organic light-emitting devices

Abstract

The present disclosure provides organic light emitting devices with improved driving voltage, efficiency, and lifetime.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Korean Patent Application No. 10-2021-0022063 filed on February 18, 2021, in the Korean Intellectual Property Office, and Korean Patent Application No. 10-2022-0021610 filed on February 18, 2022, in the Korean Intellectual Property Office, the contents of which are incorporated herein by reference in their entirety.

[0003] The present disclosure relates to organic light emitting devices with improved driving voltage, efficiency, and lifetime. Background Art

[0004] Generally speaking, organic light emitting diodes (OLEDs) are a type of organic light emitting diode (OLED) that converts electrical energy into light energy using organic materials. These devices have been extensively researched due to their wide viewing angles, excellent contrast, fast response time, excellent brightness, driving voltage, and response speed.

[0005] An organic light-emitting device typically has a structure including an anode, a cathode, and an organic material layer interposed between the anode and cathode. The organic material layer typically has a multilayer structure containing different materials to enhance the efficiency and stability of the organic light-emitting device. For example, the organic material layer may be formed from a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of an organic light-emitting device, 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 when the excitons fall back to the ground state, light is emitted.

[0006] Among the organic light emitting devices described above, there is a continuous demand for developing organic light emitting devices having improved driving voltage, efficiency, and lifespan.

[0007] [Prior art literature]

[0008] [Patent Document]

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

[0010] Technical issues

[0011] An object of the present disclosure is to provide an organic light emitting device with improved driving voltage, efficiency, and lifetime.

[0012] Technical Solution

[0013] The present disclosure provides the following organic light-emitting devices:

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

[0015] an anode; a cathode; and a light-emitting layer between the anode and the cathode,

[0016] The light-emitting layer comprises a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2:

[0017] [Chemical Formula 1]

[0018]

[0019] In Chemical Formula 1,

[0020] Ar1 and Ar2 are each independently substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C 2-60 heteroaryl,

[0021] L1 to L3 are each independently a single bond; or a substituted or unsubstituted C 6-60 arylene groups,

[0022] R1 is hydrogen; deuterium; or substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C 2-60 Heteroaryl, and

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

[0024] [Chemical Formula 2]

[0025]

[0026] In Chemical Formula 2,

[0027] R'1 to R' 12 Any one of them is the following chemical formula 3, and the remainder is hydrogen or deuterium,

[0028] [Chemical Formula 3]

[0029]

[0030] In Chemical Formula 3,

[0031] L'1 is a single bond; substituted or unsubstituted C 6-60 arylene groups,

[0032] L'2 and L'3 are each independently a single bond; substituted or unsubstituted C 6-60 Arylene; or a substituted or unsubstituted C containing any one or more selected from N, O and S2-60 Heteroarylene, and

[0033] Ar'1 and Ar'2 are each independently substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C 2-60 Heteroaryl.

[0034] Beneficial effects

[0035] The organic light emitting device includes the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2, and thus can improve efficiency, achieve low driving voltage, and / or improve lifespan characteristics in the organic light emitting device. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 An example of an organic light-emitting device including a substrate 1 , an anode 2 , a light-emitting layer 3 , and a cathode 4 is shown.

[0037] Figure 2 An example of an organic light emitting device including 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 is shown. DETAILED DESCRIPTION

[0038] Hereinafter, embodiments of the present disclosure will be described in more detail to help understanding the present invention.

[0039] As used herein, the symbol or It refers to the bond to another substituent.

[0040] As used herein, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a nitrile group, a nitro group, a hydroxyl group, a carbonyl group, an ester group, an imide group, an amino group, a phosphine oxide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a silyl group, a boron group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an aralkenyl group, an alkylaryl group, an alkylamino group, an aralkylamino group, a heteroarylamino group, an arylamino group, an arylphosphino group, and a heterocyclic group containing at least one of N, O, and S atoms, or unsubstituted or substituted with a substituent in which two or more substituents are linked together from among the substituents exemplified above. For example, a "substituent in which two or more substituents are linked together" may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are linked together.

[0041] In the present disclosure, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a substituent having the following structural formula, but is not limited thereto.

[0042]

[0043] In the present disclosure, the ester group may have a structure in which the oxygen of the ester group may be substituted by a linear, branched, or cyclic alkyl group having 1 to 25 carbon atoms, or an aryl group having 6 to 25 carbon atoms. Specifically, the ester group may be a substituent having the following structural formula, but is not limited thereto.

[0044]

[0045] In the present disclosure, the carbon number of the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the imide group may be a substituent having the following structural formula, but is not limited thereto.

[0046]

[0047] In the present disclosure, the silyl group specifically includes trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl and the like, but is not limited thereto.

[0048] In the present disclosure, the boryl group specifically includes a trimethylboryl group, a triethylboryl group, a tert-butyldimethylboryl group, a triphenylboryl group, and a phenylboryl group, but is not limited thereto.

[0049] In the present disclosure, examples of halogen groups include fluorine, chlorine, bromine, or iodine.

[0050] In the present disclosure, the alkyl group may be linear or branched, and its carbon number is not particularly limited, but is preferably 1 to 40. According to one embodiment, the carbon number of the alkyl group is 1 to 20. According to another embodiment, the carbon number of the alkyl group is 1 to 10. According to another embodiment, the carbon number of the alkyl group is 1 to 6. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like, but are not limited thereto.

[0051] In the present disclosure, the alkenyl group may be linear or branched, and its carbon number is not particularly limited, but is preferably 2 to 40. According to one embodiment, the carbon number of the alkenyl group is 2 to 20. According to another embodiment, the carbon number of the alkenyl group is 2 to 10. According to yet another embodiment, the carbon number of the alkenyl group is 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbene, styryl, etc., but are not limited thereto.

[0052] In the present disclosure, the cycloalkyl group is not particularly limited, but its carbon number is preferably 3 to 60. According to one embodiment, the carbon number of the cycloalkyl group is 3 to 30. According to another embodiment, the carbon number of the cycloalkyl group is 3 to 20. According to yet another embodiment, the carbon number of the cycloalkyl group is 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.

[0053] In the present disclosure, the aryl group is not particularly limited, but its carbon number is preferably 6 to 60, and it may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the carbon number of the aryl group is 6 to 30. According to one embodiment, the carbon number of the aryl group is 6 to 20. As a monocyclic aryl group, the aryl group may be phenyl, biphenyl, terphenyl, etc., but is not limited thereto. Polycyclic aryl groups include naphthyl, anthracenyl, phenanthrenyl, pyrenyl, peryl, fluorenyl, etc., but not limited thereto.

[0054] In the present disclosure, the fluorenyl group may be substituted, and two substituents may be connected to each other to form a spirocyclic structure. In the case where the fluorenyl group is substituted, etc. However, the structure is not limited thereto.

[0055] In the present disclosure, the heterocyclic group is a heterocyclic group containing at least one of O, N, Si and S as a heteroatom, and the carbon number thereof is not particularly limited, but is preferably 2 to 60. Examples of the heterocyclic group include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, Azolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolinyl, indolyl, carbazolyl, benzo[omicron] oxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophenyl, dibenzothiophenyl, benzofuranyl, phenanthroline, isothiophene oxazolyl, thiadiazolyl, phenothiazinyl, dibenzofuranyl, etc., but are not limited thereto.

[0056] In the present disclosure, the aryl group in aralkyl, aralkenyl, alkylaryl, and arylamine groups is the same as the above-mentioned examples of aryl groups. In the present disclosure, the alkyl group in aralkyl, alkylaryl, and alkylamine groups is the same as the above-mentioned examples of alkyl groups. In the present disclosure, the heteroaryl group in heteroarylamine groups can be applied to the above-mentioned description of heterocyclic groups. In the present disclosure, the alkenyl group in aralkenyl groups is the same as the above-mentioned examples of alkenyl groups. In the present disclosure, the above-mentioned description of aryl groups can be applied, except that the arylene group is a divalent group. In the present disclosure, the above-mentioned description of heterocyclic groups can be applied, except that the heteroarylene group is a divalent group. In the present disclosure, the above-mentioned description of aryl or cycloalkyl groups can be applied, except that the hydrocarbon ring is not a monovalent group but is formed by combining two substituents. In the present disclosure, the above-mentioned description of heterocyclic groups can be applied, except that the heterocyclic ring is not a monovalent group but is formed by combining two substituents.

[0057] Hereinafter, the present disclosure will be described in detail with respect to each configuration.

[0058] anode and cathode

[0059] The anode and cathode used herein refer to electrodes used in an organic light emitting device.

[0060] As the anode material, it is generally preferred to use a material with a large work function so that holes can 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; etc., but are not limited thereto.

[0061] As the cathode material, a material with a small work function is generally preferred, so that electrons can be easily injected into the organic material layer. Specific examples of cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structure materials such as LiF / Al or LiO2 / Al; and the like.

[0062] hole injection layer

[0063] If necessary, the organic light-emitting device according to the present disclosure may further include a hole injection layer on the anode.

[0064] The hole injection layer is a layer that injects holes from the electrode. The hole injection material is preferably a compound that has the ability to transport holes, has an effect of injecting holes into the anode, and has an excellent hole injection effect into the light-emitting layer or light-emitting material, prevents excitons generated in the light-emitting layer from migrating to the electron injection layer or electron injection material, and has excellent thin film forming ability. In addition, the HOMO (highest occupied molecular orbital) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer.

[0065] Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinone, polyaniline-based and polythiophene-based conductive polymers, etc., but are not limited thereto.

[0066] hole transport layer

[0067] If necessary, the organic light-emitting device according to the present disclosure may further include a hole transport layer on the anode (or on the hole injection layer when the hole injection layer is present).

[0068] The hole transport layer receives holes from the anode or the hole injection layer and transports the holes to the light emitting layer. The hole transport material is suitably a material having a large hole mobility that can receive holes from the anode or the hole injection layer and transfer the holes to the light emitting layer.

[0069] Specific examples of the hole transport material include arylamine-based organic materials, conductive polymers, block copolymers in which a conjugated portion and a non-conjugated portion exist simultaneously, and the like, but are not limited thereto.

[0070] electron blocking layer

[0071] If necessary, the organic light-emitting device according to the present disclosure may include an electron blocking layer on the anode (or on the hole injection layer when a hole injection layer is present; on the electron transport layer when an electron transport layer is present).

[0072] An electron-blocking layer is a layer positioned between the hole-transporting layer and the light-emitting layer to prevent electrons injected from the cathode from transferring to the hole-transporting layer and not recombining in the light-emitting layer. It is also referred to as an electron-suppressing layer or electron-blocking layer. The electron-blocking layer is preferably made of a material with a lower electron affinity than the electron-transporting layer.

[0073] light-emitting layer

[0074] The light-emitting layer used in the present disclosure refers to a layer that can emit light in the visible light region by combining holes and electrons transferred from the anode and cathode. Generally, the light-emitting layer includes a host material and a dopant material. In the present disclosure, the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 are included as the host.

[0075] Preferably, the compound represented by Chemical Formula 1 may be represented by the following Chemical Formula 1A:

[0076] [Chemical Formula 1A]

[0077]

[0078] In Chemical Formula 1A,

[0079] Ar1 and Ar2, L1 to L3, R1 and a are as defined in Chemical Formula 1.

[0080] Preferably, the compound represented by Chemical Formula 1 may be represented by any one of the following Chemical Formulas 1-1 to 1-3:

[0081] [Chemical Formula 1-1]

[0082]

[0083] [Chemical formula 1-2]

[0084]

[0085] [Chemical formula 1-3]

[0086]

[0087] In Chemical Formulas 1-1 to 1-3,

[0088] Ar1 and Ar2, L1 to L3, and R1 are as defined in Chemical Formula 1.

[0089] Preferably, Ar1 and Ar2 can each independently be a substituted or unsubstituted C 6-20 Aryl; or a substituted or unsubstituted C 2-20 Heteroaryl.

[0090] More preferably, Ar1 and Ar2 may each independently be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrenyl group, a dibenzofuranyl group, or a dibenzothiophenyl group.

[0091] Most preferably, Ar1 and Ar2 can each independently be any one selected from the following:

[0092]

[0093] Preferably, L1 to L3 can each independently be a single bond; or a substituted or unsubstituted C 6-20 Arylene.

[0094] More preferably, L1 to L3 may each independently be a single bond, a phenylene group, a biphenylene group, or a naphthylene group.

[0095] Most preferably, L1 to L3 may each independently be a single bond or any one selected from the following:

[0096]

[0097] Preferably, R1 can be hydrogen; deuterium; or substituted or unsubstituted C 6-20 Aryl; or a substituted or unsubstituted C 2-20 Heteroaryl.

[0098] More preferably, R1 can be hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, naphthylphenyl, phenylnaphthyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl.

[0099] Preferably, a can be 0 or 1.

[0100] Representative examples of the compound represented by Chemical Formula 1 are as follows:

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

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[0115]

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[0264]

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[0279]

[0280]

[0281]

[0282]

[0283] The compound represented by Chemical Formula 1 can be prepared by a preparation method as shown in the following Reaction Scheme 1 as an example, and other remaining compounds can be prepared in a similar manner.

[0284] [Reaction Scheme 1]

[0285]

[0286] In Reaction Scheme 1, Ar1, Ar2, L1 to L3, R1 and a are the same as those defined in Chemical Formula 1, and X is a halogen, preferably, X is chlorine or bromine.

[0287] Reaction Scheme 1 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups used in the Suzuki coupling reaction can be modified as known in the art. The above preparation method can be further embodied in the preparation examples described below.

[0288] Preferably, R'1, R'3 to R' 10 and R' 12 Any one of them may be a substituent represented by Chemical Formula 3, and the rest may be each independently hydrogen or deuterium, and R'2 and R' 11 can be independently hydrogen or deuterium. More preferably, R'1, R'3 to R' 10 and R' 12 Any one of them may be a substituent represented by Chemical Formula 3, and the rest may be hydrogen, and R'2 and R' 11 It may be hydrogen.

[0289] Preferably, the compound represented by Chemical Formula 2 may be represented by any one of the following Chemical Formulas 2-1 to 2-6:

[0290] [Chemical Formula 2-1]

[0291]

[0292] [Chemical Formula 2-2]

[0293]

[0294] [Chemical formula 2-3]

[0295]

[0296] [Chemical formula 2-4]

[0297]

[0298] [Chemical Formula 2-5]

[0299]

[0300] [Chemical Formula 2-6]

[0301]

[0302] In Chemical Formulas 2-1 to 2-6,

[0303] R'1 to R' 12 , L'1 to L'3, Ar'1 and Ar'2 are as defined in Chemical Formula 2.

[0304] Preferably, L'1 can be a single bond; substituted or unsubstituted C 6-20 Arylene.

[0305] More preferably, L'1 may be a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenyldiyl group, or a substituted or unsubstituted naphthalenediyl group.

[0306] More preferably, L'1 can be any one selected from the following:

[0307]

[0308] Most preferably, L'1 can be any one selected from the following:

[0309]

[0310] Preferably, L'2 and L'3 can each independently be a single bond; substituted or unsubstituted C 6-20 Arylene; or a substituted or unsubstituted C containing any one or more selected from N, O and S 2-20 Heteroarylene.

[0311] More preferably, L'2 and L'3 may each independently be a single bond, a phenylene group, a phenylene group substituted with one phenyl group, a biphenyldiyl group, or a naphthalenediyl group.

[0312] Most preferably, L'2 and L'3 may each independently be a single bond or any one selected from the following:

[0313]

[0314] Preferably, Ar'1 and Ar'2 can each independently be a substituted or unsubstituted C6-20 Aryl; or a substituted or unsubstituted C 2-20 Heteroaryl.

[0315] Preferably, Ar'1 and Ar'2 may each independently be a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a dibenzofuranyl group, a dibenzothiophenyl group, a phenylcarbazolyl group, a dimethylfluorenyl group, a benzonaphthofuranyl group, or a benzonaphthothiophenyl group.

[0316] Preferably, Ar'1 and Ar'2 can each independently be phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, dibenzofuranyl, dibenzothiophenyl, 9-phenyl-9H-carbazolyl, dimethylfluorenyl, benzo[b]naphtho[2,1-d]furanyl, benzo[b]naphtho[2,3-d]furanyl, benzo[b]naphtho[1,2-d]furanyl, benzo[b]naphtho[2,1-d]thiophenyl, benzo[b]naphtho[2,3-d]thiophenyl, or benzo[b]naphtho[1,2-d]thiophenyl.

[0317] More preferably, Ar'1 and Ar'2 can each independently be any one selected from the following:

[0318]

[0319] More preferably, Ar'1 and Ar'2 can each independently be any one selected from the following:

[0320]

[0321] Representative examples of the compound represented by Chemical Formula 2 are as follows:

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330]

[0331]

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[0459]

[0460]

[0461]

[0462]

[0463]

[0464]

[0465]

[0466]

[0467]

[0468]

[0469]

[0470]

[0471]

[0472]

[0473]

[0474]

[0475]

[0476]

[0477]

[0478]

[0479]

[0480]

[0481]

[0482] where R'1 to R' 12 The compound represented by Chemical Formula 2, in which any one of them is a substituent represented by the following Chemical Formula 3 and the remainder is hydrogen, can be prepared by the preparation method shown in the following Reaction Scheme 2 as an example, and the other remaining compounds can be prepared in a similar manner.

[0483] [Reaction Scheme 2]

[0484]

[0485] In Reaction Scheme 2, L'1 to L'3, Ar'1 and Ar'2 are as defined in Chemical Formula 2, and X' is a halogen, preferably, chlorine or bromine.

[0486] Reaction Scheme 2 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactive groups used in the Suzuki coupling reaction can be modified as known in the art. The above preparation method can be further embodied in the preparation examples described below.

[0487] Preferably, the weight ratio between the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 in the light emitting layer is 10:90 to 90:10, more preferably, 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40.

[0488] Meanwhile, in addition to the host, the light-emitting layer may further include a dopant. The dopant material is not particularly limited as long as it is a material used for an organic light-emitting device. As examples, aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, etc. may be mentioned. Specific examples of aromatic amine derivatives include substituted or unsubstituted fused aromatic ring derivatives having an arylamino group, examples of which include pyrene, anthracene, and diindenopyrene. Styrylamine compounds are compounds in which a substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, 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, styrylamine, styryldiamine, styryltriamine, and styryltetramine. Furthermore, examples of metal complexes include, but are not limited to, iridium complexes and platinum complexes.

[0489] Preferably, the dopant material may be at least one selected from the following:

[0490]

[0491]

[0492]

[0493] hole blocking layer

[0494] If necessary, the organic light emitting device according to the present disclosure may include a hole blocking layer on the light emitting layer.

[0495] The hole blocking layer is provided between the electron transport layer and the light emitting layer to prevent holes injected from the anode from transferring to the electron transport layer and not recombining in the light emitting layer.

[0496] electron transport layer

[0497] The organic light-emitting device according to the present disclosure may include an electron transport layer on the light-emitting layer (or on the hole blocking layer when the hole blocking layer is present).

[0498] The electron transport layer is a layer that receives electrons from the cathode and the electron injection layer formed on the cathode and transports the electrons to the light-emitting layer, and inhibits the transfer of holes from the light-emitting layer. The electron transport material is suitably a material that can well receive electrons from the cathode and transfer the electrons to the light-emitting layer and has a large electron mobility.

[0499] Specific examples of electron transport materials include, but are not limited to, Al complexes of 8-hydroxyquinoline; complexes containing Alq3; organic free radical compounds; and hydroxyflavone-metal complexes. The electron transport layer can be used with any desired cathode material, as used in conventional techniques. Suitable cathode materials are typically materials with a low work function followed by an aluminum or silver layer. Specific examples include cesium, barium, calcium, ytterbium, and samarium, each followed by an aluminum or silver layer.

[0500] electron injection layer

[0501] If necessary, the organic light-emitting device according to the present disclosure may further include an electron injection layer on the light-emitting layer (or on the electron transport layer when the electron transport layer is present).

[0502] The electron injection layer is a layer that injects electrons from the electrode, and is preferably a compound that has the ability to transport electrons, has an effect of injecting electrons from the cathode and an excellent effect of injecting electrons into the light-emitting layer or the light-emitting material, prevents excitons generated by the light-emitting layer from moving to the hole injection layer, and is also excellent in the ability to form a thin film.

[0503] Specific examples of materials that can be used as the electron injection layer include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, Azoles, The examples include, but are not limited to, diazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylmethane, anthrone and their derivatives, metal complex compounds, nitrogen-containing 5-membered ring derivatives and the like.

[0504] Examples of metal complex compounds include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h]quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)(o-cresol)gallium, bis(2-methyl-8-quinolinato)(1-naphthol)aluminum, bis(2-methyl-8-quinolinato)(2-naphthol)gallium, and the like, but are not limited thereto.

[0505] Meanwhile, in the present disclosure, “electron injection and transport layer” is a layer that functions as both an electron injection layer and an electron transport layer, and materials that function as each layer may be used alone or in combination, but are not limited thereto.

[0506] organic light-emitting devices

[0507] Figure 1 and Figure 2 The structure of an organic light emitting device according to the present disclosure is shown. Figure 1 An example of an organic light-emitting device including a substrate 1 , an anode 2 , a light-emitting layer 3 , and a cathode 4 is shown. Figure 2 An example of an organic light emitting device including 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 is shown.

[0508] The organic light-emitting device according to the present disclosure can be manufactured by stacking the above-mentioned structures in sequence. 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 to form an anode by using a PVD (physical vapor deposition) method such as sputtering or electron beam evaporation to form the anode, forming the above-mentioned layers on the anode, and then depositing a material that can be used as a cathode thereon. In addition to such a method, the organic light-emitting device can also be manufactured by sequentially depositing the cathode material to the anode material on the substrate in the reverse order of the above-mentioned configuration (WO2003 / 012890). In addition, the light-emitting layer can be formed by subjecting the host and the dopant to a vacuum deposition method and a solution coating method. In this article, the solution coating method means spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roller coating, etc., but is not limited thereto.

[0509] Meanwhile, the organic light-emitting device according to the present disclosure may be a bottom-emitting device, a top-emitting device, or a double-sided light-emitting device, and in particular, may be a bottom-emitting device requiring relatively high light-emitting efficiency.

[0510] Hereinafter, preferred embodiments are presented to help understand the present disclosure. However, the following embodiments are provided only for a better understanding of the present disclosure and are not intended to limit the content of the present disclosure.

[0511] [Preparation Example]

[0512] Preparation Example 1-1

[0513]

[0514] Compound 1-A (15 g, 60.9 mmol) and compound Trz1 (19.3 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (16.8 g, 121.7 mmol) was then dissolved in 50 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.9 g of compound sub1-A-1. (Yield: 71%, MS: [M+H] + =484)

[0515]

[0516] Under a nitrogen atmosphere, compound sub1-A-1 (15 g, 31 mmol) and compound sub1 (6.1 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-1. (Yield: 66%, MS: [M+H] + =602)

[0517] Preparation Example 1-2

[0518]

[0519] Under a nitrogen atmosphere, compound 1-A (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5 g of compound sub1-A-2. (Yield: 74%, MS: [M+H] + =434)

[0520]

[0521] Under a nitrogen atmosphere, compound sub1-A-2 (15 g, 34.6 mmol) and compound sub2 (9.4 g, 34.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.6 g, 69.1 mmol) was dissolved in 29 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-2. (Yield: 66%, MS: [M+H] + =626)

[0522] Preparation Examples 1-3

[0523]

[0524] Compound 1-A (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.2 g of compound sub1-A-3. (Yield: 79%, MS: [M+H] + =484)

[0525]

[0526] Under a nitrogen atmosphere, compound sub1-A-3 (15 g, 31 mmol) and compound sub3 (7.1 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-3. (Yield: 66%, MS: [M+H] + =632)

[0527] Preparation Examples 1-4

[0528]

[0529] Compound 1-A (15 g, 60.9 mmol) and compound Trz4 (27 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of compound sub1-A-4. (Yield: 70%, MS: [M+H] + =610)

[0530]

[0531] Under a nitrogen atmosphere, compound sub1-A-4 (15 g, 24.6 mmol) and compound sub4 (5.6 g, 24.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (6.8 g, 49.2 mmol) was dissolved in 20 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.2 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of compound 1-4. (Yield: 60%, MS: [M+H] + =758)

[0532] Preparation Examples 1-5

[0533]

[0534] Compound 1-B (15 g, 60.9 mmol) and compound Trz5 (24 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2 g of compound sub1-B-1. (Yield: 77%, MS: [M+H] + =560)

[0535]

[0536] Under a nitrogen atmosphere, compound sub1-B-1 (15 g, 26.8 mmol) and compound sub5 (3.3 g, 26.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in 22 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-5. (Yield: 80%, MS: [M+H] + =602)

[0537] Preparation Examples 1-6

[0538]

[0539] Compound 1-B (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.2 g of compound sub1-B-2. (Yield: 62%, MS: [M+H] + =484)

[0540]

[0541] Under a nitrogen atmosphere, compound sub1-B-2 (15 g, 31 mmol) and compound sub6 (7.6 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3 g of compound 1-6. (Yield: 76%, MS: [M+H] + =650)

[0542] Preparation Examples 1-7

[0543]

[0544] Compound 1-B (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound sub1-B-3. (Yield: 79%, MS: [M+H] + =434)

[0545]

[0546] Under a nitrogen atmosphere, compound sub1-B-3 (15 g, 34.6 mmol) and compound sub7 (8.6 g, 34.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.6 g, 69.1 mmol) was dissolved in 29 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of compound 1-7. (Yield: 74%, MS: [M+H] + =602)

[0547] Preparation Examples 1-8

[0548]

[0549] Under a nitrogen atmosphere, compound sub1-B-2 (15 g, 31 mmol) and compound sub8 (8.1 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.5 g of compound 1-8. (Yield: 75%, MS: [M+H] + =666)

[0550] Preparation Examples 1-9

[0551]

[0552] Compound 1-B (15 g, 60.9 mmol) and compound Trz6 (22.4 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.7 g of compound sub1-B-4. (Yield: 73%, MS: [M+H] + =534)

[0553]

[0554] Under a nitrogen atmosphere, compound sub1-B-4 (15 g, 28.1 mmol) and compound sub9 (6 g, 28.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (7.8 g, 56.2 mmol) was dissolved in 23 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6 g of compound 1-9. (Yield: 62%, MS: [M+H] + =666)

[0555] Preparation Example 1-10

[0556]

[0557] Compound 1-B (15 g, 60.9 mmol) and compound Trz7 (28.6 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.6 g of compound sub1-B-5. (Yield: 74%, MS: [M+H] + =636)

[0558]

[0559] Under a nitrogen atmosphere, compound sub1-B-5 (15 g, 23.6 mmol) and compound sub5 (2.9 g, 23.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (6.5 g, 47.2 mmol) was dissolved in 20 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.2 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4 g of compound 1-10. (Yield: 65%, MS: [M+H] + =678)

[0560] Preparation Example 1-11

[0561]

[0562] Compound 1-B (15 g, 60.9 mmol) and compound Trz8 (21.8 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.1 g of compound sub1-B-6. (Yield: 63%, MS: [M+H] + =524)

[0563]

[0564] Under a nitrogen atmosphere, compound sub1-B-6 (15 g, 28.6 mmol) and compound sub10 (4.9 g, 28.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (7.9 g, 57.3 mmol) was dissolved in 24 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of compound 1-11. (Yield: 65%, MS: [M+H] + =616)

[0565] Preparation Example 1-12

[0566]

[0567] Compound 1-C (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g of compound sub1-C-1. (Yield: 60%, MS: [M+H] + =484)

[0568]

[0569] Under a nitrogen atmosphere, compound sub1-C-1 (15 g, 31 mmol) and compound sub10 (5.3 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-12. (Yield: 72%, MS: [M+H] + =576)

[0570] Preparation Example 1-13

[0571]

[0572] Under a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz9 (24 g, 60.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.5 g of compound sub1-C-2. (Yield: 69%, MS: [M+H] + =560)

[0573]

[0574] Under a nitrogen atmosphere, compound sub1-C-2 (15 g, 26.8 mmol) and compound sub10 (4.6 g, 26.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in 22 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound 1-13. (Yield: 80%, MS: [M+H] + =652)

[0575] Preparation Example 1-14

[0576]

[0577] Compound 1-C (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.5 g of compound sub1-C-3. (Yield: 66%, MS: [M+H] + =510)

[0578]

[0579] Under a nitrogen atmosphere, compound sub1-C-3 (15 g, 29.4 mmol) and compound sub11 (7.3 g, 29.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (8.1 g, 58.8 mmol) was dissolved in 24 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3 g of compound 1-14. (Yield: 77%, MS: [M+H] + =678)

[0580] Preparation Example 1-15

[0581]

[0582] Compound 1-C (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7 g of compound sub1-C-4. (Yield: 71%, MS: [M+H]+=434)

[0583]

[0584] Under a nitrogen atmosphere, compound sub1-C-4 (15 g, 37.1 mmol) and compound sub12 (9.7 g, 37.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.3 g, 74.3 mmol) was dissolved in 31 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of compound 1-15. (Yield: 64%, MS: [M+H] + =616)

[0585] Preparation Example 1-16

[0586]

[0587] Under a nitrogen atmosphere, compound sub1-C-2 (15 g, 26.8 mmol) and compound sub13 (7.4 g, 26.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in 22 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.2 g of compound 1-16. (Yield: 80%, MS: [M+H] + =758)

[0588] Preparation Example 1-17

[0589]

[0590] Under a nitrogen atmosphere, compound sub1-C-4 (15 g, 34.6 mmol) and compound sub14 (7.7 g, 34.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.6 g, 69.1 mmol) was dissolved in 29 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-17. (Yield: 62%, MS: [M+H] + =576)

[0591] Preparation Example 1-18

[0592]

[0593] Under a nitrogen atmosphere, compound sub1-C-1 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of compound 1-18. (Yield: 63%, MS: [M+H] + =616)

[0594] Preparation Example 1-19

[0595]

[0596] Compound 1-C (15 g, 60.9 mmol) and compound Trz11 (22.4 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.4 g of compound sub1-C-5. (Yield: 69%, MS: [M+H] + =534)

[0597]

[0598] Under a nitrogen atmosphere, compound sub1-C-5 (15 g, 28.1 mmol) and compound sub15 (6 g, 28.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (7.8 g, 56.2 mmol) was dissolved in 23 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-19. (Yield: 71%, MS: [M+H] + =666)

[0599] Preparation Example 1-20

[0600]

[0601] Compound 1-C (15 g, 60.9 mmol) and compound Trz12 (21.8 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21 g of compound sub1-C-6. (Yield: 66%, MS: [M+H] + =524)

[0602]

[0603] Under a nitrogen atmosphere, compound sub1-C-6 (15 g, 28.6 mmol) and compound sub10 (4.9 g, 28.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-20. (Yield: 70%, MS: [M+H] + =616)

[0604] Preparation Example 1-21

[0605]

[0606] Compound 1-C (15 g, 60.9 mmol) and compound Trz13 (24 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2 g of compound sub1-C-7. (Yield: 77%, MS: [M+H] + =560)

[0607]

[0608] Under a nitrogen atmosphere, compound sub1-C-7 (15 g, 26.8 mmol) and compound sub5 (3.3 g, 26.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5 g of compound 1-21. (Yield: 65%, MS: [M+H] + =602)

[0609] Preparation Example 1-22

[0610]

[0611] Compound 1-D (15 g, 60.9 mmol) and compound Trz14 (19.3 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.9 g of compound sub1-D-1. (Yield: 67%, MS: [M+H] + =586)

[0612]

[0613] Under a nitrogen atmosphere, compound sub1-D-1 (15 g, 25.6 mmol) and compound sub5 (3.1 g, 25.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.6 g, 76.8 mmol) was dissolved in 32 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.3 g of compound 1-22. (Yield: 64%, MS: [M+H] + =628)

[0614] Preparation Example 1-23

[0615]

[0616] Compound 1-D (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20 g of compound sub1-D-2. (Yield: 76%, MS: [M+H] + =434)

[0617]

[0618] Under a nitrogen atmosphere, compound sub1-D-2 (15 g, 34.6 mmol) and compound sub16 (9.1 g, 34.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of compound 1-23. (Yield: 66%, MS: [M+H] + =616)

[0619] Preparation Example 1-24

[0620]

[0621] Compound 1-D (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound sub1-D-3. (Yield: 67%, MS: [M+H] + =510)

[0622]

[0623] Under a nitrogen atmosphere, compound sub1-D-3 (15 g, 29.4 mmol) and compound sub17 (7.7 g, 29.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound 1-24. (Yield: 61%, MS: [M+H] + =692)

[0624] Preparation Example 1-25

[0625]

[0626] Compound 1-D (15 g, 60.9 mmol) and compound Trz15 (21.8 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.3 g of compound sub1-D-4. (Yield: 67%, MS: [M+H] + =524)

[0627]

[0628] Under a nitrogen atmosphere, compound sub1-D-4 (15 g, 28.6 mmol) and compound sub10 (4.9 g, 28.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.7 g of compound 1-25. (Yield: 61%, MS: [M+H] + =616)

[0629] Preparation Example 1-26

[0630]

[0631] Under a nitrogen atmosphere, compound sub1-D-3 (15 g, 29.4 mmol) and compound sub18 (6.2 g, 29.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-26. (Yield: 76%, MS: [M+H] + =642)

[0632] Preparation Example 1-27

[0633]

[0634] Compound 1-D (15 g, 60.9 mmol) and compound Trz16 (27 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.1 g of compound sub1-D-5. (Yield: 73%, MS: [M+H] + =610)

[0635]

[0636] Under a nitrogen atmosphere, compound sub1-D-5 (15 g, 24.6 mmol) and compound sub9 (5.2 g, 24.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.2 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-27. (Yield: 70%, MS: [M+H] + =742)

[0637] Preparation Example 1-28

[0638]

[0639] Compound 1-D (15 g, 60.9 mmol) and compound Trz13 (24 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound sub1-D-6. (Yield: 61%, MS: [M+H] + =560)

[0640]

[0641] Under a nitrogen atmosphere, compound sub1-D-6 (15 g, 26.8 mmol) and compound sub10 (4.6 g, 26.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-28. (Yield: 70%, MS: [M+H] + =652)

[0642] Preparation Example 1-29

[0643]

[0644] Under a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.1 g of compound sub1-E-1. (Yield: 65%, MS: [M+H] + =434)

[0645]

[0646] Under a nitrogen atmosphere, compound sub1-E-1 (15 g, 34.6 mmol) and compound sub2 (9.4 g, 34.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5 g of compound 1-29. (Yield: 67%, MS: [M+H] + =626)

[0647] Preparation Example 1-30

[0648]

[0649] Compound 1-E (15 g, 60.9 mmol) and compound Trz9 (24 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.9 g of compound sub1-E-2. (Yield: 79%, MS: [M+H] + =560)

[0650]

[0651] Under a nitrogen atmosphere, compound sub1-E-2 (15 g, 26.8 mmol) and compound sub19 (7 g, 26.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.9 g of compound 1-30. (Yield: 80%, MS: [M+H] + =742)

[0652] Preparation Example 1-31

[0653]

[0654] Compound 1-E (15 g, 60.9 mmol) and compound Trz17 (22.4 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.3 g of compound sub1-E-3. (Yield: 78%, MS: [M+H] + =534)

[0655]

[0656] Under a nitrogen atmosphere, compound sub1-E-3 (15 g, 28.1 mmol) and compound sub20 (7.8 g, 28.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.6 g, 84.3 mmol) was dissolved in 35 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8 g of compound 1-31. (Yield: 72%, MS: [M+H] + =732)

[0657] Preparation Example 1-32

[0658]

[0659] Under a nitrogen atmosphere, compound sub1-E-1 (15 g, 34.6 mmol) and compound sub21 (7.7 g, 34.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-32. (Yield: 65%, MS: [M+H] + =576)

[0660] Preparation Example 1-33

[0661]

[0662] Compound 1-E (15 g, 60.9 mmol) and compound Trz15 (21.8 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.5 g of compound sub1-E-4. (Yield: 80%, MS: [M+H] + =524)

[0663]

[0664] Under a nitrogen atmosphere, compound sub1-E-4 (15 g, 28.6 mmol) and compound sub10 (4.9 g, 28.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of compound 1-33. (Yield: 60%, MS: [M+H] + =616)

[0665] Preparation Example 1-34

[0666]

[0667] Compound 1-E (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g of compound sub1-E-5. (Yield: 60%, MS: [M+H] + =484)

[0668]

[0669] Under a nitrogen atmosphere, compound sub1-E-5 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of compound 1-34. (Yield: 60%, MS: [M+H] + =616)

[0670] Preparation Example 1-35

[0671]

[0672] Compound 1-E (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7 g of compound sub1-E-6. (Yield: 70%, MS: [M+H] + =510)

[0673]

[0674] Under a nitrogen atmosphere, compound sub1-E-6 (15 g, 29.4 mmol) and compound sub22 (7.7 g, 29.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of compound 1-35. (Yield: 72%, MS: [M+H] + =692)

[0675] Preparation Example 1-36

[0676]

[0677] Under a nitrogen atmosphere, compound sub1-E-5 (15 g, 31 mmol) and compound sub23 (8.1 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound 1-36. (Yield: 60%, MS: [M+H] + =666)

[0678] Preparation Example 1-37

[0679]

[0680] Under a nitrogen atmosphere, compound sub1-E-5 (15 g, 31 mmol) and compound sub10 (5.3 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of compound 1-37. (Yield: 79%, MS: [M+H] + =576)

[0681] Preparation Example 1-38

[0682]

[0683] Compound 1-E (15 g, 60.9 mmol) and compound Trz18 (27 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.1 g of compound sub1-E-7. (Yield: 65%, MS: [M+H] + =610)

[0684]

[0685] Under a nitrogen atmosphere, compound sub1-E-7 (15 g, 24.6 mmol) and compound sub5 (3 g, 24.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.2 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1 g of compound 1-38. (Yield: 63%, MS: [M+H] + =652)

[0686] Preparation Example 1-39

[0687]

[0688] Compound 1-E (15 g, 60.9 mmol) and compound Trz13 (24 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2 g of compound sub1-E-8. (Yield: 77%, MS: [M+H] + =560)

[0689]

[0690] Under a nitrogen atmosphere, compound sub1-E-8 (15 g, 26.8 mmol) and compound sub5 (3.3 g, 26.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9 g of compound 1-39. (Yield: 68%, MS: [M+H] + =602)

[0691] Preparation Example 1-40

[0692]

[0693] Compound 1-F (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.2 g of compound sub1-F-1. (Yield: 73%, MS: [M+H] + =434)

[0694]

[0695] Compound 1-F-1 (15 g, 34.6 mmol) and compound sub6 (8.5 g, 34.6 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (14.3 g, 103.7 mmol) was then dissolved in 43 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of compound 1-40. (Yield: 71%, MS: [M+H] + =600)

[0696] Preparation Example 1-41

[0697]

[0698] Compound 1-F (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1 g of compound sub1-F-2. (Yield: 68%, MS: [M+H] + =510)

[0699]

[0700] Under a nitrogen atmosphere, compound sub1-F-2 (15 g, 29.4 mmol) and compound sub1 (5.8 g, 29.4 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 1-41. (Yield: 77%, MS: [M+H] + =628)

[0701] Preparation Example 1-42

[0702]

[0703] Under a nitrogen atmosphere, compound Trz7 (15 g, 31.9 mmol) and compound sub9 (6.8 g, 31.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (13.2 g, 95.8 mmol) was then dissolved in 40 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of compound 1-42. (Yield: 79%, MS: [M+H] + =602)

[0704] Preparation Example 1-43

[0705]

[0706] Under a nitrogen atmosphere, compound Trz16 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound 1-43. (Yield: 77%, MS: [M+H] + =576)

[0707] Preparation Example 1-44

[0708]

[0709] Under a nitrogen atmosphere, compound Trz4 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 1-44. (Yield: 73%, MS: [M+H] + =576)

[0710] Preparation Example 1-45

[0711]

[0712] Under a nitrogen atmosphere, compound Trz1' (15 g, 35.7 mmol) and compound sub9 (7.6 g, 35.7 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in 44 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-45. (Yield: 62%, MS: [M+H] + =552)

[0713] Preparation Example 1-46

[0714]

[0715] Under a nitrogen atmosphere, compound Trz19 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of compound 1-46. (Yield: 70%, MS: [M+H] + =576)

[0716] Preparation Example 1-47

[0717]

[0718] Under a nitrogen atmosphere, compound Trz20 (15 g, 35.9 mmol) and compound sub9 (7.6 g, 35.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 45 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound 1-47. (Yield: 76%, MS: [M+H] + =550)

[0719] Preparation Example 1-48

[0720]

[0721] Compound Trz3 (15 g, 47.2 mmol) and compound sub24 (9.7 g, 47.2 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (19.6 g, 141.6 mmol) was dissolved in 59 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.5 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of compound sub1-G-1. (Yield: 62%, MS: [M+H] + =444)

[0722]

[0723] Under a nitrogen atmosphere, compound sub1-G-1 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of compound 1-48. (Yield: 78%, MS: [M+H] + =576)

[0724] Preparation Example 1-49

[0725]

[0726] Compound Trz15 (15 g, 41.9 mmol) and compound sub25 (8.7 g, 41.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (17.4 g, 125.8 mmol) was then dissolved in 52 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6 g of compound sub1-G-2. (Yield: 62%, MS: [M+H] + =484)

[0727]

[0728] Under a nitrogen atmosphere, compound sub1-G-2 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound 1-49. (Yield: 72%, MS: [M+H] + =616)

[0729] Preparation Example 1-50

[0730]

[0731] Compound Trz21 (15 g, 36.8 mmol) and compound sub26 (5.8 g, 36.8 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (15.2 g, 110.3 mmol) was then dissolved in 46 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound sub1-G-3. (Yield: 72%, MS: [M+H] + =484)

[0732]

[0733] Under a nitrogen atmosphere, compound sub1-G-3 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of compound 1-50. (Yield: 69%, MS: [M+H] + =616)

[0734] Preparation Example 1-51

[0735]

[0736] Compound Trz16 (15 g, 33.8 mmol) and compound sub27 (5.3 g, 33.8 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound sub1-G-4. (Yield: 76%, MS: [M+H] + =520)

[0737]

[0738] Under a nitrogen atmosphere, compound sub1-G-4 (15 g, 28.8 mmol) and compound sub9 (6.1 g, 28.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12 g, 86.5 mmol) was dissolved in 36 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-51. (Yield: 71%, MS: [M+H] + =652)

[0739] Preparation Example 1-52

[0740]

[0741] Compound Trz22 (15 g, 36.8 mmol) and compound sub28 (5.8 g, 36.8 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (15.2 g, 110.3 mmol) was then dissolved in 46 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound sub1-G-5. (Yield: 72%, MS: [M+H] + =484)

[0742]

[0743] Under a nitrogen atmosphere, compound sub1-G-5 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of compound 1-52. (Yield: 68%, MS: [M+H] + =616)

[0744] Preparation Example 1-53

[0745]

[0746] Compound Trz23 (15 g, 34.6 mmol) and compound sub27 (5.4 g, 34.6 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3 g of compound sub1-G-6. (Yield: 64%, MS: [M+H] + =510)

[0747]

[0748] Under a nitrogen atmosphere, compound sub1-G-6 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of compound 1-53. (Yield: 68%, MS: [M+H]+=616)

[0749] Preparation Example 1-54

[0750]

[0751] Under a nitrogen atmosphere, compound sub1-G-1 (15 g, 33.8 mmol) and compound 1-E (8.3 g, 33.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of compound sub1-E-9. (Yield: 70%, MS: [M+H] + =610)

[0752]

[0753] Under a nitrogen atmosphere, compound sub1-E-9 (15 g, 24.6 mmol) and compound sub5 (3 g, 24.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.2 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-54. (Yield: 76%, MS: [M+H] + =652)

[0754] Preparation Example 1-55

[0755]

[0756] Compound Trz2 (15 g, 56 mmol) and compound sub24 (11.6 g, 56 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (23.2 g, 168.1 mmol) was then dissolved in 70 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6 g of compound sub1-G-7. (Yield: 71%, MS: [M+H] + =394)

[0757]

[0758] Under a nitrogen atmosphere, compound sub1-G-7 (15 g, 38.1 mmol) and compound 1-B (9.4 g, 38.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound sub1-B-7. (Yield: 65%, MS: [M+H] + =560)

[0759]

[0760] Under a nitrogen atmosphere, compound sub1-B-7 (15 g, 26.8 mmol) and compound sub5 (3.3 g, 26.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of compound 1-55. (Yield: 80%, MS: [M+H] + =602)

[0761] Preparation Example 1-56

[0762]

[0763] Compound Trz24 (15 g, 38.1 mmol) and compound sub25 (9.4 g, 38.1 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (15.8 g, 114.3 mmol) was then dissolved in 47 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound sub1-G-8. (Yield: 65%, MS: [M+H] + =560)

[0764]

[0765] Under a nitrogen atmosphere, compound sub1-G-8 (15 g, 30 mmol) and compound sub9 (6.4 g, 30 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.4 g, 90 mmol) was dissolved in 37 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound 1-56. (Yield: 71%, MS: [M+H] + =632)

[0766] Preparation Example 1-57

[0767]

[0768] Compound Trz25 (15 g, 41.9 mmol) and compound sub24 (8.7 g, 41.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (17.4 g, 125.8 mmol) was then dissolved in 52 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound sub1-G-9. (Yield: 61%, MS: [M+H] + =484)

[0769]

[0770] Under a nitrogen atmosphere, compound sub1-G-9 (15 g, 31 mmol) and compound 1-F (7.6 g, 31 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound sub1-F-3. (Yield: 62%, MS: [M+H] + =650)

[0771]

[0772] Under a nitrogen atmosphere, compound sub1-F-3 (15 g, 23.1 mmol) and compound sub5 (2.8 g, 23.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.6 g, 69.2 mmol) was dissolved in 29 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.2 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-57. (Yield: 80%, MS: [M+H] + =692)

[0773] Preparation Example 1-58

[0774]

[0775] Compound Trz26 (15 g, 33.8 mmol) and compound sub26 (5.3 g, 33.8 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5 g of compound sub1-G-10. (Yield: 60%, MS: [M+H] + =520)

[0776]

[0777] Under a nitrogen atmosphere, compound sub1-G-10 (15 g, 28.8 mmol) and compound 1-D (7.1 g, 28.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12 g, 86.5 mmol) was dissolved in 36 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound sub1-D-7. (Yield: 76%, MS: [M+H] + =686)

[0778]

[0779] Under a nitrogen atmosphere, compound sub1-D-7 (15 g, 21.9 mmol) and compound sub5 (2.7 g, 21.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.1 g, 65.6 mmol) was dissolved in 27 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.2 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9 g of compound 1-58. (Yield: 62%, MS: [M+H] + =728)

[0780] Preparation Example 1-59

[0781]

[0782] Compound Trz15 (15 g, 41.9 mmol) and compound sub24 (8.7 g, 41.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (17.4 g, 125.8 mmol) was then dissolved in 52 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound sub1-G-11. (Yield: 61%, MS: [M+H] + =484)

[0783]

[0784] Under a nitrogen atmosphere, compound sub1-G-11 (15 g, 28.8 mmol) and compound 1-F (7.1 g, 28.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (12 g, 86.5 mmol) was dissolved in 36 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.3 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound sub1-F-4. (Yield: 76%, MS: [M+H] + =686)

[0785]

[0786] Under a nitrogen atmosphere, compound sub1-F-4 (15 g, 23.1 mmol) and compound sub5 (2.8 g, 23.1 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.6 g, 69.2 mmol) was dissolved in 29 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1 g of compound 1-59. (Yield: 76%, MS: [M+H] + =692)

[0787] Preparation Example 1-60

[0788]

[0789] Compound Trz12 (15 g, 41.9 mmol) and compound sub28 (6.6 g, 41.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (17.4 g, 125.8 mmol) was then dissolved in 52 ml of water and added thereto, the mixture was thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1 g of compound sub1-G-12. (Yield: 61%, MS: [M+H] + =434)

[0790]

[0791] Under a nitrogen atmosphere, compound sub1-G-12 (15 g, 34.6 mmol) and compound 1-D (8.5 g, 34.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of compound sub1-D-8. (Yield: 79%, MS: [M+H] + =500)

[0792]

[0793] Under a nitrogen atmosphere, compound sub1-D-8 (15 g, 25 mmol) and compound sub10 (4.3 g, 25 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.4 g, 75 mmol) was dissolved in 31 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.1 g, 0.2 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of compound 1-60. (Yield: 77%, MS: [M+H] + =692)

[0794] Preparation Example 1-61

[0795]

[0796] Under a nitrogen atmosphere, compound Trz27 (15 g, 31.9 mmol) and compound sub9 (6.8 g, 31.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (13.2 g, 95.8 mmol) was then dissolved in 40 ml of water and added thereto, the mixture was thoroughly stirred, and tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.3 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10 g of compound 1-61. (Yield: 52%, MS: [M+H] + =602)

[0797] Preparation Example 1-62

[0798]

[0799] Under a nitrogen atmosphere, compound Trz28 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (14 g, 101.4 mmol) was then dissolved in 42 ml of water and added thereto, the mixture was thoroughly stirred, and tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.3 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-62. (Yield: 63%, MS: [M+H] + =576)

[0800] Preparation Example 1-63

[0801]

[0802] Under a nitrogen atmosphere, compound Trz29 (15 g, 31.9 mmol) and compound sub9 (6.8 g, 31.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (13.2 g, 95.8 mmol) was dissolved in 40 ml of water and added thereto, the mixture was fully stirred, and then tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.3 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7 g of compound 1-63. (Yield: 66%, MS: [M+H] + =602)

[0803] Preparation Example 1-64

[0804]

[0805] Under a nitrogen atmosphere, compound Trz30 (15 g, 31.9 mmol) and compound sub9 (6.8 g, 31.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (13.2 g, 95.8 mmol) was dissolved in 40 ml of water and added thereto, the mixture was fully stirred, and then tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.3 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of compound 1-64. (Yield: 69%, MS: [M+H] + =602)

[0806] Preparation Example 1-65

[0807]

[0808] Under a nitrogen atmosphere, compound Trz31 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 ml of water and added thereto, the mixture was fully stirred, and then tetrakis(triphenylphosphine)palladium(0) (0.4 g, 0.3 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of compound 1-65. (Yield: 75%, MS: [M+H] + =576)

[0809] Preparation Example 1-66

[0810]

[0811] Compound 1-B (15 g, 60.9 mmol) and compound Trz30 (28.6 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then tetrakis(triphenylphosphine)palladium(0) (0.7 g, 0.6 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.3 g of compound sub1-B-7. (Yield: 50%, MS: [M+H] + =636)

[0812]

[0813] Under a nitrogen atmosphere, compound sub1-B-7 (15 g, 23.6 mmol) and compound sub5 (2.9 g, 23.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (9.8 g, 70.7 mmol) was dissolved in 29 ml of water and added thereto, the mixture was fully stirred, and then tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.2 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.5 g of compound 1-66. (Yield: 53%, MS: [M+H] + =678)

[0814] Preparation Example 1-67

[0815]

[0816] Compound 1-C (15 g, 60.9 mmol) and compound Trz32 (25.6 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then tetrakis(triphenylphosphine)palladium(0) (0.7 g, 0.6 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.9 g of compound sub1-C-8. (Yield: 70%, MS: [M+H] + =586)

[0817]

[0818] Under a nitrogen atmosphere, compound sub1-C-8 (15 g, 25.6 mmol) and compound sub5 (3.1 g, 25.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.6 g, 76.8 mmol) was dissolved in 32 ml of water and added thereto, the mixture was thoroughly stirred, and then tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of compound 1-67. (Yield: 66%, MS: [M+H] + =628)

[0819] Preparation Example 1-68

[0820]

[0821] Compound 1-D (15 g, 60.9 mmol) and compound Trz33 (27 g, 60.9 mmol) were added to 300 ml of THF under a nitrogen atmosphere, and the mixture was stirred and refluxed. Potassium carbonate (25.2 g, 182.6 mmol) was then dissolved in 76 ml of water and added thereto, the mixture was thoroughly stirred, and then tetrakis(triphenylphosphine)palladium(0) (0.7 g, 0.6 mmol) was added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 29.7 g of compound sub1-D-7. (Yield: 80%, MS: [M+H] + =610)

[0822]

[0823] Under a nitrogen atmosphere, compound sub1-D-7 (15 g, 24.6 mmol) and compound sub5 (3 g, 24.6 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 ml of water and added thereto, the mixture was thoroughly stirred, and then tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.2 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of compound 1-68. (Yield: 70%, MS: [M+H] + =652)

[0824] Preparation Example 1-69

[0825]

[0826] Under a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz34 (24 g, 60.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and added thereto, the mixture was fully stirred, and then tetrakis(triphenylphosphine)palladium(0) (0.7 g, 0.6 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.8 g of compound sub1-E-9. (Yield: 64%, MS: [M+H] + =560)

[0827]

[0828] Under a nitrogen atmosphere, compound sub1-E-9 (15 g, 26.8 mmol) and compound sub5 (3.3 g, 26.8 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water and added thereto, the mixture was fully stirred, and then tetrakis(triphenylphosphine)palladium(0) (0.3 g, 0.3 mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, and then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10 g of compound 1-69. (Yield: 62%, MS: [M+H] + =602)

[0829] Preparation Example 2-1

[0830]

[0831] Under a nitrogen atmosphere, compound 2-A (15g, 57.1mmol) and compound amine 1 (29.5g, 59.9mmol) were added to 300ml THF, and the mixture was stirred and refluxed. Then, potassium carbonate (23.7g, 171.3mmol) was dissolved in 71ml water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3g, 0.6mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9g of compound 2-1. (yield: 31%, MS: [M+H] + =674)

[0832] Preparation Example 2-2

[0833]

[0834] Under a nitrogen atmosphere, compound 2-A (15 g, 57.1 mmol) and compound amine 2 (31.3 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3 g of compound 2-2. (yield: 38%, MS: [M+H] + =704)

[0835] Preparation Example 2-3

[0836]

[0837] Under a nitrogen atmosphere, compound 2-A (15g, 57.1mmol) and compound amine 3 (26.5g, 59.9mmol) were added to 300ml THF, and the mixture was stirred and refluxed. Then, potassium carbonate (23.7g, 171.3mmol) was dissolved in 71ml water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3g, 0.6mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4g of compound 2-3. (yield: 32%, MS: [M+H] + =624)

[0838] Preparation Example 2-4

[0839]

[0840] Under a nitrogen atmosphere, compound 2-A (15 g, 57.1 mmol) and compound amine 4 (35.6 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of compound 2-4. (yield: 33%, MS: [M+H] + =776)

[0841] Preparation Example 2-5

[0842]

[0843] Under a nitrogen atmosphere, compound 2-A (15 g, 57.1 mmol) and compound amine 5 (35.6 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound 2-5. (yield: 34%, MS: [M+H] + =776)

[0844] Preparation Example 2-6

[0845]

[0846] Under a nitrogen atmosphere, compound 2-B (15g, 57.1mmol) and compound amine 6 (24.9g, 59.9mmol) were added to 300ml THF, and the mixture was stirred and refluxed. Then, potassium carbonate (23.7g, 171.3mmol) was dissolved in 71ml water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3g, 0.6mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.6g of compound 2-6. (yield: 72%, MS: [M+H] + =598)

[0847] Preparation Example 2-7

[0848]

[0849] Under a nitrogen atmosphere, compound 2-B (15g, 57.1mmol) and compound amine 7 (26.5g, 59.9mmol) were added to 300ml THF, and the mixture was stirred and refluxed. Then, potassium carbonate (23.7g, 171.3mmol) was dissolved in 71ml water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3g, 0.6mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.7g of compound 2-7. (Yield: 75%, MS: [M+H] + =624)

[0850] Preparation Example 2-8

[0851]

[0852] Under a nitrogen atmosphere, compound 2-B (15g, 57.1mmol) and compound amine 8 (27.3g, 59.9mmol) were added to 300ml THF, and the mixture was stirred and refluxed. Then, potassium carbonate (23.7g, 171.3mmol) was dissolved in 71ml water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3g, 0.6mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.6g of compound 2-8. (yield: 65%, MS: [M+H] + =638)

[0853] Preparation Example 2-9

[0854]

[0855] Under a nitrogen atmosphere, compound 2-B (15g, 57.1mmol) and compound amine 9 (22.7g, 59.9mmol) were added to 300ml THF, and the mixture was stirred and refluxed. Then, potassium carbonate (23.7g, 171.3mmol) was dissolved in 71ml water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3g, 0.6mmol) was added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.8g of compound 2-9. (yield: 68%, MS: [M+H] + =562)

[0856] Preparation Example 2-10

[0857]

[0858] Under a nitrogen atmosphere, compound 2-B (15g, 57.1mmol) and compound amine 10 (29.1g, 59.9mmol) were added to 300ml THF, and the mixture was stirred and refluxed. Then, potassium carbonate (23.7g, 171.3mmol) was dissolved in 71ml water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3g, 0.6mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27g of compound 2-10. (yield: 71%, MS: [M+H] + =668)

[0859] Preparation Example 2-11

[0860]

[0861] Under a nitrogen atmosphere, compound 2-B (15g, 57.1mmol) and compound amine 11 (32.5g, 59.9mmol) were added to 300ml THF, and the mixture was stirred and refluxed. Then, potassium carbonate (23.7g, 171.3mmol) was dissolved in 71ml water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3g, 0.6mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 33g of compound 2-11. (yield: 80%, MS: [M+H] + =724)

[0862] Preparation Example 2-12

[0863]

[0864] Under a nitrogen atmosphere, compound 2-B (15g, 57.1mmol) and compound amine 12 (38.6g, 59.9mmol) were added to 300ml THF, and the mixture was stirred and refluxed. Then, potassium carbonate (23.7g, 171.3mmol) was dissolved in 71ml water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3g, 0.6mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 33.5g of compound 2-12. (Yield: 71%, MS: [M+H] + =826)

[0865] Preparation Example 2-13

[0866]

[0867] Under a nitrogen atmosphere, compound 2-B (15 g, 57.1 mmol) and compound amine 13 (32.5 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (23.7 g, 171.3 mmol) was dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.3 g of compound 2-13. (Yield: 66%, MS: [M+H] + =724)

[0868] Preparation Example 2-14

[0869]

[0870] Under a nitrogen atmosphere, compound 2-B (15g, 57.1mmol) and compound amine 14 (34g, 59.9mmol) were added to 300ml THF, and the mixture was stirred and refluxed. Then, potassium carbonate (23.7g, 171.3mmol) was dissolved in 71ml water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3g, 0.6mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 30.8g of compound 2-14. (Yield: 72%, MS: [M+H] + =750)

[0871] Preparation Example 2-15

[0872]

[0873] Under a nitrogen atmosphere, compound 2-C (15 g, 57.1 mmol) and compound amine 15 (26.5 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.5 g of compound 2-15. (yield: 80%, MS: [M+H] + =624)

[0874] Preparation Example 2-16

[0875]

[0876] Under a nitrogen atmosphere, compound 2-C (15 g, 57.1 mmol) and compound amine 16 (29.5 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.8 g of compound 2-16. (yield: 62%, MS: [M+H] + =674)

[0877] Preparation Example 2-17

[0878]

[0879] Under a nitrogen atmosphere, compound 2-C (15 g, 57.1 mmol) and compound amine 17 (27.2 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.7 g of compound 2-17. (Yield: 68%, MS: [M+H] + =637)

[0880] Preparation Example 2-18

[0881]

[0882] Under a nitrogen atmosphere, compound 2-C (15 g, 57.1 mmol) and compound amine 18 (28.1 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.3 g of compound 2-18. (Yield: 76%, MS: [M+H] + =652)

[0883] Preparation Example 2-19

[0884]

[0885] Under a nitrogen atmosphere, compound 2-C (15 g, 57.1 mmol) and compound amine 19 (30.7 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 30.5 g of compound 2-19. (Yield: 77%, MS: [M+H] + =694)

[0886] Preparation Example 2-20

[0887]

[0888] Under a nitrogen atmosphere, compound 2-C (15 g, 57.1 mmol) and compound amine 20 (25.7 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.4 g of compound 2-20. (yield: 70%, MS: [M+H] + =612)

[0889] Preparation Example 2-21

[0890]

[0891] Under a nitrogen atmosphere, compound 2-C (15 g, 57.1 mmol) and compound amine 21 (29.5 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.4 g of compound 2-21. (yield: 66%, MS: [M+H] + =674)

[0892] Preparation Example 2-22

[0893]

[0894] Under a nitrogen atmosphere, compound 2-C (15 g, 57.1 mmol) and compound amine 22 (38.6 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 30.2 g of compound 2-22. (yield: 64%, MS: [M+H] + =826)

[0895] Preparation Example 2-23

[0896]

[0897] Under a nitrogen atmosphere, compound 2-C (15 g, 57.1 mmol) and compound amine 23 (38.6 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 33.9 g of compound 2-23. (Yield: 72%, MS: [M+H] + =826)

[0898] Preparation Example 2-24

[0899]

[0900] Under a nitrogen atmosphere, compound 2-C (15g, 57.1mmol) and compound amine 24 (29.5g, 59.9mmol) are added to 300ml THF, and the mixture is stirred and refluxed. Then, potassium carbonate (23.7g, 171.3mmol) is dissolved in 71ml water and added thereto, the mixture is fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3g, 0.6mmol) is added. After reacting for 8 hours, the reaction mixture is cooled to room temperature, the organic layer and the aqueous layer are separated, and the organic layer is then distilled. It is redissolved in chloroform, washed twice with water, and then the organic layer is separated, anhydrous magnesium sulfate is added thereto, stirred, then filtered, and the filtrate is distilled under reduced pressure. The concentrated compound is purified by silica gel column chromatography to prepare 23.8g of compound 2-24. (yield: 62%, MS: [M+H] + = 674)

[0901] Preparation Example 2-25

[0902]

[0903] Under a nitrogen atmosphere, compound 2-D (15 g, 57.1 mmol) and compound amine 25 (31 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 29.5 g of compound 2-25. (Yield: 74%, MS: [M+H] + =700)

[0904] Preparation Example 2-26

[0905]

[0906] Under a nitrogen atmosphere, compound 2-D (15 g, 57.1 mmol) and compound amine 26 (30.1 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 9 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.4 g of compound 2-26. (yield: 65%, MS: [M+H] + =684)

[0907] Preparation Example 2-27

[0908]

[0909] Under a nitrogen atmosphere, compound 2-D (15 g, 57.1 mmol) and compound amine 27 (28.9 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 29.2 g of compound 2-27. (Yield: 77%, MS: [M+H] + =664)

[0910] Preparation Example 2-28

[0911]

[0912] Under a nitrogen atmosphere, compound 2-D (15 g, 57.1 mmol) and compound amine 28 (26.7 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.8 g of compound 2-28. (yield: 61%, MS: [M+H] + =628)

[0913] Preparation Example 2-29

[0914]

[0915] Under a nitrogen atmosphere, compound 2-D (15 g, 57.1 mmol) and compound amine 29 (31 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 31.9 g of compound 2-29. (yield: 80%, MS: [M+H] + =700)

[0916] Preparation Example 2-30

[0917]

[0918] Under a nitrogen atmosphere, compound 2-D (15 g, 57.1 mmol) and compound amine 30 (37 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 32.4 g of compound 2-30. (yield: 71%, MS: [M+H] + =800)

[0919] Preparation Example 2-31

[0920]

[0921] Under a nitrogen atmosphere, compound 2-D (15 g, 57.1 mmol) and compound amine 31 (32.5 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 29.3 g of compound 2-31. (Yield: 71%, MS: [M+H] + =724)

[0922] Preparation Example 2-32

[0923]

[0924] Under a nitrogen atmosphere, compound 2-E (15 g, 57.1 mmol) and compound amine 32 (21.9 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.1 g of compound 2-32. (Yield: 61%, MS: [M+H] + =548)

[0925] Preparation Example 2-33

[0926]

[0927] Under a nitrogen atmosphere, compound 2-E (15 g, 57.1 mmol) and compound amine 33 (35.6 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (23.7 g, 171.3 mmol) was dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 31.9 g of compound 2-33. (Yield: 72%, MS: [M+H] + =776)

[0928] Preparation Example 2-34

[0929]

[0930] Under a nitrogen atmosphere, compound 2-E (15 g, 57.1 mmol) and compound amine 34 (28.3 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Then, potassium carbonate (23.7 g, 171.3 mmol) was dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and then bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and then the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25 g of compound 2-34. (yield: 67%, MS: [M+H] + =654)

[0931] Preparation Example 2-35

[0932]

[0933] Under a nitrogen atmosphere, compound 2-E (15 g, 57.1 mmol) and compound amine 35 (31.8 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.4 g of compound 2-35. (yield: 65%, MS: [M+H] + =713)

[0934] Preparation Example 2-36

[0935]

[0936] Under a nitrogen atmosphere, compound 2-E (15 g, 57.1 mmol) and compound amine 36 (24.3 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1 g of compound 2-36. (yield: 63%, MS: [M+H] + =588)

[0937] Preparation Example 2-37

[0938]

[0939] Under a nitrogen atmosphere, compound 2-E (15 g, 57.1 mmol) and compound amine 37 (25.7 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.5 g of compound 2-37. (Yield: 73%, MS: [M+H] + =612)

[0940] Preparation Example 2-38

[0941]

[0942] Under a nitrogen atmosphere, compound 2-E (15 g, 57.1 mmol) and compound amine 38 (26.5 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.1 g of compound 2-38. (yield: 65%, MS: [M+H] + =624)

[0943] Preparation Example 2-39

[0944]

[0945] Under a nitrogen atmosphere, compound 2-E (15 g, 57.1 mmol) and compound amine 39 (32.5 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.2 g of compound 2-39. (Yield: 61%, MS: [M+H] + =724)

[0946] Preparation Example 2-40

[0947]

[0948] Under a nitrogen atmosphere, compound 2-F (15 g, 57.1 mmol) and compound amine 40 (32.5 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of compound 2-40. (yield: 63%, MS: [M+H] + =724)

[0949] Preparation Example 2-41

[0950]

[0951] Under a nitrogen atmosphere, compound 2-F (15 g, 57.1 mmol) and compound amine 41 (27.9 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 11 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.6 g of compound 2-41. (Yield: 72%, MS: [M+H] + =648)

[0952] Preparation Example 2-42

[0953]

[0954] Under a nitrogen atmosphere, compound 2-F (15 g, 57.1 mmol) and compound amine 42 (27.3 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 29.1 g of compound 2-42. (yield: 80%, MS: [M+H] + =638)

[0955] Preparation Example 2-43

[0956]

[0957] Under a nitrogen atmosphere, compound 2-F (15 g, 57.1 mmol) and compound amine 43 (26.7 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.3 g of compound 2-43. (Yield: 65%, MS: [M+H] + =628)

[0958] Preparation Example 2-44

[0959]

[0960] Under a nitrogen atmosphere, compound 2-F (15 g, 57.1 mmol) and compound amine 44 (26.5 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 10 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was then separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of compound 2-44. (Yield: 73%, MS: [M+H] + =624)

[0961] Preparation Example 2-45

[0962]

[0963] Under a nitrogen atmosphere, compound 2-F (15 g, 57.1 mmol) and compound amine 45 (32.5 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 30.6 g of compound 2-45. (yield: 74%, MS: [M+H] + =724)

[0964] Preparation Example 2-46

[0965]

[0966] Under a nitrogen atmosphere, compound 2-F (15 g, 57.1 mmol) and compound amine 46 (31 g, 59.9 mmol) were added to 300 ml of THF, and the mixture was stirred and refluxed. Potassium carbonate (23.7 g, 171.3 mmol) was then dissolved in 71 ml of water and added thereto, the mixture was fully stirred, and bis(tri-tert-butylphosphine)palladium (0) (0.3 g, 0.6 mmol) was then added. After reacting for 8 hours, the reaction mixture was cooled to room temperature, the organic layer and the aqueous layer were separated, and the organic layer was then distilled. It was redissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, then filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.6 g of compound 2-46. (yield: 64%, MS: [M+H] + =700)

[0967] [Example]

[0968] Example 1

[0969] It is coated with a thickness of The glass substrate of ITO (indium tin oxide) film is put into the distilled water that comprises the detergent that is dissolved therein, and washes by ultrasonic wave.In this case, the detergent used is the product that can be commercially available from Fisher Co., and distilled water is the distilled water that is filtered twice by using the filter that can be commercially available from Millipore Co..ITO was washed 30 minutes, then repeated twice ultrasonic wave washing 10 minutes by using distilled water.After completing with distilled water washing, substrate is carried out ultrasonic wave washing with isopropyl alcohol, acetone and methanol solvent, drying, after this is transferred to plasma cleaning machine.Then, substrate is cleaned 5 minutes with oxygen plasma, is then transferred to vacuum evaporator.

[0970] On the thus prepared ITO transparent electrode, the following compound HI-1 was formed into The hole injection layer was prepared by vacuum deposition of the following compound HT-1 to form a film having a thickness of Then, the following compound EB-1 was vacuum deposited on the hole transport layer. Then, the previously prepared compound 1-2, compound 2-1 and compound Dp-7 were vacuum deposited in a weight ratio of 49:49:2 in the film deposited with EB-1 to form a film with a thickness of The following compound HB-1 was vacuum deposited on the luminescent layer. Then, the following compound ET-1 and the following compound LiQ were vacuum deposited on the hole blocking layer at a weight ratio of 2:1 to form a film with a thickness of The electron injection and transport layer is formed by sequentially depositing lithium fluoride (LiF) and aluminum on the electron injection and transport layer to have and thickness, thereby forming a cathode.

[0971]

[0972] During the above process, the deposition rate of the organic material is kept at to The deposition rates of lithium fluoride and aluminum at the cathode were kept at and The vacuum level during deposition was maintained at 2 × 10 -7 Up to 5×10 -6 support, thereby manufacturing an organic light-emitting device.

[0973] Example 2 to Example 200

[0974] An organic light-emitting device was manufactured in the same manner as in Example 1, except that in the organic light-emitting device of Example 1, the first host compound and the second host compound described in Tables 1 to 5 were co-deposited at a 1:1 ratio and used instead of Compound 1-2 and / or Compound 2-1.

[0975] Comparative Examples 1 to 60

[0976] An organic light-emitting device was manufactured in the same manner as in Example 1, except that in the organic light-emitting device of Example 1, the first host compound and the second host compound described in Tables 6 and 7 were co-deposited at a ratio of 1:1 instead of Compound 1-2 and / or Compound 2-1. The structures of Compounds B-1 to B-12 in Tables 6 and 7 are as follows.

[0977]

[0978] Comparative Examples 61 to 132

[0979] An organic light-emitting device was manufactured in the same manner as in Example 1, except that in the organic light-emitting device of Example 1, the first host compound and the second host compound described in Tables 8 and 9 were co-deposited at a 1:1 ratio instead of Compound 1-2 and / or Compound 2-1. The structures of Compounds C-1 to C-9 in Tables 8 and 9 are as follows.

[0980]

[0981] [Experimental example]

[0982] The driving voltage and efficiency (15 mA / cm 2) were measured by applying current to the organic light emitting devices manufactured in Examples 1 to 200 and Comparative Examples 1 to 132. 2 ), and the results are shown in the following Tables 1 to 9. The lifespan T95 was measured based on 7000 nits, and T95 means the time required for the lifespan to decrease to 95% of the initial lifespan.

[0983] [Table 1]

[0984]

[0985]

[0986] [Table 2]

[0987]

[0988]

[0989]

[0990] [Table 3]

[0991]

[0992]

[0993]

[0994] [Table 4]

[0995]

[0996]

[0997]

[0998] [Table 5]

[0999]

[1000]

[1001]

[1002] [Table 6]

[1003]

[1004]

[1005]

[1006] [Table 7]

[1007]

[1008]

[1009] [Table 8]

[1010]

[1011]

[1012] [Table 9]

[1013]

[1014]

[1015] When current was applied to the organic light-emitting devices manufactured in Examples 1 to 200 and Comparative Examples 1 to 132, the results shown in Tables 1 to 9 were obtained. Materials widely used in the prior art were used as components of the red organic light-emitting device of Example 1, Compound EB-1 was used as an electron blocking layer, and Compound Dp-7 was used as a dopant for the red-emitting layer.

[1016] Compared to the combination of the present disclosure, when any of the comparative example compounds B-1 to B-12 and the compound represented by Chemical Formula 2 of the present disclosure were co-deposited together and used as a red-emitting layer as shown in Tables 6 and 7, the results showed that, in general, the driving voltage increased, and the efficiency and lifespan decreased. Even when any of the comparative example compounds C-1 to C-9 and the compound represented by Chemical Formula 1 of the present disclosure were co-deposited together and used as a red-emitting layer as shown in Tables 8 and 9, the results showed that the driving voltage increased, and the efficiency and lifespan decreased.

[1017] From the above, it can be seen that when the compound represented by Chemical Formula 1 as the first host and the compound represented by Chemical Formula 2 as the second host according to the present disclosure are used in combination, energy transfer to the red dopant in the red-light-emitting layer is well achieved, and electrons and holes in the light-emitting layer are combined with a more stable balance to form excitons, thereby improving the driving voltage and increasing the efficiency and lifespan.

[1018] In summary, when the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 according to the present disclosure are combined, co-evaporated and used as a host for a layer emitting red light, it is determined that the driving voltage, luminous efficiency and lifespan characteristics of an organic light-emitting device can be improved.

[1019] <Description of Reference Numerals>

[1020] 1: substrate 2: anode

[1021] 3: Light-emitting layer 4: Cathode

[1022] 5: Hole injection layer 6: Hole transport layer

[1023] 7: Electron blocking layer 8: Hole blocking layer

[1024] 9: Electron transport and injection layer

Claims

1. An organic light-emitting device, comprising: anode; cathode; as well as a light-emitting layer between the anode and the cathode, The light-emitting layer comprises a compound represented by the following Chemical Formula 1A and a compound represented by the following Chemical Formula 2: [Chemical Formula 1A] In Chemical Formula 1A, Ar1 and Ar2 are each independently substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C 2-60 heteroaryl, L1 to L3 are each independently a single bond; or a substituted or unsubstituted C 6-60 arylene groups, R1 is hydrogen; deuterium; or substituted or unsubstituted C 6-60 Aryl; or a substituted or unsubstituted C 2-60 Heteroaryl, and a is an integer from 0 to 7, [Chemical Formula 2] In Chemical Formula 2, R'1 to R' 12 Any one of them is the following chemical formula 3, and the remainder is hydrogen or deuterium, [Chemical Formula 3] In Chemical Formula 3, L'1 is a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenyldiyl group, or a substituted or unsubstituted naphthalenediyl group, L'2 and L'3 are each independently a single bond; substituted or unsubstituted C 6-60 Arylene; or a substituted or unsubstituted C containing any one or more selected from N, O and S 2-60 Heteroarylene, and Ar'1 and Ar'2 are each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a dibenzofuranyl group, a dibenzothiophenyl group, a phenylcarbazolyl group, a dimethylfluorenyl group, a benzonaphthofuranyl group, or a benzonaphthothiophenyl group.

2. The organic light-emitting device according to claim 1, wherein: The compound represented by Chemical Formula 1A is represented by any one of the following Chemical Formulas 1-2 to 1-3: [Chemical formula 1-2] [Chemical formula 1-3] In Chemical Formulas 1-2 to 1-3, Ar1 and Ar2, L1 to L3 and R1 are as defined in claim 1.

3. The organic light emitting device according to claim 1, wherein: The compound represented by Chemical Formula 1A is represented by the following Chemical Formula 1-1: [Chemical Formula 1-1] In Chemical Formula 1-1, Ar1 and Ar2 and L1 to L3 are as defined in claim 1 .

4. The organic light emitting device according to claim 1, wherein: Ar1 and Ar2 are each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrenyl group, a dibenzofuranyl group, or a dibenzothiophenyl group.

5. The organic light emitting device according to claim 1, wherein: L1 to L3 are each independently a single bond or any one selected from the following:

6. The organic light emitting device according to claim 1, wherein: R1 is hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, naphthylphenyl, phenylnaphthyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl.

7. The organic light emitting device according to claim 1, wherein: a is 0 or 1.

8. The organic light emitting device according to claim 1, wherein: The compound represented by Chemical Formula 1A is any one selected from the following:

9. The organic light emitting device according to claim 1, wherein: The compound represented by Chemical Formula 2 is represented by any one of the following Chemical Formulas 2-1 to 2-6: [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical formula 2-3] [Chemical formula 2-4] [Chemical Formula 2-5] [Chemical Formula 2-6] In Chemical Formulas 2-1 to 2-6, R'1 to R' 12 , L'1 to L'3, Ar'1 and Ar'2 are as defined in claim 1.

10. The organic light emitting device according to claim 1, wherein: L'2 and L'3 are each independently a single bond, a phenylene group, a phenylene group substituted with one phenyl group, a biphenyldiyl group, or a naphthalenediyl group.

11. The organic light emitting device according to claim 1, wherein: The compound represented by Chemical Formula 2 is any one selected from the following:

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