KR20230071754A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting element. The organic light emitting element comprises: an anode; a cathode; and a light emitting layer between the anode and the cathode. Therefore, the present invention is capable of having excellence in driving voltage, efficiency, and lifespan.

Description

Organic light emitting device {Organic light emitting device}

The present invention relates to an organic light emitting device.

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, and a fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An organic light emitting device generally has a structure including an anode, a cathode, and an organic material layer between the anode and the cathode. In order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often composed of a multi-layered structure composed of different materials, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.

The development of new materials for organic materials used in the organic light emitting device as described above is continuously required.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light emitting diode having improved driving voltage, efficiency and lifetime.

In order to solve the above problems, the present invention,

anode; cathode; And a light emitting layer between the anode and the cathode,

The light emitting layer includes a compound represented by Formula 1 and a compound represented by Formula 2 below.

An organic light emitting device is provided:

[Formula 1]

In Formula 1,

Any one of Y ₁ to Y ₇ is N, the others are CR,

R are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

L ₁ to L ₃ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or a C _2-60 heteroarylene containing at least one selected from the group consisting of unsubstituted N, O and S,

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,

[Formula 2]

In Formula 2,

A is a benzene ring unsubstituted or substituted with deuterium, fused with an adjacent pentagonal ring; Or a naphthalene ring unsubstituted or substituted with deuterium,

L' ₁ to L' ₄ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or a C _2-60 heteroarylene containing at least one selected from the group consisting of unsubstituted N, O and S,

Ar' ₁ to Ar' ₃ are each independently a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.

The organic light emitting device described above is excellent in driving voltage, efficiency and lifetime.

1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3 and a cathode 4.
2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7, an electron injection layer 8, and a cathode 4. It shows an example of an organic light emitting device made of.
3 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 9, a light emitting layer 3, a hole blocking layer 10, and an electron injection and transport layer. 11, and an example of an organic light emitting element composed of a cathode 4 is shown.

Hereinafter, in order to aid understanding of the present invention, it will be described in more detail.

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

means a bond connected to another substituent.

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; nitrile group; nitro group; hydroxy group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; Alkyl thioxy group; Arylthioxy group; an alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; Aralkenyl group; Alkyl aryl group; Alkylamine group; Aralkylamine group; heteroarylamine group; Arylamine group; Arylphosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing at least one of N, O, and S atoms, or substituted or unsubstituted with two or more substituents linked to each other among the substituents exemplified above. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with an aryl group having 6 to 25 carbon atoms or a straight-chain, branched-chain or cyclic chain alkyl group having 1 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group is specifically a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. but not limited to

In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, a phenyl boron group, but is not limited thereto.

In this specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. 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, etc., but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, etc., but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc. as a monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

etc. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N, Si, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, and an acridyl group. , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia A zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, an aralkyl group, an aralkenyl group, an alkylaryl group, and an aryl group among arylamine groups are the same as the examples of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the examples of the above-mentioned alkyl group. In the present specification, the description of the heterocyclic group described above may be applied to the heteroaryl of the heteroarylamine. In the present specification, the alkenyl group among the aralkenyl groups is the same as the examples of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the heterocyclic group described above may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied, except that the hydrocarbon ring is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

Hereinafter, the present invention will be described in detail for each configuration.

anode and cathode

An anode and a cathode used in the present invention refer to electrodes used in an organic light emitting device.

As the anode material, a material having a high work function is generally preferred so that holes can be smoothly injected into the organic layer. Specific examples of the cathode material 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 SnO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function so as to easily inject electrons into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

light emitting layer

The light emitting layer used in the present invention means a layer capable of emitting light in the visible ray region by combining holes and electrons transferred from the anode and the cathode. In general, the light emitting layer includes a host material and a dopant material, and in the present invention, the compound represented by Formula 1 and the compound represented by Formula 2 are included as hosts.

The compound of Formula 1 includes a benzopuropyridine ring and a triazine substituent bonded thereto. In Formula 1, one or more hydrogens may be substituted with deuterium.

Preferably, any one of Y ₁ to Y ₇ is N, the other is CR, and each R is independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-20 aryl; Or a C _2-20 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S. Preferably, each R is independently hydrogen; heavy hydrogen; phenyl; biphenylyl; naphthyl; (phenyl) naphthyl; (naphthyl)phenyl; phenanthrenyl; chrysenyl; benzophenanthrenyl; triphenylenyl; carbazolyl; fluoranthenyl; benzocarbazolyl; dibenzofuranyl; dibenzothiophenyl; benzonaphthofuranil; or benzonaphthothiophenyl. When R is a substituent other than hydrogen or deuterium, it may be substituted with one or more deuterium.

In one embodiment, any one of Y ₁ to Y ₇ may be N, and the others may be CH or CD, respectively.

Alternatively, any one of Y ₁ to Y ₇ is N and the others are CR, but any one of 6 R is phenyl; biphenylyl; naphthyl; (phenyl) naphthyl; (naphthyl)phenyl; phenanthrenyl; chrysenyl; benzophenanthrenyl; triphenylenyl; carbazolyl; fluoranthenyl; benzocarbazolyl; dibenzofuranyl; dibenzothiophenyl; benzonaphthofuranil; or benzonaphthothiophenyl, and the remaining 5 R's may all be hydrogen or deuterium. The R that is not hydrogen or deuterium may be substituted with one or more deuterium.

Preferably, L ₁ to L ₃ are each independently a single bond; or a substituted or unsubstituted C _6-20 arylene.

Preferably, L ₁ to L ₃ are each independently a single bond; Or any one selected from the group consisting of:

In the above, one or more hydrogens may be replaced with deuterium.

Preferably, Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-20 aryl; Or a C _2-20 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl; biphenylyl; terphenylyl; naphthyl; phenanthrenyl; fluoranthenyl; chrysenyl; benzophenanthrenyl; dibenzofuranyl; or dibenzothiophenyl. In this case, Ar ₁ and Ar ₂ may each independently be substituted with one or more deuterium atoms.

The compound of Formula 1 may not contain deuterium or may contain one or more deuterium atoms.

For example, when the compound of Formula 1 contains deuterium, the deuterium substitution rate of the compound may be 1% to 100%. Specifically, the deuterium substitution rate of the compound is 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 75% or more, 80% or more, Alternatively, it may be 90% or more and 100% or less. The deuterium substitution rate of these compounds is calculated as the number of substituted deuteriums relative to the total number of hydrogens that may exist in the formula. Spectrometer) analysis.

Representative examples of the compound represented by Formula 1 are as follows:

In addition, the present invention provides a method for preparing the compound represented by Formula 1 above.

For example, Chemical Formula 1 may be prepared by a preparation method as shown in Reaction Scheme 1 below.

[Scheme 1]

In the above, the rest except X are as defined in Formula 1, X is halogen, preferably X is chloro or bromo.

Scheme 1 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and a reactor for the Suzuki coupling reaction may be modified as known in the art.

The preparation method of the compound represented by Chemical Formula 1 may be more specific in a synthesis example to be described later.

Formula 2 includes a carbazole or benzocarbazole core and an aryl amine substituent bonded thereto. In Formula 2, one or more hydrogens may be substituted with deuterium.

Preferably, L' ₁ to L' ₄ are each independently a single bond; or a substituted or unsubstituted C _6-20 arylene.

Preferably, L' ₁ to L' ₄ are each independently a single bond; phenylene; or naphthylene. The L' ₁ to L' ₄ may each independently be unsubstituted or substituted with one or more deuterium atoms.

Preferably, Ar' ₁ to Ar' ₃ are each independently substituted or unsubstituted C _6-20 aryl; Or a C _2-20 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S.

Preferably, Ar' ₁ to Ar' ₃ are each independently phenyl; biphenylyl; terphenylyl; naphthyl; dibenzofuranyl; dibenzothiophenyl; or 9,9-dimethylfluorenyl. Ar' ₁ to Ar' ₃ may each independently be unsubstituted or substituted with one or more deuterium atoms.

Preferably, L' ₁ is a single bond or phenylene; Ar' ₁ is phenyl, biphenylyl, terphenylyl, or naphthyl. The L' ₁ and Ar' ₁ may each independently be unsubstituted or substituted with one or more deuterium atoms.

Preferably, L' ₂ to L' ₄ are each independently a single bond, phenylene, or naphthylene; Ar' ₂ and Ar' ₃ are each independently phenyl; biphenylyl; terphenylyl; naphthyl; dibenzofuranyl; dibenzothiophenyl; or 9,9-dimethylfluorenyl. The L' ₂ to L' ₄ and Ar' ₂ to Ar' ₃ may each independently be unsubstituted or substituted with one or more deuterium atoms.

Preferably, L' ₂ is a single bond or phenylene; L' ₃ and L' ₄ are each independently a single bond, phenylene, or naphthylene; Ar' ₂ and Ar' ₃ are each independently phenyl; biphenylyl; terphenylyl; naphthyl; dibenzofuranyl; dibenzothiophenyl; or 9,9-dimethylfluorenyl. The L' ₂ to L' ₄ and Ar' ₂ to Ar' ₃ may each independently be unsubstituted or substituted with one or more deuterium atoms.

The compound of Formula 2 may not contain deuterium or may contain one or more deuterium atoms.

For example, when the compound of Formula 2 contains deuterium, the deuterium substitution rate of the compound may be 1% to 100%. Specifically, the deuterium substitution rate of the compound is 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 75% or more, 80% or more, Alternatively, it may be 90% or more and 100% or less.

Representative examples of the compound represented by Formula 2 are as follows:

In addition, the present invention provides a method for preparing the compound represented by Formula 2 above.

Specifically, the compound represented by Chemical Formula 2 may be prepared by a preparation method shown in Scheme 2-1 below.

[Scheme 2-1]

상기에서, X’를 제외한 나머지는 화학식 2에서 정의한 바와 같고, X'은 할로겐이고, 바람직하게는 X'은 클로로 또는 브로모이다.

In the above, the rest except for X' is as defined in Formula 2, X' is halogen, and preferably X' is chloro or bromo.

Reaction Scheme 2-1 is a Suzuki coupling reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and a reactor for the Suzuki coupling reaction may be modified as known in the art.

Alternatively, when L' ₂ is a single bond, the compound of Formula 2 may be prepared by a preparation method shown in Scheme 2-2 below.

[Scheme 2-2]

In the above, the rest except for X' is as defined in Formula 2, X' is halogen, and preferably X' is chloro or bromo.

Reaction Scheme 2-2 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may be modified as known in the art.

The preparation method of the compound of Chemical Formula 2 may be more specific in a synthesis example to be described later.

In the light emitting layer, the weight ratio of the compound represented by Formula 1 and the compound represented by Formula 2 is 1:99 to 99:1, 5:95 to 95:5, or 10:90 to 90:10.

The dopant material is not particularly limited as long as it is a material used in an organic light emitting device. For example, there are aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, aromatic amine derivatives are condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, periplanthene, etc. having an arylamino group, and styrylamine compounds include substituted or unsubstituted arylamine is substituted with at least one arylvinyl group, wherein one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but is not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

In one embodiment, one or more of the following compounds may be used as the dopant material, but is not limited thereto:

hole transport layer

The organic light emitting device according to the present invention may include a hole transport layer between the light emitting layer and the anode.

The hole transport layer is a layer that receives holes from the anode or the hole injection layer and transports them to the light emitting layer. The hole transport material is a material that receives holes from the anode or the hole injection layer and transfers them to the light emitting layer, and has high hole mobility. material is suitable.

Specific examples of the hole transport material include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.

hole injection layer

The organic light emitting device according to the present invention may further include a hole injection layer between the anode and the hole transport layer, if necessary.

The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation ability is preferred. In addition, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer.

Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

electron suppression layer

The organic light emitting device according to the present invention may include an electron blocking layer between the hole transport layer and the light emitting layer, if necessary.

The electron blocking layer prevents electrons injected from the cathode from passing to the hole transport layer without recombination in the light emitting layer, and is also called an electron blocking layer. A material having a smaller electron affinity than the electron transport layer is preferable for the electron blocking layer.

electron transport layer

The organic light emitting device according to the present invention may include an electron transport layer between the light emitting layer and the cathode.

The electron transport layer is a layer that receives electrons from the cathode or an electron injection layer formed on the cathode, transports electrons to the light emitting layer, and suppresses the transfer of holes in the light emitting layer. As an electron transport material, electrons are well injected from the cathode. As a material that can be received and transferred to the light emitting layer, a material having high electron mobility is suitable.

Specific examples of the electron transport material include Al complexes of 8-hydroxyquinoline; Complexes containing Alq ₃ ; organic radical compounds; Hydroxyflavone-metal complexes, etc., but are not limited thereto. The electron transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by a layer of aluminum or silver.

electron injection layer

The organic light emitting device according to the present invention may further include an electron injection layer between the electron transport layer and the cathode, if necessary.

The electron injection layer is a layer for injecting electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes of excitons generated in the light emitting layer. It is preferable to use a compound that prevents migration to a layer and has excellent thin film forming ability.

Specific examples of materials that can be used as the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preore nylidene methane, anthrone, etc. and their derivatives, metal complex compounds, nitrogen-containing 5-membered ring derivatives, etc., but are not limited thereto.

Examples of the metal complex compound 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)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.

hole blocking layer

The organic light emitting device according to the present invention may include a hole blocking layer between the electron transport layer and the light emitting layer, if necessary.

The hole blocking layer prevents holes injected from the anode from passing to the electron transport layer without recombination in the light emitting layer, and a material having high ionization energy is preferable for the hole blocking layer.

organic light emitting device

The structure of the organic light emitting device according to the present invention is illustrated in FIG. 1 . 1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 3 and a cathode 4. 2 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7, an electron injection layer 8, and a cathode 4 ) It shows an example of an organic light emitting device made of. 3 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 9, a light emitting layer 3, a hole blocking layer 10, electron injection And an example of an organic light emitting device composed of the transport layer 11 and the cathode 4 is shown.

The organic light emitting device according to the present invention can be manufactured by sequentially stacking the above-described components. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode And, after forming each of the above-described layers thereon, it can be manufactured by depositing a material that can be used as a cathode thereon.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material on a substrate and an anode material in the reverse order of the above configuration (WO 2003/012890). In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method of a host and a dopant. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

Meanwhile, the organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

Manufacturing of the organic light emitting device according to the present invention described above will be described in detail in the following examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

<Synthesis Example 1: Preparation of Compound Represented by Chemical Formula 1>

Synthesis Example 1-1

Compound A (15g, 45.5mmol) and Trz1 (15.2g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9 g of subA-1. (Yield 63%, MS: [M+H]+= 485)

Compounds subA-1 (15g, 30.9mmol) and sub1 (7.2g, 32.5mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.8g, 92.8mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6 g of Compound 1-1. (Yield 60%, MS: [M+H]+= 627)

Synthesis Example 1-2

Compound B (15g, 45.5mmol) and Trz2 (12.8g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of subB-1. (Yield 69%, MS: [M+H]+= 435)

Compounds subB-1 (15 g, 34.5 mmol) and sub2 (9.9 g, 36.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3g, 103.5mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5 g of Compound 1-2. (Yield 67%, MS: [M+H]+= 627)

Synthesis Example 1-3

Compound C (15g, 45.5mmol) and Trz2 (12.8g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6 g of subC-1. (Yield 64%, MS: [M+H]+= 435)

Compounds subC-1 (15 g, 34.5 mmol) and sub3 (8.9 g, 36.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3g, 103.5mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of Compound 1-3. (Yield 68%, MS: [M+H]+= 601)

Synthesis Example 1-4

Compound D (15g, 45.5mmol) and Trz3 (21.2g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1 g of subD-1. (Yield 76%, MS: [M+H]+= 611)

Compounds subD-1 (15g, 24.5mmol) and sub4 (3.1g, 25.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (10.2g, 73.6mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of Compound 1-4. (Yield 80%, MS: [M+H]+= 653)

Synthesis Example 1-5

Compound E (15g, 50.8mmol) and Trz4 (25g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4 g of Compound 1-5. (Yield 67%, MS: [M+H]+= 601)

Synthesis Example 1-6

Compound E (15g, 50.8mmol) and Trz5 (25.8g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4 g of Compound 1-6. (Yield 65%, MS: [M+H]+= 617)

Synthesis Example 1-7

Compound E (15g, 50.8mmol) and Trz6 (28.5g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.7 g of Compound 1-7. (Yield 61%, MS: [M+H]+= 667)

Synthesis Example 1-8

Compound E (15g, 50.8mmol) and Trz7 (26.4g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.2 g of Compound 1-8. (Yield 76%, MS: [M+H]+= 627)

Synthesis Example 1-9

Compound F (15g, 45.5mmol) and Trz8 (19.5g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17 g of subF-1. (Yield 65%, MS: [M+H]+= 575)

Compounds subF-1 (15 g, 26.1 mmol) and sub4 (3.3 g, 27.4 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (10.8g, 78.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of Compound 1-9. (Yield 80%, MS: [M+H]+= 617)

Synthesis Example 1-10

Compound G (15g, 45.5mmol) and Trz9 (20.7g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.9 g of subG-1. (Yield 80%, MS: [M+H]+= 601)

Compounds subG-1 (15g, 25mmol) and sub5 (4.5g, 26.2mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (10.3g, 74.9mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.2mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of Compound 1-10. (Yield 75%, MS: [M+H]+= 693)

Synthesis Example 1-11

Compound G (15g, 45.5mmol) and Trz2 (12.8g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of subG-2. (Yield 70%, MS: [M+H]+= 435)

Compounds subG-2 (15g, 34.5mmol) and sub6 (17.5g, 36.2mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3g, 103.5mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of Compound 1-11. (Yield 65%, MS: [M+H]+= 627)

Synthesis Example 1-12

Compound G (15g, 45.5mmol) and Trz10 (16.4g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of subG-3. (Yield 61%, MS: [M+H]+= 511)

Compound subG-3 (10 g, 19.6 mmol), sub7 (4.3 g, 20 mmol), and sodium tert-butoxide (2.4 g, 25.4 mmol) were added to 200 ml of xylene in a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.5 g of compound 1-12. (Yield 70%, MS: [M+H]+= 692)

Synthesis Example 1-13

Compound H (15g, 45.5mmol) and Trz11 (17.1g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.2 g of subH-1. (Yield 68%, MS: [M+H]+= 525)

Compounds subH-1 (15g, 28.6mmol) and sub5 (5.2g, 30mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.8g, 85.7mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.9 g of Compound 1-13. (Yield 62%, MS: [M+H]+= 617)

Synthesis Example 1-14

Compound I (15g, 50.8mmol) and Trz12 (23.7g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g of Compound 1-14. (Yield 60%, MS: [M+H]+= 577)

Synthesis Example 1-15

Compound I (15g, 50.8mmol) and Trz13 (25g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7 g of Compound 1-15. (Yield 71%, MS: [M+H]+= 601)

Synthesis Example 1-16

Compound I (15g, 50.8mmol) and Trz14 (25.1g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.4 g of Compound 1-16. (Yield 70%, MS: [M+H]+= 603)

Synthesis Example 1-17

Compound J (15g, 45.5mmol) and Trz15 (17.6g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6 g of subJ-1. (Yield 64%, MS: [M+H]+= 535)

Compounds subJ-1 (15g, 28mmol) and sub5 (5.1g, 29.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.6g, 84.1mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of Compound 1-17. (Yield 78%, MS: [M+H]+= 627)

Synthesis Example 1-18

Compound K (15g, 45.5mmol) and Trz1 (15.2g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9 g of subK-1. (Yield 63%, MS: [M+H]+= 485)

Compounds subK-1 (15 g, 30.9 mmol) and sub8 (6.9 g, 32.5 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.8g, 92.8mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of Compound 1-18. (Yield 65%, MS: [M+H]+= 617)

Synthesis Example 1-19

Compound L (15g, 45.5mmol) and Trz2 (12.8g, 47.8mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of subL-1. (Yield 69%, MS: [M+H]+= 435)

Compounds subL-1 (15 g, 34.5 mmol) and sub9 (8.9 g, 36.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3g, 103.5mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of Compound 1-19. (Yield 64%, MS: [M+H]+= 601)

Synthesis Example 1-20

Compounds subL-1 (15 g, 34.5 mmol) and sub10 (10.1 g, 36.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3g, 103.5mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of Compound 1-20. (Yield 66%, MS: [M+H]+= 633)

Synthesis Example 1-21

Compound K (15g, 45.5mmol) and Trz16 (17.9g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.7 g of subK-2. (Yield 68%, MS: [M+H]+= 541)

SubK-2 (10 g, 18.5 mmol), sub11 (3.2 g, 18.9 mmol), and sodium tert-butoxide (2.3 g, 24 mmol) were added to 200 ml of xylene under nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.8 g of compound 1-21. (Yield 63%, MS: [M+H]+= 672)

Synthesis Example 1-22

Compound K (15g, 45.5mmol) and Trz17 (16.4g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3 g of subK-3. (Yield 66%, MS: [M+H]+= 511)

Compounds subK-3 (15 g, 29.4 mmol) and sub5 (5.3 g, 30.8 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.2g, 88.1mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of Compound 1-22. (Yield 78%, MS: [M+H]+= 603)

Synthesis Example 1-23

Compound M (15g, 50.8mmol) and Trz18 (25.1g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.9 g of Compound 1-23. (Yield 65%, MS: [M+H]+= 603)

Synthesis Example 1-24

Compound M (15g, 50.8mmol) and Trz19 (25g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4 g of Compound 1-24. (Yield 67%, MS: [M+H]+= 601)

Synthesis Example 1-25

Compound M (15g, 50.8mmol) and Trz20 (25.8g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.7 g of Compound 1-25. (Yield 63%, MS: [M+H]+= 617)

Synthesis Example 1-26

Compound N (15g, 45.5mmol) and Trz1 (15.2g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.9 g of subN-1. (Yield 72%, MS: [M+H]+= 485)

Compounds subN-1 (15g, 30.9mmol) and sub5 (5.6g, 32.5mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.8g, 92.8mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7 g of Compound 1-26. (Yield 71%, MS: [M+H]+= 577)

Synthesis Example 1-27

Compound O (15g, 45.5mmol) and Trz2 (12.8g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of subO-1. (Yield 76%, MS: [M+H]+= 435)

Compounds subO-1 (15g, 34.5mmol) and sub12 (9.9g, 36.2mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3g, 103.5mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.8 g of Compound 1-27. (Yield 73%, MS: [M+H]+= 627)

Synthesis Example 1-28

Compound N (15g, 45.5mmol) and Trz8 (12.8g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.4 g of subN-2. (Yield 78%, MS: [M+H]+= 575)

Compounds subN-2 (15g, 26.1mmol) and sub13 (5.4g, 27.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (10.8g, 78.3mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of Compound 1-28. (Yield 60%, MS: [M+H]+= 693)

Synthesis Example 1-29

Compound P (15g, 45.5mmol) and Trz1 (15.2g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of subP-1. (Yield 62%, MS: [M+H]+= 485)

Compound subP-1 (10 g, 20.6 mmol), sub11 (3.5 g, 21 mmol), and sodium tert-butoxide (2.6 g, 26.8 mmol) were added to 200 ml of xylene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 4 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of compound 1-29. (Yield 51%, MS: [M+H]+= 616)

Synthesis Example 1-30

Compound Q (15g, 45.5mmol) and Trz21 (17.1g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.5 g of subQ-1. (Yield 69%, MS: [M+H]+= 525)

Compounds subQ-1 (15g, 28.6mmol) and sub14 (5.9g, 30mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.8g, 85.7mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of Compound 1-30. (Yield 80%, MS: [M+H]+= 643)

Synthesis Example 1-31

Compound R (15g, 50.8mmol) and Trz22 (23.7g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7 g of Compound 1-31. (Yield 64%, MS: [M+H]+= 577)

Synthesis Example 1-32

Compound R (15g, 50.8mmol) and Trz23 (23.6g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.1 g of Compound 1-32. (Yield 79%, MS: [M+H]+= 575)

Synthesis Example 1-33

Compound R (15g, 50.8mmol) and Trz24 (29.9g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of Compound 1-33. (Yield 74%, MS: [M+H]+= 693)

Synthesis Example 1-34

Compound S (15g, 45.5mmol) and Trz15 (17.6g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19 g of subS-1. (Yield 78%, MS: [M+H]+= 535)

Compounds subS-1 (15g, 28mmol) and sub15 (6.5g, 29.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.6g, 84.1mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of Compound 1-34. (Yield 70%, MS: [M+H]+= 677)

Synthesis Example 1-35

Compound T (15g, 45.5mmol) and Trz2 (12.8g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of subT-1. (Yield 73%, MS: [M+H]+= 435)

Compounds subT-1 (15 g, 34.5 mmol) and sub16 (9.5 g, 36.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3g, 103.5mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17 g of compound 1-35. (Yield 80%, MS: [M+H]+= 617)

Synthesis Example 1-36

Compound S (15g, 45.5mmol) and Trz25 (18.8g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.6 g of subS-2. (Yield 77%, MS: [M+H]+= 561)

Compound subS-2 (10 g, 17.8 mmol), sub17 (4 g, 18.2 mmol), and sodium tert-butoxide (2.2 g, 23.2 mmol) were added to 200 ml of xylene in a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.3 g of compound 1-36. (Yield 55%, MS: [M+H]+= 742)

Synthesis Example 1-37

Compound U (15g, 45.5mmol) and Trz26 (17.9g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7 g of subU-1. (Yield 76%, MS: [M+H]+= 541)

Compounds subU-1 (15g, 27.7mmol) and sub18 (6.6g, 29.1mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.5g, 83.2mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.5 g of Compound 1-37. (Yield 71%, MS: [M+H]+= 689)

Synthesis Example 1-38

Compound V (15g, 50.8mmol) and Trz27 (22.3g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.8 g of Compound 1-38. (Yield 60%, MS: [M+H]+= 551)

Synthesis Example 1-39

Compound V (15g, 50.8mmol) and Trz28 (23.2g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.1 g of Compound 1-39. (Yield 70%, MS: [M+H]+= 567)

Synthesis Example 1-40

Compound V (15g, 50.8mmol) and Trz29 (30.4g, 53.4mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.6 g of Compound 1-40. (Yield 69%, MS: [M+H]+= 703)

Synthesis Example 1-41

Compound V (15g, 50.8mmol) and Trz30 (25.8g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.8 g of Compound 1-41. (Yield 76%, MS: [M+H]+= 617)

Synthesis Example 1-42

Compound W (15g, 45.5mmol) and Trz2 (12.8g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of subW-1. (Yield 66%, MS: [M+H]+= 435)

Compounds subW-1 (15g, 34.5mmol) and sub19 (9.9g, 36.2mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3g, 103.5mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.4 g of Compound 1-42. (Yield 76%, MS: [M+H]+= 627)

Synthesis Example 1-43

Compound X (15g, 45.5mmol) and Trz2 (12.8g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of subX-1. (Yield 71%, MS: [M+H]+= 435)

Compounds subX-1 (15 g, 34.5 mmol) and sub20 (10.1 g, 36.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3g, 103.5mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of Compound 1-43. (Yield 64%, MS: [M+H]+= 633)

Synthesis Example 1-44

Compound Y (15g, 45.5mmol) and Trz2 (12.6g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.8 g of subY-1. (Yield 80%, MS: [M+H]+= 435)

Compounds subY-1 (15 g, 34.5 mmol) and sub21 (9.5 g, 36.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3g, 103.5mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 5 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9 g of Compound 1-44. (Yield 70%, MS: [M+H]+= 617)

Synthesis Example 1-45

Compound X (15g, 45.5mmol) and Trz31 (18.8g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.1 g of subX-2. (Yield 71%, MS: [M+H]+= 561)

Compounds subX-2 (15 g, 26.7 mmol) and sub22 (7.6 g, 28.1 mmol) were added to 300 ml of THF and stirred and refluxed. After that, potassium carbonate (11.1g, 80.2mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7 g of Compound 1-45. (Yield 78%, MS: [M+H]+= 753)

Synthesis Example 1-46

Compound Z (15g, 50.8mmol) and Trz32 (21g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.6 g of Compound 1-46. (Yield 62%, MS: [M+H]+= 527)

Synthesis Example 1-47

Compound Z (15g, 50.8mmol) and Trz33 (22.3g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.3 g of Compound 1-47. (Yield 69%, MS: [M+H]+= 551)

Synthesis Example 1-48

Compound Z (15g, 50.8mmol) and Trz34 (25.7g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.1 g of Compound 1-48. (Yield 74%, MS: [M+H]+= 615)

Synthesis Example 1-49

Compound Z (15g, 50.8mmol) and Trz35 (25.8g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (21.1g, 152.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.9 g of Compound 1-49. (Yield 73%, MS: [M+H]+= 617)

Synthesis Example 1-50

Compound Z (15g, 50.8mmol) and Trz36 (25.8g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.4 g of Compound 1-50. (Yield 62%, MS: [M+H]+= 617)

Synthesis Example 1-51

Compound Z (15g, 50.8mmol) and Trz37 (27.8g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.9 g of Compound 1-51. (Yield 60%, MS: [M+H]+= 653)

Synthesis Example 1-52

Compound AA (15g, 45.5mmol) and Trz1 (15.2g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.2 g of subAA-1. (Yield 78%, MS: [M+H]+= 485)

Compounds subAA-1 (15 g, 30.9 mmol) and sub23 (7.4 g, 32.5 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12.8g, 92.8mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.9 g of Compound 1-52. (Yield 71%, MS: [M+H]+= 633)

Synthesis Example 1-53

Compound AB (15g, 45.5mmol) and Trz2 (12.8g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of subAB-1. (Yield 71%, MS: [M+H]+= 435)

Compounds subAB-1 (14 g, 32 mmol) and sub24 (8.9 g, 33.8 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (13.3g, 96.6mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After 5 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.5 g of compound 1-53. (Yield 62%, MS: [M+H]+= 617)

Synthesis Example 1-54

Compound AA (15g, 45.5mmol) and Trz2 (12.8g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6 g of subAA-2. (Yield 64%, MS: [M+H]+= 435)

Compounds subAA-2 (15 g, 34.5 mmol) and sub25 (10.1 g, 36.2 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.3g, 103.5mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of Compound 1-54. (Yield 61%, MS: [M+H]+= 633)

Synthesis Example 1-55

Compound AB (15g, 45.5mmol) and Trz21 (17.1g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.5 g of subAB-2. (Yield 65%, MS: [M+H]+= 525)

Compounds subAB-2 (15 g, 28.6 mmol) and sub26 (7.4 g, 30 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.8g, 85.7mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of Compound 1-55. (Yield 63%, MS: [M+H]+= 693)

Synthesis Example 1-56

Compound AB (15g, 45.5mmol) and Trz38 (20.1g, 47.8mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (18.9g, 136.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4 g of subAB-3. (Yield 69%, MS: [M+H]+= 587)

Compounds subAB-3 (15 g, 25.6 mmol) and sub27 (5.7 g, 26.8 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (10.6g, 76.7mmol) was dissolved in 100ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 4 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of Compound 1-56. (Yield 73%, MS: [M+H]+= 719)

Synthesis Example 1-57

Compound AC (15g, 50.8mmol) and Trz39 (22.3g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.1 g of Compound 1-57. (Yield 79%, MS: [M+H]+= 551)

Synthesis Example 1-58

Compound AC (15g, 50.8mmol) and Trz40 (23.7g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (21.1g, 152.5mmol) was dissolved in 100ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.3g, 0.5mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.3 g of Compound 1-58. (Yield 66%, MS: [M+H]+= 577)

Synthesis Example 1-59

Compound AC (15g, 50.8mmol) and Trz41 (28.5g, 53.4mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (21.1 g, 152.5 mmol) was dissolved in 100 ml of water, and after sufficiently stirred, bis (tri-tert-butylphosphine) palladium (0) (0.3 g, 0.5 mmol) was added. After reacting for 3 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.7 g of Compound 1-59. (Yield 73%, MS: [M+H]+= 667)

<Synthesis Example 2: Preparation of Compound Represented by Chemical Formula 2>

Synthesis Example 2-1

Formula E (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.6 g of subE-1. (Yield 66%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subE-1 (10 g, 30.5 mmol), amine1 (11.9 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.7 g of Compound 2-1. (Yield 63%, MS: [M+H]+= 664)

Synthesis Example 2-2

In a nitrogen atmosphere, subE-1 (10 g, 30.5 mmol), amine2 (11.9 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.9 g of Compound 2-2. (Yield 54%, MS: [M+H]+= 664)

Synthesis Example 2-3

질소 분위기에서 subE-1 (10 g, 30.5mmol), amine3 (10.7g, 32 mmol), sodium tert-butoxide (5.9 g, 61 mmol)을 xylene200 ml에 넣고 교반 및 환류했다. 이 후 bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol)을 투입했다. 2시간 후 반응이 종결되어 상온으로 식히고 감압하여 용매를 제거했다. 이 후 화합물을 다시 클로로포름에 완전히 녹이고 물로 2회 세척 후에 유기층을 분리하여 무수황산마그네슘 처리 후 여과하여 여액을 감압 증류했다. 농축한 화합물을 실리카 겔 컬럼 크로마토그래피로 정제해서 화합물 2-3 12.4g을 얻었다. (수율 65%, MS: [M+H]+= 628)

In a nitrogen atmosphere, subE-1 (10 g, 30.5 mmol), amine3 (10.7 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.4 g of Compound 2-3. (Yield 65%, MS: [M+H]+= 628)

Synthesis Example 2-4

Formula F (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9 g of subF-1. (Yield 69%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subF-1 (10 g, 30.5 mmol), amine4 (10.3 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.4 g of Compound 2-4. (Yield 61%, MS: [M+H]+= 614)

Synthesis Example 2-5

In a nitrogen atmosphere, subF-1 (10 g, 30.5 mmol), amine5 (11.3 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.2 g of Compound 2-5. (Yield 62%, MS: [M+H]+= 644)

Synthesis Example 2-6

Formula G (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.8 g of subG-1. (Yield 60%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subG-1 (10 g, 30.5 mmol), amine6 (10.3 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.4 g of compound 2-6. (Yield 61%, MS: [M+H]+= 614)

Synthesis Example 2-7

In a nitrogen atmosphere, subG-1 (10 g, 30.5 mmol), amine7 (11.6 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.1 g of Compound 2-7. (Yield 66%, MS: [M+H]+= 654)

Synthesis Example 2-8

In a nitrogen atmosphere, subG-1 (10 g, 30.5 mmol), amine8 (11.3 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 g of Compound 2-8. (Yield 59%, MS: [M+H]+= 644)

Synthesis Example 2-9

In a nitrogen atmosphere, subG-1 (10 g, 30.5 mmol), amine9 (11.2 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.5 g of Compound 2-9. (Yield 69%, MS: [M+H]+= 642)

Synthesis Example 2-10

Formula H (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.3 g of subH-1. (Yield 64%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subh-1 (10 g, 30.5 mmol), amine10 (11.9 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.9 g of Compound 2-10. (Yield 54%, MS: [M+H]+= 664)

Synthesis Example 2-11

In a nitrogen atmosphere, subH-1 (10 g, 30.5 mmol), amine11 (11.6 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.6 g of Compound 2-11. (Yield 53%, MS: [M+H]+= 654)

Synthesis Example 2-12

In a nitrogen atmosphere, subH-1 (10 g, 30.5 mmol), amine12 (12.2 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.5 g of compound 2-12. (Yield 61%, MS: [M+H]+= 674)

Synthesis Example 2-13

Formula I (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.8 g of subI-1. (Yield 60%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subI-1 (10 g, 30.5 mmol), amine6 (10.3 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.5 g of compound 2-13. (Yield 51%, MS: [M+H]+= 614)

Synthesis Example 2-14

In a nitrogen atmosphere, subI-1 (10 g, 30.5 mmol), amine13 (11.6 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.5 g of compound 2-14. (Yield 68%, MS: [M+H]+= 654)

Synthesis Example 2-15

Chemical Formula J (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.6 g of subJ-1. (Yield 51%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subJ-1 (10 g, 30.5 mmol), amine3 (10.7 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.8 g of compound 2-15. (Yield 51%, MS: [M+H]+= 628)

Synthesis Example 2-16

In a nitrogen atmosphere, subJ-1 (10 g, 30.5 mmol), amine1 (11.9 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.3 g of compound 2-16. (Yield 66%, MS: [M+H]+= 664)

Synthesis Example 2-17

Formula K (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.4 g of subK-1. (Yield 65%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subK-1 (10 g, 30.5 mmol), amine6 (10.3 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.5 g of compound 2-17. (Yield 67%, MS: [M+H]+= 614)

Synthesis Example 2-18

In a nitrogen atmosphere, subK-1 (10 g, 30.5 mmol), amine14 (11.9 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.2 g of compound 2-18. (Yield 70%, MS: [M+H]+= 664)

Synthesis Example 2-19

Formula L (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of subL-1. (Yield 50%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subL-1 (10 g, 30.5 mmol), amine15 (12.7 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.9 g of compound 2-19. (Yield 66%, MS: [M+H]+= 690)

Synthesis Example 2-20

Formula M (10 g, 39.7 mmol), sub34 (9.3 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.1 g of subM-1. (Yield 69%, MS: [M+H]+= 404)

In a nitrogen atmosphere, subM-1 (10 g, 24.8 mmol), amine16 (7.7 g, 26 mmol), and sodium tert-butoxide (4.8 g, 49.5 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.5 g of compound 2-20. (Yield 52%, MS: [M+H]+= 664)

Synthesis Example 2-21

Formula N (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.8 g of subN-1. (Yield 68%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subN-1 (10 g, 30.5 mmol), amine17 (7.9 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.2 g of compound 2-21. (Yield 50%, MS: [M+H]+= 538)

Synthesis Example 2-22

In a nitrogen atmosphere, subN-1 (10 g, 30.5 mmol), amine18 (10.7 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13 g of compound 2-22. (Yield 68%, MS: [M+H]+= 628)

Synthesis Example 2-23

Formula O (10 g, 39.7 mmol), sub35 (8.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.6 g of subO-1. (Yield 64%, MS: [M+H]+= 378)

In a nitrogen atmosphere, subO-1 (10 g, 26.5 mmol), amine4 (8.9 g, 27.8 mmol), and sodium tert-butoxide (5.1 g, 52.9 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.5 g of compound 2-23. (Yield 60%, MS: [M+H]+= 664)

Synthesis Example 2-24

Formula O (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9 g of subO-2. (Yield 69%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subO-2 (10 g, 30.5 mmol), amine19 (12.7 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6 g of compound 2-24. (Yield 60%, MS: [M+H]+= 690)

Synthesis Example 2-25

Formula P (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.1 g of subP-1. (Yield 70%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subP-1 (10 g, 30.5 mmol), amine20 (5.4 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.6 g of compound 2-25. (Yield 68%, MS: [M+H]+= 462)

Synthesis Example 2-26

In a nitrogen atmosphere, subP-1 (10 g, 30.5 mmol), amine6 (10.3 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.9 g of compound 2-26. (Yield 69%, MS: [M+H]+= 614)

Synthesis Example 2-27

In a nitrogen atmosphere, subP-1 (10 g, 30.5 mmol), amine3 (10.7 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.8 g of compound 2-27. (Yield 67%, MS: [M+H]+= 628)

Synthesis Example 2-28

In a nitrogen atmosphere, subP-1 (10 g, 30.5 mmol), amine21 (11.7 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.4 g of compound 2-28. (Yield 67%, MS: [M+H]+= 658)

Synthesis Example 2-29

Formula P (10 g, 39.7 mmol), sub36 (9.3 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.1 g of subP-2. (Yield 57%, MS: [M+H]+= 404)

In a nitrogen atmosphere, subP-2 (10 g, 24.8 mmol), amine22 (8.7 g, 26 mmol), and sodium tert-butoxide (4.8 g, 49.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.1 g of compound 2-29. (Yield 64%, MS: [M+H]+= 704)

Synthesis Example 2-30

Formula P (10 g, 39.7 mmol), sub35 (8.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10 g of subP-3. (Yield 67%, MS: [M+H]+= 378)

In a nitrogen atmosphere, subP-3 (10 g, 26.5 mmol), amine5 (9.8 g, 27.8 mmol), and sodium tert-butoxide (5.1 g, 52.9 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.5 g of Compound 2-30. (Yield 57%, MS: [M+H]+= 694)

Synthesis Example 2-31

Chemical Formula Q (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.1 g of subQ-1. (Yield 70%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subQ-1 (10 g, 30.5 mmol), amine23 (11.6 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.7 g of compound 2-31. (Yield 64%, MS: [M+H]+= 654)

Synthesis Example 2-32

In a nitrogen atmosphere, subQ-1 (10 g, 30.5 mmol), amine24 (10.7 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.3 g of compound 2-32. (Yield 59%, MS: [M+H]+= 628)

Synthesis Example 2-33

In a nitrogen atmosphere, subQ-1 (10 g, 30.5 mmol), amine25 (11.3 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.8 g of compound 2-33. (Yield 50%, MS: [M+H]+= 644)

Synthesis Example 2-34

Formula R (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.8 g of subR-1. (Yield 52%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subR-1 (10 g, 30.5 mmol), amine26 (12.7 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 14.3 g of compound 2-34. (Yield 68%, MS: [M+H]+= 690)

Synthesis Example 2-35

Formula R (10 g, 39.7 mmol), sub37 (9.3 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.5 g of subR-2. (Yield 53%, MS: [M+H]+= 404)

In a nitrogen atmosphere, subR-2 (10 g, 24.8 mmol), amine3 (8.7 g, 26 mmol), and sodium tert-butoxide (4.8 g, 49.5 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.6 g of compound 2-35. (Yield 61%, MS: [M+H]+= 704)

Synthesis Example 2-36

Formula S (10 g, 39.7 mmol), sub33 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.6 g of subS-1. (Yield 66%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subS-1 (10 g, 30.5 mmol), amine6 (10.3 g, 32 mmol), and sodium tert-butoxide (5.9 g, 61 mmol) were added to 200 ml of xylene and stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.5 g of compound 2-36. (Yield 56%, MS: [M+H]+= 614)

Synthesis Example 2-37

Formula S (10 g, 39.7 mmol), sub35 (8.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.5 g of subS-2. (Yield 50%, MS: [M+H]+= 378)

In a nitrogen atmosphere, subS-2 (10 g, 26.5 mmol), amine27 (8.9 g, 27.8 mmol), and sodium tert-butoxide (5.1 g, 52.9 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.7 g of compound 2-37. (Yield 61%, MS: [M+H]+= 664)

Synthesis Example 2-38

Formula T (10 g, 39.7 mmol), sub35 (8.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.4 g of subT-1. (Yield 56%, MS: [M+H]+= 378)

In a nitrogen atmosphere, subT-1 (10 g, 26.5 mmol), amine9 (9.7 g, 27.8 mmol), and sodium tert-butoxide (5.1 g, 52.9 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6 g of compound 2-38. (Yield 69%, MS: [M+H]+= 692)

Synthesis Example 2-39

Formula U (10 g, 39.7 mmol), sub35 (8.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.6 g of subU-1. (Yield 51%, MS: [M+H]+= 378)

In a nitrogen atmosphere, subU-1 (10 g, 26.5 mmol), amine13 (10 g, 27.8 mmol), and sodium tert-butoxide (5.1 g, 52.9 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.2 g of compound 2-39. (Yield 60%, MS: [M+H]+= 704)

Synthesis Example 2-40

In a nitrogen atmosphere, subE-1 (15g, 45.8mmol) and amine28 (21.9g, 48mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (19g, 137.3mmol) was dissolved in 57ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.9 g of compound 2-40. (Yield 65%, MS: [M+H]+= 703)

Synthesis Example 2-41

Formula V (10 g, 39.7 mmol), sub33 (6.9 g, 43.7 mmol), and sodium tert-butoxide (11.5 g, 119.2 mmol) were added to 200 ml of Toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 6.5 g of subV-1. (Yield 50%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subV-1 (15g, 45.8mmol) and amine29 (22.6g, 48mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (19g, 137.3mmol) was dissolved in 57ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23 g of compound 2-41. (Yield 70%, MS: [M+H]+= 719)

Synthesis Example 2-42

In a nitrogen atmosphere, subJ-1 (15g, 45.8mmol) and amine30 (17.5g, 48mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (19g, 137.3mmol) was dissolved in 57ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.6 g of compound 2-42. (Yield 70%, MS: [M+H]+= 613)

Synthesis Example 2-43

In a nitrogen atmosphere, subK-1 (15 g, 45.8 mmol) and amine31 (17.5 g, 48 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (19g, 137.3mmol) was dissolved in 57ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.6 g of compound 2-43. (Yield 70%, MS: [M+H]+= 613)

Synthesis Example 2-44

In a nitrogen atmosphere, subP-1 (15g, 45.8mmol) and amine32 (21.2g, 48mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (19g, 137.3mmol) was dissolved in 57ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5 g of compound 2-44. (Yield 62%, MS: [M+H]+= 689)

Synthesis Example 2-45

In a nitrogen atmosphere, subP-1 (15g, 45.8mmol) and amine33 (21.9g, 48mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (19g, 137.3mmol) was dissolved in 57ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.5 g of compound 2-45. (Yield 73%, MS: [M+H]+= 703)

Synthesis Example 2-46

Formula U (10 g, 39.7 mmol), sub33 (6.9 g, 43.7 mmol), and sodium tert-butoxide (11.5 g, 119.2 mmol) were added to 200 ml of Toluene in a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.4 g, 0.8 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.1 g of subU-2. (Yield 62%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subU-2 (15g, 45.8mmol) and amine34 (22.6g, 48mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (19g, 137.3mmol) was dissolved in 57ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21 g of compound 2-46. (Yield 64%, MS: [M+H]+= 719)

<Examples and Comparative Examples>

Example 1

A glass substrate coated with ITO (indium tin oxide) to a thickness of 1,000 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a Fischer Co. product was used as the detergent, and distilled water filtered through a second filter of a Millipore Co. product was used as the distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water and ultrasonic cleaning was performed for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.

The following compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5%. On the hole injection layer, the following HT-1 compound was vacuum deposited to form a hole transport layer having a thickness of 800 Å. Subsequently, an electron blocking layer was formed on the hole transport layer by vacuum depositing the following EB-1 compound to a film thickness of 150 Å. Then, on the EB-1 deposited film, compound 1-1, formula 2-1, and compound Dp-7 were vacuum co-deposited in a weight ratio of 49:49:2 as the host to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed on the light emitting layer by vacuum depositing the following HB-1 compound to a film thickness of 30 Å. Then, on the hole blocking layer, the following ET-1 compound and the following LiQ compound were vacuum deposited at a weight ratio of 2:1 to form an electron injection and transport layer with a thickness of 300 Å. A negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å/sec, the deposition rate of lithium fluoride on the anode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum level during deposition was 2 x 10 ^- Maintaining ⁷ to 5 x 10 ^-6 torr, an organic light emitting device was fabricated.

Examples 2 to 220

An organic light emitting device was manufactured in the same manner as in Example 1, except that the first host and the second host were co-deposited with the compounds of Table 1 in a ratio of 1:1.

Comparative Examples 1 to 60

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the first host and the second host were co-deposited with the compounds of Table 2 in a ratio of 1:1.

<Experimental example>

When current was applied to the organic light emitting devices prepared in Examples 1 to 220 and Comparative Examples 1 to 60, voltage and efficiency were measured (based on 15 mA/cm ² ) and the results are shown in Tables 1 and 60 below. shown in 2. The lifetime T95 means the time required for the luminance to decrease from the initial luminance (6,000 nit) to 95%.

Referring to Tables 1 and 2, Examples 1 to 220 using the compound of Formula 1 and the compound of Formula 2 as cohosts show a lower driving voltage and significantly improve efficiency and lifetime compared to Comparative Examples 1 to 60. can be checked. From this, it can be confirmed that the combination of the compound of Formula 1 and the compound of Formula 2 is effective in transferring energy to the dopant in the light emitting layer.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron transport layer 8: electron injection layer
9: electron blocking layer 10: hole blocking layer
11: electron injection and transport layer

Claims (9)

anode; cathode; And a light emitting layer between the anode and the cathode,
The light emitting layer includes a compound represented by Formula 1 and a compound represented by Formula 2 below.
Organic Light-Emitting Elements:
[Formula 1]

In Formula 1,
Any one of Y ₁ to Y ₇ is N, the others are CR,
R are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
L ₁ to L ₃ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or a C _2-60 heteroarylene containing at least one selected from the group consisting of unsubstituted N, O and S,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing at least one selected from the group consisting of substituted or unsubstituted N, O and S,
[Formula 2]

In Formula 2,
A is a benzene ring unsubstituted or substituted with deuterium, fused with an adjacent pentagonal ring; Or a naphthalene ring unsubstituted or substituted with deuterium,
L' ₁ to L' ₄ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or a C _2-60 heteroarylene containing at least one selected from the group consisting of unsubstituted N, O and S,
Ar' ₁ to Ar' ₃ are each independently a substituted or unsubstituted C _6-60 aryl; Or a C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.
According to claim 1,
R are each independently hydrogen; heavy hydrogen; phenyl; biphenylyl; naphthyl; (phenyl) naphthyl; (naphthyl)phenyl; phenanthrenyl; chrysenyl; benzophenanthrenyl; triphenylenyl; carbazolyl; fluoranthenyl; benzocarbazolyl; dibenzofuranyl; dibenzothiophenyl; benzonaphthofuranil; or benzonaphthothiophenyl;
R, which is not hydrogen or deuterium, is unsubstituted or substituted with one or more deuterium,
organic light emitting device.
According to claim 1,
L ₁ to L ₃ are each independently a single bond; Or any one selected from the group consisting of,
Organic Light-Emitting Elements:

According to claim 1,
Ar ₁ and Ar ₂ are each independently phenyl; biphenylyl; terphenylyl; naphthyl; phenanthrenyl; fluoranthenyl; chrysenyl; benzophenanthrenyl; dibenzofuranyl; or dibenzothiophenyl;
Wherein Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with one or more deuterium atoms,
organic light emitting device.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic Light-Emitting Elements:

According to claim 1,
L' ₁ to L' ₄ are each independently a single bond; phenylene unsubstituted or substituted with one or more deuterium; Or naphthylene unsubstituted or substituted with one or more deuterium,
organic light emitting device.
According to claim 1,
Ar' ₁ to Ar' ₃ are each independently phenyl; biphenylyl; terphenylyl; naphthyl; dibenzofuranyl; dibenzothiophenyl; or 9,9-dimethylfluorenyl;
Ar' ₁ to Ar' ₃ are each independently unsubstituted or substituted with one or more deuterium atoms,
organic light emitting device.
According to claim 1,
L' ₁ is a single bond or phenylene unsubstituted or substituted with one or more deuterium atoms;
Ar' ₁ is phenyl substituted or unsubstituted with 1 or more deuterium, biphenylyl substituted or unsubstituted with 1 or more deuterium, terphenylyl substituted or unsubstituted with 1 or more deuterium, or substituted or unsubstituted with 1 or more deuterium naphthyl,
organic light emitting device.
According to claim 1,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic Light-Emitting Elements:

Images