KR20210133891A - Organic light emitting device - Google Patents

Abstract

The present invention provides an organic light emitting device having improved driving voltage, efficiency, and lifetime. According to an embodiment of the present invention, an organic light emitting device includes an anode, a cathode, and a light emitting layer between the anode and the cathode. The light emitting layer includes a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2.

Description

Organic light emitting device

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.

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,

L is a single bond; Or a substituted or unsubstituted C _6-60 arylene,

X is N; or CH, provided that at least two or more of X are N;

one of R is substituted or unsubstituted C _6-60 aryl; _{or C 2-60} heteroaryl including at least one selected from the group consisting of substituted or unsubstituted N, O and S, and the remainder is hydrogen; or deuterium,

Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl, wherein Ar ₁ And Ar ₂ are each independently, unsubstituted or substituted with one or more deuterium,

[Formula 2]

In Formula 2,

L ₁ and L ₂ are each independently a single bond; substituted or unsubstituted C _6-60 arylene; _{Or or substituted or unsubstituted C 5-60} heteroarylene comprising at least one selected from the group consisting of N, O and S,

Ar ₃ and Ar ₄ are each independently substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 5-60} heteroaryl comprising any one or more selected from the group consisting of N, O and S,

R ₁ is all hydrogen or deuterium; or two adjacent R ₁ combine to form a benzene ring, and the remainder is hydrogen or deuterium;

R ₂ is all hydrogen or deuterium; Or two adjacent R ₂ are combined to form a benzene ring, and the remainder is hydrogen or deuterium.

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

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 shows an example of an organic light emitting device including a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4 did it

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

또는

는 다른 치환기에 연결되는 결합을 의미한다. 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 arylphosphine 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 atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents . 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 in the carbonyl group is not particularly limited, but preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, 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 compound of the following structural formula, but is not limited thereto.

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

In the present specification, the silyl group 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.

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

etc. 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 above-described examples of the alkenyl group. 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.

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.

In Formula 1, preferably, L is a single bond; phenylene; or naphthylene. More preferably, L is a single bond; 1,4-phenylene; 1,3-phenylene; 1,2-phenylene; or 1,4-naphthylene.

Preferably, all X are N.

Preferably, one of R is phenyl, biphenylyl, terphenylyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenanthrenyl, triphenylenyl, fluoranthenyl, dibenzofunyl, benzonaphthofuranyl, dibenzothiophenyl, or benzonaphthothiophenyl; The remainder is hydrogen, or deuterium.

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

On the other hand, the present invention provides a method for preparing a compound in which R is substituted at the 3-substituted position of dibenzofuran among compounds represented by Formula 1 as shown in Scheme 1 below, and the remaining compounds are prepared in a similar manner to the following. can do.

[Scheme 1]

In Scheme 1, definitions other than X' are the same as defined above, and X' is halogen, more preferably chloro or bromo. The first and second reactions are Suzuki coupling reactions, respectively, and 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.

In Formula 2, preferably, L ₁ and L ₂ are each independently a single bond; or phenylene.

Preferably, Ar ₃ and Ar ₄ are each independently Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl , triphenylenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, fluorenyl, fluoranthenyl, dibenzofuranyl, or dibenzothiophenyl.

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

On the other hand, the present invention provides a method for preparing a compound represented by the formula (2) as shown in Scheme 2 below as an example:

[Scheme 2]

In Scheme 2, definitions other than X' are the same as defined above, and X' is halogen, more preferably chloro or bromo. The reaction 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.

Meanwhile, 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 transport layer

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

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. A material capable of transporting holes from the anode or hole injection layer to the light emitting layer as a hole transport material. This is 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.

hole injection layer

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

The hole injection layer is a layer for injecting holes from the electrode, and 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.

electron transport layer

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

The electron transport layer is a layer that receives electrons from the 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 between the electron transport layer and the cathode, if necessary.

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 movement 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.

organic light emitting device

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

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 anode material on the substrate in the reverse order of the above-described configuration from the cathode 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 application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

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

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

[Production Example]

Preparation 1-1

Compound A (10 g, 40.6 mmol) and compound Trz1 (16 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, 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 15.4 g of compound subA-1. (Yield 68%, MS: [M+H] ⁺ = 560)

Compound subA-1 (10 g, 17.9 mmol) and compound sub1 (3.9 g, 19.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in water (22 ml), 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 9.1 g of compound 1-1. (yield 75%, MS: [M+H] ⁺ = 678)

Preparation 1-2

Compound A (10 g, 40.6 mmol) and compound Trz2 (16 g, 40.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), 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 17.9 g of compound subA-2. (yield 79%, MS: [M+H] ⁺ = 560)

Compound subA-2 (10 g, 17.9 mmol) and compound sub2 (2.4 g, 19.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in water (22 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 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 8.5 g of compound 1-2. (yield 79%, MS: [M+H] ⁺ = 602)

Preparation 1-3

Compound A (10 g, 40.6 mmol) and compound Trz3 (14.9 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, 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 13.4 g of compound subA-3. (Yield 62%, MS: [M+H] ⁺ = 534)

Compound subA-3 (10 g, 18.7 mmol) and compound sub3 (4.4 g, 20.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, stirred and refluxed. Thereafter, potassium carbonate (7.8 g, 56.2 mmol) was dissolved in water (23 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 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 9 g of compound 1-3. (Yield 72%, MS: [M+H] ⁺ = 666)

Preparation Example 1-4

Compound A (10 g, 40.6 mmol) and compound Trz4 (10.7 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, 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 10.7 g of compound subA-4. (Yield 61%, MS: [M+H] ⁺ = 434)

Compound subA-4 (10 g, 23 mmol) and compound sub4 (5.6 g, 25.4 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (9.6 g, 69.1 mmol) was dissolved in water (29 ml), and after sufficient stirring, 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 10.2 g of compound 1-4. (Yield 77%, MS: [M+H] ⁺ = 576)

Preparation 1-5

Compound A (10 g, 40.6 mmol) and compound Trz5 (14 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), 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 13.6 g of compound subA-5. (Yield 66%, MS: [M+H] ⁺ = 510)

Compound subA-5 (10 g, 19.6 mmol) and compound sub5 (5.4 g, 21.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (8.1 g, 58.8 mmol) was dissolved in water (24 ml), 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 9.8 g of compound 1-5. (Yield 74%, MS: [M+H] ⁺ = 678)

Preparation 1-6

Compound A (10 g, 40.6 mmol) and compound Trz6 (12.9 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, stirred and refluxed. After that, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), 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 13.5 g of compound subA-6. (yield 69%, MS: [M+H] ⁺ = 484)

Compound subA-6 (10 g, 20.7 mmol) and compound sub6 (6 g, 22.7 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (8.6 g, 62 mmol) was dissolved in water (26 ml), 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 9.9 g of compound 1-6. (Yield 72%, MS: [M+H] ⁺ = 666)

Preparation 1-7

Compound A (10 g, 40.6 mmol) and compound Trz7 (17.2 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), 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 15.3 g of compound subA-7. (Yield 64%, MS: [M+H] ⁺ = 590)

Compound subA-7 (10 g, 16.9 mmol) and compound sub7 (4.6 g, 18.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7 g, 50.8 mmol) was dissolved in water (21 ml), and after sufficient stirring, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 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 8.5 g of compound 1-7. (Yield 66%, MS: [M+H] ⁺ = 758)

Preparation 1-8

Compound A (10 g, 40.6 mmol) and compound Trz8 (16.5 g, 40.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, 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 14.7 g of compound subA-8. (Yield 63%, MS: [M+H] ⁺ = 574)

Compound subA-8 (10 g, 17.4 mmol) and compound sub3 (4.1 g, 19.2 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7.2 g, 52.3 mmol) was dissolved in water (22 ml), 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 7.9 g of compound 1-8. (Yield 64%, MS: [M+H] ⁺ = 706)

Preparation 1-9

Compound subA-2 (10 g, 17.9 mmol) and compound sub8 (5.1 g, 19.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in water (22 ml), 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 8.5 g of compounds 1-9. (Yield 64%, MS: [M+H] ⁺ = 742)

Preparation Example 1-10

Compound A (10 g, 40.6 mmol) and compound Trz9 (20.3 g, 40.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, 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 17.8 g of compound subA-9. (Yield 66%, MS: [M+H] ⁺ = 666)

Compound subA-9 (10 g, 15 mmol) and compound sub9 (2.8 g, 16.5 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (6.2 g, 45 mmol) was dissolved in water (19 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 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 8.5 g of compound 1-10. (yield 75%, MS: [M+H] ⁺ = 758)

Preparation Example 1-11

Compound A (10 g, 40.6 mmol) and compound Trz10 (21.1 g, 40.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), 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 21.7 g of compound subA-10. (Yield 78%, MS: [M+H] ⁺ = 686)

Compound subA-10 (10 g, 14.6 mmol) and compound sub2 (2 g, 16 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (6 g, 43.7 mmol) was dissolved in water (18 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.1 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 6.9 g of compound 1-11. (Yield 65%, MS: [M+H] ⁺ = 728)

Preparation Example 1-12

Formula B (10 g, 40.6 mmol) and compound Trz6 (12.9 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), 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 13.3 g of compound subB-1. (Yield 68%, MS: [M+H] ⁺ = 484)

Compound subB-1 (10 g, 20.7 mmol) and compound sub9 (3.9 g, 22.7 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (8.6 g, 62 mmol) was dissolved in water (26 ml), and after sufficient stirring, 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 9.2 g of compound 1-12. (Yield 77%, MS: [M+H] ⁺ = 576)

Preparation 1-13

Formula B (10 g, 40.6 mmol) and compound Trz11 (14.9 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, 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 15.4 g of compound subB-2. (Yield 71%, MS: [M+H] ⁺ = 534)

Compound subB-2 (10 g, 18.7 mmol) and compound sub2 (2.5 g, 20.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7.8 g, 56.2 mmol) was dissolved in water (23 ml), and after sufficient stirring, 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 7.9 g of compound 1-13. (Yield 73%, MS: [M+H] ⁺ = 576)

Preparation 1-14

Formula B (10 g, 40.6 mmol) and compound Trz4 (10.9 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, 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 subB-3. (yield 69%, MS: [M+H] ⁺ = 434)

Compound subB-3 (10 g, 23 mmol) and compound sub10 (6.2 g, 25.4 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (9.6 g, 69.1 mmol) was dissolved in water (29 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 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 9.3 g of compound 1-14. (Yield 67%, MS: [M+H] ⁺ = 600)

Preparation Example 1-15

Formula B (10 g, 40.6 mmol) and compound Trz13 (17.6 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, 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 17.7 g of compound subB-4. (Yield 73%, MS: [M+H] ⁺ = 600)

Compound subB-4 (10 g, 16.7 mmol) and compound sub9 (3.2 g, 18.3 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (6.9 g, 50 mmol) was dissolved in water (21 ml), 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 8.6 g of compound 1-15. (yield 75%, MS: [M+H] ⁺ = 692)

Preparation 1-16

Formula B (10 g, 40.6 mmol) and compound Trz14 (17.6 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, 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 14.8 g of compound subB-5. (Yield 60%, MS: [M+H] ⁺ = 610)

In a nitrogen atmosphere, compound subB-5 (10 g, 16.4 mmol) and compound sub2 (2.2 g, 18 mmol) were added to THF (200 ml), stirred and refluxed. After that, potassium carbonate (6.8 g, 49.2 mmol) was dissolved in water (20 ml), and after stirring sufficiently, 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 6.8 g of compound 1-16. (Yield 64%, MS: [M+H] ⁺ = 652)

Preparation 1-17

Compound subB-5 (10 g, 16.4 mmol) and compound sub3 (3.8 g, 18 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (6.8 g, 49.2 mmol) was dissolved in water (20 ml), and after stirring sufficiently, 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 8.1 g of compound 1-17. (Yield 67%, MS: [M+H] ⁺ = 742)

Preparation Example 1-18

Compound C (10 g, 40.6 mmol) and compound Trz15 (17 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, 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 g of compound subC-1. (yield 76%, MS: [M+H] ⁺ = 584)

Compound subC-1 (10 g, 17.1 mmol) and compound sub2 (2.3 g, 18.8 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7.1 g, 51.4 mmol) was dissolved in water (21 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 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 7.3 g of compound 1-18. (Yield 68%, MS: [M+H] ⁺ = 626)

Preparation 1-19

Compound C (10 g, 40.6 mmol) and compound Trz16 (17 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, 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 subC-2. (Yield 62%, MS: [M+H] ⁺ = 586)

Compound subC-2 (10 g, 17.1 mmol) and compound sub2 (2.3 g, 18.8 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (7.1 g, 51.2 mmol) was dissolved in water (21 ml), 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 7.2 g of compound 1-19. (Yield 67%, MS: [M+H] ⁺ = 628)

Preparation 1-20

Compound C (10 g, 40.6 mmol) and compound Trz17 (17.6 g, 40.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, 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 16.8 g of compound subC-3. (yield 69%, MS: [M+H] ⁺ = 600)

Compound subC-3 (10 g, 16.7 mmol) and compound sub11 (4.2 g, 18.3 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (6.9 g, 50 mmol) was dissolved in water (21 ml), and after sufficient stirring, 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 7.7 g of compound 1-20. (Yield 62%, MS: [M+H] ⁺ = 748)

Preparation 1-21

Compound C (10 g, 40.6 mmol) and compound Trz18 (14.9 g, 40.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, 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 16.4 g of compound subC-4. (Yield 76%, MS: [M+H] ⁺ = 534)

Compound subC-4 (10 g, 18.7 mmol) and compound sub9 (3.5 g, 20.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, stirred and refluxed. Thereafter, potassium carbonate (7.8 g, 56.2 mmol) was dissolved in water (23 ml), 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 7.8 g of compound 1-21. (Yield 67%, MS: [M+H] ⁺ = 626)

Preparation 1-22

Compound C (10 g, 40.6 mmol) and compound Trz4 (10.9 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), 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 14.1 g of compound subC-5. (yield 80%, MS: [M+H] ⁺ = 434)

Compound subC-5 (10 g, 23 mmol) and compound sub12 (6.9 g, 25.4 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (9.6 g, 69.1 mmol) was dissolved in water (29 ml), and after sufficient stirring, 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 10.7 g of compound 1-22. (Yield 74%, MS: [M+H] ⁺ = 626)

Preparation 1-23

Compound C (10 g, 40.6 mmol) and compound Trz12 (10.9 g, 40.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, 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 16.4 g of compound subC-6. (Yield 76%, MS: [M+H] ⁺ = 534)

Compound subC-6 (10 g, 18.7 mmol) and compound sub13 (5.7 g, 20.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7.8 g, 56.2 mmol) was dissolved in water (23 ml), and after sufficient stirring, 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 8.2 g of compound 1-23. (yield 60%, MS: [M+H] ⁺ = 732)

Preparation 1-24

Compound C (10 g, 40.6 mmol) and compound Trz5 (14 g, 40.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, 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 16.5 g of compound subC-7. (yield 80%, MS: [M+H] ⁺ = 510)

Compound subC-7 (10 g, 19.6 mmol) and compound sub14 (6 g, 21.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (8.1 g, 58.8 mmol) was dissolved in water (24 ml), and after sufficient stirring, 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 9.4 g of compound 1-24. (Yield 68%, MS: [M+H] ⁺ = 708)

Preparation 1-25

Compound C (10 g, 40.6 mmol) and compound Trz19 (16 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), 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 15.4 g of compound subC-8. (Yield 68%, MS: [M+H] ⁺ = 560)

Compound subC-8 (10 g, 17.9 mmol) and compound sub9 (3.4 g, 19.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, stirred and refluxed. After that, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in water (22 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 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 7.8 g of compound 1-25. (Yield 67%, MS: [M+H] ⁺ = 652)

Preparation 1-26

Compound C (10 g, 40.6 mmol) and compound Trz20 (19.1 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, 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 19.8 g of compound subC-9. (Yield 77%, MS: [M+H] ⁺ = 636)

Compound subC-9 (10 g, 15.7 mmol) and compound sub9 (3 g, 17.3 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (6.5 g, 47.2 mmol) was dissolved in water (20 ml), and after sufficient stirring, 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 8.5 g of compound 1-26. (Yield 74%, MS: [M+H] ⁺ = 728)

Preparation Example 1-27

Compound D (10 g, 40.6 mmol) and compound Trz21 (16 g, 40.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, 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 g of compound subD-1. (yield 75%, MS: [M+H] ⁺ = 560)

Compound subD-1 (10 g, 17.9 mmol) and compound sub2 (2.4 g, 19.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. After that, potassium carbonate (7.4 g, 53.6 mmol) was dissolved in water (22 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.1 g, 0.2 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 6.4 g of compound 1-27. (yield 60%, MS: [M+H] ⁺ = 602)

Preparation 1-28

Compound D (10 g, 40.6 mmol) and compound Trz6 (12.9 g, 40.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, 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 15.1 g of compound subD-2. (Yield 77%, MS: [M+H] ⁺ = 484)

Compound subD-2 (10 g, 20.7 mmol) and compound sub9 (3.9 g, 22.7 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (8.6 g, 62 mmol) was dissolved in water (26 ml), 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 7.5 g of compound 1-28. (Yield 63%, MS: [M+H] ⁺ = 576)

Preparation 1-29

Compound D (10 g, 40.6 mmol) and compound Trz22 (15.2 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, 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 subD-3. (Yield 71%, MS: [M+H] ⁺ = 540)

Compound subD-3 (10 g, 18.5 mmol) and compound sub15 (4.3 g, 20.4 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7.7 g, 55.6 mmol) was dissolved in water (23 ml), 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 8.3 g of compound 1-29. (Yield 67%, MS: [M+H] ⁺ = 672)

Preparation 1-30

Compound D (10 g, 40.6 mmol) and compound Trz23 (14.5 g, 40.6 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), and after stirring sufficiently, 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 15.1 g of compound subD-4. (Yield 71%, MS: [M+H] ⁺ = 52

Compound subD-4 (10 g, 19.1 mmol) and compound sub9 (3.6 g, 21 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7.9 g, 57.3 mmol) was dissolved in water (24 ml), and after sufficient stirring, 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 8.3 g of compound 1-30. (Yield 71%, MS: [M+H] ⁺ = 616)

Preparation Example 1-31

Compound subD-4 (10 g, 19.1 mmol) and compound sub16 (5.5 g, 21 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (7.9 g, 57.3 mmol) was dissolved in water (24 ml), 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 10.1 g of compound 1-31. (yield 75%, MS: [M+H] ⁺ = 706)

Preparation Example 1-32

Compound D (10 g, 40.6 mmol) and compound Trz24 (18.3 g, 40.6 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (11.2 g, 81.2 mmol) was dissolved in water (34 ml), 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 18.5 g of compound subD-5. (Yield 74%, MS: [M+H] ⁺ = 616)

Compound subD-5 (10 g, 16.2 mmol) and compound sub17 (4.1 g, 17.9 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (6.7 g, 48.7 mmol) was dissolved in water (20 ml), 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 8.4 g of compound 1-32. (Yield 68%, MS: [M+H] ⁺ = 764)

Preparation 2-1

In a nitrogen atmosphere, compound E (10 g, 40.6 mmol) and compound sub18 (12.8 g, 44.7 mmol) were added to THF (200 ml), stirred and refluxed. Thereafter, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in water (51 ml), 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 13.3 g of compound subE-1. (Yield 80%, MS: [M+H] ⁺ = 409)

Compound subE-1 (10 g, 24.5 mmol), compound sub19 (5.8 g, 25 mmol), and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 9.1 g of Compound 2-1. (Yield 66%, MS: [M+H] ⁺ = 561)

Preparation Example 2-2

Compound subE-1 (10 g, 24.5 mmol), compound sub20 (7.1 g, 25 mmol), and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 8.7 g of Compound 2-2. (Yield 58%, MS: [M+H] ⁺ = 611)

Preparation 2-3

Compound subE-1 (10 g, 24.5 mmol), compound sub21 (7.7 g, 25 mmol), and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 9.3 g of compound 2-3. (Yield 60%, MS: [M+H] ⁺ = 637)

Preparation 2-4

Compound subE-1 (10 g, 24.5 mmol), compound sub22 (7.7 g, 25 mmol), and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 9.9 g of compound 2-4. (Yield 64%, MS: [M+H] ⁺ = 635)

Preparation Example 2-5

Compound subE-1 (10 g, 24.5 mmol), compound sub23 (9.9 g, 25 mmol), and sodium tert-butoxide (3.5 g, 36.7 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 2-5. (Yield 60%, MS: [M+H] ⁺ = 725)

Preparation 2-6

In a nitrogen atmosphere, compound E (10 g, 40.6 mmol) and compound sub24 (16.2 g, 44.7 mmol) were added to THF (200 ml), stirred and refluxed. Thereafter, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in water (51 ml), and after sufficient stirring, 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 15.3 g of compound subE-2. (Yield 78%, MS: [M+H] ⁺ = 485)

In a nitrogen atmosphere, compound subE-2 (10 g, 20.6 mmol), compound sub19 (4.9 g, 21 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to xylene (200 ml), stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 8.4 g of compound 2-6. (Yield 64%, MS: [M+H] ⁺ = 637)

Preparation 2-7

In a nitrogen atmosphere, compound subE-2 (10 g, 20.6 mmol), compound sub25 (4.9 g, 21 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to xylene (200 ml), stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 9.2 g of Compound 2-7. (Yield 70%, MS: [M+H] ⁺ = 637)

Preparation 2-8

Compound subE-2 (10 g, 20.6 mmol), compound sub26 (6.5 g, 21 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 7.5 g of compound 2-8. (Yield 51%, MS: [M+H] ⁺ = 713)

Preparation 2-9

Compound subE-2 (10 g, 20.6 mmol), compound sub27 (5.4 g, 21 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 7.8 g of compound 2-9. (Yield 57%, MS: [M+H] ⁺ = 661)

Preparation Example 2-10

Compound subE-2 (10 g, 20.6 mmol), compound sub28 (4.4 g, 21 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 6.5 g of Compound 2-10. (Yield 52%, MS: [M+H] ⁺ = 611)

Preparation Example 2-11

Compound E (10 g, 40.6 mmol) and compound sub29 (16.2 g, 44.7 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in water (51 ml), and after sufficient stirring, 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 14 g of compound subE-3. (Yield 71%, MS: [M+H] ⁺ = 485)

Compound subE-3 (10 g, 20.6 mmol), compound sub30 (4.9 g, 21 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 7.1 g of compound 2-11. (Yield 54%, MS: [M+H] ⁺ = 637)

Preparation Example 2-12

Compound subE-3 (10 g, 20.6 mmol), compound sub31 (5.5 g, 21 mmol), and sodium tert-butoxide (3 g, 31 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 6.9 g of Compound 2-12. (Yield 50%, MS: [M+H] ⁺ = 667)

Preparation Example 2-13

In a nitrogen atmosphere, compound E (10 g, 40.6 mmol) and compound sub32 (15.1 g, 44.7 mmol) were added to THF (200 ml), stirred and refluxed. Thereafter, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in water (51 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, 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 subE-4. (yield 75%, MS: [M+H] ⁺ = 459)

Compound subE-4 (10 g, 21.8 mmol), compound sub32 (4.6 g, 22.2 mmol), and sodium tert-butoxide (3.1 g, 32.7 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 6.8 g of compound 2-13. (Yield 53%, MS: [M+H] ⁺ = 585)

Preparation Example 2-14

Compound subE-4 (10 g, 21.8 mmol), compound sub33 (6.3 g, 22.2 mmol), and sodium tert-butoxide (3.1 g, 32.7 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 8.5 g of Compound 2-14. (yield 59%, MS: [M+H] ⁺ = 659)

Preparation Example 2-15

Compound subE-1 (10 g, 24.5 mmol), compound sub34 (6.2 g, 25 mmol), sodium tert-butoxide (3.5 g, 36.7 mmol) in xylene (200 ml) in a nitrogen atmosphere was stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 9.1 g of compound 2-15. (Yield 65%, MS: [M+H] ⁺ = 575)

Preparation Example 2-16

In a nitrogen atmosphere, compound E (10 g, 40.6 mmol) and compound sub35 (18.5 g, 44.7 mmol) were added to THF (200 ml), stirred and refluxed. Thereafter, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in water (51 ml), and after sufficient stirring, 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 13 g of compound subE-5. (yield 60%, MS: [M+H] ⁺ = 535)

In a nitrogen atmosphere, compound subE-5 (10 g, 18.7 mmol), compound sub36 (4.7 g, 19.1 mmol), sodium tert-butoxide (2.7 g, 28.1 mmol) were added to xylene (200 ml), and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 6.8 g of Compound 2-16. (Yield 52%, MS: [M+H] ⁺ = 701)

Preparation Example 2-17

Compound E (10 g, 40.6 mmol) and compound sub37 (16.9 g, 44.7 mmol) were placed in THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in water (51 ml), and after sufficient stirring, bis (tri-tert-butylphosphine) palladium (0) (0.2 g, 0.4 mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, 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 subE-6. (Yield 60%, MS: [M+H] ⁺ = 499)

In a nitrogen atmosphere, compound subE-6 (10 g, 20.1 mmol), compound sub31 (5.4 g, 20.5 mmol), sodium tert-butoxide (2.9 g, 30.1 mmol) was added to xylene (200 ml), and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 9.5 g of Compound 2-17. (Yield 70%, MS: [M+H] ⁺ = 681)

Preparation Example 2-18

Compound E (10 g, 40.6 mmol) and compound sub38 (18.5 g, 44.7 mmol) were added to THF (200 ml) in a nitrogen atmosphere, and the mixture was stirred and refluxed. Thereafter, potassium carbonate (16.8 g, 121.9 mmol) was dissolved in water (51 ml), 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 14.8 g of compound subE-7. (Yield 68%, MS: [M+H] ⁺ = 535)

In a nitrogen atmosphere, compound subE-7 (10 g, 18.7 mmol), compound sub39 (5 g, 19.1 mmol), sodium tert-butoxide (2.7 g, 28.1 mmol) was added to xylene (200 ml), and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 8.3 g of compound 2-18. (Yield 62%, MS: [M+H] ⁺ = 717)

Preparation Example 2-19

Compound subE-4 (10 g, 21.8 mmol), compound sub40 (5.9 g, 22.2 mmol), and sodium tert-butoxide (3.1 g, 32.7 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 9.6 g of compound 2-19. (yield 69%, MS: [M+H] ⁺ = 641)

Preparation 2-20

Compound subE-6 (10 g, 20.1 mmol), compound sub34 (5.1 g, 20.5 mmol), and sodium tert-butoxide (2.9 g, 30.1 mmol) were added to xylene (200 ml) in a nitrogen atmosphere, and stirred and refluxed. . Thereafter, bis(tri-tert-butylphosphine)palladium(0) (0.1 g, 0.2 mmol) was added thereto. When the reaction was completed after 5 hours, the solvent was removed under reduced pressure and cooled to room temperature. 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 7.7 g of Compound 2-20. (Yield 58%, MS: [M+H] ⁺ = 665)

[Example]

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1,000 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, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, the following HI-1 compound was formed as a hole injection layer to a thickness of 1150 Å, but the following compound A-1 was p-doped at a concentration of 1.5 wt%. The following HT-1 compound was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 800 Å. Then, the following EB-1 compound 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 1-3 and compound 2-1 prepared previously as a host, and the following Dp-7 compound as a dopant were vacuum-deposited in a weight ratio of 49:49:2 to form a 400 Å thick red light emitting layer. formed. A hole blocking layer was formed by vacuum-depositing the following HB-1 compound to a thickness of 30 Å on the light emitting layer. Then, the following ET-1 compound and the following LiQ compound were vacuum deposited on the hole blocking layer 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 1,000 Å on the electron injection and transport layer.

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

Examples 2 to 95

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the host compound used in preparing the light emitting layer was prepared in the same manner as in Example 1, except that the compounds shown in Tables 1 to 4 were used.

Comparative Examples 1 to 92

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the host compound used in preparing the light emitting layer was prepared in the same manner as in Example 1, except that the compounds shown in Tables 5 to 8 were used. The compounds shown in Tables 5 to 8 are as follows.

When a current was applied to the organic light emitting diodes prepared in Examples and Comparative Examples, voltage and efficiency were measured (based on 15 mA/cm ² ), and the results are shown in Tables 1 to 8 below. The lifetime T95 means the time (hr) required for the luminance to decrease from the initial luminance (6,000 nits) to 95%.

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Example 1 compound 1-3 compound 2-1 3.78 20.3 217 Red Example 2 compound 2-6 3.84 21.1 230 Red Example 3 compound 2-10 3.80 21.4 228 Red Example 4 compound 2-11 3.83 20.7 233 Red Example 5 compound 2-15 3.85 20.9 215 Red Example 6 compound 1-4 compound 2-3 3.76 19.9 221 Red Example 7 compound 2-7 3.78 20.3 216 Red Example 8 compound 2-10 3.74 20.1 220 Red Example 9 compound 2-14 3.79 20.6 208 Red Example 10 compound 2-17 3.82 20.4 215 Red Example 11 compound 1-6 compound 2-4 3.93 19.3 201 Red Example 12 compound 2-9 3.90 20.0 228 Red Example 13 compound 2-10 3.92 20.6 210 Red Example 14 compound 2-11 3.88 19.7 224 Red Example 15 compound 2-18 3.86 20.0 217 Red Example 16 compounds 1-9 compound 2-5 3.88 19.7 227 Red Example 17 compound 2-9 3.84 20.8 218 Red Example 18 compound 2-10 3.78 19.3 215 Red Example 19 compound 2-14 3.82 19.5 220 Red Example 20 compound 2-15 3.86 20.2 218 Red Example 21 compound 1-11 compound 2-1 3.68 22.3 281 Red Example 22 compound 2-6 3.65 22.0 277 Red Example 23 compound 2-10 3.70 21.3 288 Red Example 24 compound 2-11 3.69 22.7 270 Red Example 25 compound 2-15 3.71 21.8 274 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Example 26 compound 1-12 compound 2-3 3.92 18.9 191 Red Example 27 compound 2-7 3.88 19.2 208 Red Example 28 compound 2-10 3.90 19.6 197 Red Example 29 compound 2-14 3.89 18.7 191 Red Example 30 compound 2-17 3.92 185 205 Red Example 31 compound 1-13 compound 2-4 3.85 18.4 203 Red Example 32 compound 2-9 3.81 18.6 205 Red Example 33 compound 2-10 3.80 18.7 197 Red Example 34 compound 2-11 3.88 19.0 206 Red Example 35 compound 2-18 3.83 18.9 194 Red Example 36 compound 1-14 compound 2-5 3.96 19.6 203 Red Example 37 compound 2-9 3.94 19.3 207 Red Example 38 compound 2-10 3.97 19.8 198 Red Example 39 compound 2-14 3.88 20.4 185 Red Example 40 compound 2-15 3.93 19.1 193 Red Example 41 compound 1-15 compound 2-1 3.88 19.3 203 Red Example 42 compound 2-6 3.80 19.7 210 Red Example 43 compound 2-10 3.84 19.0 207 Red Example 44 compound 2-11 3.89 18.6 201 Red Example 45 compound 2-15 3.86 19.2 195 Red Example 46 compound 1-19 compound 2-3 3.79 19.3 208 Red Example 47 compound 2-7 3.72 20.2 211 Red Example 48 compound 2-10 3.74 20.7 210 Red Example 49 compound 2-14 3.70 19.8 203 Red Example 50 compound 2-17 3.77 20.6 215 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Example 51 compound 1-22 compound 2-4 3.72 21.0 275 Red Example 52 compound 2-9 3.70 22.1 271 Red Example 53 compound 2-10 3.75 21.5 284 Red Example 54 compound 2-11 3.74 21.3 268 Red Example 55 compound 2-18 3.71 22.3 275 Red Example 56 compound 1-23 compound 2-5 3.86 19.3 213 Red Example 57 compound 2-9 3.82 19.8 212 Red Example 58 compound 2-10 3.86 18.1 207 Red Example 59 compound 2-14 3.83 19.5 218 Red Example 60 compound 2-15 3.81 18.7 195 Red Example 61 compound 1-24 compound 2-1 3.73 20.7 225 Red Example 62 compound 2-6 3.70 19.1 238 Red Example 63 compound 2-10 3.76 19.7 231 Red Example 64 compound 2-11 3.74 19.0 240 Red Example 65 compound 2-15 3.80 19.4 234 Red Example 66 compounds 1-25 compound 2-3 3.76 22.2 263 Red Example 67 compound 2-7 3.70 21.9 275 Red Example 68 compound 2-10 3.74 22.0 279 Red Example 69 compound 2-14 3.79 21.8 256 Red Example 70 compound 2-17 3.74 21.5 275 Red Example 71 compound 1-27 compound 2-4 3.76 20.5 238 Red Example 72 compound 2-9 3.82 19.3 211 Red Example 73 compound 2-10 3.79 19.6 223 Red Example 74 compound 2-11 3.78 19.1 226 Red Example 75 compound 2-18 3.82 20.3 230 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Example 76 compound 1-28 compound 2-5 3.80 20.9 234 Red Example 77 compound 2-9 3.81 20.5 221 Red Example 78 compound 2-10 3.87 19.9 216 Red Example 79 compound 2-14 3.86 20.6 224 Red Example 80 compound 2-15 3.93 20.4 225 Red Example 81 compounds 1-30 compound 2-1 3.98 20.3 256 Red Example 82 compound 2-6 3.92 20.0 248 Red Example 83 compound 2-10 3.95 20.5 251 Red Example 84 compound 2-11 3.90 20.1 252 Red Example 85 compound 2-15 3.93 19.8 265 Red Example 86 compound 1-31 compound 2-3 3.81 20.1 203 Red Example 87 compound 2-7 3.83 20.3 214 Red Example 88 compound 2-10 3.80 20.8 209 Red Example 89 compound 2-14 3.85 20.5 205 Red Example 90 compound 2-17 3.84 21.0 215 Red Example 91 compound 1-32 compound 2-4 3.89 20.1 213 Red Example 92 compound 2-9 3.87 20.3 215 Red Example 93 compound 2-10 3.88 20.2 201 Red Example 94 compound 2-11 3.86 19.5 217 Red Example 95 compound 2-18 3.86 20.4 220 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Comparative Example 1 compound B-1 compound 2-1 4.35 13.1 91 Red Comparative Example 2 compound 2-6 4.38 13.8 103 Red Comparative Example 3 compound 2-10 4.36 13.6 97 Red Comparative Example 4 compound 2-11 4.40 14.0 102 Red Comparative Example 5 compound 2-15 4.42 13.9 95 Red Comparative Example 6 compound B-2 compound 2-3 4.23 13.3 152 Red Comparative Example 7 compound 2-7 4.20 13.8 161 Red Comparative Example 8 compound 2-10 4.21 13.6 143 Red Comparative Example 9 compound 2-14 4.18 13.9 138 Red Comparative Example 10 compound 2-17 4.24 14.1 148 Red Comparative Example 11 compound B-3 compound 2-4 4.31 13.2 124 Red Comparative Example 12 compound 2-9 4.33 14.0 118 Red Comparative Example 13 compound 2-10 4.32 13.4 109 Red Comparative Example 14 compound 2-11 4.30 14.3 120 Red Comparative Example 15 compound 2-18 4.32 14.2 127 Red Comparative Example 16 compound B-4 compound 2-5 4.05 13.8 159 Red Comparative Example 17 compound 2-9 4.08 14.2 172 Red Comparative Example 18 compound 2-10 4.07 13.6 150 Red Comparative Example 19 compound 2-14 4.01 14.1 146 Red Comparative Example 20 compound 2-15 4.09 13.7 157 Red Comparative Example 21 compound B-5 compound 2-1 4.25 15.0 99 Red Comparative Example 22 compound 2-6 4.31 14.8 87 Red Comparative Example 23 compound 2-10 4.28 15.3 105 Red Comparative Example 24 compound 2-11 4.29 14.9 100 Red Comparative Example 25 compound 2-15 4.25 14.7 92 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Comparative Example 26 compound B-6 compound 2-3 4.30 15.3 122 Red Comparative Example 27 compound 2-7 4.28 15.0 137 Red Comparative Example 28 compound 2-10 4.26 15.5 115 Red Comparative Example 29 compound 2-14 4.31 15.8 122 Red Comparative Example 30 compound 2-17 4.27 14.6 119 Red Comparative Example 31 compound B-7 compound 2-4 4.29 15.6 149 Red Comparative Example 32 compound 2-9 4.31 14.7 137 Red Comparative Example 33 compound 2-10 4.27 15.0 155 Red Comparative Example 34 compound 2-11 4.24 14.9 131 Red Comparative Example 35 compound 2-18 4.28 14.6 142 Red Comparative Example 36 compound B-8 compound 2-5 4.21 14.0 151 Red Comparative Example 37 compound 2-9 4.29 15.3 167 Red Comparative Example 38 compound 2-10 4.25 14.1 147 Red Comparative Example 39 compound 2-14 4.23 15.2 153 Red Comparative Example 40 compound 2-15 4.20 15.0 130 Red Comparative Example 41 compound B-9 compound 2-1 4.11 15.5 164 Red Comparative Example 42 compound 2-6 4.10 15.7 177 Red Comparative Example 43 compound 2-10 4.13 15.8 152 Red Comparative Example 44 compound 2-11 4.15 14.9 168 Red Comparative Example 45 compound 2-15 4.09 15.1 170 Red Comparative Example 46 compound B-10 compound 2-3 4.13 15.6 93 Red Comparative Example 47 compound 2-7 4.15 16.1 97 Red Comparative Example 48 compound 2-10 4.17 16.0 84 Red Comparative Example 49 compound 2-14 4.10 15.7 91 Red Comparative Example 50 compound 2-17 4.14 15.4 104 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Comparative Example 51 compound B-11 compound 2-4 4.10 15.8 72 Red Comparative Example 52 compound 2-9 4.09 16.3 65 Red Comparative Example 53 compound 2-10 4.17 15.9 62 Red Comparative Example 54 compound 2-11 4.16 16.4 79 Red Comparative Example 55 compound 2-18 4.18 16.1 85 Red Comparative Example 56 compound B-12 compound 2-5 4.31 12.0 37 Red Comparative Example 57 compound 2-9 4.38 11.5 49 Red Comparative Example 58 compound 2-10 4.43 12.8 53 Red Comparative Example 59 compound 2-14 4.46 10.9 37 Red Comparative Example 60 compound 2-15 4.39 11.4 40 Red Comparative Example 61 compound 1-3 compound C-1 4.31 13.0 121 Red Comparative Example 62 compound 1-11 4.36 14.1 127 Red Comparative Example 63 compound 1-12 4.37 13.3 117 Red Comparative Example 64 compound 1-14 4.28 13.9 108 Red Comparative Example 65 compound 1-23 4.36 13.5 118 Red Comparative Example 66 compounds 1-25 4.33 12.9 122 Red Comparative Example 67 compound 1-28 4.27 13.1 111 Red Comparative Example 68 compound 1-31 4.32 13.6 120 Red Comparative Example 69 compound 1-4 compound C-2 4.13 17.0 144 Red Comparative Example 70 compound 1-6 4.16 16.8 135 Red Comparative Example 71 compound 1-13 4.20 17.1 159 Red Comparative Example 72 compound 1-15 4.18 17.5 142 Red Comparative Example 73 compound 1-19 4.11 16.9 143 Red Comparative Example 74 compound 1-24 4.23 17.3 137 Red Comparative Example 75 compound 1-27 4.12 16.8 140 Red Comparative Example 76 compounds 1-30 4.21 16.4 154 Red

first host second host drive voltage
(V) efficiency
(cd/A) life span
T95(hr) luminous color Comparative Example 77 compound 1-3 compound C-3 4.04 15.2 165 Red Comparative Example 78 compound 1-11 4.02 15.9 154 Red Comparative Example 79 compound 1-12 4.00 16.1 147 Red Comparative Example 80 compound 1-14 4.07 15.3 155 Red Comparative Example 81 compound 1-23 4.02 16.0 164 Red Comparative Example 82 compounds 1-25 4.10 17.0 152 Red Comparative Example 83 compound 1-28 4.07 17.2 147 Red Comparative Example 84 compound 1-31 4.06 16.5 151 Red Comparative Example 85 compound 1-4 compound C-4 4.17 16.0 131 Red Comparative Example 86 compound 1-6 4.23 16.2 125 Red Comparative Example 87 compound 1-13 4.15 16.0 137 Red Comparative Example 88 compound 1-15 4.21 16.2 113 Red Comparative Example 89 compound 1-19 4.24 15.5 128 Red Comparative Example 90 compound 1-24 4.20 16.1 119 Red Comparative Example 91 compound 1-27 4.25 16.3 126 Red Comparative Example 92 compounds 1-30 4.22 15.9 138 Red

For the red organic light emitting diode of Example 1, a material widely used in the prior art was used, and Compound 1-3, Compound 2-1, and Compound Dp-7 were used as the light emitting layer. When used as a red light emitting layer by co-evaporation like the compounds of Comparative Examples B-1 to B-12 and the compound of Formula 2 of the present invention, the driving voltage generally increased and the efficiency and lifespan decreased compared to the combination of the present invention, When used as a red light emitting layer by co-deposition like the compounds C-1 to C-4 as another comparative example and the compound of Formula 1 of the present invention, the driving voltage increased and the efficiency and lifespan decreased.

From this, the reason that the driving voltage is improved and the efficiency and lifespan are increased is that the combination of the compound of Formula 1 as the first host and the compound of Formula 2 as the second host of the present invention has good energy transfer to the red dopant in the red light emitting layer. knew it was going to happen. That is, it was confirmed that the combination of Formula 1 and Formula 2 of the present invention, rather than the combination with the compound of Comparative Example, improved efficiency and lifespan by combining electrons and holes to form excitons through a more stable balance in the light emitting layer. In conclusion, it can be confirmed that the driving voltage, luminous efficiency and lifespan characteristics of the organic light emitting device can be improved when the compound of Formula 1 and the compound of Formula 2 are combined and used as a host for the red light emitting layer by co-evaporation.

1: Substrate 2: Anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: light emitting layer 8: electron transport layer

Claims (8)

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,
L is a single bond; Or a substituted or unsubstituted C _6-60 arylene,
X is N; or CH, provided that at least two or more of X are N;
one of R is substituted or unsubstituted C _6-60 aryl; _{or C 2-60} heteroaryl including at least one selected from the group consisting of substituted or unsubstituted N, O and S, and the remainder is hydrogen; or deuterium,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl, dibenzofuranyl, or dibenzothiophenyl, wherein Ar ₁ And Ar ₂ are each independently, unsubstituted or substituted with one or more deuterium,
[Formula 2]

In Formula 2,
L ₁ and L ₂ are each independently a single bond; substituted or unsubstituted C _6-60 arylene; _{Or or substituted or unsubstituted C 5-60} heteroarylene comprising at least one selected from the group consisting of N, O and S,
Ar ₃ and Ar ₄ are each independently substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 5-60} heteroaryl comprising any one or more selected from the group consisting of N, O and S,
R ₁ is all hydrogen or deuterium; or two adjacent R ₁ combine to form a benzene ring, and the remainder is hydrogen or deuterium;
R ₂ is all hydrogen or deuterium; Or two adjacent R ₂ are combined to form a benzene ring, and the remainder is hydrogen or deuterium.
According to claim 1,
L is a single bond; phenylene; or naphthylene,
organic light emitting device.
According to claim 1,
X is all N;
organic light emitting device.
According to claim 1,
One of R is phenyl, biphenylyl, terphenylyl, naphthyl, phenylnaphthyl, naphthylphenyl, phenanthrenyl, triphenylenyl, fluoranthenyl, dibenzofuranyl, benzonaphthofuranyl, dibenzothiophenyl , or benzonaphthothiophenyl; the rest is hydrogen or deuterium,
organic light emitting device.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
Organic light emitting device:

According to claim 1,
L ₁ and L ₂ are each independently a single bond; or phenylene;
organic light emitting device.
According to claim 1,
Ar ₃ and Ar ₄ are each independently phenyl, biphenylyl, terphenylyl, quaterphenylyl, naphthyl, naphthylphenyl, phenylnaphthyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, diphenylflu orenyl, spirobifluorenyl, fluorenyl, fluoranthenyl, dibenzofuranyl, or dibenzothiophenyl;
organic light emitting device.
According to claim 1,
The compound represented by Formula 2 is any one selected from the group consisting of
Organic light emitting device:

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