WO2021230715A1 - Organic light-emitting element - Google Patents

Abstract

The present invention provides an organic light-emitting element having improved driving voltage, efficiency, and service life.

Description

organic light emitting device

Cross-Citation with Related Application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0057863 dated May 14, 2020 and Korean Patent Application No. 10-2021-0062251 dated May 13, 2021, All content disclosed in the literature is incorporated as a part of this specification.

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and 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 layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, and may include, for example, 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 the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up.

In the organic light emitting device as described above, the development of an organic light emitting device having improved driving voltage, efficiency, and lifespan is continuously required.

Prior art literature

Patent Literature

(Patent Document 1) Korean Patent Publication No. 10-2000-0051826

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

The present invention provides the following organic light emitting device:

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

The light emitting layer comprises a compound represented by the following formula (1) and a compound represented by the following formula (2),

Organic light emitting device:

[Formula 1]

In Formula 1,

Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl comprising any one or more selected from the group consisting of N, O and S,

L ₁ to L ₃ are each independently, a single bond; Or a substituted or unsubstituted C _6-60 arylene,

R ₁ is hydrogen; heavy hydrogen; substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl comprising any one or more selected from the group consisting of N, O and S,

a is an integer from 0 to 7,

[Formula 2]

In Formula 1,

Ar ₃ and Ar ₄ are each independently, substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl comprising any one or more selected from the group consisting of N, O and S,

L ₄ to L ₆ are each independently, a single bond; or substituted or unsubstituted C _6-60 arylene.

The above-described organic light emitting device includes the compound represented by Formula 1 and the compound represented by Formula 2 in the light emitting layer, thereby improving efficiency, low driving voltage, and/or lifespan characteristics in the organic light emitting device.

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 .

2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), electron blocking layer (7), light emitting layer (3), hole blocking layer (8), electron transport layer (9) ), an example of an organic light-emitting device comprising an electron injection layer 10 and a cathode 4 is shown.

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

In this specification,

or

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an aryl phosphine group; Or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more, or substituted or unsubstituted, two or more of the above-exemplified substituents are linked. . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

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

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

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

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a phenylboron group, and the like.

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 number of carbon atoms in the alkyl group is 1 to 20. 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 linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. 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 carbon number of the cycloalkyl group is 3 to 20. 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, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. The aryl group may be a monocyclic aryl group, such as a phenyl group, a biphenyl group, or a terphenyl group, but 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,

etc. can be However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an 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, thiadia and a jolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

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

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

positive and negative

The anode and cathode used in the present invention mean electrodes used in an organic light emitting device.

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

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

hole injection layer

The organic light emitting diode according to the present invention may further include a hole injection layer on the anode, if necessary.

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. In addition, it is preferable that the highest occupied molecular orbital (HOMO) 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, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

hole transport layer

The organic light emitting diode according to the present invention may include a hole transport layer on the anode (or on the hole injection layer when there is a hole injection layer) if necessary.

The hole transport layer is a layer that receives holes from the anode or hole injection layer and transports the holes to the light emitting layer. Larger materials are suitable.

Specific examples of the hole transport material include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together.

electron blocking layer

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

The electron blocking layer is a layer placed between the hole transport layer and the light emitting layer to prevent electrons injected from the cathode from passing to the hole transport layer without recombination in the light emitting layer, and is also called an electron blocking layer or an electron blocking layer. For the electron blocking layer, a material having a lower electron affinity than the electron transport layer is preferable.

light emitting layer

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

Preferably, the compound represented by Formula 1 may be represented by any one of Formulas 1-1 to 1-3 below:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,

Ar ₁ , Ar ₂ , L ₁ to L ₃ and R ₁ are as defined in Formula 1.

Preferably, Ar ₁ and Ar ₂ are each independently selected from substituted or unsubstituted C _6-20 aryl; Or it may be _{a C 2-20} heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, Ar ₁ and Ar ₂ may each independently be phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl,

Most preferably, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of:

.

Preferably, L _{One To} L ₃ Each independently, a single bond; Or it may be a substituted or unsubstituted C _{6-20 arylene,}

More preferably, L ₁ to L ₃ may each independently be a single bond, phenylene, biphenylylene, or naphthylene,

Most preferably, L ₁ to L ₃ may each independently be any one selected from the group consisting of a single bond or the following:

.

Preferably, _{each R 1} is independently hydrogen; heavy hydrogen; substituted or unsubstituted C _6-20 aryl; Or it may be _{a C 2-20} heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, _{each R 1} is independently hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthyl phenyl, phenyl naphthyl, fluoranthenyl, di benzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl.

Preferably, a may be 0 or 1. More preferably, a may be 1.

Preferably _{, at least one of Ar 1} , Ar ₂ and R ₁ is naphthyl, phenyl naphthyl, naphthyl phenyl, phenanthrenyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl.

More preferably _{, at least one of Ar 1} , Ar ₂ and R ₁ may be naphthyl, phenyl naphthyl, naphthyl phenyl, fluoranthenyl, dibenzofuranyl, benzonaphthofuranyl, or benzonaphthothiophenyl have.

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

.

The compound represented by Formula 1 may be prepared by, for example, a preparation method as in Scheme 1 below, and other compounds may be prepared similarly.

[Scheme 1]

In Scheme 1, Ar ₁ , Ar ₂ , L ₁ to L ₃ , R ₁ and a are as defined in Formula 1 above, X ₁ is halogen, and preferably X ₁ is chloro or bromo.

The Suzuki coupling reaction in Scheme 1 is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Preferably, Ar ₃ and Ar ₄ are each independently selected from substituted or unsubstituted C _6-20 aryl; Or it may be _{a C 2-20} heteroaryl comprising at least one selected from the group consisting of substituted or unsubstituted N, O and S,

More preferably, Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthrenyl, naphthyl phenyl, phenyl naphthyl, dimethylfluorenyl, di phenylfluorenyl, spirobifluorenyl, carbazolyl, phenyl carbazolyl, dibenzofuranyl, dibenzothiophenyl, or benzonaphthofuranyl;

Most preferably, Ar ₃ and Ar ₄ may each independently be any one selected from the group consisting of:

.

Preferably, L ₄ to L ₆ are each independently, a single bond; Or it may be a substituted or unsubstituted C _{6-20 arylene,}

More preferably, L ₄ to L ₆ may each independently be a single bond, phenylene, biphenylrylene, naphthylene, or dimethyl fluorenylene,

Most preferably, L ₄ to L ₆ may each independently be any one selected from the group consisting of a single bond or the following:

.

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

The compound represented by Chemical Formula 2 may be prepared by, for example, a preparation method as shown in Scheme 2 below, and other compounds may be prepared similarly.

[Scheme 2]

In Scheme 2, Ar ₃ , Ar ₄ and L ₄ to L ₆ are as defined in Formula 2 above, X ₂ is halogen, and preferably X ₂ is chloro or bromo.

Scheme 2 is an amine substitution reaction, preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

Preferably, the weight ratio of the compound represented by Formula 1 and the compound represented by Formula 2 in the emission layer is 10:90 to 90:10, more preferably 20:80 to 80:20, 30:70 to 70:30 or 40:60 to 60:40.

Meanwhile, the light emitting layer may further include a dopant in addition to the host. The dopant material is not particularly limited as long as it is a material used in an organic light emitting device. Examples include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, and periflanthene having an arylamino group. As the styrylamine compound, a substituted or unsubstituted It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

hole blocking layer

The organic light emitting diode according to the present invention may include an electron transport layer on the light emitting layer, if necessary.

The hole blocking layer is a layer placed between the electron transport layer and the light emitting layer to prevent the holes injected from the anode from passing to the electron transport layer without recombination in the light emitting layer, and is also called a hole blocking layer or a hole blocking layer. A material having high ionization energy is preferable for the hole blocking layer.

electron transport layer

The organic light emitting diode according to the present invention may include an electron transport layer on the light emitting layer (or hole blocking layer) if necessary.

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

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

electron injection layer

The organic light emitting diode according to the present invention may further include an electron injection layer on the light emitting layer (or on the electron transport layer if the electron transport layer is present) as needed.

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

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

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

On the other hand, in the present invention, the "electron injection and transport layer" is a layer that performs both the role of the electron injection layer and the electron transport layer, and the materials acting as the respective layers may be used alone or in combination, but limited thereto. doesn't happen

organic light emitting device

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

The organic light emitting device according to the present invention may be manufactured by sequentially stacking the above-described components. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. And, after forming each of the above-mentioned 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 the cathode material on the substrate in the reverse order of the above-described configuration to the anode material (WO 2003/012890). In addition, the light emitting layer may be formed by a solution coating method as well as a vacuum deposition method for the host and dopant. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

Meanwhile, the organic light emitting device according to the present invention may be a bottom emission device, a top emission device, or a double-sided light emitting device, and in particular, may be a bottom light emitting device requiring relatively high luminous efficiency.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the content of the present invention is not limited thereto.

[Production Example]

Preparation 1-1: Preparation of compound 1-1

In a nitrogen atmosphere, compound 1-A (15 g, 60.9 mmol) and compound Trz27 (25.6 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.1 g of compound sub1-A-1 (yield 65%, MS: [M+H] ⁺ = 484).

In a nitrogen atmosphere, compound sub1-A-1 (15 g, 31 mmol) and compound sub1 (6.1 g, 31 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-1 (yield 66%, MS: [M+H] ⁺ = 602).

Preparation 1-2: Preparation of compound 1-2

In a nitrogen atmosphere, compound 1-A (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.5 g of compound sub1-A-2 (yield 74%, MS: [M+H] ⁺ = 434).

In a nitrogen atmosphere, compound sub1-A-2 (15 g, 34.6 mmol) and compound sub2 (9.4 g, 34.6 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (9.6 g, 69.1 mmol) was dissolved in 29 ml of water and thoroughly stirred, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-2 (yield 66%, MS: [M+H] ⁺ = 626).

Preparation Example 1-3: Preparation of compound 1-3

In a nitrogen atmosphere, compound 1-A (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.2 g of compound sub1-A-3 (yield 79%, MS: [M+H] ⁺ = 484).

In a nitrogen atmosphere, compound sub1-A-3 (15 g, 31 mmol) and compound sub3 (7.1 g, 31 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After the reaction for 12 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 1-3 (yield 66%, MS: [M+H] ⁺ = 632).

Preparation Example 1-4: Preparation of compound 1-4

In a nitrogen atmosphere, compound 1-A (15 g, 60.9 mmol) and compound Trz4 (27 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26 g of compound sub1-A-4 (yield 70%, MS: [M+H] ⁺ = 610).

In a nitrogen atmosphere, compound sub1-A-4 (15 g, 24.6 mmol) and compound sub4 (5.6 g, 24.6 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (6.8 g, 49.2 mmol) was dissolved in 20 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-4 (yield 60%, MS: [M+H] ⁺ = 758)

Preparation Example 1-5: Preparation of compound 1-5

In a nitrogen atmosphere, compound 1-B (15 g, 60.9 mmol) and compound Trz5 (24 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2 g of compound sub1-B-1 (yield 77%, MS: [M+H] ⁺ = 560).

In a nitrogen atmosphere, compound sub1-B-1 (15 g, 26.8 mmol) and compound sub5 (3.3 g, 26.8 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in 22 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 1-5 (yield 80%, MS: [M+H] ⁺ = 602).

Preparation 1-6: Preparation of compound 1-6

In a nitrogen atmosphere, compound 1-B (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.2 g of compound sub1-B-2 (yield 62%, MS: [M+H] ⁺ = 484).

In a nitrogen atmosphere, compound sub1-B-2 (15 g, 31 mmol) and compound sub6 (7.6 g, 31 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-6 (yield 76%, MS: [M+H] ⁺ = 650).

Preparation Example 1-7: Preparation of compound 1-7

In a nitrogen atmosphere, compound 1-B (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 12 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound sub1-B-3 (yield 79%, MS: [M+H] ⁺ = 434).

In a nitrogen atmosphere, compound sub1-B-3 (15 g, 34.6 mmol) and compound sub7 (8.6 g, 34.6 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (9.6 g, 69.1 mmol) was dissolved in 29 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-7 (yield 74%, MS: [M+H] ⁺ = 602).

Preparation Example 1-8: Preparation of compound 1-8

In a nitrogen atmosphere, compound sub1-B-2 (15 g, 31 mmol) and compound sub8 (8.1 g, 31 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-8 (yield 75%, MS: [M+H] ⁺ = 666).

Preparation 1-9: Preparation of compound 1-9

In a nitrogen atmosphere, compound 1-B (15 g, 60.9 mmol) and compound Trz6 (22.4 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.7 g of compound sub1-B-4 (yield 73%, MS: [M+H] ⁺ = 534).

In a nitrogen atmosphere, compound sub1-B-4 (15 g, 28.1 mmol) and compound sub9 (6 g, 28.1 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (7.8 g, 56.2 mmol) was dissolved in 23 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6 g of compound 1-9 (yield 62%, MS: [M+H] ⁺ = 666).

Preparation Example 1-10: Preparation of compound 1-10

In a nitrogen atmosphere, compound 1-B (15 g, 60.9 mmol) and compound Trz7 (28.6 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 28.6 g of compound sub1-B-5 (yield 74%, MS: [M+H] ⁺ = 636)

In a nitrogen atmosphere, compound sub1-B-5 (15 g, 23.6 mmol) and compound sub5 (2.9 g, 23.6 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (6.5 g, 47.2 mmol) was dissolved in 20 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.2 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-10 (yield 65%, MS: [M+H] ⁺ = 678)

Preparation Example 1-11: Preparation of compound 1-11

In a nitrogen atmosphere, compound 1-B (15 g, 60.9 mmol) and compound Trz8 (21.8 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.1 g of compound sub1-B-6 (yield 63%, MS: [M+H] ⁺ = 524).

In a nitrogen atmosphere, compound sub1-B-6 (15 g, 28.6 mmol) and compound sub10 (4.9 g, 28.6 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (7.9 g, 57.3 mmol) was dissolved in 24 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-11 (yield 65%, MS: [M+H] ⁺ = 616).

Preparation 1-12: Preparation of compound 1-12

In a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g of compound sub1-C-1 (yield 60%, MS: [M+H] ⁺ = 484).

In a nitrogen atmosphere, compound sub1-C-1 (15 g, 31 mmol) and compound sub10 (5.3 g, 31 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-12 (yield 72%, MS: [M+H] ⁺ = 576).

Preparation 1-13: Preparation of compound 1-13

In a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz9 (24 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 12 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.5 g of compound sub1-C-2 (yield 69%, MS: [M+H] ⁺ = 560).

In a nitrogen atmosphere, compound sub1-C-2 (15 g, 26.8 mmol) and compound sub10 (4.6 g, 26.8 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in 22 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 1-13 (yield 80%, MS: [M+H] ⁺ = 652).

Preparation Example 1-14: Preparation of compound 1-14

In a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.5 g of compound sub1-C-3 (yield 66%, MS: [M+H] ⁺ = 510).

In a nitrogen atmosphere, compound sub1-C-3 (15 g, 29.4 mmol) and compound sub11 (7.3 g, 29.4 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (8.1 g, 58.8 mmol) was dissolved in 24 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-14 (yield 77%, MS: [M+H] ⁺ = 678).

Preparation Example 1-15: Preparation of compound 1-15

In a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.7 g of compound sub1-C-4 (yield 71%, MS: [M+H] ⁺ = 434).

In a nitrogen atmosphere, compound sub1-C-4 (15 g, 37.1 mmol) and compound sub12 (9.7 g, 37.1 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (10.3 g, 74.3 mmol) was dissolved in 31 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.4 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-15 (yield 64%, MS: [M+H] ⁺ = 616).

Preparation Example 1-16: Preparation of compound 1-16

In a nitrogen atmosphere, compound sub1-C-3 (15 g, 26.8 mmol) and compound sub13 (7.4 g, 26.8 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in 22 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.2 g of compound 1-16 (yield 80%, MS: [M+H] ⁺ = 758).

Preparation Example 1-17: Preparation of compound 1-17

In a nitrogen atmosphere, compound sub1-C-4 (15 g, 34.6 mmol) and compound sub14 (7.7 g, 34.6 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (9.6 g, 69.1 mmol) was dissolved in 29 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-17 (yield 62%, MS: [M+H] ⁺ = 576).

Preparation Example 1-18: Preparation of compound 1-18

Compound sub1-C-1 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to 300 ml of THF in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (8.6 g, 62 mmol) was dissolved in 26 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 1-18 (yield 63%, MS: [M+H] ⁺ = 616).

Preparation Example 1-19: Preparation of compound 1-19

In a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz11 (22.4 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.4 g of compound sub1-C-5 (yield 69%, MS: [M+H] ⁺ = 534).

In a nitrogen atmosphere, compound sub1-C-5 (15 g, 28.1 mmol) and compound sub15 (6 g, 28.1 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (7.8 g, 56.2 mmol) was dissolved in 23 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 1-19 (yield 71%, MS: [M+H] ⁺ = 666).

Preparation Example 1-20: Preparation of compound 1-20

In a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz12 (21.8 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21 g of compound sub1-C-6 (yield 66%, MS: [M+H] ⁺ = 524).

In a nitrogen atmosphere, compound sub1-C-6 (15 g, 28.6 mmol) and compound sub10 (4.9 g, 28.6 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of compound 1-20 (yield 70%, MS: [M+H] ⁺ = 616).

Preparation 1-21: Preparation of compound 1-21

In a nitrogen atmosphere, compound 1-C (15 g, 60.9 mmol) and compound Trz13 (24 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 12 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2 g of compound sub1-C-7 (yield 77%, MS: [M+H] ⁺ = 560).

In a nitrogen atmosphere, compound sub1-C-7 (15 g, 26.8 mmol) and compound sub5 (3.3 g, 26.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-21 (yield 65%, MS: [M+H] ⁺ = 602).

Preparation 1-22: Preparation of compound 1-22

In a nitrogen atmosphere, compound 1-D (15 g, 60.9 mmol) and compound Trz14 (19.3 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 23.9 g of compound sub1-D-1 (yield 67%, MS: [M+H] ⁺ = 586).

In a nitrogen atmosphere, compound sub1-D-1 (15 g, 25.6 mmol) and compound sub5 (3.1 g, 25.6 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (10.6 g, 76.8 mmol) was dissolved in 32 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.3 g of compound 1-22 (yield 64%, MS: [M+H] ⁺ = 628).

Preparation 1-23: Preparation of compound 1-23

In a nitrogen atmosphere, compound 1-D (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20 g of compound sub1-D-2 (yield 76%, MS: [M+H] ⁺ = 434).

In a nitrogen atmosphere, compound sub1-D-2 (15 g, 34.6 mmol) and compound sub16 (9.1 g, 34.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 1-23 (yield 66%, MS: [M+H] ⁺ = 616).

Preparation 1-24: Preparation of compound 1-24

In a nitrogen atmosphere, compound 1-D (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 12 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound sub1-D-3 (yield 67%, MS: [M+H] ⁺ = 510).

In a nitrogen atmosphere, compound sub1-D-3 (15 g, 29.4 mmol) and compound sub17 (7.7 g, 29.4 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-24 (yield 61%, MS: [M+H] ⁺ = 692).

Preparation Example 1-25: Preparation of compound 1-25

In a nitrogen atmosphere, compound 1-D (15 g, 60.9 mmol) and compound Trz15 (21.8 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.3 g of compound sub1-D-4 (yield 67%, MS: [M+H] ⁺ = 524).

In a nitrogen atmosphere, compound sub1-D-4 (15 g, 28.6 mmol) and compound sub10 (4.9 g, 28.6 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-25 (yield 61%, MS: [M+H] ⁺ = 616).

Preparation 1-26: Preparation of compound 1-26

In a nitrogen atmosphere, compound sub1-D-3 (15 g, 29.4 mmol) and compound sub18 (6.2 g, 29.4 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of compound 1-26 (yield 76%, MS: [M+H] ⁺ = 642).

Preparation 1-27: Preparation of compound 1-27

In a nitrogen atmosphere, compound 1-D (15 g, 60.9 mmol) and compound Trz16 (27 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 27.1 g of compound sub1-D-5 (yield 73%, MS: [M+H] ⁺ = 610).

In a nitrogen atmosphere, compound sub1-D-5 (15 g, 24.6 mmol) and compound sub9 (5.2 g, 24.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.2 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-27 (yield 70%, MS: [M+H] ⁺ = 742).

Preparation 1-28: Preparation of compound 1-28

Compound 1-D (15 g, 60.9 mmol) and compound Trz13 (24 g, 60.9 mmol) were added to 300 ml of THF in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound sub1-D-6 (yield 61%, MS: [M+H] ⁺ = 560).

In a nitrogen atmosphere, compound sub1-D-6 (15 g, 26.8 mmol) and compound sub10 (4.6 g, 26.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-28 (yield 70%, MS: [M+H] ⁺ = 652).

Preparation 1-29: Preparation of compound 1-29

Compound 1-E (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 ml of THF in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.1 g of compound sub1-E-1 (yield 65%, MS: [M+H] ⁺ = 434).

In a nitrogen atmosphere, compound sub1-E-1 (15 g, 34.6 mmol) and compound sub2 (9.4 g, 34.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-29 (yield 67%, MS: [M+H] ⁺ = 626).

Preparation Example 1-30: Preparation of compound 1-30

In a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz9 (24 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.9 g of compound sub1-E-2 (yield 79%, MS: [M+H] ⁺ = 560).

In a nitrogen atmosphere, compound sub1-E-2 (15 g, 26.8 mmol) and compound sub19 (7 g, 26.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 Compound 1-30 (yield 80%, MS: [M+H] ⁺ = 742).

Preparation Example 1-31: Preparation of compound 1-31

In a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz17 (22.4 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.3 g of compound sub1-E-3 (yield 78%, MS: [M+H] ⁺ = 534).

In a nitrogen atmosphere, compound sub1-E-3 (15 g, 28.1 mmol) and compound sub20 (7.8 g, 28.1 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (11.6 g, 84.3 mmol) was dissolved in 35 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8 g of compound 1-31 (yield 72%, MS: [M+H] ⁺ = 732).

Preparation Example 1-32: Preparation of compound 1-32

In a nitrogen atmosphere, compound sub1-E-1 (15 g, 34.6 mmol) and compound sub21 (7.7 g, 34.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 1-32 (yield 65%, MS: [M+H] ⁺ = 576).

Preparation Example 1-33: Preparation of compound 1-33

In a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz15 (21.8 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.5 g of compound sub1-E-4 (yield 80%, MS: [M+H] ⁺ = 524).

In a nitrogen atmosphere, compound sub1-E-4 (15 g, 28.6 mmol) and compound sub10 (4.9 g, 28.6 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (11.9 g, 85.9 mmol) was dissolved in 36 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-33 (yield 60%, MS: [M+H] ⁺ = 616).

Preparation Example 1-34: Preparation of compound 1-34

In a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz3 (19.3 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g of compound sub1-E-5 (yield 60%, MS: [M+H] ⁺ = 484).

In a nitrogen atmosphere, compound sub1-E-5 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-34 (yield 60%, MS: [M+H] ⁺ = 616).

Preparation Example 1-35: Preparation of compound 1-35

In a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7 g of compound sub1-E-6 (yield 70%, MS: [M+H] ⁺ = 510).

In a nitrogen atmosphere, compound sub1-E-6 (15 g, 29.4 mmol) and compound sub22 (7.7 g, 29.4 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-35 (yield 72%, MS: [M+H] ⁺ = 692).

Preparation Example 1-36: Preparation of compound 1-36

In a nitrogen atmosphere, compound sub1-E-5 (15 g, 31 mmol) and compound sub23 (8.1 g, 31 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 12 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-36 (yield 60%, MS: [M+H] ⁺ = 666).

Preparation Example 1-37: Preparation of compound 1-37

Compound sub1-E-5 (15 g, 31 mmol) and compound sub10 (5.3 g, 31 mmol) were added to 300 ml of THF in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 12 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-37 (yield 79%, MS: [M+H] ⁺ = 576).

Preparation Example 1-38: Preparation of compound 1-38

In a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz18 (27 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.1 g of compound sub1-E-7 (yield 65%, MS: [M+H] ⁺ = 610).

In a nitrogen atmosphere, compound sub1-E-7 (15 g, 24.6 mmol) and compound sub5 (3 g, 24.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.2 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.1 g of compound 1-38 (yield 63%, MS: [M+H] ⁺ = 652).

Preparation Example 1-39: Preparation of compound 1-39

In a nitrogen atmosphere, compound 1-E (15 g, 60.9 mmol) and compound Trz13 (24 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 12 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 26.2 g of compound sub1-E-8 (yield 77%, MS: [M+H] ⁺ = 560).

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

Preparation 1-40: Preparation of compound 1-40

In a nitrogen atmosphere, compound 1-F (15 g, 60.9 mmol) and compound Trz2 (16.3 g, 60.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 12 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.2 g of compound sub1-F-1 (yield 73%, MS: [M+H] ⁺ = 434).

In a nitrogen atmosphere, compound 1-F-1 (15 g, 34.6 mmol) and compound sub6 (8.5 g, 34.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-40 (yield 71%, MS: [M+H] ⁺ = 600).

Preparation Example 1-41: Preparation of compound 1-41

In a nitrogen atmosphere, compound 1-F (15 g, 60.9 mmol) and compound Trz10 (20.9 g, 60.9 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (25.2 g, 182.6 mmol) was dissolved in 76 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.1 g of compound sub1-F-2 (yield 68%, MS: [M+H] ⁺ = 510).

In a nitrogen atmosphere, compound sub1-F-2 (15 g, 29.4 mmol) and compound sub1 (5.8 g, 29.4 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12.2 g, 88.2 mmol) was dissolved in 37 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added thereto. After the reaction for 12 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-41 (yield 77%, MS: [M+H] ⁺ = 628).

Preparation Example 1-42: Preparation of compound 1-42

In a nitrogen atmosphere, compound Trz7 (15 g, 31.9 mmol) and compound sub9 (6.8 g, 31.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (13.2 g, 95.8 mmol) was dissolved in 40 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-42 (yield 79%, MS: [M+H] ⁺ = 602).

Preparation Example 1-43: Preparation of compound 1-43

In a nitrogen atmosphere, compound Trz16 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 12 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound 1-43 (yield 77%, MS: [M+H] ⁺ = 576).

Preparation Example 1-44: Preparation of compound 1-44

In a nitrogen atmosphere, compound Trz4 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-44 (yield 73%, MS: [M+H] ⁺ = 576).

Preparation Example 1-45: Preparation of compound 1-45

In a nitrogen atmosphere, compound Trz1 (15 g, 35.7 mmol) and compound sub9 (7.6 g, 35.7 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (14.8 g, 107.2 mmol) was dissolved in 44 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-45 (yield 62%, MS: [M+H] ⁺ = 552).

Preparation Example 1-46: Preparation of compound 1-46

In a nitrogen atmosphere, compound Trz19 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-46 (yield 70%, MS: [M+H] ⁺ = 576).

Preparation Example 1-47: Preparation of compound 1-47

In a nitrogen atmosphere, compound Trz20 (15 g, 35.9 mmol) and compound sub9 (7.6 g, 35.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (14.9 g, 107.7 mmol) was dissolved in 45 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound 1-47 (yield 76%, MS: [M+H] ⁺ = 550).

Preparation Example 1-48: Preparation of compound 1-48

In a nitrogen atmosphere, compound Trz3 (15 g, 47.2 mmol) and compound sub24 (9.7 g, 47.2 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (19.6 g, 141.6 mmol) was dissolved in 59 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.5 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound sub1-G-1 (yield 62%, MS: [M+H] ⁺ = 444).

In a nitrogen atmosphere, compound sub1-G-1 (15 g, 33.8 mmol) and compound sub9 (7.2 g, 33.8 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-48 (yield 78%, MS: [M+H] ⁺ = 576).

Preparation Example 1-49: Preparation of compound 1-49

In a nitrogen atmosphere, compound Trz15 (15 g, 41.9 mmol) and compound sub25 (8.7 g, 41.9 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.6 g of compound sub1-G-2 (yield 62%, MS: [M+H] ⁺ = 484).

In a nitrogen atmosphere, compound sub1-G-2 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound 1-49 (yield 72%, MS: [M+H] ⁺ = 616).

Preparation Example 1-50: Preparation of compound 1-50

In a nitrogen atmosphere, compound Trz21 (15 g, 36.8 mmol) and compound sub26 (5.8 g, 36.8 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 46 ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.4 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound sub1-G-3 (yield 72%, MS: [M+H] ⁺ = 484).

In a nitrogen atmosphere, compound sub1-G-3 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of compound 1-50 (yield 69%, MS: [M+H] ⁺ = 616).

Preparation 1-51: Preparation of compound 1-51

In a nitrogen atmosphere, compound Trz16 (15 g, 33.8 mmol) and compound sub27 (5.3 g, 33.8 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound sub1-G-4 (yield 76%, MS: [M+H] ⁺ = 520).

In a nitrogen atmosphere, compound sub1-G-4 (15 g, 28.8 mmol) and compound sub9 (6.1 g, 28.8 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12 g, 86.5 mmol) was dissolved in 36 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 1-51 (yield 71%, MS: [M+H] ⁺ = 652).

Preparation Example 1-52: Preparation of compound 1-52

In a nitrogen atmosphere, compound Trz22 (15 g, 36.8 mmol) and compound sub28 (5.8 g, 36.8 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (15.2 g, 110.3 mmol) was dissolved in 46 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.4 mmol) was added. After the reaction for 12 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound sub1-G-5 (yield 72%, MS: [M+H] ⁺ = 484).

In a nitrogen atmosphere, compound sub1-G-5 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 1-52 (yield 68%, MS: [M+H] ⁺ = 616).

Preparation 1-53: Preparation of compound 1-53

In a nitrogen atmosphere, compound Trz23 (15 g, 34.6 mmol) and compound sub27 (5.4 g, 34.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.3 g of compound sub1-G-6 (yield 64%, MS: [M+H] ⁺ = 510)

In a nitrogen atmosphere, compound sub1-G-6 (15 g, 31 mmol) and compound sub9 (6.6 g, 31 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 1-53 (yield 68%, MS: [M+H] ⁺ = 616)

Preparation 1-54: Preparation of compound 1-54

In a nitrogen atmosphere, compound sub1-G-1 (15 g, 33.8 mmol) and compound 1-E (8.3 g, 33.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 8 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 sub1-E-9 (yield 70%, MS: [M+H] ⁺ = 610).

In a nitrogen atmosphere, compound sub1-E-9 (15 g, 24.6 mmol) and compound sub5 (3 g, 24.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (10.2 g, 73.8 mmol) was dissolved in 31 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.2 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.2 g of compound 1-54 (yield 76%, MS: [M+H] ⁺ = 652).

Preparation 1-55: Preparation of compound 1-55

In a nitrogen atmosphere, compound Trz2 (15 g, 56 mmol) and compound sub24 (11.6 g, 56 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (23.2 g, 168.1 mmol) was dissolved in 70 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 sub1-G-7 (yield 71%, MS: [M+H] ⁺ = 394).

In a nitrogen atmosphere, compound sub1-G-7 (15 g, 38.1 mmol) and compound 1-B (9.4 g, 38.1 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.4 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 sub1-B-7 (yield 65%, MS: [M+H] ⁺ = 560)

In a nitrogen atmosphere, compound sub1-B-7 (15 g, 26.8 mmol) and compound sub5 (3.3 g, 26.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.1 g, 80.3 mmol) was dissolved in 33 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.3 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 1-55 (yield 80%, MS: [M+H] ⁺ = 602)

Preparation 1-56: Preparation of compound 1-56

In a nitrogen atmosphere, compound Trz24 (15 g, 38.1 mmol) and compound sub25 (9.4 g, 38.1 mmol) were added to 300 ml of THF, followed by stirring and reflux. Thereafter, potassium carbonate (15.8 g, 114.3 mmol) was dissolved in 47 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.4 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 sub1-G-8 (yield 65%, MS: [M+H] ⁺ = 560).

In a nitrogen atmosphere, compound sub1-G-8 (15 g, 30 mmol) and compound sub9 (6.4 g, 30 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12.4 g, 90 mmol) was dissolved in 37 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-56 (yield 71%, MS: [M+H] ⁺ = 632).

Preparation 1-57: Preparation of compound 1-57

In a nitrogen atmosphere, compound Trz25 (15 g, 41.9 mmol) and compound sub24 (8.7 g, 41.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 sub1-G-9 (yield 61%, MS: [M+H] ⁺ = 484).

In a nitrogen atmosphere, compound sub1-G-9 (15 g, 31 mmol) and compound 1-F (7.6 g, 31 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12.9 g, 93 mmol) was dissolved in 39 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 sub1-F-3 (yield 62%, MS: [M+H] ⁺ = 650).

In a nitrogen atmosphere, compound sub1-F-3 (15 g, 23.1 mmol) and compound sub5 (2.8 g, 23.1 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (9.6 g, 69.2 mmol) was dissolved in 29 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of compound 1-57 (yield 80%, MS: [M+H] ⁺ = 692).

Preparation 1-58: Preparation of compound 1-58

In a nitrogen atmosphere, compound Trz26 (15 g, 33.8 mmol) and compound sub26 (5.3 g, 33.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14 g, 101.4 mmol) was dissolved in 42 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 sub1-G-10 (yield 60%, MS: [M+H] ⁺ = 520).

In a nitrogen atmosphere, compound sub1-G-10 (15 g, 28.8 mmol) and compound 1-D (7.1 g, 28.8 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (12 g, 86.5 mmol) was dissolved in 36 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound sub1-D-7 (yield 76%, MS: [M+H] ⁺ = 686)

In a nitrogen atmosphere, compound sub1-D-7 (15 g, 21.9 mmol) and compound sub5 (2.7 g, 21.9 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (9.1 g, 65.6 mmol) was dissolved in 27 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.2 mmol) was added. After the reaction for 12 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 9.9 g of compound 1-58 (yield 62%, MS: [M+H] ⁺ = 728)

Preparation 1-59: Preparation of compound 1-59

In a nitrogen atmosphere, compound Trz15 (15 g, 41.9 mmol) and compound sub24 (8.7 g, 41.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After the reaction for 11 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 sub1-G-11 (yield 61%, MS: [M+H] ⁺ = 484).

In a nitrogen atmosphere, compound sub1-G-11 (15 g, 28.8 mmol) and compound 1-F (7.1 g, 28.8 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (12 g, 86.5 mmol) was dissolved in 36 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.3 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15 g of compound sub1-F-7 (yield 76%, MS: [M+H] ⁺ = 686).

In a nitrogen atmosphere, compound sub1-F-4 (15 g, 23.1 mmol) and compound sub5 (2.8 g, 23.1 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (9.6 g, 69.2 mmol) was dissolved in 29 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 1-59 (yield 76%, MS: [M+H] ⁺ = 692).

Preparation Example 1-60: Preparation of compound 1-60

In a nitrogen atmosphere, compound Trz12 (15 g, 41.9 mmol) and compound sub28 (6.6 g, 41.9 mmol) were added to 300 ml of THF, stirred and refluxed. After that, potassium carbonate (17.4 g, 125.8 mmol) was dissolved in 52 ml of water and thoroughly stirred, and then bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1 g of compound sub1-G-12 (yield 61%, MS: [M+H] ⁺ = 434).

In a nitrogen atmosphere, compound sub1-G-12 (15 g, 34.6 mmol) and compound 1-D (8.5 g, 34.6 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.3 g, 103.7 mmol) was dissolved in 43 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.3 mmol) was added. After the reaction for 9 hours, it 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 sub1-D-8 (yield 79%, MS: [M+H] ⁺ = 500).

In a nitrogen atmosphere, compound sub1-D-8 (15 g, 25 mmol) and compound sub10 (4.3 g, 25 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (10.4 g, 75 mmol) was dissolved in 31 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.1 g, 0.2 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 compound 1-60 (yield 77%, MS: [M+H] ⁺ = 692).

Preparation 2-1: Preparation of compound 2-1

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

Preparation 2-2: Preparation of compound 2-2

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

Preparation 2-3: Preparation of compound 2-3

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

Preparation 2-4: Preparation of compound 2-4

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

Preparation 2-5: Preparation of compound 2-5

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

Preparation 2-6: Preparation of compound 2-6

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

Preparation Example 2-7: Preparation of compound 2-7

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

Preparation 2-8: Preparation of compound 2-8

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

Preparation 2-9: Preparation of compound 2-9

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

Preparation Example 2-10: Preparation of compound 2-10

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

Preparation 2-11: Preparation of compound 2-11

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

Preparation 2-12: Preparation of compound 2-12

In a nitrogen atmosphere, compound H (15 g, 48.8 mmol) and compound I (7.6 g, 48.8 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (13.5 g, 97.7 mmol) was dissolved in 40 ml of water, and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0)(0.2 g, 0.5 mmol) was added. After 10 hours of reaction, 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, the organic layer was separated, anhydrous magnesium sulfate was added, 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 subH-1 (yield 75%, MS: [M+H] ⁺ = 339).

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

Preparation 2-13: Preparation of compound 2-13

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

Preparation 2-14: Preparation of compound 2-14

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

Preparation Example 2-15: Preparation of compound 2-15

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

Preparation 2-16: Preparation of compound 2-16

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

Preparation Example 2-17: Preparation of compound 2-17

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

Preparation 2-18: Preparation of compound 2-18

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

Preparation 2-19: Preparation of compound 2-19

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

Preparation Example 2-20: Preparation of compound 2-20

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

[Example]

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was 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 compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at 1.5 wt%. The following compound HT-1 was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Then, the following compound EB-1 was vacuum-deposited to a thickness of 150 Å on the hole transport layer to form an electron blocking layer. Then, on the EB-1 deposition film, the compound 1-2 prepared previously as the following host and compound Dp-7 as the dopant were vacuum-deposited at a weight ratio of 49:49:2 to form a 400 Å thick red light emitting layer. did. A hole blocking layer was formed by vacuum-depositing the following compound HB-1 to a thickness of 30 Å on the light emitting layer. Then, on the hole blocking layer, the following compound ET-1 and the following compound LiQ were vacuum-deposited at a weight ratio of 2:1 to form an electron injection and transport layer to a thickness of 300 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.

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

Examples 2 to 132

An organic light emitting device was manufactured in the same manner as in Example 1, except that the first host and the second host described in Table 1 were used as hosts of the organic light emitting device.

Comparative Examples 1 to 51

An organic light emitting device was manufactured in the same manner as in Example 1, except that the first host and the second host described in Table 2 were used as hosts of the organic light emitting device. Compounds B-1 to B-12 of Table 2 are as follows.

Comparative Examples 52 to 99

An organic light emitting device was manufactured in the same manner as in Preparation Example 1, except that the first host and the second host described in Table 3 were used as hosts of the organic light emitting device. Compounds C-1 to C-6 of Table 2 are as follows.

[Experimental example]

When a current is applied to the organic light emitting diodes prepared in Examples 1 to 132 and Comparative Examples 1 to 99, voltage and efficiency are measured (based on 15 mA/cm ² ), and the results are shown in Tables 1 to Table 3 shows. The lifetime T95 means the time required for the luminance to decrease from the initial luminance (6,000 nits) to 95%.

division	1st host	2nd host	drive voltage (V)	efficiency (cd/A)	Life T95 (hr)	luminous color
Example 1	compound 1-2	compound 2-1	3.53	22.95	197	Red
Example 2	compound 1-2	compound 2-5	3.65	21.30	193	Red
Example 3	compound 1-2	compound 2-11	3.62	19.69	180	Red
Example 4	compound 1-2	compound 2-15	3.60	19.68	195	Red
Example 5	compound 1-2	compound 2-20	3.60	22.65	183	Red
Example 6	compound 1-3	compound 2-3	3.55	21.94	192	Red
Example 7	compound 1-3	compound 2-6	3.55	22.15	198	Red
Example 8	compound 1-3	compound 2-13	3.64	22.09	182	Red
Example 9	compound 1-3	compound 2-18	3.65	21.37	181	Red
Example 10	compound 1-7	compound 2-2	3.98	18.04	197	Red
Example 11	compound 1-7	compound 2-7	3.95	17.64	193	Red
Example 12	compound 1-7	compound 2-14	3.95	17.62	180	Red
Example 13	compound 1-7	compound 2-16	3.90	17.03	195	Red
Example 14	compound 1-9	compound 2-4	3.99	17.84	192	Red
Example 15	compound 1-9	compound 2-8	3.97	17.43	198	Red
Example 16	compound 1-9	compound 2-9	3.90	17.86	182	Red
Example 17	compound 1-9	compound 2-17	3.96	17.91	181	Red
Example 18	compound 1-11	compound 2-1	3.65	20.24	279	Red
Example 19	compound 1-11	compound 2-5	3.67	20.20	273	Red
Example 20	compound 1-11	compound 2-11	3.74	20.46	246	Red
Example 21	compound 1-11	compound 2-15	3.75	19.38	253	Red
Example 22	compound 1-11	compound 2-20	3.69	19.30	270	Red
Example 23	compound 1-14	compound 2-3	3.73	20.24	248	Red
Example 24	compound 1-14	compound 2-6	3.79	19.00	261	Red
Example 25	compound 1-14	compound 2-13	3.68	20.17	261	Red
Example 26	compound 1-14	compound 2-18	3.68	19.39	276	Red
Example 27	compound 1-15	compound 2-2	3.88	18.12	245	Red
Example 28	compound 1-15	compound 2-7	3.83	19.29	239	Red
Example 29	compound 1-15	compound 2-14	3.87	19.05	217	Red
Example 30	compound 1-15	compound 2-16	3.87	18.05	241	Red
Example 31	compound 1-16	compound 2-4	3.68	17.52	280	Red
Example 32	compound 1-16	compound 2-8	3.60	17.65	302	Red
Example 33	compound 1-16	compound 2-9	3.62	17.02	309	Red
Example 34	compound 1-16	compound 2-17	3.65	17.08	302	Red
Example 35	compound 1-17	compound 2-1	3.65	18.15	279	Red
Example 36	compound 1-17	compound 2-5	3.69	17.91	278	Red
Example 37	compound 1-17	compound 2-11	3.62	17.47	292	Red
Example 38	compound 1-17	compound 2-15	3.63	17.59	280	Red
Example 39	compound 1-17	compound 2-20	3.69	17.67	297	Red
Example 40	compound 1-20	compound 2-3	3.98	18.41	180	Red
Example 41	compound 1-20	compound 2-6	3.95	17.80	193	Red
Example 42	compound 1-20	compound 2-13	3.95	18.42	180	Red
Example 43	compound 1-20	compound 2-18	3.93	18.32	193	Red
Example 44	compound 1-22	compound 2-2	3.94	17.79	191	Red
Example 45	compound 1-22	compound 2-7	3.93	18.19	192	Red
Example 46	compound 1-22	compound 2-14	3.97	17.19	192	Red
Example 47	compound 1-22	compound 2-16	3.99	18.32	189	Red
Example 48	compound 1-24	compound 2-4	3.56	17.36	200	Red
Example 49	compound 1-24	compound 2-8	3.63	17.92	192	Red
Example 50	compound 1-24	compound 2-9	3.56	18.45	180	Red
Example 51	compound 1-24	compound 2-17	3.60	17.70	196	Red
Example 52	compound 1-27	compound 2-1	3.59	18.01	197	Red
Example 53	compound 1-27	compound 2-5	3.65	18.19	185	Red
Example 54	compound 1-27	compound 2-11	3.62	17.28	196	Red
Example 55	compound 1-27	compound 2-15	3.65	17.65	197	Red
Example 56	compound 1-27	compound 2-20	3.61	17.20	192	Red
Example 57	compound 1-28	compound 2-3	3.67	20.26	245	Red
Example 58	compound 1-28	compound 2-6	3.77	20.31	254	Red
Example 59	compound 1-28	compound 2-13	3.77	19.90	267	Red
Example 60	compound 1-28	compound 2-18	3.65	20.21	241	Red
Example 61	compound 1-31	compound 2-2	3.68	19.08	265	Red
Example 62	compound 1-31	compound 2-7	3.65	19.71	256	Red
Example 63	compound 1-31	compound 2-14	3.70	19.91	258	Red
Example 64	compound 1-31	compound 2-16	3.70	19.97	245	Red
Example 65	compound 1-33	compound 2-4	3.69	17.85	281	Red
Example 66	compound 1-33	compound 2-8	3.67	17.87	294	Red
Example 67	compound 1-33	compound 2-9	3.68	18.34	299	Red
Example 68	compound 1-33	compound 2-17	3.61	18.19	286	Red
Example 69	compound 1-37	compound 2-1	3.67	17.01	295	Red
Example 70	compound 1-37	compound 2-5	3.67	17.25	288	Red
Example 71	compound 1-37	compound 2-11	3.69	17.32	294	Red
Example 72	compound 1-37	compound 2-15	3.62	18.35	306	Red
Example 73	compound 1-37	compound 2-20	3.69	18.14	301	Red
Example 74	compound 1-38	compound 2-3	3.57	21.36	295	Red
Example 75	compound 1-38	compound 2-6	3.64	19.79	298	Red
Example 76	compound 1-38	compound 2-13	3.63	20.78	298	Red
Example 77	compound 1-38	compound 2-18	3.65	20.80	285	Red
Example 78	compound 1-40	compound 2-2	3.57	21.10	290	Red
Example 79	compound 1-40	compound 2-7	3.57	21.90	290	Red
Example 80	compound 1-40	compound 2-14	3.63	19.59	308	Red
Example 81	compound 1-40	compound 2-16	3.62	22.84	306	Red
Example 82	compound 1-41	compound 2-4	3.90	18.23	195	Red
Example 83	compound 1-41	compound 2-8	3.94	17.72	192	Red
Example 84	compound 1-41	compound 2-9	3.95	17.16	185	Red
Example 85	compound 1-41	compound 2-17	3.93	17.94	188	Red
Example 86	compound 1-43	compound 2-1	3.90	17.07	192	Red
Example 87	compound 1-43	compound 2-5	3.90	17.81	195	Red
Example 88	compound 1-43	compound 2-11	3.95	18.41	183	Red
Example 89	compound 1-43	compound 2-15	3.98	17.50	194	Red
Example 90	compound 1-43	compound 2-20	3.98	18.03	197	Red
Example 91	compound 1-45	compound 2-3	3.65	17.84	199	Red
Example 92	compound 1-45	compound 2-6	3.64	18.27	186	Red
Example 93	compound 1-45	compound 2-13	3.57	17.87	181	Red
Example 94	compound 1-45	compound 2-18	3.58	18.37	193	Red
Example 95	compound 1-47	compound 2-2	3.66	17.36	302	Red
Example 96	compound 1-47	compound 2-7	3.69	18.31	287	Red
Example 97	compound 1-47	compound 2-14	3.60	17.37	293	Red
Example 98	compound 1-47	compound 2-16	3.68	18.23	307	Red
Example 99	compound 1-48	compound 2-4	3.66	17.53	283	Red
Example 100	compound 1-48	compound 2-8	3.61	17.99	271	Red
Example 101	compound 1-48	compound 2-9	3.61	18.09	303	Red
Example 102	compound 1-48	compound 2-17	3.66	18.26	282	Red
Example 103	compound 1-52	compound 2-1	3.55	21.59	199	Red
Example 104	compound 1-52	compound 2-5	3.64	21.19	186	Red
Example 105	compound 1-52	compound 2-11	3.57	21.82	181	Red
Example 106	compound 1-52	compound 2-15	3.58	21.67	193	Red
Example 107	compound 1-52	compound 2-20	3.61	21.24	195	Red
Example 108	compound 1-53	compound 2-3	3.65	20.46	267	Red
Example 109	compound 1-53	compound 2-6	3.79	19.73	277	Red
Example 110	compound 1-53	compound 2-13	3.66	19.07	273	Red
Example 111	compound 1-53	compound 2-18	3.66	20.48	246	Red
Example 112	compound 1-55	compound 2-2	3.66	19.65	280	Red
Example 113	compound 1-55	compound 2-7	3.70	19.06	267	Red
Example 114	compound 1-55	compound 2-14	3.67	19.25	271	Red
Example 115	compound 1-55	compound 2-16	3.78	20.45	275	Red
Example 116	compound 1-56	compound 2-4	3.97	18.47	194	Red
Example 117	compound 1-56	compound 2-8	3.94	17.67	195	Red
Example 118	compound 1-56	compound 2-9	3.93	17.88	186	Red
Example 119	compound 1-56	compound 2-17	3.92	17.36	198	Red
Example 120	compound 1-57	compound 2-1	3.99	18.29	196	Red
Example 121	compound 1-57	compound 2-5	3.99	18.17	195	Red
Example 122	compound 1-57	compound 2-11	3.90	18.27	187	Red
Example 123	compound 1-57	compound 2-15	3.91	18.35	199	Red
Example 124	compound 1-57	compound 2-20	3.99	18.04	187	Red
Example 125	compound 1-58	compound 2-3	3.77	19.23	212	Red
Example 126	compound 1-58	compound 2-6	3.77	19.50	227	Red
Example 127	compound 1-58	compound 2-13	3.79	19.00	219	Red
Example 128	compound 1-58	compound 2-18	3.79	18.85	212	Red
Example 129	compound 1-60	compound 2-2	3.75	19.37	236	Red
Example 130	compound 1-60	compound 2-7	3.76	18.70	221	Red
Example 131	compound 1-60	compound 2-14	3.81	18.16	232	Red
Example 132	compound 1-60	compound 2-16	3.84	18.53	229	Red

division	1st host	2nd host	drive voltage (V)	efficiency (cd/A)	Life T95 (hr)	luminous color
Comparative Example 1	Compound B-1	compound 2-1	4.11	17.35	147	Red
Comparative Example 2	Compound B-1	compound 2-5	4.08	16.99	148	Red
Comparative Example 3	Compound B-1	compound 2-11	4.11	16.80	137	Red
Comparative Example 4	Compound B-1	compound 2-15	4.05	17.46	140	Red
Comparative Example 5	Compound B-1	compound 2-20	4.05	16.22	138	Red
Comparative Example 6	compound B-2	compound 2-3	4.05	17.28	140	Red
Comparative Example 7	compound B-2	compound 2-6	4.13	17.16	135	Red
Comparative Example 8	compound B-2	compound 2-13	4.14	17.36	134	Red
Comparative Example 9	compound B-2	compound 2-18	4.14	16.34	145	Red
Comparative Example 10	compound B-3	compound 2-2	4.30	16.21	133	Red
Comparative Example 11	compound B-3	compound 2-7	4.26	16.18	108	Red
Comparative Example 12	compound B-3	compound 2-14	4.22	15.62	110	Red
Comparative Example 13	compound B-3	compound 2-16	4.22	16.48	126	Red
Comparative Example 14	Compound B-4	compound 2-4	4.32	16.71	128	Red
Comparative Example 15	Compound B-4	compound 2-8	4.27	16.58	122	Red
Comparative Example 16	Compound B-4	compound 2-9	4.26	15.70	123	Red
Comparative Example 17	Compound B-4	compound 2-17	4.23	15.51	135	Red
Comparative Example 18	compound B-5	compound 2-1	4.24	17.03	153	Red
Comparative Example 19	compound B-5	compound 2-5	4.02	18.07	158	Red
Comparative Example 20	compound B-5	compound 2-11	4.08	18.10	154	Red
Comparative Example 21	compound B-5	compound 2-15	4.09	17.48	165	Red
Comparative Example 22	compound B-5	compound 2-20	4.01	17.22	155	Red
Comparative Example 23	compound B-6	compound 2-3	4.01	17.62	156	Red
Comparative Example 24	compound B-6	compound 2-6	4.07	17.51	164	Red
Comparative Example 25	compound B-6	compound 2-13	4.05	17.30	152	Red
Comparative Example 26	compound B-6	compound 2-18	4.02	17.59	167	Red
Comparative Example 27	compound B-7	compound 2-2	4.11	17.41	135	Red
Comparative Example 28	compound B-7	compound 2-7	4.15	16.40	151	Red
Comparative Example 29	compound B-7	compound 2-14	4.11	16.97	147	Red
Comparative Example 30	compound B-7	compound 2-16	4.05	17.18	144	Red
Comparative Example 31	compound B-8	compound 2-4	4.15	17.31	133	Red
Comparative Example 32	compound B-8	compound 2-8	4.07	16.01	151	Red
Comparative Example 33	compound B-8	compound 2-9	4.14	16.55	150	Red
Comparative Example 34	compound B-8	compound 2-17	4.05	16.18	139	Red
Comparative Example 35	compound B-9	compound 2-1	4.17	17.28	164	Red
Comparative Example 36	compound B-9	compound 2-5	4.14	17.11	158	Red
Comparative Example 37	compound B-9	compound 2-11	4.02	18.10	162	Red
Comparative Example 38	compound B-9	compound 2-15	4.02	17.39	167	Red
Comparative Example 39	compound B-9	compound 2-20	4.06	17.12	155	Red
Comparative Example 40	Compound B-10	compound 2-3	4.11	17.61	157	Red
Comparative Example 41	Compound B-10	compound 2-6	4.11	17.13	160	Red
Comparative Example 42	compound B-10	compound 2-13	4.04	17.47	153	Red
Comparative Example 43	Compound B-10	compound 2-18	4.03	17.29	152	Red
Comparative Example 44	compound B-11	compound 2-2	4.24	16.49	114	Red
Comparative Example 45	compound B-11	compound 2-7	4.34	16.80	121	Red
Comparative Example 46	compound B-11	compound 2-14	4.28	15.56	118	Red
Comparative Example 47	compound B-11	compound 2-16	4.35	16.21	115	Red
Comparative Example 48	Compound B-12	compound 2-4	4.24	16.88	115	Red
Comparative Example 49	Compound B-12	compound 2-8	4.32	16.72	131	Red
Comparative Example 50	Compound B-12	compound 2-9	4.20	15.82	125	Red
Comparative Example 51	Compound B-12	compound 2-17	4.33	15.53	128	Red

division	1st host	2nd host	drive voltage (V)	efficiency (cd/A)	Life T95 (hr)	luminous color
Comparative Example 52	compound 1-2	compound C-1	4.19	18.06	153	Red
Comparative Example 53	compound 1-11	compound C-1	4.04	17.88	151	Red
Comparative Example 54	compound 1-15	compound C-1	4.07	17.63	169	Red
Comparative Example 55	compound 1-28	compound C-1	4.10	18.03	170	Red
Comparative Example 56	compound 1-33	compound C-1	4.07	17.69	157	Red
Comparative Example 57	compound 1-40	compound C-1	4.15	17.97	154	Red
Comparative Example 58	compound 1-43	compound C-1	4.14	17.02	169	Red
Comparative Example 59	compound 1-55	compound C-1	4.04	17.31	151	Red
Comparative Example 60	compound 1-3	compound C-2	4.04	17.12	148	Red
Comparative Example 61	compound 1-7	compound C-2	4.03	17.93	156	Red
Comparative Example 62	compound 1-17	compound C-2	4.01	16.37	151	Red
Comparative Example 63	compound 1-24	compound C-2	4.10	17.32	146	Red
Comparative Example 64	compound 1-37	compound C-2	4.07	17.47	137	Red
Comparative Example 65	compound 1-47	compound C-2	4.11	16.14	147	Red
Comparative Example 66	compound 1-48	compound C-2	4.06	16.57	152	Red
Comparative Example 67	compound 1-58	compound C-2	4.07	16.18	139	Red
Comparative Example 68	compound 1-9	compound C-3	4.02	16.99	148	Red
Comparative Example 69	compound 1-16	compound C-3	4.10	16.34	152	Red
Comparative Example 70	compound 1-22	compound C-3	4.19	18.06	153	Red
Comparative Example 71	compound 1-38	compound C-3	4.04	17.88	151	Red
Comparative Example 72	compound 1-41	compound C-3	4.07	17.63	169	Red
Comparative Example 73	compound 1-45	compound C-3	4.10	18.03	170	Red
Comparative Example 74	compound 1-53	compound C-3	4.07	17.69	157	Red
Comparative Example 75	compound 1-57	compound C-3	4.15	17.97	154	Red
Comparative Example 76	compound 1-2	compound C-4	4.31	16.69	109	Red
Comparative Example 77	compound 1-14	compound C-4	4.27	15.83	114	Red
Comparative Example 78	compound 1-20	compound C-4	4.22	16.06	114	Red
Comparative Example 79	compound 1-27	compound C-4	4.29	15.91	124	Red
Comparative Example 80	compound 1-31	compound C-4	4.28	15.50	123	Red
Comparative Example 81	compound 1-52	compound C-4	4.30	15.61	117	Red
Comparative Example 82	compound 1-56	compound C-4	4.22	15.67	117	Red
Comparative Example 83	compound 1-60	compound C-4	4.22	16.04	131	Red
Comparative Example 84	compound 1-2	compound C-5	4.26	16.61	113	Red
Comparative Example 85	compound 1-11	compound C-5	4.34	16.08	111	Red
Comparative Example 86	compound 1-15	compound C-5	4.15	17.50	167	Red
Comparative Example 87	compound 1-28	compound C-5	4.05	17.03	155	Red
Comparative Example 88	compound 1-33	compound C-5	4.05	16.56	148	Red
Comparative Example 89	compound 1-40	compound C-5	4.03	17.21	153	Red
Comparative Example 90	compound 1-43	compound C-5	4.39	15.08	95	Red
Comparative Example 91	compound 1-55	compound C-5	4.49	14.76	98	Red
Comparative Example 92	compound 1-3	compound C-6	4.37	15.17	93	Red
Comparative Example 93	compound 1-7	compound C-6	4.35	15.43	102	Red
Comparative Example 94	compound 1-17	compound C-6	4.43	14.85	104	Red
Comparative Example 95	compound 1-24	compound C-6	4.49	15.29	94	Red
Comparative Example 96	compound 1-37	compound C-6	4.41	15.00	95	Red
Comparative Example 97	compound 1-47	compound C-6	4.37	14.68	88	Red
Comparative Example 98	compound 1-48	compound C-6	4.42	15.01	105	Red
Comparative Example 99	compound 1-58	compound C-6	4.38	15.38	113	Red

The results shown in Tables 1 to 3 were obtained by applying a current to the organic light emitting devices prepared in Examples 1 to 132 and Comparative Examples 1 to 99.

In one embodiment of the present invention, when the compound represented by Formula 1 and the compound represented by Formula 2 are co-deposited and used as a red light emitting layer, as shown in Table 1, the driving voltage is decreased and the efficiency and lifespan are increased compared to the Comparative Example. Confirmed. In addition, as shown in Table 2, when the compounds of Comparative Examples B-1 to B-12 and the compound represented by Formula 2 of the present invention were co-deposited and used as a red light emitting layer, the driving voltage was generally increased and the efficiency was higher than that of the combination of the present invention. and decreased life expectancy. As shown in Table 3, even when the compounds of Comparative Examples C-1 to C-6 and the compound represented by Formula 1 of the present invention were co-deposited and used as a red light emitting layer, the driving voltage increased and the efficiency and lifespan decreased.

Judging from the above results, as in an embodiment of the present invention, when a combination of a compound represented by Formula 1 as a first host and a compound represented by Formula 2 as a second host is used as a host in the red light emitting layer, energy as a dopant It was confirmed that the transfer was successful. This can be inferred because the combination of Formula 1 and Formula 2 of the present invention causes a more stable balance in the light emitting layer than the combination with the comparative compound. Therefore, it was confirmed that when electrons and holes in the organic light emitting device of an embodiment of the present invention combine to form excitons, efficiency and lifetime are further increased.

In conclusion, it was confirmed that the driving voltage, luminous efficiency and lifespan characteristics of the organic light emitting device could be improved when the compound represented by Formula 1 and the compound represented by Formula 2 were combined and used as a host for the light emitting layer by co-deposition of the present invention. did.

Explanation of symbols

1: Substrate 2: Anode

3: light emitting layer 4: cathode

5: hole injection layer 6: hole transport layer

7: electron blocking layer 8: hole blocking layer

9: electron transport layer 10: electron injection layer

Claims (12)

1. anode;

   cathode; and

   a light emitting layer between the anode and the cathode;

   The light emitting layer comprises a compound represented by the following formula (1) and a compound represented by the following formula (2),

   Organic light emitting device:

   [Formula 1]

   

   In Formula 1,

   Ar ₁ and Ar ₂ are each independently, substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl comprising any one or more selected from the group consisting of N, O and S,

   L ₁ to L ₃ are each independently, a single bond; Or a substituted or unsubstituted C _6-60 arylene,

   R ₁ is hydrogen; heavy hydrogen; substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl comprising any one or more selected from the group consisting of N, O and S,

   a is an integer from 0 to 7,

   [Formula 2]

   

   In Formula 1,

   Ar ₃ and Ar ₄ are each independently, substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl comprising any one or more selected from the group consisting of N, O and S,

   L ₄ to L ₆ are each independently, a single bond; or substituted or unsubstituted C _6-60 arylene.
2. According to claim 1,

   The compound represented by Formula 1 is represented by any one of the following Formulas 1-1 to 1-3,

   Organic light emitting device:

   [Formula 1-1]

   

   [Formula 1-2]

   

   [Formula 1-3]

   

   In Formulas 1-1 to 1-3,

   Ar ₁ , Ar ₂ , L ₁ to L ₃ and R ₁ are as defined in claim 1.
3. According to claim 1,

   Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl;

   organic light emitting device.
4. According to claim 1,

   L _{1 To} L _{3 Are} each independently any one selected from the group consisting of a single bond or the following,

   Organic light emitting device:

   

   .
5. According to claim 1,

   R ₁ is each independently hydrogen, deuterium, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, naphthyl phenyl, phenyl naphthyl, fluoranthenyl, dibenzofuranyl, di which is benzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl;

   organic light emitting device.
6. According to claim 1,

   At least one of Ar ₁ , Ar ₂ and R ₁ is naphthyl, phenyl naphthyl, naphthyl phenyl, phenanthrenyl, fluoranthenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or benzonaphtho thiophenyl,

   organic light emitting device.
7. According to claim 1,

   a is 0 or 1;

   organic light emitting device.
8. According to claim 1,

   The compound represented by Formula 1 is any one selected from the group consisting of

   Organic light emitting device:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   .
9. According to claim 1,

   Ar ₃ and Ar ₄ are each independently, phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, phenanthrenyl, naphthyl phenyl, phenyl naphthyl, dimethylfluorenyl, diphenylfluorenyl, which is spirobifluorenyl, carbazolyl, phenyl carbazolyl, dibenzofuranyl, dibenzothiophenyl, or benzonaphthofuranyl;

   organic light emitting device.
10. According to claim 1,

    Ar ₃ and Ar ₄ are each independently any one selected from the group consisting of

    Organic light emitting device:

    

    

    .
11. According to claim 1,

    L _{4 To} L ₆ are each independently a single bond, phenylene, biphenylrylene, naphthylene, or dimethyl fluorenylene,

    organic light emitting device.
12. According to claim 1,

    The compound represented by Formula 2 is any one selected from the group consisting of

    Organic light emitting device:

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    .

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