WO2021096332A1 - Organic light-emitting diode - Google Patents

Abstract

The present invention provides an organic light-emitting diode.

Description

Organic light emitting element

Cross-reference with related application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0143627 filed on November 11, 2019 and Korean Patent Application No. 10-2020-0150020 filed on November 11, 2020. All contents disclosed in the literature are included as part of this specification.

The present invention relates to an organic light emitting device.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and 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 and a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often made of a multilayer structure made of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an 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 excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows.

Development of new materials for organic materials used in organic light emitting devices as described above is continuously required.

[Prior technical literature]

[Patent Literature]

(Patent Document 0001) Korean Patent Publication No. 10-2000-0051826

The present invention relates to an organic light emitting device.

The present invention provides the following organic light emitting device:

anode;

A negative electrode provided to face the positive electrode; And

Including a light emitting layer provided between the anode and the cathode,

The emission layer includes a first compound represented by Formula 1 and a second compound represented by Formula 2:

[Formula 1]

In Formula 1,

X is O or S,

L ₁ and L ₂ are each independently a single bond, or any one selected from the group consisting of,

One of Ar ₁ and Ar ₂ is substituted or unsubstituted C _6-60 aryl, and the other is substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing one or more heteroatoms of N, O and S,

Each R is independently hydrogen or deuterium,

a is an integer of 1 to 3,

b is an integer from 1 to 6,

[Formula 2]

In Chemical Formula 2,

B ₁ to B ₄ are each independently a C _6-60 aromatic ring fused with an adjacent ring,

L' ₁ and L' ₂ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; _{Or a substituted or unsubstituted C 2-60} heteroarylene containing one or more heteroatoms of N, O and S,

Ar' ₁ and Ar' ₂ are each independently substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing one or more heteroatoms of N, O and S,

Each R'is independently hydrogen or deuterium,

c, d, e and f are each independently an integer of 1 to 6,

When a, b, c, d, e, and f are each 2 or more, the substituents in parentheses are the same as or different from each other.

The above-described organic light-emitting device includes two kinds of host compounds in the light-emitting layer, so that efficiency, driving voltage, and/or lifespan characteristics in the organic light-emitting device can be improved.

1 shows an example of an organic light-emitting device comprising 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), an electron suppression layer (7), a light emitting layer (3), a hole blocking layer (8), an electron injection and transport layer ( 9) and a cathode 4 are shown as an example of an organic light-emitting device.

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

In this specification,

, or

Means a bond connected to another substituent, D means deuterium, and Ph means a phenyl group.

In the present specification, the term "substituted or unsubstituted" refers to 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; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, or may be interpreted as a substituent to 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 a C1-C25 linear, branched or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms in the oxygen of 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 it 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 trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

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, and the like, but is not limited thereto.

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. 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, and the like, but are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary 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, and the like, but are 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 cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, adamantyl, and the like, but are not limited thereto.

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

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,

Can be, etc. However, it is not limited thereto.

In the present specification, the heteroaryl group is a heterocyclic group containing one or more heteroatoms of O, N, Si and S as heterogeneous elements, and the number of carbons is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of the heteroaryl group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl 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, thiiadia There may be a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the aromatic ring refers to a condensed monocyclic or condensed polycyclic ring including only carbon as a ring-forming atom and having aromaticity in the entire molecule. The number of carbon atoms in the aromatic ring is 6 to 60, or 6 to 30, or 6 to 20, but is not limited thereto. In addition, the aromatic ring may be a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, or a pyrene ring, but is not limited thereto.

In the present specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl group is the same as the example 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 example of the aforementioned alkyl group. In the present specification, the heteroaryl among the heteroarylamines may be described above for heteroaryl. In the present specification, the alkenyl group of the aralkenyl group is the same as the example 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 above-described heteroaryl 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 bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the above-described heteroaryl may be applied except that the heterocycle is formed by bonding of two substituents.

In the present specification, the meaning of the term "deuterated or substituted with deuterium" means that at least one available hydrogen in each chemical formula is substituted with deuterium. Specifically, being substituted with deuterium in the definition of each chemical formula or substituent means that at least one or more of the positions at which hydrogen can be bonded in the molecule will be substituted with deuterium, and more specifically, at least 10% of the available hydrogen is It means substituted by deuterium. In one example, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, or 100% deuterated in each formula.

anode; A negative electrode provided to face the positive electrode; And an emission layer provided between the anode and the cathode, wherein the emission layer includes a first compound represented by Chemical Formula 1 and a second compound represented by Chemical Formula 2.

The organic light-emitting device according to the present invention may simultaneously include two types of compounds having a specific structure in the light-emitting layer as host materials, thereby improving efficiency, driving voltage, and/or lifetime characteristics in the organic light-emitting device.

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

Anode and cathode

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material 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.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are a multi-layered material such as LiF/Al or LiO _{2 /Al, but are not limited thereto.}

Hole injection layer

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

The hole injection layer is positioned on the anode and injects holes from the anode, and includes a hole injection material. Such a hole injection material has the ability to transport holes, has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and prevents the movement of excitons generated in the light emitting layer to the electron injection layer or the electron injection material. In addition, a compound having excellent thin film formation ability is preferable. In particular, it is suitable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer.

Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene. Organic materials, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto.

Hole transport layer

The organic light-emitting device according to the present invention may include a hole transport layer between the anode and the emission layer. The hole transport layer is a layer that receives holes from an anode or a hole injection layer formed on the anode and transports holes to the emission layer, and includes a hole transport material. As the hole transport material, a material capable of transporting holes from an anode or a hole injection layer to the light emitting layer and having high mobility for holes is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

E-low layer

The organic light-emitting device according to the present invention may include an electron blocking layer between the hole transport layer and the emission layer, if necessary. The electron blocking layer is formed on the hole transport layer and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons to increase the probability of hole-electron coupling, thereby increasing the efficiency of the organic light-emitting device. It refers to the layer that plays a role in improving the value. The electron blocking layer includes an electron blocking material, and an arylamine-based organic material may be used as an example of the electron blocking material, but is not limited thereto.

Light emitting layer

The organic light-emitting device according to the present invention includes an emission layer between an anode and a cathode, and the emission layer includes the first compound and the second compound as a host material. Specifically, the first compound functions as an N-type host material having an electron transport ability superior to that of a hole transporting ability, and the second compound functions as a P-type host material having a hole transport ability that is superior to an electron transporting ability. The ratio of the electron to the electron can be properly maintained. Accordingly, excitons are evenly emitted from the entire emission layer, so that the luminous efficiency and lifetime characteristics of the organic light-emitting device can be improved at the same time.

Hereinafter, the first compound and the second compound will be sequentially described.

(First compound)

The first compound is represented by Formula 1 above. Specifically, the first compound is a compound in which a triazinyl group is substituted in a furan/thiophene condensed ring core in which at least one naphthalene ring is condensed, and the compound is a dibenzofuran/dibenzothiophene core substituted with a triazinyl group. Compared to the compound, the electron transport ability is excellent, and the electron-hole recombination probability in the light emitting layer can be increased by efficiently transferring electrons to the dopant material.

Preferably, L ₁ is a single bond,

, or

Can be

In addition, L ₂ may be a single bond, or any one selected from the group consisting of:

.

On the other hand, in Formula 1, in the case of a compound in which L ₂ does not have a linker having the above structure, for example, the compound in which L ₂ is 1,3-phenylene or 1,2-phenylene is Compared to 1 compound, the stability against electrons and holes is poor, so it is difficult to effectively transfer energy to the dopant. Accordingly, compared to an organic light-emitting device employing the first compound as one of the cohosts, a compound in which L ₂ does not have a linker having the above structure may have poor efficiency and lifespan characteristics.

Preferably _{, one of Ar 1} and Ar ₂ is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, or fluorenyl, and the other is phenyl, biphenylyl, terphenylyl, naphthyl, Phenanthryl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl,

Here, Ar ₁ and Ar ₂ may be unsubstituted or substituted with one or more substituents selected from the group consisting of _{deuterium, C 1-10} alkyl and C _{6-20 aryl.}

Specifically, Ar ₁ and Ar ₂ are each independently phenyl, phenyl substituted with deuterium, biphenylyl, terphenylyl, phenanthryl, naphthyl, 9,9-dimethylfluorenyl, dibenzofuranyl, dibenzo Thiophenyl, or 9-phenylcarbazole.

In addition, Ar ₁ and Ar ₂ may be the same as each other or may be different from each other.

In addition, one of Ar ₁ and Ar ₂ may be unsubstituted or C _{6-20 aryl substituted with deuterium.}

Alternatively, both Ar ₁ and Ar ₂ may be _{C 6-20} aryl unsubstituted or substituted with deuterium.

Preferably, Ar ₁ is phenyl, biphenylyl, or naphthyl,

Ar ₂ may be phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, 9,9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenylcarbazolyl, or carbazolyl .

For example, Ar ₁ is any one selected from the group consisting of,

Ar ₂ may be any one selected from the group consisting of:

.

Preferably, each R is independently hydrogen or deuterium.

In addition, a, which means the number of R, may be 1, 2, or 3, and b may be 1, 2, 3, 4, 5, or 6.

Preferably, the first compound may be represented by any one of the following 1-1-1 to 1-1-3:

In Formulas 1-1-1 to 1-1-3,

X, L ₂ , Ar ₁ and Ar ₂ are as defined in Chemical Formula 1.

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

.

Meanwhile, among the compounds represented by Formula 1, a compound in which Z is a substituent represented by Formula 1 may be prepared by a manufacturing method such as the following Scheme 1:

[Scheme 1]

In Reaction Scheme 1, X" is halogen, preferably bromo, or chloro, and definitions for other substituents are as described above.

Specifically, the compound represented by Formula 1 may be prepared through a Suzuki-coupling reaction of starting materials A1 and A2. This Suzuki-coupling reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki-coupling reaction may be appropriately changed. The method for preparing the compound represented by Formula 1 may be more specific in Preparation Examples to be described later.

(2nd compound)

The second compound is represented by Chemical Formula 2. Specifically, the second compound has a biscarbazole-based structure, so that holes can be efficiently transferred to a dopant material, and thus, the probability of recombination of holes and electrons in the emission layer together with the first compound having excellent electron transport ability is improved. You can increase it.

In the second compound, B ₁ to B ₄ may each independently be a benzene or naphthalene ring.

For example, B ₁ and B ₂ may each independently be a benzene or naphthalene ring, and B ₃ and B ₄ may be a benzene ring. In this case, the second compound may be represented by the following Formula 2':

[Formula 2']

In Formula 2',

B ₁ and B ₂ are each independently a benzene or naphthalene ring,

L' ₁ , L' ₂ , Ar' ₁ , Ar' ₂ , R', c and d are as defined in Chemical Formula 2.

Preferably, L' ₁ and L' ₂ may each independently be a single bond, or a C _6-20 arylene unsubstituted or substituted with deuterium.

For example, L' ₁ and L' ₂ are each independently a single bond, unsubstituted or deuterium substituted phenylene; Or it may be unsubstituted or naphthylene substituted with deuterium.

For example, L' ₁ and L' ₂ may each independently be a single bond, or any one selected from the group consisting of:

.

In this case, L' ₁ and L' ₂ may be the same as or different from each other.

Preferably, Ar' ₁ and Ar' ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, triphenylenyl, fluoranthenyl, fluorenyl, 9,9'-spirobi Fluorenyl, dibenzofuranyl, or dibenzothiophenyl,

Here, Ar' ₁ and Ar' ₂ are unsubstituted or one or more substituents selected from the group consisting of _{deuterium, C 1-10} alkyl and C _{6-20 aryl, for example, 1 or 2 substituents.} Can be substituted with

For example, Ar' ₁ and Ar' ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, triphenylenyl, fluoranthenyl, fluorenyl, 9,9-dimethylfluore Nil, 9,9-diphenylfluorenyl, 9,9'-spirobifluorenyl, dibenzofuranyl, or dibenzothiophenyl.

In addition, Ar' ₁ and Ar' ₂ may be the same or different from each other.

In addition, R'may be all hydrogen or all deuterium.

In addition, c, d, e, and f indicating the number of R′ may each independently be an integer of 1 to 6. For example, when B ₁ and B ₂ are a benzene ring, c and d are each independently an integer of 1 to 4, and when B ₁ and B ₂ are a naphthalene ring, c and d are each independently an integer of 1 to 6 , When B ₃ and B ₄ are a benzene ring, e and f are each independently an integer of 1 to 3, and when B ₃ and B ₄ are a naphthalene ring, e and f are each independently an integer of 1 to 5.

On the other hand, _{when all of B 1} to B ₄ are benzene rings, the second compound may be represented by the following Formula 2-1:

In Formula 2-1,

L' ₁ , L' ₂ , Ar' ₁ , and Ar' ₂ are as defined in Chemical Formula 2.

Alternatively, when B ₁ is a naphthalene ring, and B ₂ to B ₄ are all benzene rings, the second compound may be represented by the following Formulas 2-2 to 2-4:

.

In Formulas 2-1 to 2-4,

L' ₁ , L' ₂ , Ar' ₁ , and Ar' ₂ are as defined in Chemical Formula 2.

Alternatively, when B ₁ and B ₂ are a naphthalene ring, and B ₃ and B ₄ are a benzene ring, the second compound may be represented by the following Formulas 2-5 to 2-10:

In Formulas 2-5 to 2-10,

L' ₁ , L' ₂ , Ar' ₁ , and Ar' ₂ are as defined in Chemical Formula 2.

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

.

On the other hand, the compound represented by Formula 2 may be prepared by a manufacturing method such as the following Scheme 2 as an example:

[Scheme 2]

In Reaction Scheme 2, X" is halogen, preferably bromo, or chloro, and the definition of other substituents is as described above.

Specifically, the compound represented by Formula 2 may be prepared through a Suzuki-coupling reaction of starting materials A3 and A4. This Suzuki-coupling reaction is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki-coupling reaction may be appropriately changed. The method for preparing the compound represented by Formula 2 may be more specific in Preparation Examples to be described later.

In addition, the first compound and the second compound may be included in a weight ratio of 1:99 to 99:1 in the emission layer. In this case, it is more preferable that the first compound and the second compound are included in a weight ratio of 30:70 to 70:30 in terms of appropriately maintaining the ratio of holes and electrons in the emission layer.

Meanwhile, the emission layer may further include a dopant material in addition to the two kinds of host materials. Such dopant substances include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene and the like having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, examples of the metal complex include an iridium complex and a platinum complex, but are not limited thereto.

More specifically, the following compound may be used as the dopant material, but is not limited thereto:

.

Hole bottom

The organic light emitting device according to the present invention may include a hole blocking layer between the light emitting layer and the electron transport layer to be described later, if necessary. The hole blocking layer is formed on the emission layer and is preferably provided in contact with the emission layer to improve the efficiency of the organic light-emitting device by increasing the probability of hole-electron bonding by controlling electron mobility and preventing excessive movement of holes. It means the layer that plays a role. The hole-blocking layer includes a hole-blocking material, and examples of the hole-blocking material include: a subazine derivative including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; A compound into which an electron withdrawing group is introduced, such as a phosphine oxide derivative, may be used, but is not limited thereto.

Electron injection and transport layer

The electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from an electrode and transporting received electrons to the emission layer, and is formed on the emission layer or the hole blocking layer. As the electron injection and transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high mobility for electrons is suitable. Examples of specific electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complexes containing Alq _3; Organic radical compounds; Hydroxyflavone-metal complex; Triazine derivatives and the like may be used, but are not limited thereto. Or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and their derivatives, metal complex compounds , Or nitrogen-containing 5-membered cyclic derivatives, but are not limited thereto.

The electron injection and transport layer may be formed as separate layers such as an electron injection layer and an electron transport layer. In this case, the electron transport layer is formed on the emission layer or the hole blocking layer, and the electron injection and transport material described above may be used as the electron transport material included in the electron transport layer. In addition, the electron injection layer is formed on the electron transport layer, and electron injection materials included in the electron injection layer include LiF, NaCl, CsF, Li ₂ O, BaO, fluorenone, anthraquinodimethane, diphenoquinone, Thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and the like, their derivatives, metal complex compounds, and nitrogen-containing 5-membered ring derivatives.

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)( o-cresolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. It is not limited thereto.

Organic light emitting element

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 comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4. In such a structure, the first compound and the second compound may be included in the emission layer.

2 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron suppression layer (7), a light emitting layer (3), a hole blocking layer (8), an electron injection and transport layer ( 9) and a cathode 4 are shown as an example of an organic light-emitting device.

In such a structure, the first compound and the second compound may be included in the emission layer.

The organic light-emitting device according to the present invention can be manufactured by sequentially stacking the above-described configurations. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming each of the above-described layers thereon, it can be prepared 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, an organic material layer, and an anode material on a substrate. In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum evaporation method for a host and a dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (WO 2003/012890). However, the manufacturing method is not limited thereto.

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

The fabrication of the organic light emitting device will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[Synthesis Example of First Compound]

Synthesis Example 1: Preparation of Compound 1

In a nitrogen atmosphere, sub1 (15 g, 40.8 mmol) and formula A (11.8 g, 44.9 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (16.9 g, 122.3 mmol) was dissolved in 51 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of compound 1.

(Yield 65%, MS: [M+H] ⁺ = 550)

Synthesis Example 2: Preparation of Compound 2

In a nitrogen atmosphere, sub2 (15 g, 47.2 mmol) and formula A (13.6 g, 51.9 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (19.6 g, 141.6 mmol) was dissolved in 59 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of compound 2.

(Yield 61%, MS: [M+H] ⁺ = 500)

Synthesis Example 3: Preparation of Compound 3

In a nitrogen atmosphere, sub3 (15 g, 38.1 mmol) and formula A (11 g, 41.9 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound 3.

(Yield 61%, MS: [M+H] ⁺ = 576)

Synthesis Example 4: Preparation of compound 4

In a nitrogen atmosphere, sub4 (15 g, 43.6 mmol) and formula A (12.6 g, 48 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (18.1 g, 130.9 mmol) was dissolved in 54 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.3 g of compound 4.

(Yield 80%, MS: [M+H] ⁺ = 526)

Synthesis Example 5: Preparation of compound 5

In a nitrogen atmosphere, sub5 (15 g, 35.7 mmol) and formula A (10.3 g, 39.3 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in 44 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of compound 5.

(Yield 71%, MS: [M+H] ⁺ = 602)

Synthesis Example 6: Preparation of compound 6

In a nitrogen atmosphere, sub6 (15 g, 35.9 mmol) and formula A (10.3 g, 39.5 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 45 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of compound 6.

(Yield 61%, MS: [M+H] ⁺ = 600)

Synthesis Example 7: Preparation of compound 7

In a nitrogen atmosphere, sub7 (15 g, 35.7 mmol) and formula A (10.3 g, 39.3 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in 44 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 7.

(Yield 66%, MS: [M+H] ⁺ = 602)

Synthesis Example 8: Preparation of compound 8

In a nitrogen atmosphere, sub8 (15 g, 40.8 mmol) and formula A (11.8 g, 44.9 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (16.9 g, 122.3 mmol) was dissolved in 51 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound 8.

(Yield 60%, MS: [M+H] ⁺ = 550)

Synthesis Example 9: Preparation of compound 9

In a nitrogen atmosphere, sub9 (15 g, 40.8 mmol) and formula A (11.8 g, 44.9 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (16.9 g, 122.3 mmol) was dissolved in 51 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of compound 9.

(Yield 63%, MS: [M+H] ⁺ = 550)

Synthesis Example 10: Preparation of Compound 10

In a nitrogen atmosphere, sub10 (15 g, 38.1 mmol) and formula A (11 g, 41.9 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 10.

(Yield 72%, MS: [M+H] ⁺ = 576)

Synthesis Example 11: Preparation of Compound 11

In a nitrogen atmosphere, sub11 (15 g, 38.1 mmol) and formula A (11 g, 41.9 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 11.

(Yield 76%, MS: [M+H] ⁺ = 576)

Synthesis Example 12: Preparation of Compound 12

In a nitrogen atmosphere, sub12 (15 g, 41.9 mmol) and formula A (12.1 g, 46.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound 12.

(Yield 61%, MS: [M+H] ⁺ = 540)

Synthesis Example 13: Preparation of compound 13

In a nitrogen atmosphere, sub13 (15 g, 41.9 mmol) and formula A (12.1 g, 46.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.4 g of compound 13.

(Yield 68%, MS: [M+H] ⁺ = 540)

Synthesis Example 14: Preparation of Compound 14

In a nitrogen atmosphere, sub14 (15 g, 36.8 mmol) and formula A (10.6 g, 40.5 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 46 mL of water, stirred sufficiently, and bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.3 g of compound 14.

(Yield 75%, MS: [M+H] ⁺ = 590)

Synthesis Example 15: Preparation of compound 15

In a nitrogen atmosphere, sub10 (15 g, 36.8 mmol) and formula A (10.6 g, 40.5 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 46 mL of water, stirred sufficiently, and bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of compound 15.

(Yield 70%, MS: [M+H] ⁺ = 590)

Synthesis Example 16: Preparation of Compound 16

In a nitrogen atmosphere, sub16 (15 g, 40.1 mmol) and formula A (11.6 g, 44.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (16.6 g, 120.4 mmol) was dissolved in 50 mL of water and then sufficiently stirred, and then bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.8 g of compound 16.

(Yield 62%, MS: [M+H] ⁺ = 556)

Synthesis Example 17: Preparation of compound 17

In a nitrogen atmosphere, sub17 (15 g, 40.1 mmol) and formula A (11.6 g, 44.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (16.6 g, 120.4 mmol) was dissolved in 50 mL of water and then sufficiently stirred, and then bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.1 g of compound 17.

(Yield 68%, MS: [M+H] ⁺ = 556)

Synthesis Example 18: Preparation of Compound 18

In a nitrogen atmosphere, sub18 (15 g, 40.1 mmol) and formula A (11.6 g, 44.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (16.6 g, 120.4 mmol) was dissolved in 50 mL of water and then sufficiently stirred, and then bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.8 g of compound 18.

(Yield 80%, MS: [M+H] ⁺ = 556)

Synthesis Example 19: Preparation of compound 19

In a nitrogen atmosphere, sub19 (15 g, 34.6 mmol) and formula A (10 g, 38.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (14.4 g, 103.9 mmol) was dissolved in 43 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.5 g of compound 19.

(Yield 73%, MS: [M+H] ⁺ = 615)

Synthesis Example 20: Preparation of Compound 20

In a nitrogen atmosphere, sub20 (15 g, 34.6 mmol) and formula A (10 g, 38.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (14.4 g, 103.9 mmol) was dissolved in 43 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 20.

(Yield 80%, MS: [M+H] ⁺ = 61)

Synthesis Example 21: Preparation of Compound 21

In a nitrogen atmosphere, sub21 (15 g, 42 mmol) and formula A (12.1 g, 46.2 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (17.4 g, 126.1 mmol) was dissolved in 52 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5 g of compound 21.

(Yield 64%, MS: [M+H] ⁺ = 539)

Synthesis Example 22: Preparation of Compound 22

In a nitrogen atmosphere, sub22 (15 g, 31.1 mmol) and formula A (9 g, 34.2 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (12.9 g, 93.2 mmol) was dissolved in 39 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.4 g of compound 22.

(Yield 60%, MS: [M+H] ⁺ = 665)

Synthesis Example 23: Preparation of Compound 23

(1) Step 23-1: Preparation of intermediate compound subB-1

In a nitrogen atmosphere, sub2 (15 g, 47.2 mmol) and formula B (7.4 g, 47.2 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (19.6 g, 141.6 mmol) was dissolved in 59 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.5 g, 0.5 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 subB-1.

(Yield 75%, MS: [M+H] ⁺ = 394)

(2) Step 23-2: Preparation of compound 23

In a nitrogen atmosphere, subB-1 (15 g, 38.1 mmol) and formula A (11 g, 41.9 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.3 g of compound 23.

(Yield 70%, MS: [M+H] ⁺ = 576)

Synthesis Example 24: Preparation of Compound 24

(1) Step 24-1: Preparation of intermediate compound subB-2

In a nitrogen atmosphere, sub23 (15 g, 35.7 mmol) and formula B (5.6 g, 35.7 mmol) were added to 300 mL of THF, and stirred and refluxed. Thereafter, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in 44 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.4 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of subB-2.

(Yield 68%, MS: [M+H] ⁺ = 496)

(2) Step 24-2: Preparation of compound 24

In a nitrogen atmosphere, subB-2 (15 g, 30.2 mmol) and formula A (8.7 g, 33.3 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (12.5 g, 90.7 mmol) was dissolved in 38 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of compound 24.

(Yield 64%, MS: [M+H] ⁺ = 678)

Synthesis Example 25: Preparation of compound 25

(1) Step 25-1: Preparation of intermediate compound subB-3

In a nitrogen atmosphere, sub12 (15 g, 41.9 mmol) and formula B (6.6 g, 41.9 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.5 g, 0.4 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of subB-3.

(Yield 71%, MS: [M+H] ⁺ = 434)

(2) Step 25-2: Preparation of compound 25

In a nitrogen atmosphere, sub-3 (15 g, 34.6 mmol) and formula A (10 g, 38 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 mL of water, stirred sufficiently, and then bis(tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 25.

(Yield 80%, MS: [M+H] ⁺ = 616)

Synthesis Example 26: Preparation of Compound 26

(1) Step 26-1: Preparation of intermediate compound subB-4

In a nitrogen atmosphere, sub17 (15 g, 40.1 mmol) and formula B (6.3 g, 40.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (16.6 g, 120.4 mmol) was dissolved in 50 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.5 g, 0.4 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1 g of subB-4.

(Yield 67%, MS: [M+H] ⁺ = 450)

(2) Step 26-2: Preparation of compound 26

In a nitrogen atmosphere, subB-4 (15 g, 33.3 mmol) and formula A (9.6 g, 36.7 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (13.8 g, 100 mmol) was dissolved in 41 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 26.

(Yield 75%, MS: [M+H] ⁺ = 632)

Synthesis Example 27: Preparation of Compound 27

(1) Step 27-1: Preparation of intermediate compound subB-5

In a nitrogen atmosphere, sub3 (15 g, 38.1 mmol) and formula A (10 g, 38.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.4 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of subB-5.

(Yield 79%, MS: [M+H]+= 470)

(2) Step 27-2: Preparation of compound 27

In a nitrogen atmosphere, subB-5 (15 g, 31.9 mmol) and formula A (9.2 g, 35.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (13.2 g, 95.8 mmol) was dissolved in 40 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of compound 27.

(Yield 60%, MS: [M+H] ⁺ = 652)

Synthesis Example 28: Preparation of compound 28

(1) Step 28-1: Preparation of intermediate compound subB-6

In a nitrogen atmosphere, sub24 (15 g, 35.4 mmol) and formula B (5.5 g, 35.4 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (14.7 g, 106.2 mmol) was dissolved in 44 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.4 g, 0.4 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of subB-6.

(Yield 71%, MS: [M+H] ⁺ = 500)

(2) Step 28-2: Preparation of compound 28

In a nitrogen atmosphere, subB-6 (15 g, 30 mmol) and formula A (8.6 g, 33 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (12.4 g, 90 mmol) was dissolved in 37 mL of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 28 (yield 73%, MS: [M+H]+=682).

Synthesis Example 29: Preparation of compound 29

(1) Step 29-1: Preparation of intermediate compound subC-1

In a nitrogen atmosphere, sub25 (15 g, 56 mmol) and formula C (11.6 g, 56 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (23.2 g, 168.1 mmol) was dissolved in 70 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.6 g, 0.6 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 subC-1.

(Yield 76%, MS: [M+H] ⁺ = 394)

(2) Step 29-2: Preparation of compound 29

In a nitrogen atmosphere, subC-1 (15 g, 38.1 mmol) and formula A (10 g, 38.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16 g of compound 29.

(Yield 73%, MS: [M+H] ⁺ = 576)

Synthesis Example 30: Preparation of Compound 30

(1) Step 30-1: Preparation of intermediate compound subC-2

In a nitrogen atmosphere, sub2 (15 g, 47.2 mmol) and formula C (9.7 g, 47.2 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (19.6 g, 141.6 mmol) was dissolved in 59 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.5 g, 0.5 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14 g of subC-2.

(Yield 67%, MS: [M+H] ⁺ = 444)

(2) Step 30-2: Preparation of compound 30

In a nitrogen atmosphere, subC-2 (15 g, 33.8 mmol) and formula A (8.9 g, 33.8 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.1 g of compound 30.

(Yield 62%, MS: [M+H] ⁺ = 626)

Synthesis Example 31: Preparation of Compound 31

(1) Step 31-1: Preparation of intermediate compound subC-3

In a nitrogen atmosphere, sub26 (15 g, 40.8 mmol) and formula C (8.4 g, 40.8 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (16.9 g, 122.3 mmol) was dissolved in 51 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.5 g, 0.4 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 subC-3 (yield 67%, MS: [M+H]+= 494).

(2) Step 31-2: Preparation of compound 31

In a nitrogen atmosphere, subC-3 (15 g, 30.4 mmol) and formula A (8 g, 30.4 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (12.6 g, 91.1 mmol) was dissolved in 38 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.6 g of compound 31.

(Yield 76%, MS: [M+H] ⁺ = 676)

Synthesis Example 32: Preparation of Compound 32

(1) Step 32-1: Preparation of intermediate compound subC-4

In a nitrogen atmosphere, sub4 (15 g, 43.6 mmol) and formula C (9 g, 43.6 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (18.1 g, 130.9 mmol) was dissolved in 54 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.5 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 subC-4.

(Yield 80%, MS: [M+H] ⁺ = 470)

(2) Step 32-2: Preparation of compound 32

In a nitrogen atmosphere, subC-4 (15 g, 31.9 mmol) and formula A (8.4 g, 31.9 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (13.2 g, 95.8 mmol) was dissolved in 40 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 32.

(Yield 65%, MS: [M+H] ⁺ = 652)

Synthesis Example 33: Preparation of Compound 33

(1) Step 33-1: Preparation of intermediate compound subC-5

In a nitrogen atmosphere, sub10 (15 g, 38.1 mmol) and formula C (7.9 g, 38.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.4 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of subC-5 (yield 72%, MS: [M+H]+=520).

(2) Step 33-2: Preparation of compound 33

In a nitrogen atmosphere, subC-5 (15 g, 28.8 mmol) and formula A (7.6 g, 28.8 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (12 g, 86.5 mmol) was dissolved in 36 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1 g of compound 33.

(Yield 60%, MS: [M+H] ⁺ = 702)

Synthesis Example 34: Preparation of Compound 34

(1) Step 34-1: Preparation of intermediate compound subC-6

In a nitrogen atmosphere, sub27 (15 g, 40.8 mmol) and formula C (8.4 g, 40.8 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (16.9 g, 122.3 mmol) was dissolved in 51 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.5 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 subC-6.

(Yield 78%, MS: [M+H] ⁺ = 494)

(2) Step 34-2: Preparation of compound 34

In a nitrogen atmosphere, subC-6 (15 g, 30.4 mmol) and formula A (8 g, 30.4 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (12.6 g, 91.1 mmol) was dissolved in 38 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.2 g of compound 34.

(Yield 74%, MS: [M+H] ⁺ = 676)

Synthesis Example 35: Preparation of compound 35

(1) Step 35-1: Preparation of intermediate compound subC-7

In a nitrogen atmosphere, sub34 (15 g, 39.1 mmol) and formula C (8.1 g, 39.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (16.2 g, 117.2 mmol) was dissolved in 49 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.5 g, 0.4 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.9 g of subC-7.

(Yield 80%, MS: [M+H] ⁺ = 510)

(2) Step 35-2: Preparation of compound 35

In a nitrogen atmosphere, subC-7 (15 g, 29.4 mmol) and formula A (7.7 g, 29.4 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of compound 35.

(Yield 70%, MS: [M+H] ⁺ = 692)

Synthesis Example 36: Preparation of Compound 36

(1) Step 36-1: Preparation of intermediate compound subC-8

In a nitrogen atmosphere, sub28 (15 g, 34.6 mmol) and formula C (7.2 g, 34.6 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (14.4 g, 103.9 mmol) was dissolved in 43 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.4 g, 0.3 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.3 g of subC-8.

(Yield 69%, MS: [M+H] ⁺ = 559)

(2) Step 36-2: Preparation of compound 36

In a nitrogen atmosphere, subC-8 (15 g, 26.8 mmol) and formula A (7 g, 26.8 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (11.1 g, 80.5 mmol) was dissolved in 33 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.5 g of compound 36.

(Yield 78%, MS: [M+H] ⁺ = 741)

Synthesis Example 37: Preparation of Compound 37

(1) Step 37-1: Preparation of intermediate compound subC-9

In a nitrogen atmosphere, sub19 (15 g, 34.6 mmol) and formula C (7.2 g, 34.6 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (14.4 g, 103.9 mmol) was dissolved in 43 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.4 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 subC-9.

(Yield 72%, MS: [M+H] ⁺ = 559)

(2) Step 37-2: Preparation of compound 37

In a nitrogen atmosphere, subC-9 (15 g, 26.8 mmol) and formula A (7 g, 26.8 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (11.1 g, 80.5 mmol) was dissolved in 33 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5 g of compound 37.

(Yield 73%, MS: [M+H] ⁺ = 741)

Synthesis Example 38: Preparation of Compound 38

(1) Step 38-1: Preparation of intermediate compound subC-10

In a nitrogen atmosphere, sub12 (15 g, 41.9 mmol) and formula C (8.7 g, 41.9 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.5 g, 0.4 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.2 g of subC-10.

(Yield 70%, MS: [M+H] ⁺ = 484)

(2) Step 38-2: Preparation of compound 38

In a nitrogen atmosphere, subC-10 (15 g, 31 mmol) and formula A (8.1 g, 31 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.3 mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of compound 38.

(Yield 65%, MS: [M+H] ⁺ = 666)

Synthesis Example 39: Preparation of Compound 39

(1) Step 39-1: Preparation of intermediate compound subC-11

In a nitrogen atmosphere, sub29 (15 g, 36.8 mmol) and formula C (7.6 g, 36.8 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 46 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.4 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of subC-11.

(Yield 66%, MS: [M+H] ⁺ = 534)

(2) Step 39-2: Preparation of compound 39

In a nitrogen atmosphere, subC-11 (15 g, 28.1 mmol) and formula A (7.4 g, 28.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (11.6 g, 84.3 mmol) was dissolved in 35 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5 g of compound 39.

(Yield 72%, MS: [M+H] ⁺ = 716)

Synthesis Example 40: Preparation of Compound 40

(1) Step 40-1: Preparation of intermediate compound subC-12

In a nitrogen atmosphere, sub30 (15 g, 36.8 mmol) and formula C (7.6 g, 36.8 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 46 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.4 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.9 g of subC-12.

(Yield 66%, MS: [M+H] ⁺ = 534)

(2) Step 40-2: Preparation of compound 40

In a nitrogen atmosphere, subC-12 (15 g, 28.1 mmol) and formula A (7.4 g, 28.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (11.6 g, 84.3 mmol) was dissolved in 35 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, 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 40.

(Yield 63%, MS: [M+H] ⁺ = 716)

Synthesis Example 41: Preparation of Compound 41

(1) Step 41-1: Preparation of intermediate compound subC-13

In a nitrogen atmosphere, sub31 (15 g, 35.5 mmol) and formula C (7.3 g, 35.5 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (14.7 g, 106.4 mmol) was dissolved in 44 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.4 g, 0.4 mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.6 g of subC-13.

(Yield 75%, MS: [M+H] ⁺ = 550)

(2) Step 41-2: Preparation of compound 41

In a nitrogen atmosphere, subC-13 (15 g, 27.3 mmol) and formula A (7.1 g, 27.3 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (11.3 g, 81.8 mmol) was dissolved in 34 mL of water, and after sufficiently stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.6 g of compound 41.

(Yield 68%, MS: [M+H]+= 732)

Synthesis Example 42: Preparation of Compound 42

(1) Step 42-1: Preparation of intermediate compound subC-14

In a nitrogen atmosphere, sub17 (15 g, 40.1 mmol) and formula C (8.3 g, 40.1 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (16.6 g, 120.4 mmol) was dissolved in 50 mL of water, and after sufficiently stirring, tetrakis (triphenylphosphine) palladium (0) (0.5 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of subC-14.

(Yield 65%, MS: [M+H] ⁺ = 500)

(2) Step 42-2: Preparation of compound 42

In a nitrogen atmosphere, subC-14 (15 g, 30 mmol) and formula A (7.9 g, 30 mmol) were added to 300 mL of THF, followed by stirring and refluxing. Thereafter, potassium carbonate (12.4 g, 90 mmol) was dissolved in 37 mL of water, stirred sufficiently, and then bis(tri-tert-butylphosphine)palladium (0) (0.2 g, 0.3 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.7 g of compound 42.

(Yield 72%, MS: [M+H] ⁺ = 682)

[Synthesis Example of Second Compound]

Synthesis Example 2-1: Preparation of Compound 2-1

In a nitrogen atmosphere, intermediate 2-1-1 (10 g, 25.2 mmol) and intermediate 2-1-2 (8 g, 27.7 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.9 g, 100.7 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of compound 2-1.

(Yield 64%, MS: [M+H] ⁺ = 561)

Synthesis Example 2-2: Preparation of Compound 2-2

In a nitrogen atmosphere, intermediate 2-2-1 (10 g, 25.2 mmol) and intermediate 2-2-2 (8 g, 27.7 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.9 g, 100.7 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 4 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.6 g of compound 2-2.

(Yield 66%, MS: [M+H] ⁺ = 637)

Synthesis Example 2-3: Preparation of Compound 2-3

In a nitrogen atmosphere, intermediate 2-3-1 (10 g, 25.2 mmol) and intermediate 2-3-2 (10.1 g, 27.7 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.9 g, 100.7 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 4 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of compound 2-3.

(Yield 56%, MS: [M+H] ⁺ = 637)

Synthesis Example 2-4: Preparation of compound 2-4

In a nitrogen atmosphere, intermediate 2-4-1 (10 g, 25.2 mmol) and intermediate 2-4-2 (9.3 g, 27.7 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.9 g, 100.7 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.8 g of compound 2-4.

(Yield 51%, MS: [M+H] ⁺ = 611)

Synthesis Example 2-5: Preparation of compound 2-5

In a nitrogen atmosphere, intermediate 2-5-1 (10 g, 25.2 mmol) and intermediate 2-5-2 (10.1 g, 27.7 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.9 g, 100.7 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 4 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4 g of compound 2-5.

(Yield 65%, MS: [M+H] ⁺ = 637)

Synthesis Example 2-6: Preparation of compound 2-6

In a nitrogen atmosphere, intermediate 2-6-1 (10 g, 25.2 mmol) and intermediate 2-6-2 (11.4 g, 27.7 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.9 g, 100.7 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.5 g of compound 2-6.

(Yield 61%, MS: [M+H] ⁺ = 687)

Synthesis Example 2-7: Preparation of Compound 2-7

In a nitrogen atmosphere, intermediate 2-7-1 (10 g, 22.4 mmol) and intermediate 2-7-2 (10.2 g, 24.6 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (12.4 g, 89.5 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11 g of compound 2-7.

(Yield 67%, MS: [M+H] ⁺ = 737)

Synthesis Example 2-8: Preparation of compound 2-8

In a nitrogen atmosphere, intermediate 2-8-1 (10 g, 17.9 mmol) and intermediate 2-8-2 (5.6 g, 19.7 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (9.9 g, 71.5 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.8 g of compound 2-8.

(Yield 60%, MS: [M+H] ⁺ = 723)

Synthesis Example 2-9: Preparation of Compound 2-9

In a nitrogen atmosphere, intermediate 2-9-1 (10 g, 21.1 mmol) and intermediate 2-9-2 (6.7 g, 23.3 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (11.7 g, 84.6 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 7.4 g of compound 2-9.

(Yield 55%, MS: [M+H] ⁺ = 637)

Synthesis Example 2-10: Preparation of Compound 2-10

In a nitrogen atmosphere, intermediate 2-10-1 (10 g, 27 mmol) and intermediate 2-10-2 (10 g, 29.6 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (14.9 g, 107.8 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11 g of compound 2-10.

(Yield 70%, MS: [M+H] ⁺ = 585)

Synthesis Example 2-11: Preparation of Compound 2-11

In a nitrogen atmosphere, intermediate 2-11-1 (10 g, 27 mmol) and intermediate 2-11-2 (11.5 g, 29.6 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (14.9 g, 107.8 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.3 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.5 g of compound 2-11.

(Yield 67%, MS: [M+H] ⁺ = 635)

Synthesis Example 2-12: Preparation of Compound 2-12

In a nitrogen atmosphere, intermediate 2-12-1 (10 g, 23.8 mmol) and intermediate 2-12-2 (8.8 g, 26.1 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.1 g, 95 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.4 g of compound 2-12.

(Yield 69%, MS: [M+H] ⁺ = 635)

Synthesis Example 2-13: Preparation of Compound 2-13

In a nitrogen atmosphere, intermediate 2-13-1 (10 g, 24.3 mmol) and intermediate 2-13-2 (11.1 g, 26.8 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of compound 2-13.

(Yield 53%, MS: [M+H] ⁺ = 701)

Synthesis Example 2-14: Preparation of Compound 2-14

In a nitrogen atmosphere, intermediate 2-14-1 (10 g, 24.3 mmol) and intermediate 2-14-2 (7.7 g, 26.8 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.9 g of compound 2-14.

(Yield 64%, MS: [M+H] ⁺ = 575)

Synthesis Example 2-15: Preparation of Compound 2-15

In a nitrogen atmosphere, intermediate 2-15-1 (10 g, 24.3 mmol) and intermediate 2-15-2 (9 g, 26.8 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 4 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 8.4 g of compound 2-15.

(Yield 55%, MS: [M+H] ⁺ = 625)

Synthesis Example 2-16: Preparation of Compound 2-16

In a nitrogen atmosphere, intermediate 2-16-1 (10 g, 24.3 mmol) and intermediate 2-16-2 (11.1 g, 26.8 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of compound 2-16.

(Yield 66%, MS: [M+H] ⁺ = 701)

Synthesis Example 2-17: Preparation of Compound 2-17

In a nitrogen atmosphere, intermediate 2-17-1 (10 g, 24.3 mmol) and intermediate 2-17-2 (10.1 g, 26.8 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10 g of compound 2-17.

(Yield 62%, MS: [M+H] ⁺ = 665)

Synthesis Example 2-18: Preparation of Compound 2-18

In a nitrogen atmosphere, intermediate 2-18-1 (10 g, 24.3 mmol) and intermediate 2-18-2 (10.5 g, 26.8 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.8 g of compound 2-18.

(Yield 59%, MS: [M+H]+= 681)

Synthesis Example 2-19: Preparation of Compound 2-19

In a nitrogen atmosphere, intermediate 2-19-1 (10 g, 24.3 mmol) and intermediate 2-19-2 (10.5 g, 26.8 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (13.5 g, 97.3 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of compound 2-19.

(Yield 69%, MS: [M+H] ⁺ = 681)

Synthesis Example 2-20: Preparation of Compound 2-20

In a nitrogen atmosphere, intermediate 2-20-1 (10 g, 23.4 mmol) and intermediate 2-20-2 (9.4 g, 25.8 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (12.9 g, 93.7 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 2 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of compound 2-20.

(Yield 58%, MS: [M+H] ⁺ = 667)

Synthesis Example 2-21: Preparation of Compound 2-21

In a nitrogen atmosphere, intermediate 2-21-1 (10 g, 23.4 mmol) and intermediate 2-21-2 (10.6 g, 25.8 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (12.9 g, 93.7 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 4 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.7 g of compound 2-21.

(Yield 64%, MS: [M+H] ⁺ = 717)

Synthesis Example 2-22: Preparation of Compound 2-22

In a nitrogen atmosphere, intermediate 2-22-1 (10 g, 23.4 mmol) and intermediate 2-22-2 (11.3 g, 25.8 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (12.9 g, 93.7 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 3 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9 g of compound 2-22.

(Yield 52%, MS: [M+H] ⁺ = 743)

Synthesis Example 2-23: Preparation of Compound 2-23

In a nitrogen atmosphere, intermediate 2-23-1 (10 g, 23.4 mmol) and intermediate 2-23-2 (10.1 g, 25.8 mmol) were added to 200 mL of THF, stirred, and potassium carbonate (12.9 g, 93.7 mmol) was added to water. After dissolving, stirring, and refluxing, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 mmol) was added. After the reaction for 4 hours, the mixture was cooled to room temperature, 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, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.1 g of compound 2-23.

(Yield 56%, MS: [M+H] ⁺ = 697)

Example 1: Fabrication of an organic light emitting device

A glass substrate coated with a thin film of ITO (indium tin oxide) having a thickness of 1,000Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a product made by Fischer Co. was used as a detergent, and distilled water secondarily filtered with a filter manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

The following HI-1 compound was formed as a hole injection layer on the prepared ITO transparent electrode to a thickness of 1150Å, but the following compound A-1 was p-doped at a concentration of 1.5%. The following HT-1 compound was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Subsequently, an electron suppressing layer was formed by vacuum depositing the following EB-1 compound with a film thickness of 150 Å on the hole transport layer.

Then, on the EB-1 deposition film, the compound 1 prepared in Synthesis Example 1 was used as a first host, the compound 2-1 prepared in Synthesis Example 2-1 was used as a second host, and the following Dp-7 compound was used as a dopant. A red light emitting layer having a thickness of 400Å was formed by vacuum evaporation. In this case, the first host and the second host were used in a weight ratio of 1:1, and the total host material and the dopant material were used in a weight ratio of 98:2.

A hole blocking layer was formed by vacuum depositing the following HB-1 compound with a thickness of 30 Å on the emission layer. Subsequently, the following ET-1 compound and the following LiQ compound were vacuum-deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300 Å. Lithium fluoride (LiF) in a thickness of 12 Å and aluminum in a thickness of 1,000 Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7Å/sec, the deposition rate of lithium fluoride at the negative electrode was 0.3Å/sec, and the deposition rate of aluminum was 2Å/sec, and the vacuum degree during deposition was 2 x 10 ^{− Maintaining 7} ~ 5 x 10 ^-6 torr, an organic light emitting device was manufactured.

Examples 2 to 100

In the organic light emitting device of Example 1, an organic light emitting device was manufactured in the same manner as in Example 1, except that the compounds shown in Tables 1 to 3 were used instead of Compound 1 and Compound 2-1 as cohost materials. .

Comparative Examples 1 to 37

In the organic light-emitting device of Example 1, an organic light-emitting device was prepared in the same manner as in Example 1, except that a single host compound shown in Tables 4 and 5 was used instead of compound 1 and compound 2-1 as cohost materials. Was prepared. At this time, the structures of Comparative Compounds C-1 to C-12 in Table 5 are as follows.

Comparative Examples 38 to 85

In the organic light emitting device of Example 1, an organic light emitting device was manufactured in the same manner as in Example 1, except that the compounds shown in Tables 6 and 7 were used instead of compounds 1 and 2-1 as cohost materials. .

Experimental example

When a current was applied to the organic light-emitting devices prepared in Examples 1 to 100 and Comparative Examples 1 to 85, voltage, efficiency, and lifetime were measured (15 mA/cm ² basis) and the results are shown in the following table It is shown in 1-7. Life T95 refers to the time it takes for the luminance to decrease from the initial luminance (6,000 nit) to 95%.

division	Host 1	2nd host	Driving voltage (V)	Efficiency (cd/A)	Life T95(hr)	Luminous color
Example 1	Compound 1	Compound 2-1	3.76	24.3	260	Red
Example 2		Compound 2-2	3.78	25.4	242	Red
Example 3		Compound 2-8	3.77	25.9	241	Red
Example 4		Compound 2-19	3.76	25.4	253	Red
Example 5	Compound 3	Compound 2-9	3.68	24.4	235	Red
Example 6		Compound 2-10	3.71	24.3	242	Red
Example 7		Compound 2-12	3.70	25.7	224	Red
Example 8		Compound 2-16	3.72	24.5	246	Red
Example 9	Compound 5	Compound 2-3	3.78	25.4	237	Red
Example 10		Compound 2-4	3.72	24.8	232	Red
Example 11		Compound 2-14	3.74	25.9	247	Red
Example 12		Compound 2-21	3.76	24.4	261	Red
Example 13	Compound 9	Compound 2-1	3.65	25.1	224	Red
Example 14		Compound 2-2	3.70	25.3	211	Red
Example 15		Compound 2-8	3.74	26.4	223	Red
Example 16		Compound 2-19	3.73	25.5	234	Red
Example 17	Compound 10	Compound 2-9	3.75	25.1	242	Red
Example 18		Compound 2-10	3.71	25.3	247	Red
Example 19		Compound 2-12	3.70	26.8	252	Red
Example 20		Compound 2-16	3.78	24.6	238	Red
Example 21	Compound 14	Compound 2-3	3.77	26.1	223	Red
Example 22		Compound 2-4	3.76	26.5	231	Red
Example 23		Compound 2-14	3.81	25.2	219	Red
Example 24		Compound 2-21	3.84	25.8	214	Red
Example 25	Compound 17	Compound 2-1	3.89	24.3	231	Red
Example 26		Compound 2-2	3.92	25.2	245	Red
Example 27		Compound 2-8	3.91	25.7	227	Red
Example 28		Compound 2-19	3.95	24.8	236	Red
Example 29	Compound 19	Compound 2-9	3.88	25.9	231	Red
Example 30		Compound 2-10	3.85	26.1	223	Red
Example 31		Compound 2-12	3.92	26.9	217	Red
Example 32		Compound 2-16	3.96	25.4	235	Red
Example 33	Compound 21	Compound 2-3	3.90	26.7	251	Red
Example 34		Compound 2-4	3.91	26.5	248	Red
Example 35		Compound 2-14	3.84	27.3	232	Red
Example 36		Compound 2-21	3.93	26.7	257	Red
Example 37	Compound 23	Compound 2-1	3.94	25.8	221	Red
Example 38		Compound 2-2	3.91	26.1	216	Red
Example 39		Compound 2-8	3.97	25.3	214	Red
Example 40		Compound 2-19	3.90	26.4	218	Red

division	Host 1	2nd host	Driving voltage (V)	Efficiency (cd/A)	Life T95(hr)	Luminous color
Example 41	Compound 25	Compound 2-9	3.89	25.9	228	Red
Example 42		Compound 2-10	3.87	24.3	220	Red
Example 43		Compound 2-12	3.90	25.9	234	Red
Example 44		Compound 2-16	3.99	26.4	230	Red
Example 45	Compound 29	Compound 2-3	3.95	25.7	253	Red
Example 46		Compound 2-4	3.99	27.3	232	Red
Example 47		Compound 2-14	4.02	26.1	236	Red
Example 48		Compound 2-21	4.00	27.9	237	Red
Example 49	Compound 30	Compound 2-1	3.92	26.5	238	Red
Example 50		Compound 2-2	3.91	25.3	219	Red
Example 51		Compound 2-8	3.98	26.2	220	Red
Example 52		Compound 2-19	4.01	26.0	218	Red
Example 53	Compound 31	Compound 2-9	3.97	25.5	251	Red
Example 54		Compound 2-10	4.03	25.8	263	Red
Example 55		Compound 2-12	4.01	25.4	230	Red
Example 56		Compound 2-16	4.05	24.1	259	Red
Example 57	Compound 32	Compound 2-3	3.98	26.0	253	Red
Example 58		Compound 2-4	4.05	25.2	242	Red
Example 59		Compound 2-14	4.07	25.0	239	Red
Example 60		Compound 2-21	4.04	24.3	243	Red
Example 61	Compound 33	Compound 2-1	3.91	26.8	253	Red
Example 62		Compound 2-2	3.98	26.1	262	Red
Example 63		Compound 2-8	3.84	25.4	261	Red
Example 64		Compound 2-19	3.90	26.2	247	Red
Example 65	Compound 34	Compound 2-9	3.94	27.8	249	Red
Example 66		Compound 2-10	4.02	27.1	250	Red
Example 67		Compound 2-12	4.05	26.4	256	Red
Example 68		Compound 2-16	3.96	27.2	247	Red
Example 69	Compound 35	Compound 2-3	3.90	26.3	228	Red
Example 70		Compound 2-4	4.01	27.5	239	Red
Example 71		Compound 2-14	3.88	25.2	241	Red
Example 72		Compound 2-21	4.05	27.4	258	Red
Example 73	Compound 36	Compound 2-1	3.81	26.7	256	Red
Example 74		Compound 2-2	3.84	26.1	262	Red
Example 75		Compound 2-8	3.80	25.6	271	Red
Example 76		Compound 2-19	3.92	27.0	258	Red
Example 77	Compound 37	Compound 2-9	3.79	25.0	262	Red
Example 78		Compound 2-10	3.81	25.5	247	Red
Example 79		Compound 2-12	3.85	26.4	243	Red
Example 80		Compound 2-16	3.88	27.8	260	Red

division		Host 1	2nd host	Driving voltage (V)	Efficiency (cd/A)	Life T95(hr)	Luminous color
Example 81	Compound 38	Compound 2-3	3.74	25.5	251	Red
Example 82		Compound 2-4	3.78	24.6	230	Red
Example 83		Compound 2-14	3.72	25.4	242	Red
Example 84		Compound 2-21	3.75	26.8	237	Red
Example 85	Compound 39	Compound 2-1	3.78	27.1	271	Red
Example 86		Compound 2-2	3.80	26.7	264	Red
Example 87		Compound 2-8	3.84	25.6	270	Red
Example 88		Compound 2-19	3.81	24.4	257	Red
Example 89	Compound 40	Compound 2-9	3.61	27.8	252	Red
Example 90		Compound 2-10	3.60	25.9	265	Red
Example 91		Compound 2-12	3.63	27.0	269	Red
Example 92		Compound 2-16	3.61	26.4	258	Red
Example 93	Compound 41	Compound 2-3	3.73	25.6	268	Red
Example 94		Compound 2-4	3.76	25.8	260	Red
Example 95		Compound 2-14	3.74	24.7	271	Red
Example 96		Compound 2-21	3.73	24.4	242	Red
Example 97	Compound 42	Compound 2-1	3.60	25.8	247	Red
Example 98		Compound 2-2	3.61	25.1	234	Red
Example 99		Compound 2-8	3.60	25.3	259	Red
Example 100		Compound 2-19	3.53	25.6	252	Red

division	matter	Efficiency (cd/A)	Life T95(hr)	Luminous color
Comparative Example 1	Compound 1	20.3	122	Red
Comparative Example 2	Compound 3	21.1	135	Red
Comparative Example 3	Compound 5	23.2	148	Red
Comparative Example 4	Compound 9	22.6	127	Red
Comparative Example 5	Compound 10	21.8	143	Red
Comparative Example 6	Compound 14	23.2	157	Red
Comparative Example 7	Compound 17	22.6	145	Red
Comparative Example 8	Compound 19	21.4	128	Red
Comparative Example 9	Compound 21	23.5	172	Red
Comparative Example 10	Compound 23	19.4	126	Red
Comparative Example 11	Compound 25	20.2	129	Red
Comparative Example 12	Compound 29	21.3	141	Red
Comparative Example 13	Compound 30	21.5	133	Red
Comparative Example 14	Compound 31	20.2	145	Red
Comparative Example 15	Compound 32	21.6	157	Red
Comparative Example 16	Compound 33	22.3	140	Red
Comparative Example 17	Compound 34	21.6	152	Red
Comparative Example 18	Compound 35	22.2	143	Red
Comparative Example 19	Compound 36	22.8	142	Red
Comparative Example 20	Compound 37	21.6	158	Red
Comparative Example 21	Compound 38	22.3	141	Red
Comparative Example 22	Compound 39	21.5	151	Red
Comparative Example 23	Compound 40	20.7	160	Red
Comparative Example 24	Compound 41	22.6	159	Red
Comparative Example 25	Compound 42	23.4	163	Red

division	matter	Efficiency (cd/A)	Life T95(hr)	Luminous color
Comparative Example 26	C-1	17.4	107	Red
Comparative Example 27	C-2	16.1	83	Red
Comparative Example 28	C-3	16.4	94	Red
Comparative Example 29	C-4	16.0	87	Red
Comparative Example 30	C-5	18.7	110	Red
Comparative Example 31	C-6	16.8	51	Red
Comparative Example 32	C-7	15.5	24	Red
Comparative Example 33	C-8	15.1	37	Red
Comparative Example 34	C-9	17.3	75	Red
Comparative Example 35	C-10	17.5	92	Red
Comparative Example 36	C-11	15.8	63	Red
Comparative Example 37	C-12	16.1	78	Red

division	Host 1	2nd host	Driving voltage (V)	Efficiency (cd/A)	Life T95(hr)	Luminous color
Comparative Example 38	Compound C-1	Compound 2-1	4.25	18.1	189	Red
Comparative Example 39		Compound 2-2	4.24	19.3	190	Red
Comparative Example 40		Compound 2-8	4.22	17.8	176	Red
Comparative Example 41		Compound 2-19	4.23	18.5	187	Red
Comparative Example 42	Compound C-2	Compound 2-9	4.20	18.0	171	Red
Comparative Example 43		Compound 2-10	4.22	17.7	173	Red
Comparative Example 44		Compound 2-12	4.25	18.2	182	Red
Comparative Example 45		Compound 2-16	4.21	17.4	170	Red
Comparative Example 46	Compound C-3	Compound 2-3	4.21	17.2	169	Red
Comparative Example 47		Compound 2-4	4.23	20.8	164	Red
Comparative Example 48		Compound 2-14	4.22	19.4	158	Red
Comparative Example 49		Compound 2-21	4.08	17.0	173	Red
Comparative Example 50	Compound C-4	Compound 2-1	4.05	16.8	168	Red
Comparative Example 51		Compound 2-2	4.04	19.5	152	Red
Comparative Example 52		Compound 2-8	4.17	17.2	150	Red
Comparative Example 53		Compound 2-19	4.10	19.3	164	Red
Comparative Example 54	Compound C-5	Compound 2-9	4.23	19.0	185	Red
Comparative Example 55		Compound 2-10	4.10	20.8	195	Red
Comparative Example 56		Compound 2-12	4.17	19.1	187	Red
Comparative Example 57		Compound 2-16	4.12	19.5	194	Red
Comparative Example 58	Compound C-6	Compound 2-3	4.20	18.1	114	Red
Comparative Example 59		Compound 2-4	4.25	17.4	111	Red
Comparative Example 60		Compound 2-14	4.21	19.3	105	Red
Comparative Example 61		Compound 2-21	4.18	17.0	109	Red
Comparative Example 62	Compound C-7	Compound 2-1	4.12	17.6	54	Red
Comparative Example 63		Compound 2-2	4.25	16.1	63	Red
Comparative Example 64		Compound 2-8	4.13	18.5	58	Red
Comparative Example 65		Compound 2-19	4.17	16.4	52	Red
Comparative Example 66	Compound C-8	Compound 2-9	4.05	17.0	50	Red
Comparative Example 67		Compound 2-10	4.03	18.4	54	Red
Comparative Example 68		Compound 2-12	4.08	16.8	51	Red
Comparative Example 69		Compound 2-16	4.09	17.5	57	Red
Comparative Example 70	Compound C-9	Compound 2-3	4.11	18.5	147	Red
Comparative Example 71		Compound 2-4	4.13	18.9	169	Red
Comparative Example 72		Compound 2-14	4.15	19.3	163	Red
Comparative Example 73		Compound 2-21	4.14	18.7	161	Red
Comparative Example 74	Compound C-10	Compound 2-1	4.06	19.3	164	Red
Comparative Example 75		Compound 2-2	4.09	19.0	170	Red
Comparative Example 76		Compound 2-8	4.05	19.4	178	Red
Comparative Example 77		Compound 2-19	4.02	19.1	173	Red

division		Host 1	2nd host	Driving voltage (V)	Efficiency (cd/A)	Life T95(hr)	Luminous color
Comparative Example 78	Compound C-11	Compound 2-9	4.11	18.0	134	Red
Comparative Example 79		Compound 2-10	4.18	19.1	147	Red
Comparative Example 80		Compound 2-12	4.21	18.3	149	Red
Comparative Example 81		Compound 2-16	4.18	18.3	150	Red
Comparative Example 82	Compound C-12	Compound 2-1	4.10	18.2	158	Red
Comparative Example 83		Compound 2-2	4.11	17.5	152	Red
Comparative Example 84		Compound 2-8	4.10	17.8	156	Red
Comparative Example 85		Compound 2-19	4.14	17.9	151	Red

As shown in Tables 1 to 7, the organic light emitting device of the embodiment in which the first compound represented by Formula 1 and the second compound represented by Formula 2 were simultaneously used as the host material of the emission layer was represented by Formulas 1 and 2. Compared to the organic light-emitting device of Comparative Example in which only one or both of the displayed compounds were not employed, excellent luminous efficiency and remarkably improved lifespan characteristics were exhibited.

Specifically, the device according to the embodiment exhibited higher efficiency and longer life than the device of the comparative example employing the compound represented by Formula 1 as a single host. In addition, the device according to the embodiment has a driving voltage, efficiency, and lifespan compared to the device of the comparative example employing Comparative Examples compounds C-1 to C-12 as a first host and the compound represented by Formula 2 as a second host. All of the characteristics have been improved. Through this, when the combination of the first compound represented by Formula 1 and the second compound represented by Formula 2 was used as a cohost, it was confirmed that energy was effectively transferred to the red dopant in the red light emitting layer. This can be determined because the first compound has high stability against electrons and holes, and also because the amount of holes increased as the second compound was used at the same time, and a more stable balance of electrons and holes was maintained in the red light emitting layer. It is judged as.

Accordingly, it was confirmed that when the first compound and the second compound are simultaneously employed as host materials of the organic light-emitting device, driving voltage, luminous efficiency, and lifetime characteristics of the organic light-emitting device can be improved. In general, when considering that the luminous efficiency and lifetime characteristics of the organic light-emitting device have a trade-off relationship with each other, the organic light-emitting device employing a combination of the compounds of the present invention has significantly improved device characteristics compared to the comparative example device. It can be seen as representing.

[Explanation of code]

1: substrate 2: anode

3: light-emitting layer 4: cathode

5: hole injection layer 6: hole transport layer

7: electron suppression layer 8: hole blocking layer

9: Electron injection and transport layer

Claims (12)

1. anode;

   A negative electrode provided to face the positive electrode; And

   Including a light emitting layer provided between the anode and the cathode,

   The emission layer comprises a first compound represented by the following formula 1 and a second compound represented by the following formula 2,

   Organic Light-Emitting Element:

   [Formula 1]

   

   In Formula 1,

   X is O or S,

   L ₁ and L ₂ are each independently a single bond, or any one selected from the group consisting of,

   

   One of Ar ₁ and Ar ₂ is substituted or unsubstituted C _6-60 aryl, and the other is substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing one or more heteroatoms of N, O and S,

   Each R is independently hydrogen or deuterium,

   a is an integer of 1 to 3,

   b is an integer from 1 to 6,

   [Formula 2]

   

   In Chemical Formula 2,

   B ₁ to B ₄ are each independently a C _6-60 aromatic ring fused with an adjacent ring,

   L' ₁ and L' ₂ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; _{Or a substituted or unsubstituted C 2-60} heteroarylene containing one or more heteroatoms of N, O and S,

   Ar' ₁ and Ar' ₂ are each independently substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl containing one or more heteroatoms of N, O and S,

   Each R'is independently hydrogen or deuterium,

   c, d, e, and f are each independently an integer of 1 to 6.
2. The method of claim 1,

   L ₁ is a single bond,

   

   , or

   

   sign,

   Organic light emitting device.
3. The method of claim 1,

   L ₂ is a single bond, or any one selected from the group consisting of,

   Organic Light-Emitting Element:

   

   .
4. The method of claim 1,

   One of Ar ₁ and Ar ₂ is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, or fluorenyl, and the other is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, flu Orenyl, dibenzofuranyl, dibenzothiophenyl, or carbazolyl,

   Here, Ar ₁ and Ar ₂ are unsubstituted or substituted with one or more substituents selected from the group consisting of _{deuterium, C 1-10} alkyl and C _{6-20 aryl,}

   Organic light emitting device.
5. The method of claim 1,

   Ar ₁ is phenyl, biphenylyl, or naphthyl,

   Ar ₂ is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, 9,9-dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, 9-phenylcarbazolyl, or carbazolyl,

   Organic light emitting device.
6. The method of claim 1,

   The first compound is represented by any one of the following formulas 1-1-1 to 1-1-3,

   Organic Light-Emitting Element:

   

   In Formulas 1-1-1 to 1-1-3,

   X, L ₂ , Ar ₁ and Ar ₂ are as defined in claim 1.
7. The method of claim 1,

   The first compound is any one selected from the group consisting of the following compounds,

   Organic Light-Emitting Element:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   .
8. The method of claim 1,

   The second compound is represented by the following formula 2',

   Organic Light-Emitting Element:

   [Formula 2']

   

   In Formula 2',

   B ₁ and B ₂ are each independently a benzene or naphthalene ring,

   L' ₁ , L' ₂ , Ar' ₁ , Ar' ₂ , R', c and d are as defined in claim 1.
9. The method of claim 1,

   L' ₁ and L' ₂ are each independently a single bond; Phenylene unsubstituted or substituted with deuterium; Or naphthylene unsubstituted or substituted with deuterium,

   Organic light emitting device.
10. The method of claim 1,

    Ar' ₁ and Ar' ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthryl, triphenylenyl, fluoranthenyl, fluorenyl, 9,9-dimethylfluorenyl, 9, 9-diphenylfluorenyl, 9,9'-spirobifluorenyl, dibenzofuranyl, or dibenzothiophenyl,

    Organic light emitting device.
11. The method of claim 1,

    The second compound is represented by the following formula 2-1,

    Organic Light-Emitting Element:

    [Formula 2-1]

    

    In Formula 2-1,

    L' ₁ , L' ₂ , Ar' ₁ , and Ar' ₂ are as defined in claim 1.
12. The method of claim 1,

    The second compound is any one selected from the group consisting of the following compounds,

    Organic Light-Emitting Element:

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    .

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