Organic light emitting device

Abstract

The present disclosure provides organic light emitting devices.

Description

Technical Field

[0001] This application claims the benefit of Korean Patent Application No. 10-2019-0030167, filed on March 15, 2019, with the Korean Intellectual Property Office, and Korean Patent Application No. 10-2020-0031032, filed on March 12, 2020, the disclosures of which are incorporated herein by reference in their entirety.

[0002] This disclosure relates to organic light-emitting devices with low driving voltage, high luminous efficiency, and excellent lifetime. Background Technology

[0003] Organic light emission generally refers to the phenomenon of converting electrical energy into light energy using organic materials. Organic light-emitting devices (OLEDs) utilizing organic light emission exhibit characteristics such as wide viewing angle, excellent contrast, fast response time, and superior brightness, driving voltage, and response speed, and have therefore been the subject of much research.

[0004] Organic light-emitting devices (OLEDs) typically have a structure comprising an anode, a cathode, and an organic material layer between the anode and cathode. The organic material layer often has a multilayer structure containing different materials to improve the efficiency and stability of the OLED. For example, the organic material layer can be formed from a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. In the structure of an OLED, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic material layer, and electrons are injected from the cathode into the organic material layer. When the injected holes and electrons meet, excitons are formed, and light is emitted when the excitons return to the ground state.

[0005] There is a continued need to develop new organic materials for use in organic light-emitting devices as described above.

[0006] [Existing Technical Documents]

[0007] [Patent Literature]

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

[0009] Technical issues

[0010] The purpose of this invention is to provide an organic light-emitting device with low driving voltage, high luminous efficiency and excellent lifetime.

[0011] Technical solution

[0012] In one aspect of this disclosure, an organic light-emitting device is provided.

[0013] Organic light-emitting devices according to this disclosure include:

[0014] First electrode;

[0015] A second electrode is disposed opposite to the first electrode; and

[0016] A light-emitting layer disposed between the first electrode and the second electrode.

[0017] The luminescent layer comprises a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2:

[0018] [Chemical Formula 1]

[0019]

[0020] In chemical formula 1,

[0021] X1 to X3 are each independently N or CH, provided that at least two of X1 to X3 are N.

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

[0023] Each Z can be either hydrogen or deuterium, or two adjacent groups in Z can combine with each other to form C. 6-60 Aromatic rings or C atoms containing one or more heteroatoms selected from N, O, and S 2-60 Mixed Fragrances Ring

[0024] Where C 6-60 Aroma rings and C 2-60 The aromatic rings are either unsubstituted or deuterated.

[0025] n is an integer from 0 to 6, and

[0026] A is a substituent represented by the following chemical formula 1-1.

[0027] [Chemical Formula 1-1]

[0028]

[0029] In chemical formula 1-1,

[0030] R1 to R4 are each independently hydrogen or deuterium, or two adjacent groups among R1 to R4 can combine with each other to form C. 6-60 Aromatic rings or C atoms containing one or more heteroatoms selected from N, O, and S 2-60 Mixed Fragrances Ring

[0031] Where C 6-60 Aroma rings and C 2-60 The aromatic rings are either unsubstituted or deuterated.

[0032] D refers to deuterium, and

[0033] m is an integer from 0 to 6.

[0034] [Chemical Formula 2]

[0035]

[0036] In chemical formula 2,

[0037] T1 to T4 are each independently a substituted or unsubstituted C that is fused with the adjacent pentagonal ring. 6-60 Aromatic rings; or substituted or unsubstituted C atoms containing one or more heteroatoms selected from N, O, and S, fused with an adjacent pentagonal ring. 2-60 Mixed Fragrances Ring

[0038] L1 and L2 are each independent single bonds; substituted or unsubstituted C 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Hybrid aryl, and

[0039] Ar3 and Ar4 are each independently substituted or unsubstituted C. 6-60 aryl; or substituted or unsubstituted C containing one or more heteroatoms selected from N, O, and S. 2-60 Mixed aromatic compounds.

[0040] Beneficial effects

[0041] The aforementioned organic light-emitting devices can exhibit low driving voltage, high luminous efficiency, and long lifetime characteristics by simultaneously including a first compound and a second compound as the host materials in the light-emitting layer. Attached Figure Description

[0042] Figure 1 An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.

[0043] Figure 2 An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4. Detailed Implementation

[0044] The embodiments of this disclosure will be described in more detail below to aid in understanding this disclosure.

[0045] (Definition of the term)

[0046] As used in this article, symbols or This refers to a bond that is connected to another substituent.

[0047] As used herein, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from: deuterium; halogen group; cyano; nitro; hydroxyl; carbonyl; ester group; imide group; amino; phosphine oxide group; alkoxy group; aryloxy group; alkylthio group; arylthio group; alkylsulfonyl group; arylsulfonyl group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; arylenyl group; alkylamino group; aralkylamino group; heteroarylamino group; arylamino group; arylphosphine group; and heterocyclic group containing at least one of N, O, and S atoms, or unsubstituted or substituted with two or more substituents linked together from the substituents exemplified above. For example, "substituents linked together from two or more substituents" can be biphenyl. That is, biphenyl can be aryl, or it can be interpreted as a substituent in which two phenyl groups are linked together.

[0048] In this specification, the number of carbon atoms in the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group can be a group having the following structural formula, but is not limited thereto.

[0049]

[0050] In this specification, the ester group may have a structure in which the oxygen of the ester group is substituted by a straight-chain, branched, or cyclic alkyl group having 1 to 25 carbon atoms, or by an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a group having the following structural formulas, but is not limited thereto.

[0051]

[0052] In this specification, there is no particular limitation on the number of carbon atoms in the imide group, but it is preferably 1 to 25.

[0053] Specifically, the imide group can be a group having the following structural formula, but is not limited thereto.

[0054]

[0055] In this specification, silane specifically includes, but is not limited to, trimethylsilane, triethylsilane, tert-butyldimethylsilane, vinyldimethylsilane, propyldimethylsilane, triphenylsilane, diphenylsilane, phenylsilane, etc.

[0056] In this specification, boron groups specifically include, but are not limited to, trimethylboronyl, triethylboronyl, tert-butyldimethylboronyl, triphenylboronyl, and phenylboronyl.

[0057] Examples of halogen groups in this specification include fluorine, chlorine, bromine, or iodine.

[0058] In this specification, the alkyl group can be straight-chain or branched, and its carbon number is not particularly limited, but is preferably from 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbons. According to another embodiment, the alkyl group has 1 to 10 carbons. According to yet another embodiment, the alkyl group has 1 to 6 carbons. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc.

[0059] In this specification, the alkenyl group can be straight-chain or branched, and its carbon number is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbons. According to another embodiment, the alkenyl group has 2 to 10 carbons. According to yet another embodiment, the alkenyl group has 2 to 6 carbons. Specific examples include, but are not limited to, vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, styryl, styryl, etc.

[0060] In this specification, there is no particular limitation on the cycloalkyl group, but it is preferably composed of 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to yet another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc.

[0061] In this specification, the aryl group is not particularly limited, but it is preferably composed of 6 to 60 carbon atoms, and can be either a monocyclic aryl or a polycyclic aryl. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to another embodiment, the aryl group has 6 to 20 carbon atoms. As a monocyclic aryl group, the aryl group can be phenyl, biphenyl, terphenyl, etc., but is not limited thereto. Polycyclic aryl groups include naphthyl, anthraceneyl, phenanthryl, pyrene, perylene, etc. It includes, but is not limited to, methyl, fluorene, etc.

[0062] In this specification, the fluorene group can be substituted, and the two substituents can bond together to form a spirocyclic structure. When the fluorene group is substituted, a spirocyclic structure can be formed. However, the structure is not limited to this.

[0063] In this specification, a heteroaryl group is a heteroaryl group containing one or more of O, N, Si, and S as heteroatoms, and its carbon number is not particularly limited, but is preferably 2 to 60. Examples of heteroaryl groups include thienyl, furanyl, pyrroleyl, imidazolyl, thiazolyl, and others. azole group, Diazolyl, Triazolyl, Pyridyl, Bipyridyl, Pyrimidinyl, Triazinyl, Acridineyl, Pyridazinyl, Quinolinyl, Quinazolinyl, Quinoxalinyl, Phtharazineyl, Pyridopyrimidinyl, Pyridopyrazinyl, Pyrazenopyrazinyl, Isoquinolinyl, Indoleyl, Carbazoleyl, Benzo[] Azolyl, benzimidazolyl, benzothiazolyl, benzocarbazole, benzothiophene, dibenzothiophene, benzofuranyl, phenanthrolinel, iso Azolyl, thiadiazolyl, phenthiazinyl, dibenzofuranyl, etc., but not limited to these.

[0064] As used herein, the term "aromatic ring" is understood to include not only fused monocyclic or fused polycyclic rings in which the entire molecule contains only carbon as cyclic atoms and is aromatic, but also fused polycyclic rings formed by linking a plurality of fused monocyclic rings, such as fluorene rings, to adjacent substituents. In this case, the number of carbon atoms in the aromatic ring is 6 to 60, 6 to 30, or 6 to 20, but is not limited thereto. Furthermore, the aromatic ring can be a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a fluorene ring, but is not limited thereto.

[0065] As used herein, the term "heteroaromatic ring (heterocycle)" means a hetero-fused monocyclic or hetero-fused polycyclic ring in which the entire molecule contains at least one heteroatom from O, N, and S as a cyclic atom in addition to carbon, and is aromatic. The number of carbon atoms in the heterocycle is 2 to 60, 2 to 30, or 2 to 20, but is not limited thereto. Furthermore, the heterocycle can be a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, etc., but is not limited thereto.

[0066] In this specification, the aryl groups in aralkyl, aryl-alkenyl, alkylaryl, and arylamino groups are the same as the examples of aryl groups described above. In this specification, the alkyl groups in aralkyl, alkylaryl, and alkylamino groups are the same as the examples of alkyl groups described above. In this specification, the heteroaryl groups in heteroarylamino groups can be described using the methods described for heteroaryl groups described above. In this specification, the alkenyl groups in aryl-alkenyl groups are the same as the examples of alkenyl groups described above. In this specification, the description of aryl groups described above can be applied, except that arylene is a divalent group. In this specification, the description of heteroaryl groups described above can be applied, except that heteroarylene is a divalent group. In this specification, the description of aryl or cycloalkyl groups described above can be applied, except that the hydrocarbon ring is not a monovalent group but is formed by combining two substituents. In this specification, the description of heteroaryl groups described above can be applied, except that the heterocycle is not a monovalent group but is formed by combining two substituents.

[0067] The contents of this disclosure will be described in detail for each configuration below.

[0068] First electrode and second electrode

[0069] An organic light-emitting device according to one embodiment includes a first electrode on a substrate and a second electrode disposed opposite to the first electrode, wherein the second electrode is a cathode when the first electrode is an anode, and the second electrode is an anode when the first electrode is a cathode.

[0070] Specifically, an organic light-emitting device can be a normal type organic light-emitting device in which the anode, the light-emitting layer, and the cathode are sequentially stacked on a substrate. Alternatively, an organic light-emitting device can be an inverted type organic light-emitting device in which the cathode, the light-emitting layer, and the anode are sequentially stacked on a substrate.

[0071] As an anode material, materials with a high work function are generally preferred, allowing holes to be smoothly injected into the organic material layer. Specific examples of anode materials include: metals, such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides, such as ZnO:Al or SnO2:Sb; conductive polymers, such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline; and so on, but are not limited thereto.

[0072] As cathode materials, materials with low work functions are generally preferred, allowing electrons to be easily injected into the organic material layer. Specific examples of cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer materials such as LiF / Al or LiO2 / Al; and so on, but are not limited to these.

[0073] Emissive layer

[0074] An organic light-emitting device according to one embodiment includes a light-emitting layer disposed between a first electrode and a second electrode and serving as a layer that emits light in the visible light region by combining holes and electrons transported from a hole transport layer and an electron transport layer, wherein the light-emitting layer comprises a first compound represented by chemical formula 1 and a second compound represented by chemical formula 2.

[0075] In this case, both the first compound and the second compound are used as host materials in the light-emitting layer. Specifically, the first compound is an N-type host material, and the second compound is a P-type host material. When the light-emitting layer of an organic light-emitting device simultaneously contains both N-type and P-type host materials, it can exhibit improved efficiency and lifetime compared to using a single host material.

[0076] Specifically, the first compound has a structure in which both an N-containing 6-membered heterocyclic group and an A-substituent (based on a benzo[carbazole]yl group) are bonded to a benzene ring based on a dibenzofuran core. Compared with compounds having structures in which the N-containing 6-membered heterocyclic group and the A-substituent (based on a benzo[carbazole]yl group) are respectively bonded to different benzene rings based on a dibenzofuran core, and with compounds in which substituted / unsubstituted carbazoleyl substituents replace the A-substituent (based on a benzo[carbazole]yl group), the first compound having this structure exhibits high stability for electrons and holes and can stably maintain an electron-hole balance. Therefore, compared with organic light-emitting devices employing the first compound, organic light-emitting devices exhibit low driving voltage, high efficiency, and long lifetime characteristics. This is because the first compound has a structure in which (i) a 6-membered heterocyclic group containing N and an A substituent (based on benzocarbazolyl substituent) are respectively bonded to different benzene rings based on a dibenzofuran core, and (ii) a compound in which a substituted / unsubstituted carbazolyl substituent replaces the A substituent (based on benzocarbazolyl substituent).

[0077] Preferably, the first compound is represented by any of the following chemical formulas 1A to 1D, depending on the binding position of the N-containing 6-membered heterocyclic group in the dibenzofuran-based core:

[0078]

[0079]

[0080] In chemical formulas 1A to 1D,

[0081] The descriptions of each substituent are the same as those defined in Chemical Formula 1.

[0082] Preferably, all of X1 to X3 are N.

[0083] Preferably, Z is independently hydrogen or deuterium, or two adjacent groups in Z can combine with each other to form C. 6-20 Aromatic rings, such as unsubstituted or deuterated benzene rings.

[0084] At this point, n means that the number of Z is 0, 1, 2, 3, 4, 5 or 6.

[0085] More specifically, the first compound may be represented by any of the following chemical formulas 1A-1 to 1D-1:

[0086]

[0087] In chemical formulas 1A-1 to 1D-1,

[0088] One of Z1 to Z3 is a substituent A represented by chemical formula 1-1, and the others are each independently hydrogen or deuterium, or two adjacent groups of Z1 to Z3 can combine with each other to form an unsubstituted or deuterated benzene ring.

[0089] Z4 to Z7 are each independently hydrogen or deuterium, or two adjacent groups in Z4 to Z7 can combine with each other to form an unsubstituted or deuterated benzene ring, and

[0090] Ar1 and Ar2 are as defined in chemical formula 1.

[0091] Specifically, in chemical formula 1A-1,

[0092] Z1 is A, Z2 and Z3 are each independently hydrogen or deuterium, or Z2 and Z3 are bonded together to form an unsubstituted or deuterated benzene ring; or

[0093] Z2 is A, and Z1 and Z3 are each independently hydrogen or deuterium; or

[0094] Z3 is A, Z1 and Z2 are each independently hydrogen or deuterium, or Z1 and Z2 can combine with each other to form an unsubstituted or deuterated benzene ring.

[0095] Furthermore, in chemical formula 1B-1,

[0096] Z1 is A, Z2 and Z3 are each independently hydrogen or deuterium, or Z2 and Z3 are combined to form an unsubstituted or deuterated benzene ring; or

[0097] Z2 is A, and Z1 and Z3 are each independently hydrogen or deuterium; or

[0098] Z3 is A, and Z1 and Z2 are each independently hydrogen or deuterium.

[0099] Furthermore, in chemical formula 1C-1,

[0100] Z1 is A, and Z2 and Z3 are each independently hydrogen or deuterium; or

[0101] Z2 is A, and Z1 and Z3 are each independently hydrogen or deuterium; or

[0102] Z3 is A, Z1 and Z2 are each independently hydrogen or deuterium, or Z1 and Z2 can combine with each other to form an unsubstituted or deuterated benzene ring.

[0103] Specifically, in chemical formula 1D-1,

[0104] Z1 is A, Z2 and Z3 are each independently hydrogen or deuterium, or Z2 and Z3 can combine with each other to form an unsubstituted or deuterated benzene ring;

[0105] Z2 is A, and Z1 and Z3 are each independently hydrogen or deuterium; or

[0106] Z3 is A, Z1 and Z2 are each independently hydrogen or deuterium, or Z1 and Z2 can combine with each other to form an unsubstituted or deuterated benzene ring.

[0107] Alternatively, the first compound may be represented by any of the following chemical formulas 3-1 to 3-7:

[0108]

[0109] In chemical formulas 3-1 to 3-7,

[0110] Each R is independently either hydrogen or deuterium, and

[0111] A, Ar1, and Ar2 are as defined in chemical formula 1.

[0112] Preferably, Ar1 and Ar2 are each independently unsubstituted or deuterated or C-treated. 6-20 aryl-substituted C 6-20 Aryl.

[0113] More preferably, Ar1 and Ar2 are each independently phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, dibenzothiophene, dibenzofuranyl, or carbazole.

[0114] Ar1 and Ar2 can be selected from deuterium and C either unsubstituted or via one to five independent selections. 6-20 Substituents in aryl groups.

[0115] Most preferably, Ar1 and Ar2 are each independently selected from any of the following:

[0116]

[0117] In this case, Ar1 and Ar2 can be the same as each other, or Ar1 and Ar2 can be different.

[0118] Furthermore, in A, which is a substituent represented by chemical formula 1-1, R1 to R4 are each independently hydrogen or deuterium, or two adjacent groups among R1 to R4 can combine with each other to form an unsubstituted or deuterated benzene ring.

[0119] At this point, m, which refers to the number of deuterium (D), is 0, 1, 2, 3, 4, 5, or 6.

[0120] For example, A can be any of the substituents represented by the following chemical formulas a1 to a4:

[0121]

[0122] Specific examples of the first compound are as follows:

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[0435] Meanwhile, the compound represented by chemical formula 1 can be prepared, for example, by the method shown in reaction scheme 1 below.

[0436] [Reaction Scheme 1]

[0437]

[0438] In reaction scheme 1, each X is independently a halogen, preferably bromine or chlorine, and the definitions of other substituents are the same as described above.

[0439] Specifically, the compound represented by Formula 1 is prepared by combining starting materials SM1 and SM2 via an amine substitution reaction. Such an amine substitution reaction is preferably carried out in the presence of a palladium catalyst and a base. Furthermore, the reactive groups used in the amine substitution reaction can be suitably modified, and the method for preparing the compound represented by Formula 1 can be described in more detail in the synthetic examples described below.

[0440] Meanwhile, the second compound is a biscarbazole-based compound, preferably having T1 to T4 each independently being C. 6-20 The structure of the aromatic ring. More preferably, T1 to T4 are unsubstituted or deuterated benzene rings, or unsubstituted or deuterated naphthalene rings.

[0441] Most preferably, T1 to T4 are all benzene rings, wherein the second compound is represented by the following chemical formula 2-1:

[0442] [Chemical Formula 2-1]

[0443]

[0444] In chemical formula 2-1,

[0445] D refers to deuterium.

[0446] r and s are each independent integers from 0 to 7, and

[0447] The description of each substituent is the same as that defined in Formula 2.

[0448] Preferably, L1 and L2 are each independently a single bond, or an unsubstituted C bond. 6-20 Alpha-aryl.

[0449] More preferably, L1 and L2 are each independently a single bond, a phenylene group, or a naphthylene group.

[0450] Preferably, Ar3 and Ar4 are each independently unsubstituted or C-treated. 1-10 Alkyl or C 6-20 aryl-substituted C 6-20 aryl; or C containing O or S 2-20 Mixed aromatic compounds.

[0451] More preferably, Ar3 and Ar4 are each independently phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, triphenylene, fluorenyl, spirodifluorenyl, fluoranyl, dibenzothiophene, or dibenzofuranyl.

[0452] Ar3 and Ar4 can be selected from C16 either unsubstituted or via one to four independent C16 molecules. 1-10 Alkyl and C 6-20 Substituents of aryl groups.

[0453] Most preferably, Ar3 and Ar4 are each independently selected from any of the following:

[0454]

[0455] In this case, Ar3 and Ar4 can be the same as each other, or Ar3 and Ar4 can be different.

[0456] Preferably, the second compound is represented by the following chemical formula 2-2:

[0457] [Chemical Formula 2-2]

[0458]

[0459] In chemical formula 2-2,

[0460] L1 and L2 are each independently a single bond, a phenylene group, or a naphthylene group, and

[0461] Ar3 and Ar4 are as defined in chemical formula 2.

[0462] Specific examples of the second compound are as follows:

[0463]

[0464]

[0465]

[0466]

[0467]

[0468]

[0469]

[0470]

[0471]

[0472]

[0473]

[0474]

[0475]

[0476]

[0477]

[0478]

[0479]

[0480]

[0481]

[0482]

[0483]

[0484] Meanwhile, the compound represented by chemical formula 2 can be prepared, for example, by the preparation method shown in reaction scheme 2 below.

[0485] [Reaction Scheme 2]

[0486]

[0487] In reaction scheme 2, each X is independently a halogen, preferably bromine or chlorine, and the definitions of other substituents are the same as described above.

[0488] Specifically, the compound represented by Formula 2 is prepared by combining starting materials SM3 and SM4 via a Suzuki coupling reaction. Such a Suzuki coupling reaction is preferably carried out in the presence of a palladium catalyst and a base. Furthermore, the reactive groups used in the Suzuki coupling reaction can be appropriately modified, and the method for preparing the compound represented by Formula 2 can be described in more detail in the synthetic examples described below.

[0489] The first compound and the second compound are preferably contained in the light-emitting layer in a weight ratio of 99:1 to 1:99, and more preferably in a weight ratio of 50:50, which is preferred in terms of realizing devices with high efficiency and long lifespan.

[0490] In addition to the host material, the luminescent layer also contains dopant materials. Examples of dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, aromatic amine derivatives are substituted or unsubstituted fused aromatic ring derivatives having an aryl amino group, and examples include pyrene, anthracene, etc., having an aryl amino group. Diindrone pyrene, etc. Styrenicoamine compounds are compounds in which at least one aryl vinyl group is substituted in a substituted or unsubstituted aryl amine, wherein one or two or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamino groups are substituted or unsubstituted. Specific examples include, but are not limited to, styrenicoamines, styrenicodiamines, styrenicotriamines, styrenicotetraamines, etc. Furthermore, metal complexes include, but are not limited to, iridium complexes, platinum complexes, etc.

[0491] Preferably, the light-emitting layer may contain iridium complex compounds as dopant materials, but is not limited thereto.

[0492]

[0493]

[0494]

[0495] Hole injection layer

[0496] An organic light-emitting device according to one embodiment may further include a hole injection layer on the anode. The hole injection layer is composed of a hole injection material, and the hole injection material is preferably a compound that has the ability to transport holes, thus having the effect of injecting holes into the anode and an excellent hole injection effect on the light-emitting layer or light-emitting material, preventing excitons generated in the light-emitting layer from moving to the electron injection layer or electron injection material, and having excellent thin film formation capability.

[0497] Specific examples of hole injection materials include, but are not limited to, metalloporphyrins, oligothiophenes, arylamine-based organic materials, hexanitrile hexaazabenzophenanthrene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinones, conductive polymers based on polyaniline and polythiophene.

[0498] Hole transport layer

[0499] An organic light-emitting device according to one embodiment may further include a hole transport layer on the anode or on a hole injection layer formed on the anode. The hole transport layer is a layer that receives holes from the anode or the hole injection layer formed on the anode and transports the holes to the light-emitting layer. The hole transport material contained in the hole transport layer is suitably a material with a large hole mobility, which can receive holes from the anode or the hole injection layer and transfer the holes to the light-emitting layer.

[0500] Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers in which conjugated and non-conjugated portions coexist.

[0501] Electron blocking layer

[0502] An organic light-emitting device according to one embodiment may further include an electron blocking layer on a hole transport layer. An electron blocking layer means a layer formed on the hole transport layer, preferably positioned in contact with the light-emitting layer, thus serving to control hole mobility, prevent excessive electron movement, and increase the likelihood of hole-electron binding, thereby improving the efficiency of the organic light-emitting device. The electron blocking layer comprises an electron blocking material, and examples of such electron blocking materials include compounds represented by Formula 1, or organic materials based on arylamines, but are not limited thereto.

[0503] Cavity barrier

[0504] An organic light-emitting device according to one embodiment may further include a hole-blocking layer on the light-emitting layer. A hole-blocking layer refers to a layer formed on the light-emitting layer, preferably positioned in contact with the light-emitting layer, thus serving to control electron mobility, prevent excessive hole movement, and increase the likelihood of hole-electron binding, thereby improving the efficiency of the organic light-emitting device. The hole-blocking layer comprises a hole-blocking material, and as examples of such hole-blocking materials, compounds having introduced electron-withdrawing groups can be used, such as azazine-based derivatives including triazine; triazole derivatives; Diazole derivatives; phenanthrene-rhein derivatives; phosphine oxide derivatives, but not limited to these.

[0505] Electron transport layer

[0506] An organic light-emitting device according to one embodiment may include an electron transport layer on the light-emitting layer or on the hole-blocking layer. The electron transport layer is a layer that receives electrons from the cathode or the electron injection layer described below and transports the electrons to the light-emitting layer, and the electron transport material contained in the electron transport layer is suitably a material that can effectively receive electrons from the cathode and transfer them to the light-emitting layer, and has a high electron mobility.

[0507] Specific examples of electron transport materials include, but are not limited to: pyridine derivatives; pyrimidine derivatives; triazole derivatives; Al complexes of 8-hydroxyquinoline; complexes containing Alq3; organic radical compounds; hydroxyflavonoid-metal complexes, etc. The electron transport layer can be used with any desired cathode material as used according to the relevant art. In particular, suitable examples of cathode materials are typically materials with low work functions followed by an aluminum or silver layer. Specific examples include cesium, barium, calcium, ytterbium, and samarium, each followed by an aluminum or silver layer.

[0508] Electron injection layer

[0509] An organic light-emitting device according to one embodiment may further include an electron injection layer between an electron transport layer and a cathode. The electron injection layer is a layer that injects electrons from the cathode, and is preferably a compound that has the ability to transport electrons, the effect of injecting electrons from the cathode, and an excellent effect of injecting electrons into the light-emitting layer or light-emitting material, prevents excitons generated by the light-emitting layer from migrating to the hole injection layer, and also has excellent thin film formation capabilities.

[0510] Specific examples of materials that can be used as electron injection layers include LiF, NaCl, CsF, Li₂O, BaO, fluorenone, anthraquinone dimethyl ether, biphenylquinone, thiamethoxam dioxide, etc. azole, Diazoles, triazoles, imidazoles, perylenetetracarboxylic acid, fluorenemethane, anthrones and their derivatives, metal complex compounds, nitrogen-containing 5-membered ring derivatives, etc., but not limited to these.

[0511] Examples of metal complex compounds include, but are not limited to, lithium 8-hydroxyquinoline, bis(8-hydroxyquinoline)zinc, bis(8-hydroxyquinoline)copper, bis(8-hydroxyquinoline)manganese, tris(8-hydroxyquinoline)aluminum, tris(2-methyl-8-hydroxyquinoline)aluminum, tris(8-hydroxyquinoline)gallium, bis(10-hydroxybenzo[h]quinoline)beryllium, bis(10-hydroxybenzo[h]quinoline)zinc, bis(2-methyl-8-quinoline)chlorogallium, bis(2-methyl-8-quinoline)(o-cresol)gallium, bis(2-methyl-8-quinoline)(1-naphthol)aluminum, and bis(2-methyl-8-quinoline)(2-naphthol)gallium.

[0512] Meanwhile, the electron transport layer and the electron injection layer can be configured as an electron injection and transport layer that simultaneously performs the functions of an electron transport layer and an electron injection layer in transmitting the received electrons to the light-emitting layer.

[0513] Organic light-emitting devices

[0514] According to one implementation plan, Figure 1 The structure of an organic light-emitting device in which the first electrode is the anode and the second electrode is the cathode is shown. Figure 1 An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In such a structure, a first compound and a second compound may be contained within the light-emitting layer.

[0515] According to another implementation scheme, Figure 2 The structure of an organic light-emitting device in which the first electrode is the anode and the second electrode is the cathode is shown. Figure 2 An example of an organic light-emitting device is shown, comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light-emitting layer 3, a hole blocking layer 8, an electron injection and transport layer 9, and a cathode 4. In such a structure, a first compound and a second compound may be contained within the light-emitting layer.

[0516] The organic light-emitting device according to this disclosure can be manufactured by sequentially laminating the aforementioned components. In this case, the organic light-emitting device can be manufactured by depositing a metal, a conductive metal oxide, or an alloy thereof on a substrate using a PVD (physical vapor deposition) method (e.g., sputtering or electron beam evaporation) to form an anode, forming the aforementioned layers on the anode, and then depositing a material that can be used as a cathode thereon. Besides this method, the organic light-emitting device can also be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. Furthermore, the light-emitting layer can be formed using a substrate and dopants by solution coating and vacuum deposition methods. Here, solution coating refers to spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

[0517] In addition to this method, organic light-emitting devices can also be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate (International Publication WO 2003 / 012890). However, the fabrication method is not limited to this.

[0518] Furthermore, depending on the materials used, the organic light-emitting device according to this disclosure can be a front-emitting, rear-emitting, or dual-emitting type.

[0519] The fabrication of organic light-emitting devices will be described in detail in the following embodiments. However, these embodiments are presented for illustrative purposes only and are not intended to limit the scope of this disclosure.

[0520] Synthesis Example 1-1: Preparation of Compound 1-1

[0521]

[0522] Intermediate 1-1-1 (10 g, 20.7 mmol), compound a (4.9 g, 22.7 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8 g of compound 1-1. (Yield: 58%, MS: [M+H]) + =665)

[0523] Synthetic Example 1-2: Preparation of Compound 1-2

[0524]

[0525] Intermediate 1-2-1 (10 g, 19.1 mmol), compound a (4.6 g, 21 mmol), and sodium tert-butoxide (3.7 g, 38.2 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.5 g of compound 1-2. (Yield: 63%, MS: [M+H)) + =705)

[0526] Synthetic Examples 1-3: Preparation of Compounds 1-3

[0527]

[0528] Intermediate 1-3-1 (10 g, 16.7 mmol), compound a (4 g, 18.4 mmol), and sodium tert-butoxide (3.2 g, 33.4 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9 g of compound 1-3. (Yield: 69%, MS: [M+H)) + =780)

[0529] Synthetic Examples 1-4: Preparation of Compounds 1-4

[0530]

[0531] Intermediate 1-4-1 (10 g, 17.9 mmol), compound a (4.3 g, 19.6 mmol), and sodium tert-butoxide (3.4 g, 35.7 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.7 g of compound 1-4. (Yield: 58%, MS: [M+H]) + =741)

[0532] Synthetic Examples 1-5: Preparation of Compounds 1-5

[0533]

[0534] Intermediate 1-5-1 (10 g, 15.1 mmol), compound a (3.6 g, 16.7 mmol), and sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.7 g of compound 1-5. (Yield: 68%, MS: [M+H]) + =841)

[0535] Synthetic Examples 1-6: Preparation of Compounds 1-6

[0536]

[0537] Intermediate 1-6-1 (10 g, 15.7 mmol), compound a (3.8 g, 17.3 mmol), and sodium tert-butoxide (3 g, 31.4 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.7 g of compound 1-6. (Yield: 68%, MS: [M+H]) + =817)

[0538] Synthetic Examples 1-7: Preparation of Compounds 1-7

[0539]

[0540] Intermediate 1-7-1 (10 g, 20.7 mmol), compound a (4.9 g, 22.7 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.6 g of compound 1-7. (Yield: 63%, MS: [M+H]) + =665)

[0541] Synthetic Examples 1-8: Preparation of Compounds 1-8

[0542]

[0543] Intermediate 1-8-1 (10 g, 16.4 mmol), compound c (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.9 g of compound 1-8. (Yield: 50%, MS: [M+H)) + =841)

[0544] Synthetic Examples 1-9: Preparation of Compounds 1-9

[0545]

[0546] Intermediate 1-9-1 (10 g, 15.9 mmol), compound a (3.8 g, 17.5 mmol), and sodium tert-butoxide (3.1 g, 31.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 18.1 g of compound 1-9. (Yield: 63%, MS: [M+H)) + =810)

[0547] Synthetic Examples 1-10: Preparation of Compounds 1-10

[0548]

[0549] Intermediate 1-10-1 (10 g, 18.7 mmol), compound a (4.5 g, 20.6 mmol), and sodium tert-butoxide (3.6 g, 37.5 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9.1 g of compound 1-10. (Yield: 68%, MS: [M+H)) + =715)

[0550] Synthetic Example 1-11: Preparation of Compound 1-11

[0551]

[0552] Intermediate 1-11-1 (10 g, 19.6 mmol), compound a (4.7 g, 21.6 mmol), and sodium tert-butoxide (3.8 g, 39.2 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9.5 g of compound 1-11. (Yield: 70%, MS: [M+H)) + =691)

[0553] Synthetic Examples 1-12: Preparation of Compounds 1-12

[0554]

[0555] Intermediate 1-12-1 (10 g, 18.7 mmol), compound a (4.5 g, 20.6 mmol), and sodium tert-butoxide (3.6 g, 37.5 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.5 g of compound 1-12. (Yield: 56%, MS: [M+H)) + =715)

[0556] Synthetic Examples 1-13: Preparation of Compounds 1-13

[0557]

[0558] Intermediate 1-13-1 (10 g, 15.1 mmol), compound a (3.6 g, 16.7 mmol), and sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.7 g of compound 1-13. (Yield: 53%, MS: [M+H)) + =841)

[0559] Synthetic Examples 1-14: Preparation of Compounds 1-14

[0560]

[0561] Intermediate 1-14-1 (10 g, 15.4 mmol), compound b (4.5 g, 16.9 mmol), and sodium tert-butoxide (3 g, 30.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8 g of compound 1-14. (Yield: 59%, MS: [M+H)) + =880)

[0562] Synthetic Examples 1-15: Preparation of Compounds 1-15

[0563]

[0564] Intermediate 1-15-1 (10 g, 16.4 mmol), compound b (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9.5 g of compound 1-15. (Yield: 69%, MS: [M+H)) + =841)

[0565] Synthetic Examples 1-16: Preparation of Compounds 1-16

[0566]

[0567] Intermediate 1-16-1 (10 g, 16.9 mmol), compound a (4.1 g, 18.6 mmol), and sodium tert-butoxide (3.3 g, 33.9 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.2 g of compound 1-16. (Yield: 55%, MS: [M+H)) + =771)

[0568] Synthetic Examples 1-17: Preparation of Compounds 1-17

[0569]

[0570] Intermediate 1-17-1 (10 g, 16 mmol), compound c (4.7 g, 17.6 mmol), and sodium tert-butoxide (3.1 g, 32 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.8 g of compound 1-17. (Yield: 57%, MS: [M+H)) + =855)

[0571] Synthetic Examples 1-18: Preparation of Compounds 1-18

[0572]

[0573] Intermediate 1-18-1 (10 g, 16.4 mmol), compound d (4.8 g, 18 mmol), and sodium tert-butoxide (3.2 g, 32.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.9 g of compound 1-18. (Yield: 50%, MS: [M+H)) + =841)

[0574] Synthetic Examples 1-19: Preparation of Compounds 1-19

[0575]

[0576] Intermediate 1-19-1 (10 g, 20.7 mmol), compound a (4.9 g, 22.7 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9.2 g of compound 1-19. (Yield: 67%, MS: [M+H)) + =665)

[0577] Synthetic Examples 1-20: Preparation of Compounds 1-20

[0578]

[0579] Intermediate 1-20-1 (10 g, 16.7 mmol), compound a (4 g, 18.4 mmol), and sodium tert-butoxide (3.2 g, 33.4 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.9 g of compound 1-20. (Yield: 61%, MS: [M+H)) + =780)

[0580] Synthetic Example 1-21: Preparation of Compound 1-21

[0581]

[0582] Intermediate 1-21-1 (10 g, 15.8 mmol), compound a (3.8 g, 17.3 mmol), and sodium tert-butoxide (3 g, 31.5 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.5 g of compound 1-21. (Yield: 51%, MS: [M+H)) + =815)

[0583] Synthetic Examples 1-22: Preparation of Compounds 1-22

[0584]

[0585] Intermediate 1-22-1 (10 g, 20.7 mmol), compound a (4.9 g, 22.7 mmol), and sodium tert-butoxide (4 g, 41.3 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.6 g of compound 1-22. (Yield: 63%, MS: [M+H)) + =665)

[0586] Synthetic Examples 1-23: Preparation of Compounds 1-23

[0587]

[0588] Intermediate 1-23-1 (10 g, 16.3 mmol), compound a (3.9 g, 17.9 mmol), and sodium tert-butoxide (3.1 g, 32.6 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.5 g of compound 1-23. (Yield: 66%, MS: [M+H)) + =795)

[0589] Synthetic Examples 1-24: Preparation of Compounds 1-24

[0590]

[0591] Intermediate 1-24-1 (10 g, 18.7 mmol), compound a (4.5 g, 20.6 mmol), and sodium tert-butoxide (3.6 g, 37.5 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.8 g of compound 1-24. (Yield: 51%, MS: [M+H)) + =715)

[0592] Synthetic Examples 1-25: Preparation of Compounds 1-25

[0593]

[0594] Intermediate 1-25-1 (10 g, 15.7 mmol), compound a (3.8 g, 17.3 mmol), and sodium tert-butoxide (3 g, 31.4 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.7 g of compound 1-25. (Yield: 68%, MS: [M+H)) + =817)

[0595] Synthetic Examples 1-26: Preparation of Compounds 1-26

[0596]

[0597] Intermediate 1-26-1 (10 g, 15.4 mmol), compound d (4.5 g, 16.9 mmol), and sodium tert-butoxide (3 g, 30.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.1 g of compound 1-26. (Yield: 60%, MS: [M+H)) + =881)

[0598] Synthetic Examples 1-27: Preparation of Compounds 1-27

[0599]

[0600] Intermediate 1-27-1 (10 g, 17.9 mmol), compound a (4.3 g, 19.6 mmol), and sodium tert-butoxide (3.4 g, 35.7 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.3 g of compound 1-27. (Yield: 63%, MS: [M+H)) + =741)

[0601] Synthetic Examples 1-28: Preparation of Compounds 1-28

[0602]

[0603] Intermediate 1-28-1 (10 g, 18.7 mmol), compound a (4.5 g, 20.6 mmol), and sodium tert-butoxide (3.6 g, 37.5 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9 g of compound 1-28. (Yield: 67%, MS: [M+H)) + =715)

[0604] Synthetic Examples 1-29: Preparation of Compounds 1-29

[0605]

[0606] Intermediate 1-29-1 (10 g, 15.1 mmol), compound b (4.5 g, 16.7 mmol), and sodium tert-butoxide (2.9 g, 30.3 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9.3 g of compound 1-29. (Yield: 69%, MS: [M+H)) + =891)

[0607] Synthetic Examples 1-30: Preparation of Compounds 1-30

[0608]

[0609] Intermediate 1-30-1 (10 g, 15.4 mmol), compound a (3.7 g, 16.9 mmol), and sodium tert-butoxide (3 g, 30.8 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 6.4 g of compound 1-30. (Yield: 50%, MS: [M+H)) + =831)

[0610] Synthetic Examples 1-31: Preparation of Compounds 1-31

[0611]

[0612] Intermediate 1-31-1 (10 g, 16.9 mmol), compound a (4.1 g, 18.6 mmol), and sodium tert-butoxide (3.3 g, 33.9 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.2 g of compound 1-31. (Yield: 63%, MS: [M+H)) + =771)

[0613] Synthetic Examples 1-32: Preparation of Compounds 1-32

[0614]

[0615] Intermediate 1-32-1 (10 g, 15.6 mmol), compound c (4.6 g, 17.2 mmol), and sodium tert-butoxide (3 g, 31.2 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9.1 g of compound 1-32. (Yield: 67%, MS: [M+H)) + =871)

[0616] Synthetic Examples 1-33: Preparation of Compounds 1-33

[0617]

[0618] Intermediate 1-33-1 (10 g, 15 mmol), compound d (4.4 g, 16.5 mmol), and sodium tert-butoxide (2.9 g, 30 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, when the reaction was complete, the reaction mixture was 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, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9 g of compound 1-33. (Yield: 67%, MS: [M+H)) + =897)

[0619] Synthetic Examples 1-34: Preparation of Compounds 1-34

[0620]

[0621] Intermediate 1-34-1 (10 g, 23 mmol) and compound a (5 g, 23 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (6.6 g, 69.1 mmol) was then added, stirred thoroughly, and followed by bis(tri-tert-butylphosphine)palladium (0.2 g, 0.5 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 425 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 9.9 g of compound 1-34 as a yellow solid. (Yield: 70%, MS: [M+H]) + =615.2)

[0622] Synthetic Examples 1-35: Preparation of Compounds 1-35

[0623]

[0624] Intermediate 1-35-1 (10 g, 23 mmol) and compound a (5 g, 23 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (6.6 g, 69.1 mmol) was then added, stirred thoroughly, and followed by bis(tri-tert-butylphosphine)palladium (0.2 g, 0.5 mmol). After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 425 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 8.5 g of compound 1-35 as a yellow solid. (Yield: 60%, MS: [M+H]) + =615.2)

[0625] Synthetic Examples 1-36: Preparation of Compounds 1-36

[0626]

[0627] Intermediate 1-36-1 (10 g, 23 mmol) and compound a (5 g, 23 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (6.6 g, 69.1 mmol) was then added, stirred thoroughly, and followed by bis(tri-tert-butylphosphine)palladium (0.2 g, 0.5 mmol). After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 425 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 9.1 g of compound 1-36 as a yellow solid. (Yield: 64%, MS: [M+H]) + =615.2)

[0628] Synthetic Examples 1-37: Preparation of Compounds 1-37

[0629]

[0630] Intermediate 1-37-1 (10 g, 16.7 mmol) and compound a (3.6 g, 16.7 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (4.8 g, 50.1 mmol) was then added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (0.2 g, 0.3 mmol). After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 390 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, the mixture was stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 8.6 g of compound 1-37 as a yellow solid. (Yield: 66%, MS: [M+H]) + =780.3)

[0631] Synthetic Examples 1-38: Preparation of Compounds 1-38

[0632]

[0633] Intermediate 1-38-1 (10 g, 20.7 mmol) and compound a (4.5 g, 20.7 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (6 g, 62 mmol) was then added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (0.2 g, 0.4 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 412 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, the mixture was stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 9.1 g of compound 1-38 as a yellow solid. (Yield: 66%, MS: [M+H]) + =665.2)

[0634] Synthetic Examples 1-39: Preparation of Compounds 1-39

[0635]

[0636] Intermediate 1-39-1 (10 g, 18.7 mmol) and compound a (4.1 g, 18.7 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (5.4 g, 56.2 mmol) was then added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (0.2 g, 0.4 mmol). After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 401 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, the mixture was stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 7.8 g of compound 1-39 as a yellow solid. (Yield: 58%, MS: [M+H]) + =715.2)

[0637] Synthetic Examples 1-40: Preparation of Compounds 1-40

[0638]

[0639] Intermediate 1-40-1 (10 g, 20.7 mmol) and compound a (4.5 g, 20.7 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (6 g, 62 mmol) was then added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (0.2 g, 0.4 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 412 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, the mixture was stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 7.8 g of compound 1-40 as a yellow solid. (Yield: 57%, MS: [M+H]) + =665.2)

[0640] Synthetic Examples 1-41: Preparation of Compounds 1-41

[0641]

[0642] Intermediate 1-41-1 (10 g, 18.7 mmol) and compound a (4.1 g, 18.7 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (5.4 g, 56.2 mmol) was then added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (0.2 g, 0.4 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 401 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, the mixture was stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 8.7 g of compound 1-41 as a yellow solid. (Yield: 65%, MS: [M+H]) + =715.2)

[0643] Synthetic Examples 1-42: Preparation of Compounds 1-42

[0644]

[0645] Intermediate 1-42-1 (10 g, 15.6 mmol) and compound a (3.4 g, 15.6 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (4.5 g, 46.9 mmol) was then added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (0.2 g, 0.3 mmol). After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 384 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, the mixture was stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 8.2 g of compound 1-42 as a yellow solid. (Yield: 64%, MS: [M+H]) + =821.2)

[0646] Synthetic Examples 1-43: Preparation of Compounds 1-43

[0647]

[0648] Intermediate 1-43-1 (10 g, 17.1 mmol) and compound b (4.6 g, 17.1 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (4.9 g, 51.4 mmol) was then added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (0.2 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 418 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, the mixture was stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 8.8 g of compound 1-43 as a yellow solid. (Yield: 63%, MS: [M+H]) + =815.3)

[0649] Synthetic Examples 1-44: Preparation of Compounds 1-44

[0650]

[0651] Intermediate 1-44-1 (10 g, 14.3 mmol) and compound b (3.8 g, 14.3 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (4.1 g, 42.9 mmol) was then added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (0.1 g, 0.3 mmol). After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 399 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, the mixture was stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 7.3 g of compound 1-44 as a yellow solid. (Yield: 55%, MS: [M+H]) + =930.3)

[0652] Synthetic Examples 1-45: Preparation of Compounds 1-45

[0653]

[0654] Intermediate 1-45-1 (10 g, 23 mmol) and compound c (6.2 g, 23 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (6.6 g, 69.1 mmol) was then added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (0.2 g, 0.5 mmol). After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was then distilled. It was added again and dissolved in 459 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, the mixture was stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 9 g of compound 1-45 as a yellow solid. (Yield: 59%, MS: [M+H]) + =665.2)

[0655] Synthetic Examples 1-46: Preparation of Compounds 1-46

[0656]

[0657] Intermediate 1-46-1 (10 g, 20.7 mmol) and compound c (5.5 g, 20.7 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (6 g, 62 mmol) was then added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (0.2 g, 0.4 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 443 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, the mixture was stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 10.2 g of compound 1-46 as a yellow solid. (Yield: 69%, MS: [M+H]) + =715.2)

[0658] Synthetic Examples 1-47: Preparation of Compounds 1-47

[0659]

[0660] Intermediate 1-47-1 (10 g, 17.4 mmol) and compound c (4.7 g, 17.4 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (5 g, 52.3 mmol) was then added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (0.2 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 420 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, the mixture was stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 8 g of compound 1-47 as a yellow solid. (Yield: 57%, MS: [M+H]) + =805.2)

[0661] Synthetic Examples 1-48: Preparation of Compounds 1-48

[0662]

[0663] Intermediate 1-48-1 (10 g, 23 mmol) and compound c (6.2 g, 23 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (6.6 g, 69.1 mmol) was then added, stirred thoroughly, and followed by bis(tri-tert-butylphosphine)palladium (0.2 g, 0.5 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 459 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 0.4 g of compound 1-48 as a yellow solid. (Yield: 68%, MS: [M+H]) + =665.2)

[0664] Synthetic Examples 1-49: Preparation of Compounds 1-49

[0665]

[0666] Intermediate 1-49-1 (10 g, 16.7 mmol) and compound d (4.5 g, 16.7 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (4.8 g, 50.2 mmol) was then added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (0.2 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was distilled. It was added again and dissolved in 416 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, the mixture was stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 8 g of compound 1-49 as a yellow solid. (Yield: 58%, MS: [M+H]) + =830.3)

[0667] Synthetic Examples 1-50: Preparation of Compounds 1-50

[0668]

[0669] Intermediate 1-50-1 (10 g, 17.4 mmol) and compound a (3.8 g, 17.4 mmol) were added to 200 mL of xylene under a nitrogen atmosphere, and the mixture was stirred and refluxed. Sodium tert-butoxide (5 g, 52.3 mmol) was then added, and the mixture was stirred thoroughly, followed by the addition of bis(tri-tert-butylphosphine)palladium (0.2 g, 0.3 mmol). After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic layer was filtered to remove salts. The filtered organic layer was then distilled. It was added again and dissolved in 394 mL (30 times the volume) of chloroform, and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, the mixture was stirred, and then filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography using chloroform and ethyl acetate to give 8.3 g of compound 1-50 as a yellow solid. (Yield: 63%, MS: [M+H]) + =755.2)

[0670] Synthetic Example 2-1: Preparation of Compound 2-1

[0671]

[0672] Intermediate 2-1-1 (10 g, 25.2 mmol) and intermediate 2-1-2 (8 g, 27.7 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.9 g, 100.7 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9 g of compound 2-1. (Yield: 64%, MS: [M+H)) + =561)

[0673] Synthesis Example 2-2: Preparation of Compound 2-2

[0674]

[0675] Intermediate 2-2-1 (10 g, 25.2 mmol) and intermediate 2-2-2 (8 g, 27.7 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.9 g, 100.7 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.6 g of compound 2-2. (Yield: 66%, MS: [M+H)) + =637)

[0676] Synthetic Example 2-3: Preparation of Compound 2-3

[0677]

[0678] Intermediate 2-3-1 (10 g, 25.2 mmol) and intermediate 2-3-2 (10.1 g, 27.7 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.9 g, 100.7 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9 g of compound 2-3. (Yield: 56%, MS: [M+H)) + =637)

[0679] Synthetic Example 2-4: Preparation of Compound 2-4

[0680]

[0681] Intermediate 2-4-1 (10 g, 25.2 mmol) and intermediate 2-4-2 (9.3 g, 27.7 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.9 g, 100.7 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.8 g of compound 2-4. (Yield: 51%, MS: [M+H]) + =611)

[0682] Synthetic Example 2-5: Preparation of Compound 2-5

[0683]

[0684] Intermediate 2-5-1 (10 g, 25.2 mmol) and intermediate 2-5-2 (10.1 g, 27.7 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.9 g, 100.7 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.4 g of compound 2-5. (Yield: 65%, MS: [M+H)) + =637)

[0685] Synthetic Example 2-6: Preparation of Compound 2-6

[0686]

[0687] Intermediate 2-6-1 (10 g, 25.2 mmol) and intermediate 2-6-2 (11.4 g, 27.7 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.9 g, 100.7 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.5 g of compound 2-6. (Yield: 61%, MS: [M+H)) + =687)

[0688] Synthetic Example 2-7: Preparation of Compound 2-7

[0689]

[0690] Intermediate 2-7-1 (10 g, 22.4 mmol) and intermediate 2-7-2 (10.2 g, 24.6 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (12.4 g, 89.5 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11 g of compound 2-7. (Yield: 67%, MS: [M+H]) + =737)

[0691] Synthetic Example 2-8: Preparation of Compound 2-8

[0692]

[0693] Intermediate 2-8-1 (10 g, 17.9 mmol) and intermediate 2-8-2 (5.6 g, 19.7 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (9.9 g, 71.5 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.8 g of compound 2-8. (Yield: 60%, MS: [M+H]) + =723)

[0694] Synthetic Example 2-9: Preparation of Compound 2-9

[0695]

[0696] Intermediate 2-9-1 (10 g, 21.1 mmol) and intermediate 2-9-2 (6.7 g, 23.3 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (11.7 g, 84.6 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 7.4 g of compound 2-9. (Yield: 55%, MS: [M+H]) + =637)

[0697] Synthetic Example 2-10: Preparation of Compound 2-10

[0698]

[0699] Intermediate 2-10-1 (10 g, 27 mmol) and intermediate 2-10-2 (10 g, 29.6 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (14.9 g, 107.8 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11 g of compound 2-10. (Yield: 70%, MS: [M+H)) + =585)

[0700] Synthetic Example 2-11: Preparation of Compound 2-11

[0701]

[0702] Intermediate 2-11-1 (10 g, 27 mmol) and intermediate 2-11-2 (11.5 g, 29.6 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (14.9 g, 107.8 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.5 g of compound 2-11. (Yield: 67%, MS: [M+H]) + =635)

[0703] Synthetic Example 2-12: Preparation of Compound 2-12

[0704]

[0705] Intermediate 2-12-1 (10 g, 23.8 mmol) and intermediate 2-12-2 (8.8 g, 26.1 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.1 g, 95 mmol) dissolved in water was added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.4 g of compound 2-12. (Yield: 69%, MS: [M+H)) + =635)

[0706] Synthetic Example 2-13: Preparation of Compound 2-13

[0707]

[0708] Intermediate 2-13-1 (10 g, 24.3 mmol) and intermediate 2-13-2 (11.1 g, 26.8 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9 g of compound 2-13. (Yield: 53%, MS: [M+H)) + =701)

[0709] Synthetic Example 2-14: Preparation of Compound 2-14

[0710]

[0711] Intermediate 2-14-1 (10 g, 24.3 mmol) and intermediate 2-14-2 (7.7 g, 26.8 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.9 g of compound 2-14. (Yield: 64%, MS: [M+H]) + =575)

[0712] Synthetic Example 2-15: Preparation of Compound 2-15

[0713]

[0714] Intermediate 2-15-1 (10 g, 24.3 mmol) and intermediate 2-15-2 (9 g, 26.8 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 8.4 g of compound 2-15. (Yield: 55%, MS: [M+H)) + =625)

[0715] Synthetic Example 2-16: Preparation of Compound 2-16

[0716]

[0717] Intermediate 2-16-1 (10 g, 24.3 mmol) and intermediate 2-16-2 (11.1 g, 26.8 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.2 g of compound 2-16. (Yield: 66%, MS: [M+H)) + =701)

[0718] Synthetic Example 2-17: Preparation of Compound 2-17

[0719]

[0720] Intermediate 2-17-1 (10 g, 24.3 mmol) and intermediate 2-17-2 (10.1 g, 26.8 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10 g of compound 2-17. (Yield: 62%, MS: [M+H)) + =665)

[0721] Synthetic Example 2-18: Preparation of Compound 2-18

[0722]

[0723] Intermediate 2-18-1 (10 g, 24.3 mmol) and intermediate 2-18-2 (10.5 g, 26.8 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9.8 g of compound 2-18. (Yield: 59%, MS: [M+H)) + =681)

[0724] Synthetic Example 2-19: Preparation of Compound 2-19

[0725]

[0726] Intermediate 2-19-1 (10 g, 24.3 mmol) and intermediate 2-19-2 (10.5 g, 26.8 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (13.5 g, 97.3 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 11.4 g of compound 2-19. (Yield: 69%, MS: [M+H]) + =681)

[0727] Synthetic Example 2-20: Preparation of Compound 2-20

[0728]

[0729] Intermediate 2-20-1 (10 g, 23.4 mmol) and intermediate 2-20-2 (9.4 g, 25.8 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (12.9 g, 93.7 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 2 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9 g of compound 2-20. (Yield: 58%, MS: [M+H)) + =667)

[0730] Synthetic Example 2-21: Preparation of Compound 2-21

[0731]

[0732] Intermediate 2-21-1 (10 g, 23.4 mmol) and intermediate 2-21-2 (10.6 g, 25.8 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (12.9 g, 93.7 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 10.7 g of compound 2-21. (Yield: 64%, MS: [M+H)) + =717)

[0733] Synthetic Example 2-22: Preparation of Compound 2-22

[0734]

[0735] Intermediate 2-22-1 (10 g, 23.4 mmol) and intermediate 2-22-2 (11.3 g, 25.8 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (12.9 g, 93.7 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 3 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9 g of compound 2-22. (Yield: 52%, MS: [M+H)) + =743)

[0736] Synthetic Example 2-23: Preparation of Compound 2-23

[0737]

[0738] Intermediate 2-23-1 (10 g, 23.4 mmol) and intermediate 2-23-2 (10.1 g, 25.8 mmol) were added to 200 mL of THF under a nitrogen atmosphere and stirred. Potassium carbonate (12.9 g, 93.7 mmol) was dissolved in water and added to the mixture. The mixture was stirred thoroughly and refluxed, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 4 hours, the reaction mixture was cooled to room temperature, and the organic and aqueous layers were separated. The organic layer was then distilled. It was dissolved again in chloroform and washed twice with water. The organic layer was then separated, anhydrous magnesium sulfate was added, stirred, and filtered. The filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to give 9.1 g of compound 2-23. (Yield: 56%, MS: [M+H)) + =697)

[0739] Comparative Example 1: Fabrication of Organic Light-Emitting Devices

[0740] It is coated with a thickness of The ITO (indium tin oxide) glass substrate, used as the thin film, was immersed in distilled water containing a cleaning agent and subjected to ultrasonic cleaning. A product manufactured by Fischer Co. was used as the cleaning agent, and distilled water filtered twice using a filter manufactured by Millipore Co. was used as the distilled water. After cleaning the ITO for 30 minutes, ultrasonic cleaning was repeated twice for 10 minutes each time with distilled water. After cleaning with distilled water, the substrate was ultrasonically cleaned with isopropanol, acetone, and methanol solvents, dried, and then transferred to a plasma cleaner. Additionally, the substrate was cleaned with oxygen plasma for 5 minutes before being transferred to a vacuum depositor.

[0741] On the ITO transparent electrode prepared therefrom, The following compound HI-1 is formed as a hole injection layer with a thickness of 1.5% p-doped. Compound HT-1 is then vacuum-deposited on the hole injection layer to form a film with a thickness of [missing information]. The hole transport layer. Then, on the hole transport layer... The following compound EB-1 was vacuum deposited to form an electron blocking layer.

[0742] Then, compound 1-1 prepared in Synthesis Example 1-1 and compound Dp-7 were vacuum deposited on the EB-1 deposition film at a weight ratio of 98:2 to form a film with a thickness of The red glowing layer.

[0743] On the light-emitting layer The following compound HB-1 was vacuum deposited to form a hole-blocking layer with a film thickness of [thickness value missing]. Then, the following compounds ET-1 and LiQ were vacuum deposited on the hole-blocking layer at a weight ratio of 2:1 to form a film with a thickness of [thickness value missing]. Electron injection and transport layers were constructed. Lithium fluoride (LiF) and aluminum were sequentially deposited on the electron injection and transport layers to thicknesses of [thickness values ​​missing]. and This forms the cathode.

[0744]

[0745] In the above process, the vapor deposition rate of organic materials is maintained at / seconds / second, maintaining the lithium fluoride deposition rate of the cathode at / second, maintaining the aluminum deposition rate at / second, and maintaining a vacuum level of 2×10 during deposition. -7 Up to 5×10 -6 This allows for the fabrication of organic light-emitting devices.

[0746] Comparative Examples 2 to 15

[0747] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that compounds shown in Table 1 below were used instead of compound 1-1 in the organic light-emitting device of Comparative Example 1.

[0748] Examples 1 to 132

[0749] An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that compounds 1-1 in the organic light-emitting device of Comparative Example 1 were co-deposited at a weight ratio of 1:1 and the compounds of chemical formula 1 as the first main body and the compounds of chemical formula 2 as the second main body, as shown in Tables 2 to 5 below, were used instead of compounds 1-1.

[0750] Comparative Examples 16 to 63

[0751] The organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that the organic light-emitting device of Comparative Example 1 was co-deposited in a 1:1 weight ratio and that the comparative compounds C-1 to C-12 as the first host and the compound of chemical formula 2 as the second host, as shown in Tables 6 and 7 below, were used instead of compound 1-1 in the organic light-emitting device of Comparative Example 1.

[0752]

[0753] Experiment Example 1: Evaluation of Device Characteristics

[0754] Measurements were taken by applying a current to the organic light-emitting devices manufactured in Examples 1 to 132 and Comparative Examples 1 to 63 (based on 15 mA / cm²).2 Voltage, efficiency, and lifetime are shown in Tables 1 through 7 below. Lifetime T95 refers to the time required for the brightness to decrease to 95% of the initial brightness (10,000 nits).

[0755] [Table 1]

[0756]

[0757] [Table 2]

[0758]

[0759]

[0760] [Table 3]

[0761]

[0762]

[0763] [Table 4]

[0764]

[0765]

[0766] [Table 5]

[0767]

[0768] [Table 6]

[0769]

[0770]

[0771] [Table 7]

[0772]

[0773] As shown in the table above, compared with comparative examples that use only one of the compounds represented by chemical formulas 1 and 2, or neither of them, the organic light-emitting devices of the embodiments that use both the first compound represented by chemical formula 1 and the second compound represented by chemical formula 2 as the host materials in the light-emitting layer exhibit equal or superior luminous efficiency, low driving voltage, and significantly improved lifetime characteristics.

[0774] Specifically, compared to the devices of comparative examples using a compound represented by Chemical Formula 1 as a single host, the devices according to the embodiments exhibit higher efficiency and longer lifetime. Furthermore, compared to the devices of comparative examples using comparative compounds C-1 to C-12 as the first host and a compound represented by Chemical Formula 2 as the second host, the devices according to the embodiments exhibit improved efficiency and lifetime characteristics. Thus, when using a combination of the first compound represented by Chemical Formula 1 and the second compound represented by Chemical Formula 2 as a co-host, efficient energy transfer to the red dopant was determined in the red emitting layer. This is believed to be because the first compound has high stability for both electrons and holes, and also because using the first compound in combination with the second compound increases the number of holes and maintains a more stable balance between electrons and holes in the red emitting layer.

[0775] Therefore, when both the first and second compounds are used as the host materials of an organic light-emitting device (OLED), it is determined that the driving voltage, luminous efficiency, and / or lifetime characteristics of the OLED can be improved. Considering that the luminous efficiency and lifetime characteristics of OLEDs are typically trade-offs, it can be seen that the OLED using the combination of compounds of this disclosure exhibits significantly improved device characteristics compared to the devices of the comparative examples.

[0776] Explanation of reference numerals in the attached figures

[0777] 1: Substrate 2: Anode

[0778] 3: Light-emitting layer 4: Cathode

[0779] 5: Hole injection layer; 6: Hole transport layer

[0780] 7: Electron blocking layer; 8: Hole blocking layer

[0781] 9: Electron Injection and Transport Layer

Claims

1. An organic light-emitting device, comprising: First electrode; A second electrode disposed opposite to the first electrode; and A light-emitting layer disposed between the first electrode and the second electrode. The light-emitting layer comprises a first compound represented by the following chemical formula 1 and a second compound represented by the following chemical formula 2: [Chemical Formula 1] In the chemical formula 1, X1 to X3 are all N. Ar1 and Ar2 are each independently a substituted or unsubstituted phenyl, a substituted or unsubstituted biphenyl, a substituted or unsubstituted terphenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted phenanthryl, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothiopheneyl, or a substituted or unsubstituted carbazoleyl. Each Z can be hydrogen or deuterium independently, or two adjacent groups in Z can combine with each other to form an unsubstituted or deuterated benzene ring. n is an integer from 0 to 6, and A is a substituent represented by the following chemical formula 1-1. [Chemical Formula 1-1] In the chemical formula 1-1, R1 to R4 are each independently hydrogen or deuterium, or two adjacent groups of R1 to R4 are combined with each other to form an unsubstituted or deuterated benzene ring. D refers to deuterium, and m is an integer from 0 to 6. [Chemical Formula 2] In the chemical formula 2, T1 to T4 are each independently a deuterated or unsubstituted benzene ring. L1 and L2 are each independently a single bond, a deuterated or unsubstituted phenylene group, or a deuterated or unsubstituted naphthylene group, and Ar3 and Ar4 are each independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted fluoranyl, substituted or unsubstituted dibenzothiophene, or substituted or unsubstituted dibenzofuranyl, and, The phrase "substituted or unsubstituted" means unsubstituted or selected from deuterium, C 1-10 The alkyl and phenyl groups are substituted with one or more substituents, or are unsubstituted or substituted with two or more of the above substituents linked together.

2. The organic light-emitting device according to claim 1, Ar1 and Ar2 are each independently selected from any of the following:

3. The organic light-emitting device according to claim 1, Where A is any of the substituents represented by the following chemical formulas a1 to a4:

4. The organic light-emitting device according to claim 1, The first compound is selected from any of the following:

5. The organic light-emitting device according to claim 1, The second compound is represented by the following chemical formula 2-1: [Chemical Formula 2-1] In the chemical formula 2-1, D refers to deuterium. r and s are each independent integers from 0 to 7, and L1, L2, Ar3 and Ar4 are as defined in claim 1.

6. The organic light-emitting device according to claim 1, L1 and L2 are each independently a single bond, a phenylene group, or a naphthylene group.

7. The organic light-emitting device according to claim 1, Ar3 and Ar4 are each independently selected from any of the following:

8. The organic light-emitting device according to claim 1, The second compound is represented by the following chemical formula 2-2: [Chemical Formula 2-2] In the chemical formula 2-2, L1 and L2 are each independently a single bond, a phenylene or a naphthylene group, and Ar3 and Ar4 are as defined in claim 1.

9. The organic light-emitting device according to claim 1, The second compound is selected from any of the following:

10. The organic light-emitting device according to claim 1, The first compound and the second compound are included in a weight ratio of 99:1 to 1:99.

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