (or hole blocking layer) as needed.

[0293] The aforementioned electron transport layer is a layer that receives electrons from the cathode or an electron injection layer formed on the cathode and transports the electrons to the light-emitting layer, while also suppressing the propagation of holes from the light-emitting layer. The electron transport material is a material that can effectively receive electrons from the cathode and transfer them to the light-emitting layer, and a material with a high electron mobility is suitable.

[0294] Specific examples of the aforementioned electron transport materials include Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic radical compounds, hydroxyflavonoid-metal complexes, etc., but are not limited to these. The electron transport layer can be used with any desired cathode material as used in the prior art. In particular, examples of suitable cathode materials are common materials with low work functions and accompanied by an aluminum or silver layer. Specifically, cesium, barium, calcium, ytterbium, and samarium are all accompanied by an aluminum or silver layer in each case.

[0295] Electron injection layer

[0296] The organic light-emitting device according to the present invention may, as needed, further include an electron injection layer on the light-emitting layer (or, if an electron transport layer is present, on the electron transport layer).

[0297] The aforementioned electron injection layer is a layer that injects electrons from the electrode. Preferably, the following compounds are used: compounds that have the ability to transport electrons, have the effect of injecting electrons from the cathode, have excellent electron injection effect on the light-emitting layer or light-emitting material, prevent excitons generated in the light-emitting layer from migrating to the hole injection layer, and have excellent thin film forming ability.

[0298] Specific examples of substances that can be used in the aforementioned electron-injection layer include fluorenone, anthraquinone dimethyl ether, biphenylquinone, thiamethoxam dioxide, etc. azole, Diazoles, triazoles, imidazoles, perylenetetracarboxylic acid, fluorenemethane, anthrones, and their derivatives, metal coordination compounds, and nitrogen-containing five-membered ring derivatives, but not limited to these.

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

[0300] On the other hand, in this invention, the “electron injection and transport layer” is a layer that fully utilizes the functions of the aforementioned electron injection layer and the aforementioned electron transport layer. It can be a substance that performs the functions of the aforementioned layers, either alone or in combination, but is not limited to this.

[0301] Organic light-emitting devices

[0302] The structure of the organic light-emitting device according to the present invention is illustrated in... Figure 1and Figure 2 . Figure 1 The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. Figure 2 The illustration shows an example of an organic light-emitting device consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron transport layer 9, an electron injection layer 10, and a cathode 4.

[0303] The organic light-emitting device according to the present invention can be manufactured by sequentially stacking the above-described structures. It can be manufactured as follows: using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation, a metal or a conductive metal oxide or alloy thereof is deposited on a substrate to form an anode, then the aforementioned layers are formed on the anode, and subsequently a material suitable for use as a cathode is deposited on it. Besides this method, the organic light-emitting device can also be manufactured by sequentially depositing the cathode material onto the anode material on the substrate in the reverse order of the above-described structures (WO 2003 / 012890). Furthermore, not only vacuum evaporation but also solution coating can be used to form the light-emitting layer from the substrate and the dopant. Here, solution coating refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, roll coating, etc., but is not limited to these.

[0304] On the other hand, the organic light-emitting device according to the present invention can be a bottom-emission device, a top-emission device, or a bidirectional light-emitting device, and in particular, it can be a bottom-emission device that requires relatively high luminous efficiency.

[0305] Preferred embodiments are presented below to aid in understanding the invention. However, these embodiments are provided merely for easier understanding of the invention, and the invention is not limited thereto.

[0306] [Manufacturing Example]

[0307] Manufacturing Example 1-1: Manufacturing of Compound 1-1

[0308]

[0309] Under a nitrogen atmosphere, compound 1-A (15 g, 60.9 mmol) and compound Trz27 (25.6 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19.1 g of compound sub-1-A-1 (yield 65%, MS: [M+H]). + =484).

[0310]

[0311] Under a nitrogen atmosphere, compound 1-A-1 (15 g, 31 mmol) and compound 1 (6.1 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (8.6 g, 62 mmol) dissolved in 26 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.3 g of compound 1-1 (yield 66%, MS: [M+H)). + =602).

[0312] Manufacturing Example 1-2: Manufacturing of Compound 1-2

[0313]

[0314] Under a nitrogen atmosphere, compound 1-A (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19.5 g of compound 1-A-2 (yield 74%, MS: [M+H)). + =434).

[0315]

[0316] Under a nitrogen atmosphere, compound 1-A-2 (15 g, 34.6 mmol) and compound 2 (9.4 g, 34.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (9.6 g, 69.1 mmol) dissolved in 29 mL of water was added, and after thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.3 g of compound 1-2 (yield 66%, MS: [M+H)). + =626).

[0317] Manufacturing Examples 1-3: Manufacturing of Compound 1-3

[0318]

[0319] Under a nitrogen atmosphere, compound 1-A (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 23.2 g of compound 1-A-3 (79% yield, MS: [M+H)). + =484).

[0320]

[0321] Under a nitrogen atmosphere, compound 1-A-3 (15 g, 31 mmol) and compound 3 (7.1 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (8.6 g, 62 mmol) dissolved in 26 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.9 g of compound 1-3 (yield 66%, MS: [M+H)). + =632).

[0322] Manufacturing Examples 1-4: Manufacturing of Compounds 1-4

[0323]

[0324] Under a nitrogen atmosphere, compound 1-A (15 g, 60.9 mmol) and compound Trz4 (27 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 26 g of compound 1-A-4 (70% yield, MS: [M+H)). + =610).

[0325]

[0326] Under a nitrogen atmosphere, compound 1-A-4 (15 g, 24.6 mmol) and compound 4 (5.6 g, 24.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (6.8 g, 49.2 mmol) dissolved in 20 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.2 g of compound 1-4 (60% yield, MS: [M+H)). + =758).

[0327] Manufacturing Examples 1-5: Manufacturing of Compounds 1-5

[0328]

[0329] Under a nitrogen atmosphere, compound 1-B (15 g, 60.9 mmol) and compound Trz5 (24 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 26.2 g of compound 1-B-1 (77% yield, MS: [M+H)). + =560).

[0330]

[0331] Under a nitrogen atmosphere, compound 1-B-1 (15 g, 26.8 mmol) and compound 5 (3.3 g, 26.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in 22 mL of water and added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.9 g of compound 1-5 (yield 80%, MS: [M+H)). + =602).

[0332] Manufacturing Examples 1-6: Manufacturing of Compounds 1-6

[0333]

[0334] Under a nitrogen atmosphere, compound 1-B (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18.2 g of compound 1-B-2 (yield 62%, MS: [M+H)). + =484).

[0335]

[0336] Under a nitrogen atmosphere, compound 1-B-2 (15 g, 31 mmol) and compound 6 (7.6 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (8.6 g, 62 mmol) dissolved in 26 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compounds were purified by silica gel column chromatography to produce 15.3 g of compounds 1-6 (76% yield, MS: [M+H)). + =650).

[0337] Manufacturing Examples 1-7: Manufacturing of Compounds 1-7

[0338]

[0339] Under a nitrogen atmosphere, compound 1-B (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20.8 g of compound 1-B-3 (79% yield, MS: [M+H)). + =434).

[0340]

[0341] Under a nitrogen atmosphere, compound 1-B-3 (15 g, 34.6 mmol) and compound 7 (8.6 g, 34.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (9.6 g, 69.1 mmol) dissolved in 29 mL of water was added, and after thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.4 g of compound 1-7 (74% yield, MS: [M+H)). + =602).

[0342] Manufacturing Examples 1-8: Manufacturing of Compounds 1-8

[0343]

[0344] Under a nitrogen atmosphere, compound 1-B-2 (15 g, 31 mmol) and compound 8 (8.1 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (8.6 g, 62 mmol) dissolved in 26 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compounds were purified by silica gel column chromatography to produce 15.5 g of compounds 1-8 (75% yield, MS: [M+H)). + =666).

[0345] Manufacturing Examples 1-9: Manufacturing of Compounds 1-9

[0346]

[0347] Under a nitrogen atmosphere, compound 1-B (15 g, 60.9 mmol) and compound Trz6 (22.4 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 23.7 g of compound 1-B-4 (73% yield, MS: [M+H)). + =534).

[0348]

[0349] Under a nitrogen atmosphere, compound 1-B-4 (15 g, 28.1 mmol) and compound 9 (6 g, 28.1 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (7.8 g, 56.2 mmol) dissolved in 23 mL of water was added, and after thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compounds were purified by silica gel column chromatography to produce 11.6 g of compounds 1-9 (yield 62%, MS: [M+H)). + =666).

[0350] Manufacturing Examples 1-10: Manufacturing of Compounds 1-10

[0351]

[0352] Under a nitrogen atmosphere, compound 1-B (15 g, 60.9 mmol) and compound Trz7 (28.6 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 28.6 g of compound 1-B-5 (yield 74%, MS: [M+H)). + =636).

[0353]

[0354] Under a nitrogen atmosphere, compound 1-B-5 (15 g, 23.6 mmol) and compound 5 (2.9 g, 23.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (6.5 g, 47.2 mmol) dissolved in 20 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.4 g of compound 1-10 (65% yield, MS: [M+H)). + =678).

[0355] Manufacturing Example 1-11: Manufacturing of Compound 1-11

[0356]

[0357] Under a nitrogen atmosphere, compound 1-B (15 g, 60.9 mmol) and compound Trz8 (21.8 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20.1 g of compound 1-B-6 (yield 63%, MS: [M+H)). + =524).

[0358]

[0359] Under a nitrogen atmosphere, compound 1-B-6 (15 g, 28.6 mmol) and compound 10 (4.9 g, 28.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (7.9 g, 57.3 mmol) dissolved in 24 mL of water was added, and after thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.4 g of compound 1-11 (65% yield, MS: [M+H)). + =616).

[0360] Manufacturing Examples 1-12: Manufacturing of Compound 1-12

[0361]

[0362] Under a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.6 g of compound 1-C-1 (60% yield, MS: [M+H)). + =484).

[0363]

[0364] Under a nitrogen atmosphere, compound 1-C-1 (15 g, 31 mmol) and compound 10 (5.3 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (8.6 g, 62 mmol) dissolved in 26 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.8 g of compound 1-12 (72% yield, MS: [M+H)). + =576).

[0365] Manufacturing Examples 1-13: Manufacturing of Compound 1-13

[0366]

[0367] Under a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz9 (24 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 23.5 g of compound 1-C-2 (yield 69%, MS: [M+H)). + =560).

[0368]

[0369] Under a nitrogen atmosphere, compound 1-C-2 (15 g, 26.8 mmol) and compound 10 (4.6 g, 26.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (7.4 g, 53.6 mmol) dissolved in 22 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14 g of compound 1-13 (80% yield, MS: [M+H)). + =652).

[0370] Manufacturing Examples 1-14: Manufacturing of Compound 1-14

[0371]

[0372] Under a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20.5 g of compound 1-C-3 (yield 66%, MS: [M+H)). + =510).

[0373]

[0374] Under a nitrogen atmosphere, compound 1-C-3 (15 g, 29.4 mmol) and compound 11 (7.3 g, 29.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (8.1 g, 58.8 mmol) dissolved in 24 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.3 g of compound 1-14 (77% yield, MS: [M+H)). + =678).

[0375] Manufacturing Examples 1-15: Manufacturing of Compounds 1-15

[0376]

[0377] Under a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 18.7 g of compound 1-C-4 (71% yield, MS: [M+H)). + =434).

[0378]

[0379] Under a nitrogen atmosphere, compound 1-C-4 (15 g, 37.1 mmol) and compound 12 (9.7 g, 37.1 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.3 g, 74.3 mmol) was dissolved in 31 mL of water and added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.6 g of compound 1-15 (64% yield, MS: [M+H)). + =616).

[0380] Manufacturing Examples 1-16: Manufacturing of Compounds 1-16

[0381]

[0382] Under a nitrogen atmosphere, compound 1-C-3 (15 g, 26.8 mmol) and compound 13 (7.4 g, 26.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (7.4 g, 53.6 mmol) dissolved in 22 mL of water was added, and after thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 16.2 g of compound 1-16 (80% yield, MS: [M+H)). + =758).

[0383] Manufacturing Examples 1-17: Manufacturing of Compound 1-17

[0384]

[0385] Under a nitrogen atmosphere, compound 1-C-4 (15 g, 34.6 mmol) and compound 14 (7.7 g, 34.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (9.6 g, 69.1 mmol) dissolved in 29 mL of water was added, and after thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.3 g of compound 1-17 (62% yield, MS: [M+H)). + =576).

[0386] Manufacturing Examples 1-18: Manufacturing of Compound 1-18

[0387]

[0388] Under a nitrogen atmosphere, compound 1-C-1 (15 g, 31 mmol) and compound 9 (6.6 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (8.6 g, 62 mmol) dissolved in 26 mL of water was added, and after thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12 g of compound 1-18 (63% yield, MS: [M+H)). + =616).

[0389] Manufacturing Examples 1-19: Manufacturing of Compounds 1-19

[0390]

[0391] Under a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz11 (22.4 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 22.4 g of compound 1-C-5 (yield 69%, MS: [M+H)). + =534).

[0392]

[0393] Under a nitrogen atmosphere, compound 1-C-5 (15 g, 28.1 mmol) and compound 15 (6 g, 28.1 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (7.8 g, 56.2 mmol) dissolved in 23 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.3 g of compound 1-19 (71% yield, MS: [M+H)). + =666).

[0394] Manufacturing Examples 1-20: Manufacturing of Compounds 1-20

[0395]

[0396] Under a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz12 (21.8 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 21 g of compound 1-C-6 (66% yield, MS: [M+H)). + =524).

[0397]

[0398] Under a nitrogen atmosphere, compound 1-C-6 (15 g, 28.6 mmol) and compound 10 (4.9 g, 28.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.3 g of compound 1-20 (70% yield, MS: [M+H)). + =616).

[0399] Manufacturing Example 1-21: Manufacturing of Compound 1-21

[0400]

[0401] Under a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz13 (24 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol). After reacting for 12 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 26.2 g of compound 1-C-7 (77% yield, MS: [M+H)). + =560).

[0402]

[0403] Under a nitrogen atmosphere, compound 1-C-7 (15 g, 26.8 mmol) and compound 5 (3.3 g, 26.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol). After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.5 g of compound 1-21 (65% yield, MS: [M+H)). + =602).

[0404] Manufacturing Examples 1-22: Manufacturing of Compound 1-22

[0405]

[0406] Under a nitrogen atmosphere, compound 1-D (15 g, 60.9 mmol) and compound Trz14 (19.3 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol). After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 23.9 g of compound 1-D-1 (yield 67%, MS: [M+H)). + =586).

[0407]

[0408] Under a nitrogen atmosphere, compound 1-D-1 (15 g, 25.6 mmol) and compound 5 (3.1 g, 25.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.6 g, 76.8 mmol) was dissolved in 32 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol). After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.3 g of compound 1-22 (yield 64%, MS: [M+H)). + =628).

[0409] Manufacturing Examples 1-23: Manufacturing of Compound 1-23

[0410]

[0411] Under a nitrogen atmosphere, compound 1-D (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20 g of compound 1-D-2 (76% yield, MS: [M+H)). + =434).

[0412]

[0413] Under a nitrogen atmosphere, compound 1-D-2 (15 g, 34.6 mmol) and compound 16 (9.1 g, 34.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14 g of compound 1-23 (66% yield, MS: [M+H)). + =616).

[0414] Manufacturing Examples 1-24: Manufacturing of Compound 1-24

[0415]

[0416] Under a nitrogen atmosphere, compound 1-D (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20.8 g of compound 1-D-3 (yield 67%, MS: [M+H)). + =510).

[0417]

[0418] Under a nitrogen atmosphere, compound 1-D-3 (15 g, 29.4 mmol) and compound 17 (7.7 g, 29.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.4 g of compound 1-24 (61% yield, MS: [M+H)). + =692).

[0419] Manufacturing Examples 1-25: Manufacturing of Compounds 1-25

[0420]

[0421] Under a nitrogen atmosphere, compound 1-D (15 g, 60.9 mmol) and compound Trz15 (21.8 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 21.3 g of compound 1-D-4 (yield 67%, MS: [M+H)). + =524).

[0422]

[0423] Under a nitrogen atmosphere, compound 1-D-4 (15 g, 28.6 mmol) and compound 10 (4.9 g, 28.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.7 g of compound 1-25 (61% yield, MS: [M+H)). + =616).

[0424] Manufacturing Examples 1-26: Manufacturing of Compound 1-26

[0425]

[0426] Under a nitrogen atmosphere, compound 1-D-3 (15 g, 29.4 mmol) and compound 18 (6.2 g, 29.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.3 g of compound 1-26 (76% yield, MS: [M+H)). + =642).

[0427] Manufacturing Examples 1-27: Manufacturing of Compound 1-27

[0428]

[0429] Under a nitrogen atmosphere, compound 1-D (15 g, 60.9 mmol) and compound Trz16 (27 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 27.1 g of compound 1-D-5 (yield 73%, MS: [M+H)). + =610).

[0430]

[0431] Under a nitrogen atmosphere, compound 1-D-5 (15 g, 24.6 mmol) and compound 9 (5.2 g, 24.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.8 g of compound 1-27 (70% yield, MS: [M+H)). + =742).

[0432] Manufacturing Examples 1-28: Manufacturing of Compound 1-28

[0433]

[0434] Under a nitrogen atmosphere, compound 1-D (15 g, 60.9 mmol) and compound Trz13 (24 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 20.8 g of compound 1-D-6 (yield 61%, MS: [M+H)). + =560).

[0435]

[0436] Under a nitrogen atmosphere, compound 1-D-6 (15 g, 26.8 mmol) and compound 10 (4.6 g, 26.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol). After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.2 g of compound 1-28 (70% yield, MS: [M+H)). + =652).

[0437] Manufacturing Examples 1-29: Manufacturing of Compound 1-29

[0438]

[0439] Under a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.1 g of compound 1-E-1 (yield 65%, MS: [M+H)). + =434).

[0440]

[0441] Under a nitrogen atmosphere, compound 1-E-1 (15 g, 34.6 mmol) and compound 2 (9.4 g, 34.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.5 g of compound 1-29 (67% yield, MS: [M+H)). + =626).

[0442] Manufacturing Examples 1-30: Manufacturing of Compounds 1-30

[0443]

[0444] Under a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz9 (24 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 26.9 g of compound 1-E-2 (79% yield, MS: [M+H)). + =560).

[0445]

[0446] Under a nitrogen atmosphere, compound 1-E-2 (15 g, 26.8 mmol) and compound 19 (7 g, 26.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol). After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.9 g of compound 1-30 (80% yield, MS: [M+H)). + =742).

[0447] Manufacturing Examples 1-31: Manufacturing of Compound 1-31

[0448]

[0449] Under a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz17 (22.4 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 25.3 g of compound 1-E-3 (78% yield, MS: [M+H)). + =534).

[0450]

[0451] Under a nitrogen atmosphere, compound 1-E-3 (15 g, 28.1 mmol) and compound 20 (7.8 g, 28.1 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (11.6 g, 84.3 mmol) was dissolved in 35 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol). After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.8 g of compound 1-31 (72% yield, MS: [M+H)). + =732).

[0452] Manufacturing Examples 1-32: Manufacturing of Compounds 1-32

[0453]

[0454] Under a nitrogen atmosphere, compound 1-E-1 (15 g, 34.6 mmol) and compound 21 (7.7 g, 34.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.9 g of compound 1-32 (65% yield, MS: [M+H)). + =576).

[0455] Manufacturing Examples 1-33: Manufacturing of Compounds 1-33

[0456]

[0457] Under a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz15 (21.8 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 25.5 g of compound 1-E-4 (yield 80%, MS: [M+H)). + =524).

[0458]

[0459] Under a nitrogen atmosphere, compound 1-E-4 (15 g, 28.6 mmol) and compound 10 (4.9 g, 28.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.6 g of compound 1-33 (60% yield, MS: [M+H)). + =616).

[0460] Manufacturing Examples 1-34: Manufacturing of Compounds 1-34

[0461]

[0462] Under a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 17.6 g of compound 1-E-5 (60% yield, MS: [M+H)). + =484).

[0463]

[0464] Under a nitrogen atmosphere, compound 1-E-5 (15 g, 31 mmol) and compound 9 (6.6 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) dissolved in 39 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.4 g of compound 1-34 (60% yield, MS: [M+H)). + =616).

[0465] Manufacturing Examples 1-35: Manufacturing of Compounds 1-35

[0466]

[0467] Under a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 21.7 g of compound 1-E-6 (70% yield, MS: [M+H)). + =510).

[0468]

[0469] Under a nitrogen atmosphere, compound 1-E-6 (15 g, 29.4 mmol) and compound 22 (7.7 g, 29.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.6 g of compound 1-35 (72% yield, MS: [M+H)). + =692).

[0470] Manufacturing Examples 1-36: Manufacturing of Compounds 1-36

[0471]

[0472] Under a nitrogen atmosphere, compound 1-E-5 (15 g, 31 mmol) and compound 23 (8.1 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) dissolved in 39 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.4 g of compound 1-36 (60% yield, MS: [M+H)). + =666).

[0473] Manufacturing Examples 1-37: Manufacturing of Compounds 1-37

[0474]

[0475] Under a nitrogen atmosphere, compound 1-E-5 (15 g, 31 mmol) and compound 10 (5.3 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) dissolved in 39 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.1 g of compound 1-37 (79% yield, MS: [M+H)). + =576).

[0476] Manufacturing Examples 1-38: Manufacturing of Compounds 1-38

[0477]

[0478] Under a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz18 (27 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 24.1 g of compound 1-E-7 (65% yield, MS: [M+H)). + =610).

[0479]

[0480] Under a nitrogen atmosphere, compound 1-E-7 (15 g, 24.6 mmol) and compound 5 (3 g, 24.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol). After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.1 g of compound 1-38 (63% yield, MS: [M+H)). + =652).

[0481] Manufacturing Examples 1-39: Manufacturing of Compounds 1-39

[0482]

[0483] Under a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz13 (24 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol). After reacting for 12 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 26.2 g of compound 1-E-8 (77% yield, MS: [M+H)). + =560).

[0484]

[0485] Under a nitrogen atmosphere, compound 1-E-8 (15 g, 26.8 mmol) and compound 5 (3.3 g, 26.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol). After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.9 g of compound 1-39 (68% yield, MS: [M+H)). + =602).

[0486] Manufacturing Examples 1-40: Manufacturing of Compounds 1-40

[0487]

[0488] Under a nitrogen atmosphere, compound 1-F (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 19.2 g of compound 1-F-1 (73% yield, MS: [M+H)). + =434).

[0489]

[0490] Under a nitrogen atmosphere, compound 1-F-1 (15 g, 34.6 mmol) and compound 6 (8.5 g, 34.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.7 g of compound 1-40 (71% yield, MS: [M+H)). + =600).

[0491] Manufacturing Examples 1-41: Manufacturing of Compound 1-41

[0492]

[0493] Under a nitrogen atmosphere, compound 1-F (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 mL of water and added to the solution. After thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 21.1 g of compound 1-F-2 (yield 68%, MS: [M+H)). + =510).

[0494]

[0495] Under a nitrogen atmosphere, compound 1-F-2 (15 g, 29.4 mmol) and compound 1 (5.8 g, 29.4 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.2 g of compound 1-41 (77% yield, MS: [M+H)). + =628).

[0496] Manufacturing Examples 1-42: Manufacturing of Compounds 1-42

[0497]

[0498] Under a nitrogen atmosphere, compound Trz7 (15 g, 31.9 mmol) and compound 9 (6.8 g, 31.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (13.2 g, 95.8 mmol) was dissolved in 40 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.2 g of compound 1-42 (79% yield, MS: [M+H)). + =602).

[0499] Manufacturing Examples 1-43: Manufacturing of Compounds 1-43

[0500]

[0501] Under a nitrogen atmosphere, compound Trz16 (15 g, 33.8 mmol) and compound 9 (7.2 g, 33.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 12 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15 g of compound 1-43 (77% yield, MS: [M+H)). + =576).

[0502] Manufacturing Examples 1-44: Manufacturing of Compounds 1-44

[0503]

[0504] Under a nitrogen atmosphere, compound Trz4 (15 g, 33.8 mmol) and compound 9 (7.2 g, 33.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.2 g of compound 1-44 (73% yield, MS: [M+H)). + =576).

[0505] Manufacturing Examples 1-45: Manufacturing of Compounds 1-45

[0506]

[0507] Under a nitrogen atmosphere, compound Trz1 (15 g, 35.7 mmol) and compound substance 9 (7.6 g, 35.7 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in 44 mL of water and added, and after thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.2 g of compound 1-45 (62% yield, MS: [M+H)). + =552).

[0508] Manufacturing Examples 1-46: Manufacturing of Compounds 1-46.

[0509]

[0510] Under a nitrogen atmosphere, compound Trz19 (15 g, 33.8 mmol) and compound substance 9 (7.2 g, 33.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.6 g of compound 1-46 (70% yield, MS: [M+H)). + =576).

[0511] Manufacturing Examples 1-47: Manufacturing of Compounds 1-47

[0512]

[0513] Under a nitrogen atmosphere, compound Trz20 (15 g, 35.9 mmol) and compound substance 9 (7.6 g, 35.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 45 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15 g of compound 1-47 (76% yield, MS: [M+H)). + =550).

[0514] Manufacturing Examples 1-48: Manufacturing of Compounds 1-48

[0515]

[0516] Under a nitrogen atmosphere, compound Trz3 (15 g, 47.2 mmol) and compound 24 (9.7 g, 47.2 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (19.6 g, 141.6 mmol) was dissolved in 59 mL of water and added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13 g of compound 1-G-1 (62% yield, MS: [M+H)). + =444).

[0517]

[0518] Under a nitrogen atmosphere, compound 1-G-1 (15 g, 33.8 mmol) and compound 9 (7.2 g, 33.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.2 g of compound 1-48 (78% yield, MS: [M+H)). + =576).

[0519] Manufacturing Examples 1-49: Manufacturing of Compounds 1-49

[0520]

[0521] Under a nitrogen atmosphere, compound Trz15 (15 g, 41.9 mmol) and compound substance 25 (8.7 g, 41.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol). After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.6 g of compound substance 1-G-2 (yield 62%, MS: [M+H)). + =484).

[0522]

[0523] Under a nitrogen atmosphere, compound 1-G-2 (15 g, 31 mmol) and compound 9 (6.6 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) dissolved in 39 mL of water was added, and after thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.7 g of compound 1-49 (72% yield, MS: [M+H)). + =616).

[0524] Manufacturing Examples 1-50: Manufacturing of Compounds 1-50

[0525]

[0526] Under a nitrogen atmosphere, compound Trz21 (15 g, 36.8 mmol) and compound 26 (5.8 g, 36.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 46 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.8 g of compound 1-G-3 (72% yield, MS: [M+H)). + =484).

[0527]

[0528] Under a nitrogen atmosphere, compound 1-G-3 (15 g, 31 mmol) and compound 9 (6.6 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) dissolved in 39 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.2 g of compound 1-50 (69% yield, MS: [M+H)). + =616).

[0529] Manufacturing Examples 1-51: Manufacturing of Compound 1-51

[0530]

[0531] Under a nitrogen atmosphere, compound Trz16 (15 g, 33.8 mmol) and compound 27 (5.3 g, 33.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.3 g of compound 1-G-4 (76% yield, MS: [M+H)). + =520).

[0532]

[0533] Under a nitrogen atmosphere, compound 1-G-4 (15 g, 28.8 mmol) and compound 9 (6.1 g, 28.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12 g, 86.5 mmol) dissolved in 36 mL of water was added, and after thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.3 g of compound 1-51 (71% yield, MS: [M+H)). + =652).

[0534] Manufacturing Examples 1-52: Manufacturing of Compounds 1-52

[0535]

[0536] Under a nitrogen atmosphere, compound Trz22 (15 g, 36.8 mmol) and compound 28 (5.8 g, 36.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 46 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.8 g of compound 1-G-5 (72% yield, MS: [M+H)). + =484).

[0537]

[0538] Under a nitrogen atmosphere, compound 1-G-5 (15 g, 31 mmol) and compound 9 (6.6 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) dissolved in 39 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13 g of compound 1-52 (68% yield, MS: [M+H)). + =616).

[0539] Manufacturing Examples 1-53: Manufacturing of Compounds 1-53

[0540]

[0541] Under a nitrogen atmosphere, compound Trz23 (15 g, 34.6 mmol) and compound 27 (5.4 g, 34.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 mL of water and added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.3 g of compound 1-G-6 (64% yield, MS: [M+H)). + =510).

[0542]

[0543] Under a nitrogen atmosphere, compound 1-G-6 (15 g, 31 mmol) and compound 9 (6.6 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) dissolved in 39 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13 g of compound 1-53 (68% yield, MS: [M+H)). + =616).

[0544] Manufacturing Examples 1-54: Manufacturing of Compounds 1-54

[0545]

[0546] Under a nitrogen atmosphere, compound 1-G-1 (15 g, 33.8 mmol) and compound 1-E (8.3 g, 33.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 8 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 14.4 g of compound 1-E-9 (70% yield, MS: [M+H)). + =610).

[0547]

[0548] Under a nitrogen atmosphere, compound 1-E-9 (15 g, 24.6 mmol) and compound 5 (3 g, 24.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol). After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.2 g of compound 1-54 (76% yield, MS: [M+H)). + =652).

[0549] Manufacturing Examples 1-55: Manufacturing of Compounds 1-55

[0550]

[0551] Under a nitrogen atmosphere, compound Trz2 (15 g, 56 mmol) and compound 24 (11.6 g, 56 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (23.2 g, 168.1 mmol) was dissolved in 70 mL of water and added, stirred thoroughly, followed by bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol). After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15.6 g of compound 1-G-7 (71% yield, MS: [M+H)). + =394).

[0552]

[0553] Under a nitrogen atmosphere, compound 1-G-7 (15 g, 38.1 mmol) and compound 1-B (9.4 g, 38.1 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.8 g of compound 1-B-7 (yield 65%, MS: [M+H)). + =560).

[0554]

[0555] Under a nitrogen atmosphere, compound 1-B-7 (15 g, 26.8 mmol) and compound 5 (3.3 g, 26.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol). After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.9 g of compound 1-55 (80% yield, MS: [M+H)). +=602).

[0556] Manufacturing Examples 1-56: Manufacturing of Compounds 1-56

[0557]

[0558] Under a nitrogen atmosphere, compound Trz24 (15 g, 38.1 mmol) and compound substance 25 (9.4 g, 38.1 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol). After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.8 g of compound substance 1-G-8 (65% yield, MS: [M+H)). + =560).

[0559]

[0560] Under a nitrogen atmosphere, compounds 1-G-8 (15 g, 30 mmol) and 9 (6.4 g, 30 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.4 g, 90 mmol) dissolved in 37 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.4 g of compound 1-56 (71% yield, MS: [M+H)). + =632).

[0561] Manufacturing Examples 1-57: Manufacturing of Compounds 1-57

[0562]

[0563] Under a nitrogen atmosphere, compound Trz25 (15 g, 41.9 mmol) and compound 24 (8.7 g, 41.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol). After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.4 g of compound 1-G-9 (yield 61%, MS: [M+H)). + =484).

[0564]

[0565] Under a nitrogen atmosphere, compound 1-G-9 (15 g, 31 mmol) and compound 1-F (7.6 g, 31 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) dissolved in 39 mL of water was added, and after thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.5 g of compound 1-F-3 (yield 62%, MS: [M+H)). + =650).

[0566]

[0567] Under a nitrogen atmosphere, compound 1-F-3 (15 g, 23.1 mmol) and compound 5 (2.8 g, 23.1 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (9.6 g, 69.2 mmol) was dissolved in 29 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol). After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.8 g of compound 1-57 (80% yield, MS: [M+H)). + =692).

[0568] Manufacturing Examples 1-58: Manufacturing of Compounds 1-58

[0569]

[0570] Under a nitrogen atmosphere, compound Trz26 (15 g, 33.8 mmol) and compound substance 26 (5.3 g, 33.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol). After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 10.5 g of compound substance 1-G-10 (60% yield, MS: [M+H)). + =520).

[0571]

[0572] Under a nitrogen atmosphere, compound 1-G-10 (15 g, 28.8 mmol) and compound 1-D (7.1 g, 28.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12 g, 86.5 mmol) dissolved in 36 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15 g of compound 1-D-7 (76% yield, MS: [M+H)). + =686).

[0573]

[0574] Under a nitrogen atmosphere, compound 1-D-7 (15 g, 21.9 mmol) and compound 5 (2.7 g, 21.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (9.1 g, 65.6 mmol) dissolved in 27 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 9.9 g of compound 1-58 (62% yield, MS: [M+H)). + =728).

[0575] Manufacturing Examples 1-59: Manufacturing of Compounds 1-59

[0576]

[0577] Under a nitrogen atmosphere, compound Trz15 (15 g, 41.9 mmol) and compound 24 (8.7 g, 41.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol). After reacting for 11 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.4 g of compound 1-G-11 (yield 61%, MS: [M+H)). + =484).

[0578]

[0579] Under a nitrogen atmosphere, compound 1-G-11 (15 g, 28.8 mmol) and compound 1-F (7.1 g, 28.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (12 g, 86.5 mmol) dissolved in 36 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 15 g of compound 1-F-4 (76% yield, MS: [M+H)). + =686).

[0580]

[0581] Under a nitrogen atmosphere, compound 1-F-4 (15 g, 23.1 mmol) and compound 5 (2.8 g, 23.1 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (9.6 g, 69.2 mmol) dissolved in 29 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 12.1 g of compound 1-59 (76% yield, MS: [M+H)). + =692).

[0582] Manufacturing Examples 1-60: Manufacturing of Compounds 1-60

[0583]

[0584] Under a nitrogen atmosphere, compound Trz12 (15 g, 41.9 mmol) and compound 28 (6.6 g, 41.9 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 mL of water and added, stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol). After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then redissolved in chloroform, washed twice with water, and the organic layer was separated again. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 11.1 g of compound 1-G-12 (yield 61%, MS: [M+H)). + =434).

[0585]

[0586] Under a nitrogen atmosphere, compound 1-G-12 (15 g, 34.6 mmol) and compound 1-D (8.5 g, 34.6 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.6 g of compound 1-D-8 (79% yield, MS: [M+H)). + =500).

[0587]

[0588] Under a nitrogen atmosphere, compound 1-D-8 (15 g, 25 mmol) and compound 10 (4.3 g, 25 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (10.4 g, 75 mmol) dissolved in 31 mL of water was added, and after thorough stirring, 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 and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to produce 13.3 g of compound 1-60 (77% yield, MS: [M+H)). +=692).

[0589] Manufacturing Example 2-1: Manufacturing of Compound 2-1

[0590]

[0591] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 1 (11 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.5 g of compound 2-1 (70% yield, MS: [M+H)). + =548).

[0592] Manufacturing Example 2-2: Manufacturing of Compound 2-2

[0593]

[0594] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 2 (12.7 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13 g of compound 2-2 (yield 67%, MS: [M+H)). + =598).

[0595] Manufacturing Example 2-3: Manufacturing of Compound 2-3

[0596]

[0597] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 3 (13.6 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.4 g of compound 2-3 (yield 66%, MS: [M+H)). + =624).

[0598] Manufacturing Example 2-4: Manufacturing of Compound 2-4

[0599]

[0600] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 4 (12.7 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.7 g of compound 2-4 (60% yield, MS: [M+H)). + =598).

[0601] Manufacturing Example 2-5: Manufacturing of Compound 2-5

[0602]

[0603] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 5 (15.3 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 13.2 g of compound 2-5 (60% yield, MS: [M+H)). +=674).

[0604] Manufacturing Example 2-6: Manufacturing of Compound 2-6

[0605]

[0606] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 6 (10.1 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.9 g of compound 2-6 (yield 64%, MS: [M+H)). + =522).

[0607] Manufacturing Example 2-7: Manufacturing of Compound 2-7

[0608]

[0609] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 7 (13.6 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.6 g of compound 2-7 (yield 62%, MS: [M+H)). + =624).

[0610] Manufacturing Example 2-8: Manufacturing of Compound 2-8

[0611]

[0612] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 8 (13.6 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.2 g of compound 2-8 (yield 55%, MS: [M+H)). + =624).

[0613] Manufacturing Example 2-9: Manufacturing of Compound 2-9

[0614]

[0615] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 9 (11.8 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.6 g of compound 2-9 (yield 57%, MS: [M+H)). + =572).

[0616] Manufacturing Example 2-10: Manufacturing of Compound 2-10

[0617]

[0618] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 10 (10.9 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.3 g of compound 2-10 (yield 58%, MS: [M+H)). +=546).

[0619] Manufacturing Example 2-11: Manufacturing of Compound 2-11

[0620]

[0621] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 11 (14.4 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.7 g of compound 2-11 (yield 51%, MS: [M+H)). + =648).

[0622] Manufacturing Example 2-12: Manufacturing of Compound 2-12

[0623]

[0624] Under a nitrogen atmosphere, compound H (15 g, 48.8 mmol) and compound I (7.6 g, 48.8 mmol) were added to 300 mL of THF, stirred, and refluxed. Then, potassium carbonate (13.5 g, 97.7 mmol) was dissolved in 40 mL of water and added to the solution. After thorough stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was distilled off. It was then dissolved again in chloroform, washed twice with water, and the organic layer was separated. Anhydrous magnesium sulfate was added, the mixture was stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.4 g of substance H-1 (75% yield, MS: [M+H)). + =339).

[0625]

[0626] Under a nitrogen atmosphere, H-1 (10 g, 29.5 mmol), amine 12 (7.6 g, 31 mmol), and sodium tert-butoxide (3.7 g, 38.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10 g of compound 2-12 (62% yield, MS: [M+H)). + =548).

[0627] Manufacturing Example 2-13: Manufacturing of Compound 2-13

[0628]

[0629] Under a nitrogen atmosphere, H-1 (10 g, 29.5 mmol), amine 13 (11.5 g, 31 mmol), and sodium tert-butoxide (3.7 g, 38.4 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.9 g of compound 2-13 (yield 55%, MS: [M+H)). + =674).

[0630] Manufacturing Example 2-14: Manufacturing of Compound 2-14

[0631]

[0632] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 14 (14 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.2 g of compound 2-14 (yield 54%, MS: [M+H)). +=637).

[0633] Manufacturing Example 2-15: Manufacturing of Compound 2-15

[0634]

[0635] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 15 (12 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.6 g of compound 2-15 (67% yield, MS: [M+H)). + =578).

[0636] Manufacturing Example 2-16: Manufacturing of Compound 2-16

[0637]

[0638] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 16 (15.7 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 14.5 g of compound 2-16 (65% yield, MS: [M+H)). + =687).

[0639] Manufacturing Example 2-17: Manufacturing of Compound 2-17

[0640]

[0641] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 17 (13.2 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.7 g of compound 2-17 (yield 59%, MS: [M+H)). + =612).

[0642] Manufacturing Example 2-18: Manufacturing of Compound 2-18

[0643]

[0644] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 18 (11.9 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.5 g of compound 2-18 (yield 56%, MS: [M+H)). + =576).

[0645] Manufacturing Example 2-19: Manufacturing of Compound 2-19

[0646]

[0647] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 19 (12.5 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 12.1 g of compound 2-19 (yield 63%, MS: [M+H)).+ =592).

[0648] Manufacturing Example 2-20: Manufacturing of Compound 2-20

[0649]

[0650] Under a nitrogen atmosphere, compound H (10 g, 32.6 mmol), compound amine 20 (13 g, 34.2 mmol), and sodium tert-butoxide (4.1 g, 42.3 mmol) were added to 200 mL of xylene, stirred, and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 5 hours, the reaction was complete, cooled to room temperature, and the solvent was removed under reduced pressure. The compound was then completely dissolved again in chloroform, washed twice with water, and the organic layer was separated. After treatment with anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.1 g of compound 2-20 (yield 56%, MS: [M+H)). + =608).

[0651] [Example]

[0652] Example 1

[0653] ITO (indium tin oxide) is used as A glass substrate coated with a thin film of ITO was immersed in distilled water containing detergent and washed using ultrasound. The detergent used was from Fischer Co., and the distilled water was filtered twice using a filter manufactured by Millipore Co. After washing the ITO for 30 minutes, the process was repeated twice with distilled water for 10 minutes of ultrasonic washing. Following the distilled water washing, the substrate was ultrasonically washed with a solvent of isopropanol, acetone, and methanol, dried, and then transferred to a plasma cleaner. Additionally, the substrate was cleaned with oxygen plasma for 5 minutes before being transferred to a vacuum evaporation machine.

[0654] On the prepared ITO transparent electrode, as a hole injection layer, the following compound HI-1 is applied... The thickness is formed by p-doping the following compound A-1 at 1.5 wt%. The following compound HT-1 is then vacuum-deposited onto the hole-implanted layer to form a film thickness. The hole transport layer. Next, on the aforementioned hole transport layer, at a film thickness of... An electron blocking layer was formed by vacuum evaporation of compound EB-1. Then, on the EB-1 evaporation film, compounds 1-2 and 2-1 (the main components) and compound Dp-7 (the dopant) were vacuum evaporated in a weight ratio of 49:49:2 to form... A red luminescent layer of a certain thickness. On the aforementioned luminescent layer, a film thickness of... A hole-blocking layer was formed by vacuum evaporation of the following compound HB-1. Next, compounds ET-1 and LiQ were vacuum evaporated onto the hole-blocking layer in a 2:1 weight ratio, thereby achieving... The thickness forms an electron injection and transport layer. On this electron injection and transport layer, lithium fluoride (LiF) is sequentially applied... The thickness, using aluminum The cathode is formed by vapor deposition of a certain thickness.

[0655]

[0656] During the above process, the evaporation rate of organic matter is maintained. / second, lithium fluoride at the cathode maintains Evaporation rate of / second, aluminum maintains A vapor deposition rate of / second is achieved, while maintaining a vacuum level of 2*10 during vapor deposition. -7 ~5*10 -6 This led to the creation of organic light-emitting devices.

[0657] Examples 2 to 132

[0658] The first and second subjects described in Table 1 were used as the subjects of the organic light-emitting device. Otherwise, the organic light-emitting device was manufactured by the same method as in Example 1 above.

[0659] Comparative Examples 1 to 51

[0660] The organic light-emitting device was manufactured using the first and second substrates described in Table 2 as substrates, otherwise, by the same method as in Example 1 described above. The compounds B-1 to B-12 in Table 2 are shown below.

[0661]

[0662] Comparative Examples 52 to 99

[0663] The organic light-emitting device was manufactured using the first and second substrates described in Table 3 as substrates, otherwise manufactured by the same method as in Manufacturing Example 1 described above. The compounds C-1 to C-6 in Table 3 are shown below.

[0664]

[0665] [Experimental Example]

[0666] When a current is applied to the organic light-emitting devices manufactured in Examples 1 to 132 and Comparative Examples 1 to 99, the current (15 mA / cm²) is measured. 2 The voltage and efficiency were compared, and the results are shown in Tables 1 to 3 below. Lifetime T95 refers to the time required for the brightness to decrease from the initial brightness (6000 nits) to 95%.

[0667] [Table 1]

[0668]

[0669]

[0670]

[0671]

[0672]

[0673]

[0674]

[0675]

[0676] [Table 2]

[0677]

[0678]

[0679]

[0680] [Table 3]

[0681]

[0682]

[0683] By applying current to the organic light-emitting devices manufactured in Examples 1 to 132 and Comparative Examples 1 to 99, the results shown in Tables 1 to 3 above were obtained.

[0684] In one embodiment of the present invention, when a compound represented by Chemical Formula 1 and a compound represented by Chemical Formula 2 were co-deposited as a red emitting layer, as shown in Table 1, it was confirmed that the driving voltage was reduced and the efficiency and lifetime were increased compared to the comparative examples. Furthermore, as shown in Table 2, when comparative example compounds B-1 to B-12 and the compound represented by Chemical Formula 2 of the present invention were co-deposited as a red emitting layer, a generally higher driving voltage and lower efficiency and lifetime were observed compared to the combination of the present invention. As shown in Table 3, when comparative example compounds C-1 to C-6 and the compound represented by Chemical Formula 1 of the present invention were co-deposited as a red emitting layer, a higher driving voltage and lower efficiency and lifetime were also observed.

[0685] The results above confirm that, as shown in one embodiment of the present invention, when a combination of a compound represented by Chemical Formula 1 as the first host and a compound represented by Chemical Formula 2 as the second host is used as the host within the red emitting layer, energy transfer to the dopant is well achieved. This can ultimately be inferred to be because the combination of Chemical Formula 1 and Chemical Formula 2 of the present invention forms a more stable equilibrium within the emitting layer compared to the combination with comparative compounds. Therefore, it can be confirmed that when electrons and holes combine to form excitons in the organic light-emitting device of one embodiment of the present invention, efficiency and lifetime are further improved.

[0686] In summary, it has been confirmed that when the compounds represented by Chemical Formula 1 and Chemical Formula 2 of the present invention are combined and co-deposited as the main body of the light-emitting layer, the driving voltage, luminous efficiency and lifetime characteristics of organic light-emitting devices can be improved.

[0687] Symbol Explanation

[0688] 1: Substrate 2: Anode

[0689] 3: Light-emitting layer 4: Cathode

[0690] 5: Hole injection layer; 6: Hole transport layer

[0691] 7: Electron blocking layer; 8: Hole blocking layer

[0692] 9: Electron transport layer; 10: Electron injection layer.

Claims

1. An organic light-emitting device, wherein, include: anode; cathode; as well as The light-emitting layer between the anode and the cathode The luminescent layer comprises a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2: Chemical Formula 1 In the chemical formula 1, Ar1 and Ar2 are each independently selected from deuterium, halogens, and C. 1-10 One or more substituents of the alkyl group are substituted or unsubstituted C 6-20 Aryl; or selected from deuterium, halogens and C 1-10 One or more substituents of the alkyl group are substituted or unsubstituted, comprising a C group selected from either O or S. 2-20 Mixed aromatics, L1 to L3 are each independently a single bond, or C. 6-20 Alpha-aryl R1 is hydrogen; deuterium; selected from deuterium, halogens, and C. 1-10 One or more substituents of the alkyl group are substituted or unsubstituted C 6-20 Aryl; or selected from deuterium, halogens and C 1-10 One or more substituents of the alkyl group are substituted or unsubstituted, comprising a C group selected from either O or S. 2-20 Mixed aromatics, a is 0 or 1. Chemical formula 2 In the chemical formula 2, Ar3 and Ar4 are each independently selected from deuterium, halogens, and C. 1-10 One or more substituents of the alkyl group are substituted or unsubstituted C 6-20 Aryl; or selected from deuterium, halogens and C 1-10 An alkyl group having one or more substituents substituted or unsubstituted, comprising a C group selected from N, O, and S. 2-20 Mixed aromatics, L4 to L6 are each independently a single bond or a phenylene group.

2. The organic light-emitting device according to claim 1, wherein, Compounds represented by chemical formula 1 are represented by any one of the following chemical formulas 1-2 to 1-3: Chemical formula 1-2 Chemical formulas 1-3 In the chemical formulas 1-2 to 1-3, Ar1, Ar2, L1 to L3 and R1 are the same as defined in claim 1.

3. The organic light-emitting device according to claim 1, wherein, Compounds represented by chemical formula 1 are represented by the following chemical formula 1-1: Chemical Formula 1-1 In the chemical formula 1-1, Ar1, Ar2, and L1 to L3 are the same as defined in claim 1.

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

5. The organic light-emitting device according to claim 1, wherein, L1 to L3 are each independently a single bond, or selected from any of the following groups: 。 6. The organic light-emitting device according to claim 1, wherein, R1 can be hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, triphenylene, naphthylphenyl, phenylnaphthyl, fluoranyl, dibenzofuranyl, dibenzothiophene, benzonaphthiophene, or benzonaphthiophene.

7. The organic light-emitting device according to claim 1, wherein, At least one of Ar1, Ar2 and R1 is naphthyl, phenylnaphthyl, naphthylphenyl, phenanthryl, fluoranthyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthiophenyl, or benzonaphthiophenyl.

8. The organic light-emitting device according to claim 1, wherein, The compound represented by the chemical formula 1 is selected from any one of the following compounds: 。 9. The organic light-emitting device according to claim 1, wherein, Ar3 and Ar4 are each independently phenyl, biphenyl, terphenyl, tetraphenyl, naphthyl, phenanthryl, naphthylphenyl, phenylnaphthyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, or dibenzothiophene.

10. The organic light-emitting device according to claim 1, wherein, Ar3 and Ar4 are each independently selected from any of the following groups: 。 11. The organic light-emitting device according to claim 1, wherein, L4 to L6 are each a single bond.

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

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