KR102564848B1 - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device using the same.

Description

Novel compound and organic light emitting device using the same

The present invention relates to a novel compound and an organic light emitting device including the same.

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

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

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

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel compound and an organic light emitting device including the same.

The present invention provides a compound represented by Formula 1 below:

[Formula 1]

In Formula 1,

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

any one of R ₁ is Ar ₃ , the others are independently hydrogen or deuterium;

Ar ₁ to Ar ₃ are each independently substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5- including any one or more heteroatoms selected from the group consisting of N, O and S; ₆₀ heteroaryl;

R ₂ are each independently hydrogen or deuterium.

In addition, the present invention is an organic light emitting device including a first electrode, a second electrode provided to face the first electrode, and one or more organic material layers provided between the first electrode and the second electrode, wherein the organic material layer At least one of the layers includes the compound represented by Chemical Formula 1, and provides an organic light emitting device.

The compound represented by Chemical Formula 1 may be used as a material for an organic material layer of an organic light emitting device, and may improve efficiency, low driving voltage, and/or lifetime characteristics of an organic light emitting device.

In particular, the compound represented by Chemical Formula 1 may be used as a material for hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection.

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

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

(Definition of Terms)

는 다른 치환기에 연결되는 결합을 의미한다.In this specification, and

means a bond connected to another substituent.

As used herein, the term “substituted or unsubstituted” refers to heavy hydrogen, a halogen group, a cyano group, a nitro group, a hydroxy group, a carbonyl group, an ester group, an imide group, an amino group, a phosphine oxide group, an alkoxy group, an aryloxy group, an alkyl Thioxy group, arylthioxy group, alkylsulfoxyl group, arylsulfoxyl group, silyl group, boron group, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, aralkenyl group, alkylaryl group, alkylamine group, aralkylamine group, heteroarylamine group, arylamine group, arylphosphine group, or heteroaryl containing at least one of N, O and S atoms substituted or unsubstituted with one or more substituents selected from the group consisting of, or exemplified above It means a substituted or unsubstituted one in which two or more substituents among the substituents are connected. 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 or may be interpreted as a substituent in which two phenyl groups are connected.

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

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

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

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

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

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

In the present specification, the alkyl group may be straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.

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

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

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

In the present specification, heteroaryl is a heteroaryl containing at least one of O, N, Si, and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. Examples of the heteroaryl 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, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group, Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadiazolyl group group, a phenothiazinyl group and a dibenzofuranyl group, but are not limited thereto.

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

(compound)

The present invention provides a compound represented by Formula 1 above.

Specifically, the compound represented by Chemical Formula 1 has a structure in which 1,3,5-triazine is used as a core and three different substituents are bonded.

More specifically, the three different substituents bonded to the core are substituted or unsubstituted C _10-60 aryl (Ar ₁ ), substituted or unsubstituted C _5-60 heteroaryl (Ar ₂ ), and substituted benzo[b]naphtho[2,3-d]furanyl.

Here, Ar ₁ and Ar ₂ are each single bonded to the core, but the substituted benzo[b]naphtho[2,3-d]furanyl is single bonded to the core or bonded via a linking group (L). can

On the other hand, the substituted benzo[b]naphtho[2,3-d]furanyl is selected from R ₁ substituted or unsubstituted C _10-60 aryl, or substituted or unsubstituted C _5-60 hetero It is substituted with aryl (Ar ₃ ).

An organic light emitting device including the compound represented by Chemical Formula 1 as a component of an organic layer may exhibit high efficiency and long lifespan due to a synergistic effect obtained by combining the three different substituents.

Hereinafter, the compounds represented by Formula 1 and Formula 1 will be described in detail.

Preferably, Formula 1 is represented by any one of Formulas 1-1 to 1-3 below:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Chemical Formulas 1-1 to 1-3, Ar ₁ to Ar ₃ , R ₁ and R ₂ are defined as described above.

Preferably, all R ₂ are hydrogen.

Preferably, it is a single bond, phenylene or naphthalenediyl.

Preferably, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, or phenanthrenyl; Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with at least one phenyl or naphthyl.

Preferably, Ar ₃ is phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, or phenanthrenyl; Ar ₃ is unsubstituted or substituted with one or more phenyl groups.

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

.

.

The compound represented by Formula 1 can be prepared by a preparation method as shown in Scheme 1 below:

[Scheme 1]

In Reaction Scheme 1, Ar ₁ to Ar ₃ and L are as previously defined. The manufacturing method may be more specific in Preparation Examples to be described later.

(organic light emitting device)

Meanwhile, the present invention provides an organic light emitting device including the compound represented by Formula 1 above. As an example, the present invention provides an organic light emitting device including a first electrode, a second electrode provided to face the first electrode, and one or more organic material layers provided between the first electrode and the second electrode, wherein the At least one layer of the organic material layer includes the compound represented by Chemical Formula 1, providing an organic light emitting device.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer as organic material layers. However, the structure of the organic light emitting device is not limited thereto and may include fewer organic layers.

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. Contains the indicated compounds.

Also, the organic material layer may include a light emitting layer, and the light emitting layer includes the compound represented by Chemical Formula 1.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, or may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention further includes a hole injection layer and a hole transport layer between the first electrode and the light emitting layer, and an electron transport layer and an electron injection layer between the light emitting layer and the second electrode, in addition to the light emitting layer as an organic material layer. can have a structure that However, the structure of the organic light emitting device is not limited thereto and may include fewer or more organic layers.

In addition, the organic light emitting device according to the present invention has a structure (normal type) in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate, wherein the first electrode is an anode and the second electrode is a cathode. may be minor. In addition, the organic light emitting device according to the present invention has an inverted type organic layer in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate, wherein the first electrode is a cathode and the second electrode is an anode. It may be a light emitting element. For example, the structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2 .

1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a hole transport layer 3, a light emitting layer 4, an electron injection and transport layer 5 and a cathode 6. In this structure, the compound represented by Chemical Formula 1 may be included in the hole transport layer.

2 shows a substrate 1, an anode 2, a hole injection layer 7, a hole transport layer 3, an electron blocking layer 8, a light emitting layer 4, a hole blocking layer 9, an electron injection and transport layer ( 5) and an example of an organic light emitting element composed of a cathode 6 is shown. In this structure, the compound represented by Formula 1 may be included in the hole injection layer, the hole transport layer, or the electron suppression layer.

The organic light emitting device according to the present invention may be manufactured with materials and methods known in the art, except that at least one of the organic material layers includes the compound represented by Chemical Formula 1. Also, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, depositing a metal or a metal oxide having conductivity or an alloy thereof on the substrate to form an anode After forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

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

In one example, the first electrode is an anode and the second electrode is a cathode, or the first electrode is a cathode and the second electrode is an anode.

As the anode material, a material having a high work function is generally preferable 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, and gold or alloys thereof, metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO), ZnO: Combinations of metals and oxides such as Al or SnO ₂ :Sb, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline Conductive polymers and the like, but are not limited thereto.

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

The hole injection layer is a layer for injecting holes from the electrode, and the hole injection material has the ability to transport holes and has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and generated in the light emitting layer A compound that prevents migration of excitons to the electron injecting layer or electron injecting material and has excellent thin film formation ability is preferred. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrins, oligothiophenes, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic matter, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer. The hole transport material is a material that can receive holes from the anode or the hole injection layer and transfer them to the light emitting layer, and has high hole mobility. material is suitable. As the hole transport material, the compound represented by Formula 1, or an arylamine-based organic material, a conductive polymer, and a block copolymer having both a conjugated and a non-conjugated part may be used, but is not limited thereto. .

The electron blocking layer is formed on the hole transport layer, and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons to increase hole-electron coupling probability, thereby increasing the efficiency of the organic light emitting device. means a layer that serves to improve The electron blocking layer includes an electron blocking material, and as an example of the electron blocking material, a compound represented by Chemical Formula 1 or an arylamine-based organic material may be used, but is not limited thereto.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazole-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazoles, benzthiazoles and benzenes. Imidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, rubrene, and the like, but are not limited thereto.

For example, the light emitting layer alone contains the compound represented by Formula 1 as a host; It may further include a compound represented by Formula 1 as a first host and a compound represented by Formula 4 as a second host:

[Formula 4]

In Formula 4,

A is a substituted or unsubstituted naphthalene ring,

Ar ₄ is a substituted or unsubstituted C _6-60 aryl;

L ₃ and L ₄ are each independently a single bond or a substituted or unsubstituted C _6-60 arylene;

Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted C _6-60 aryl, a substituted or unsubstituted C _2-60 containing any one or more heteroatoms selected from the group consisting of N, O and S; heteroaryl, or adamantyl;

p is an integer from 0 to 9;

Preferably, Formula 4 is represented by any one of Formulas 4-1 to 4-3 below:

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

In Chemical Formulas 4-1 to 4-3, Ar ₄ to Ar ₆ , L ₃ , L _{4 ,} and p are defined as described above.

Preferably, Ar ₄ is phenyl, biphenylyl, or naphthyl; Ar ₄ is unsubstituted or substituted with one or more tert-butyl or phenyl.

Preferably, L ₃ and L ₄ are each independently a single bond, phenylene or naphthalenediyl; The L ₃ and L ₄ are each independently unsubstituted or substituted with one or more phenyl groups.

Preferably, Ar ₅ and Ar ₆ are each independently selected from phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9,9-dimethylfluorenyl or adamantyl; Ar ₅ and Ar ₆ are each independently unsubstituted or substituted with one or more tert-butyl or phenyl.

Preferably, p is zero.

Representative examples of the compound represented by Formula 4 are as follows:

.

.

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

Representative examples of the dopant materials are as follows:

.

.

The hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to improve the efficiency of the organic light emitting device by controlling electron mobility and preventing excessive movement of holes to increase the probability of hole-electron coupling layers that play a role. The hole blocking layer includes a hole blocking material, and examples of the hole blocking material include an electron withdrawing group such as azine derivatives, triazole derivatives, oxadiazole derivatives, phenanthroline derivatives, and phosphine oxide derivatives including triazine. Compounds may be used, but are not limited thereto.

The electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from an electrode and transporting the received electrons to the light emitting layer, and is formed on the light emitting layer or the hole blocking layer. As such an electron injecting and transporting material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. Examples of specific electron injection and transport materials include, but are not limited to, Al complexes of 8-hydroxyquinoline, complexes containing Alq ₃ , organic radical compounds, hydroxyflavone-metal complexes, and triazine derivatives. Or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, etc. and their derivatives, metal complex compounds , or may be used together with nitrogen-containing 5-membered ring derivatives, etc., but is not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. It is not limited to this.

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

In addition, the compound represented by Chemical Formula 1 may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

Preparation of the compound represented by Chemical Formula 1 and the organic light emitting device including the same will be described in detail in the following examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Synthesis Example 1

Formula A (15g, 45.2mmol) and sub1 (7.8g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of subA-1. (Yield 77%, MS: [M+H]+= 379)

SubA-1 (15g, 39.6mmol) and bis(pinacolato)diboron (11.1g, 43.6mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (5.8g, 59.4mmol) was added and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7g, 1.2mmol) and tricyclohexylphosphine (0.7g, 2.4mmol) were added. After reacting for 8 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of subA-1'. (Yield 69%, MS: [M+H]+= 471)

In a nitrogen atmosphere, subA-1' (15 g, 31.9 mmol) and Trz1 (8.5 g, 31.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (13.2g, 95.7mmol) was dissolved in 40ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7 g of Compound 1. (Yield 64%, MS: [M+H]+= 576)

Synthesis Example 2

In a nitrogen atmosphere, subA-1' (15g, 31.9mmol) and Trz2 (15.3g, 31.9mmol) were added to 300ml of THF, stirred and refluxed. After that, potassium carbonate (13.2g, 95.7mmol) was dissolved in 40ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.3 g of Compound 2. (Yield 73%, MS: [M+H]+= 742)

Synthesis Example 3

In a nitrogen atmosphere, subA-1' (15 g, 31.9 mmol) and Trz3 (13.5 g, 31.9 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (13.2g, 95.7mmol) was dissolved in 40ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.4 g of Compound 3. (Yield 79%, MS: [M+H]+= 732)

Synthesis Example 4

Formula A (15g, 45.2mmol) and sub2 (5.5g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7 g of subA-2. (Yield 79%, MS: [M+H]+= 329)

SubA-2 (15g, 45.6mmol) and bis(pinacolato)diboron (12.7g, 50.2mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (6.7g, 68.4mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.8g, 1.4mmol) and tricyclohexylphosphine (0.8g, 2.7mmol) were added. After reacting for 9 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8 g of subA-2'. (Yield 77%, MS: [M+H]+= 421)

In a nitrogen atmosphere, subA-2' (15g, 35.7mmol) and Trz4 (12.8g, 35.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.8g, 107.1mmol) was dissolved in 44ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.2 g of Compound 4. (Yield 60%, MS: [M+H]+= 616)

Synthesis Example 5

In a nitrogen atmosphere, subA-2' (15g, 35.7mmol) and Trz5 (15.6g, 35.7mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.8g, 107.1mmol) was dissolved in 44ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17 g of compound 5. (Yield 73%, MS: [M+H]+= 652)

Synthesis Example 6

Formula A (15g, 45.2mmol) and sub3 (10.3g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.1 g of subA-3. (Yield 72%, MS: [M+H]+= 435)

SubA-3 (15g, 34.5mmol) and bis(pinacolato)diboron (9.6g, 37.9mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. Then, potassium acetate (5.1g, 51.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1mmol) and tricyclohexylphosphine (0.6g, 2.1mmol) were added. After reacting for 8 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7 g of subA-3'. (Yield 70%, MS: [M+H]+= 527)

In a nitrogen atmosphere, subA-3' (15g, 28.5mmol) and Trz1 (7.6g, 28.5mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.8g, 85.5mmol) was dissolved in 35ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.7 g of compound 6. (Yield 76%, MS: [M+H]+= 632)

Synthesis Example 7

Formula A (15g, 45.2mmol) and sub4 (10g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere and stirred and refluxed. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6 g of subA-4. (Yield 60%, MS: [M+H]+= 429)

SubA-3 (15g, 34.5mmol) and bis(pinacolato)diboron (9.6g, 37.9mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. Then, potassium acetate (5.1g, 51.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1mmol) and tricyclohexylphosphine (0.6g, 2.1mmol) were added. After reacting for 8 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7 g of subA-3'. (Yield 70%, MS: [M+H]+= 527)

In a nitrogen atmosphere, subA-4' (15 g, 28.8 mmol) and Trz6 (12.5 g, 28.8 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (12g, 86.5mmol) was dissolved in 36ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16.6 g of Compound 7. (Yield 73%, MS: [M+H]+= 792)

Synthesis Example 8

Formula A (15g, 45.2mmol) and sub5 (9.6g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.8 g of subA-5. (Yield 78%, MS: [M+H]+= 419)

SubA-5 (15g, 35.8mmol) and bis(pinacolato)diboron (10g, 39.4mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (5.3g, 53.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1.1mmol) and tricyclohexylphosphine (0.6g, 2.1mmol) were added. After reacting for 6 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of subA-5'. (Yield 76%, MS: [M+H]+= 527)

In a nitrogen atmosphere, subA-5' (15 g, 28.5 mmol) and Trz1 (7.6 g, 28.5 mmol) were added to 300 ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.8g, 85.5mmol) was dissolved in 35ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of Compound 8. (Yield 70%, MS: [M+H]+= 616)

Synthesis Example 9

Formula A (15g, 45.2mmol) and sub6 (10.3g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere and stirred and refluxed. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.7 g of subA-6. (Yield 80%, MS: [M+H]+= 435)

SubA-6 (15g, 34.5mmol) and bis(pinacolato)diboron (9.6g, 37.9mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. Then, potassium acetate (5.1g, 51.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1mmol) and tricyclohexylphosphine (0.6g, 2.1mmol) were added. After reacting for 8 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6 g of subA-6'. (Yield 64%, MS: [M+H]+= 527)

In a nitrogen atmosphere, subA-6' (15 g, 28.5 mmol) and Trz1 (7.6 g, 28.5 mmol) were added to 300 ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.8g, 85.5mmol) was dissolved in 35ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of compound 9. (Yield 80%, MS: [M+H]+= 632)

Synthesis Example 10

Formula A (15g, 45.2mmol) and sub7 (9.6g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of subA-7. (Yield 65%, MS: [M+H]+= 419)

SubA-7 (15g, 35.8mmol) and bis(pinacolato)diboron (10g, 39.4mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (5.3g, 53.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1.1mmol) and tricyclohexylphosphine (0.6g, 2.1mmol) were added. After reacting for 7 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.8 g of subA-7'. (Yield 70%, MS: [M+H]+= 511)

In a nitrogen atmosphere, subA-7' (15 g, 29.4 mmol) and Trz1 (7.9 g, 29.4 mmol) were added to 300 ml of THF and stirred and refluxed. After that, potassium carbonate (12.2g, 88.2mmol) was dissolved in 37ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of Compound 10. (Yield 62%, MS: [M+H]+= 616)

Synthesis Example 11

Formula B (15g, 45.2mmol) and sub2 (5.5g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of subB-1. (Yield 73%, MS: [M+H]+= 329)

SubB-1 (15g, 45.6mmol) and bis(pinacolato)diboron (12.7g, 50.2mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (6.7g, 68.4mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.8g, 1.4mmol) and tricyclohexylphosphine (0.8g, 2.7mmol) were added. After reacting for 9 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13 g of subB-1'. (Yield 68%, MS: [M+H]+= 421)

In a nitrogen atmosphere, subB-1' (15g, 35.7mmol) and Trz7 (11.3g, 35.7mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.8g, 107.1mmol) was dissolved in 44ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of Compound 11. (Yield 61%, MS: [M+H]+= 576)

Synthesis Example 12

In a nitrogen atmosphere, subB-1' (15g, 35.7mmol) and Trz8 (14.1g, 35.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.8g, 107.1mmol) was dissolved in 44ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.8 g of Compound 12. (Yield 68%, MS: [M+H]+= 652)

Synthesis Example 13

Formula B (15g, 45.2mmol) and sub1 (7.8g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of subB-2. (Yield 63%, MS: [M+H]+= 379)

SubB-2 (15g, 39.6mmol) and bis(pinacolato)diboron (11.1g, 43.6mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (5.8g, 59.4mmol) was added and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.7g, 1.2mmol) and tricyclohexylphosphine (0.7g, 2.4mmol) were added. After reacting for 6 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.5 g of subB-2'. (Yield 67%, MS: [M+H]+= 471)

In a nitrogen atmosphere, subB-2' (15g, 31.9mmol) and Trz9 (11g, 31.9mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (13.2g, 95.7mmol) was dissolved in 40ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of Compound 13. (Yield 69%, MS: [M+H]+= 652)

Synthesis Example 14

In a nitrogen atmosphere, subB-2' (15g, 31.9mmol) and Trz10 (12.4g, 31.9mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (13.2g, 95.7mmol) was dissolved in 40ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.9 g of Compound 14. (Yield 76%, MS: [M+H]+= 616)

Synthesis Example 15

Formula B (15g, 45.2mmol) and sub8 (7.8g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.7 g of subB-3. (Yield 74%, MS: [M+H]+= 379)

SubB-3 (15g, 35.8mmol) and bis(pinacolato)diboron (10g, 39.4mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (5.3g, 53.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1.1mmol) and tricyclohexylphosphine (0.6g, 2.1mmol) were added. After reacting for 10 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1 g of subB-3'. (Yield 66%, MS: [M+H]+= 471)

In a nitrogen atmosphere, subB-3' (15g, 31.9mmol) and Trz11 (16.9g, 31.9mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (13.2g, 95.7mmol) was dissolved in 40ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.2 g of Compound 15. (Yield 80%, MS: [M+H]+= 792)

Synthesis Example 16

Formula B (15g, 45.2mmol) and sub5 (9.6g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.3 g of subB-4. (Yield 65%, MS: [M+H]+= 419)

SubB-4 (15g, 35.8mmol) and bis(pinacolato)diboron (10g, 39.4mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (5.3g, 53.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1.1mmol) and tricyclohexylphosphine (0.6g, 2.1mmol) were added. After reacting for 5 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.9 g of subB-4'. (Yield 65%, MS: [M+H]+= 511)

In a nitrogen atmosphere, subB-4' (15g, 29.4mmol) and Trz1 (7.9g, 29.4mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (12.2g, 88.2mmol) was dissolved in 37ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 10.8 g of Compound 16. (Yield 60%, MS: [M+H]+= 616)

Synthesis Example 17

Formula B (15g, 45.2mmol) and sub7 (9.6g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of subB-5. (Yield 71%, MS: [M+H]+= 419)

SubB-5 (15g, 35.8mmol) and bis(pinacolato)diboron (10g, 39.4mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (5.3g, 53.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1.1mmol) and tricyclohexylphosphine (0.6g, 2.1mmol) were added. After reacting for 8 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11 g of subB-5'. (Yield 60%, MS: [M+H]+= 511)

In a nitrogen atmosphere, subB-5' (15g, 29.4mmol) and Trz1 (7.9g, 29.4mmol) were added to 300ml of THF, stirred and refluxed. After that, potassium carbonate (12.2g, 88.2mmol) was dissolved in 37ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.2 g of Compound 17. (Yield 62%, MS: [M+H]+= 616)

Synthesis Example 18

In a nitrogen atmosphere, subB-4' (15 g, 29.4 mmol) and Trz7 (9.3 g, 29.4 mmol) were added to 300 ml of THF, followed by stirring and reflux. After that, potassium carbonate (12.2g, 88.2mmol) was dissolved in 37ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.3 g of Compound 18. (Yield 73%, MS: [M+H]+= 666)

Synthesis Example 19

Formula C (15g, 45.2mmol) and sub10 (10.3g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.5 g of subC-1. (Yield 74%, MS: [M+H]+= 435)

SubC-1 (15g, 34.5mmol) and bis(pinacolato)diboron (9.6g, 37.9mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. Then, potassium acetate (5.1g, 51.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1mmol) and tricyclohexylphosphine (0.6g, 2.1mmol) were added. After reacting for 7 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6 g of subC-1'. (Yield 64%, MS: [M+H]+= 527)

In a nitrogen atmosphere, subC-1' (15g, 28.5mmol) and Trz12 (12g, 28.5mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (11.8g, 85.5mmol) was dissolved in 35ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.6 g of Compound 19. (Yield 79%, MS: [M+H]+= 784)

Synthesis Example 20

Formula C (15g, 45.2mmol) and sub2 (5.5g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.1 g of subC-2. (Yield 75%, MS: [M+H]+= 329)

SubC-2 (15g, 45.6mmol) and bis(pinacolato)diboron (12.7g, 50.2mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (6.7g, 68.4mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.8g, 1.4mmol) and tricyclohexylphosphine (0.8g, 2.7mmol) were added. After reacting for 6 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 14.4 g of subC-2'. (Yield 75%, MS: [M+H]+= 421)

In a nitrogen atmosphere, subC-2' (15g, 35.7mmol) and Trz4 (12.8g, 35.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.8g, 107.1mmol) was dissolved in 44ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 15.1 g of Compound 20. (Yield 69%, MS: [M+H]+= 616)

Synthesis Example 21

In a nitrogen atmosphere, subC-2' (15g, 35.7mmol) and Trz13 (15g, 35.7mmol) were added to 300ml of THF, stirred and refluxed. Thereafter, potassium carbonate (14.8g, 107.1mmol) was dissolved in 44ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 16 g of compound 21. (Yield 66%, MS: [M+H]+= 678)

Synthesis Example 22

In a nitrogen atmosphere, subC-2' (15g, 35.7mmol) and Trz14 (9.6g, 35.7mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (14.8g, 107.1mmol) was dissolved in 44ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.4mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.2 g of Compound 22. (Yield 68%, MS: [M+H]+= 752)

Synthesis Example 23

Formula C (15g, 45.2mmol) and sub11 (9.6g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 13.4 g of subC-3. (Yield 71%, MS: [M+H]+= 419)

SubC-3 (15g, 35.8mmol) and bis(pinacolato)diboron (10g, 39.4mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (5.3g, 53.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1.1mmol) and tricyclohexylphosphine (0.6g, 2.1mmol) were added. After reacting for 9 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of subC-3'. (Yield 68%, MS: [M+H]+= 471)

In a nitrogen atmosphere, subC-3' (15g, 29.4mmol) and Trz1 (7.9g, 29.4mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (12.2g, 88.2mmol) was dissolved in 37ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11 g of compound 23. (Yield 61%, MS: [M+H]+= 616)

Synthesis Example 24

Formula C (15g, 45.2mmol) and sub6 (10.3g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. Thereafter, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 11 hours, it was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12 g of subC-4. (Yield 61%, MS: [M+H]+= 435)

SubC-4 (15g, 34.5mmol) and bis(pinacolato)diboron (9.6g, 37.9mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. Then, potassium acetate (5.1g, 51.7mmol) was added, and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1mmol) and tricyclohexylphosphine (0.6g, 2.1mmol) were added. After reacting for 6 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.4 g of subC-4'. (Yield 63%, MS: [M+H]+= 527)

In a nitrogen atmosphere, subC-4' (15g, 28.5mmol) and Trz1 (7.6g, 28.5mmol) were added to 300ml of THF and stirred and refluxed. Thereafter, potassium carbonate (11.8g, 85.5mmol) was dissolved in 35ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.1g, 0.3mmol) was added. After reacting for 9 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.7 g of Compound 24. (Yield 65%, MS: [M+H]+= 632)

Synthesis Example 25

Formula C (15g, 45.2mmol) and sub12 (9g, 45.2mmol) were added to 300ml of THF under a nitrogen atmosphere, followed by stirring and refluxing. After that, potassium carbonate (18.8g, 135.7mmol) was dissolved in 56ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 12.1 g of subC-5. (Yield 66%, MS: [M+H]+= 405)

SubC-5 (15g, 37mmol) and bis(pinacolato)diboron (10.3g, 40.8mmol) were refluxed and stirred in 300ml of 1,4-dioxane in a nitrogen atmosphere. After that, potassium acetate (5.5g, 55.6mmol) was added and after sufficient stirring, bis(dibenzylideneacetone)palladium(0) (0.6g, 1.1mmol) and tricyclohexylphosphine (0.6g, 2.2mmol) were added. After reacting for 9 hours, cooling to room temperature and separating the organic layer using chloroform and water, the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 11.6 g of subC-5'. (Yield 63%, MS: [M+H]+= 497)

In a nitrogen atmosphere, subC-5' (15g, 30.2mmol) and Trz15 (18.8g, 30.2mmol) were added to 300ml of THF and stirred and refluxed. After that, potassium carbonate (12.5g, 90.7mmol) was dissolved in 38ml of water, and after stirring sufficiently, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.3mmol) was added. After reacting for 12 hours, the reaction mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.9 g of compound 25. (Yield 76%, MS: [M+H]+= 910)

Example 1

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

The following compound HI-1 was formed to a thickness of 1150 Å as a hole injection layer on the prepared ITO transparent electrode, but the following compound A-1 was p-doped at a concentration of 1.5%. On the hole injection layer, the following HT-1 compound was vacuum deposited to form a hole transport layer having a thickness of 800 Å. Subsequently, an electron blocking layer was formed on the hole transport layer by vacuum depositing the following EB-1 compound to a film thickness of 150 Å. Subsequently, the following compound 1 and the following compound Dp-7 were vacuum deposited on the EB-1 deposited film in a weight ratio of 98:2 to form a red light emitting layer having a thickness of 400 Å. A hole blocking layer was formed on the light emitting layer by vacuum depositing the following HB-1 compound to a film thickness of 30 Å. Subsequently, the following ET-1 compound and the following LiQ compound were vacuum deposited at a weight ratio of 2:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300 Å. A negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7Å / sec, the deposition rate of lithium fluoride on the cathode was 0.3Å / sec, and the deposition rate of aluminum was 2Å / sec, and the vacuum level during deposition was 2ⅹ10 ^-7 ~ While maintaining 5x10 ^-6 torr, an organic light emitting device was fabricated.

Examples 2 to 25

The organic light emitting devices of Examples 2 to 25 were prepared in the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of Compound 1 in the organic light emitting device of Example 1.

Comparative Examples 1 to 12

Organic light emitting devices of Comparative Examples 1 to 12 were prepared in the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of Compound 1 in the organic light emitting device of Example 1.

Examples 26 to 75

In the organic light emitting device of Example 1, instead of Compound 1, the first host and the second host described in Table 2 below were vacuum co-evaporated at a ratio of 1: 1, and Examples 26 to 26 were carried out in the same manner as in Example 1 except for this. 75 organic light emitting devices were manufactured.

Comparative Examples 13 to 36

In the organic light emitting device of Example 1, instead of Compound 1, the first host and the second host described in Table 2 below were vacuum co-deposited at a ratio of 1: 1, and Comparative Examples 13 to 10 were performed in the same manner as in Example 1 except for this. 36 organic light emitting devices were manufactured.

When current was applied to the organic light emitting devices prepared in Examples 1 to 75 and Comparative Examples 1 to 36, voltage and efficiency were measured (based on 15 mA/cm ² ), and the results are shown in Tables 1 and 2 below. The lifetime T95 means the time required for the luminance to decrease from the initial luminance (7000 nit) to 95%.

division matter Efficiency (cd/A) Lifetime T95(hr) luminescent color Example 1 compound 1 23.4 184 Red Example 2 compound 2 20.9 133 Red Example 3 compound 3 20.8 155 Red Example 4 compound 4 23.1 147 Red Example 5 compound 5 23.5 160 Red Example 6 compound 6 21.3 152 Red Example 7 compound 7 22.9 143 Red Example 8 compound 8 23.7 152 Red Example 9 compound 9 21.3 158 Red Example 10 compound 10 23.7 163 Red Example 11 compound 11 21.8 151 Red Example 12 compound 12 20.3 140 Red Example 13 compound 13 23.4 159 Red Example 14 compound 14 22.4 163 Red Example 15 compound 15 22.0 143 Red Example 16 compound 16 23.7 184 Red Example 17 compound 17 23.1 189 Red Example 18 compound 18 23.3 192 Red Example 19 compound 19 20.1 151 Red Example 20 compound 20 22.3 164 Red Example 21 compound 21 21.9 142 Red Example 22 compound 22 20.4 167 Red Example 23 compound 23 22.3 158 Red Example 24 compound 24 23.5 193 Red Example 25 compound 25 20.4 167 Red Comparative Example 1 C-1 17.9 154 Red Comparative Example 2 C-2 17.4 133 Red Comparative Example 3 C-3 17.1 110 Red Comparative Example 4 C-4 18.1 138 Red Comparative Example 5 C-5 17.2 76 Red Comparative Example 6 C-6 17.9 134 Red Comparative Example 7 C-7 17.5 112 Red Comparative Example 8 C-8 17.0 98 Red Comparative Example 9 C-9 15.1 101 Red Comparative Example 10 C-10 17.8 129 Red Comparative Example 11 C-11 16.3 129 Red Comparative Example 12 C-12 20.4 129 Red

division 1st host 2nd host Driving voltage (V) Efficiency (cd/A) Lifetime T95(hr) luminescent color Example 26 compound 1 Z-1 3.45 26.4 362 Red Example 27 compound 2 3.53 23.2 301 Red Example 28 compound 3 3.54 22.1 312 Red Example 29 compound 4 3.57 23.0 294 Red Example 30 compound 5 3.60 25.5 320 Red Example 31 compound 6 3.58 20.4 301 Red Example 32 compound 7 3.61 21.7 299 Red Example 33 compound 8 3.43 26.7 347 Red Example 34 compound 9 3.61 23.0 313 Red Example 35 compound 10 3.54 24.2 327 Red Example 36 compound 11 3.52 23.1 304 Red Example 37 compound 12 3.60 25.8 297 Red Example 38 compound 13 3.57 22.5 317 Red Example 39 compound 14 3.54 22.0 324 Red Example 40 compound 15 3.61 24.3 296 Red Example 41 compound 16 3.41 26.8 352 Red Example 42 compound 17 3.44 27.1 327 Red Example 43 compound 18 3.40 26.3 359 Red Example 44 compound 19 3.53 23.1 303 Red Example 45 compound 20 3.62 25.3 320 Red Example 46 compound 21 3.57 23.9 285 Red Example 47 compound 22 3.60 22.4 294 Red Example 48 compound 23 3.52 24.3 311 Red Example 49 compound 24 3.42 26.5 353 Red Example 50 compound 25 3.61 23.8 282 Red Example 51 compound 1 Z-2 3.37 27.0 341 Red Example 52 compound 2 3.50 24.1 324 Red Example 53 compound 3 3.58 22.5 308 Red Example 54 compound 4 3.51 23.8 312 Red Example 55 compound 5 3.63 26.1 302 Red Example 56 compound 6 3.54 21.0 329 Red Example 57 compound 7 3.60 21.3 320 Red Example 58 compound 8 3.45 27.3 334 Red Example 59 compound 9 3.54 22.4 294 Red Example 60 compound 10 3.58 23.7 318 Red Example 61 compound 11 3.48 22.8 321 Red Example 62 compound 12 3.55 25.9 304 Red Example 63 compound 13 3.61 22.1 301 Red Example 64 compound 14 3.55 22.6 311 Red Example 65 compound 15 3.60 24.5 303 Red Example 66 compound 16 3.46 27.2 322 Red Example 67 compound 17 3.39 27.3 331 Red Example 68 compound 18 3.45 26.7 364 Red Example 69 compound 19 3.60 24.2 297 Red Example 70 compound 20 3.58 25.8 312 Red Example 71 compound 21 3.59 24.2 304 Red Example 72 compound 22 3.54 21.8 290 Red Example 73 compound 23 3.55 26.1 301 Red Example 74 compound 24 3.40 26.9 335 Red Example 75 compound 25 3.57 24.7 300 Red Comparative Example 13 C-1 Z-1 3.76 23.5 250 Red Comparative Example 14 C-2 3.93 22.0 217 Red Comparative Example 15 C-3 3.94 21.2 226 Red Comparative Example 16 C-4 3.91 21.8 238 Red Comparative Example 17 C-5 4.08 19.4 204 Red Comparative Example 18 C-6 3.95 20.4 213 Red Comparative Example 19 C-7 3.91 19.3 222 Red Comparative Example 20 C-8 3.73 22.4 248 Red Comparative Example 21 C-9 3.85 19.3 223 Red Comparative Example 22 C-10 3.91 21.8 254 Red Comparative Example 23 C-11 3.88 19.7 239 Red Comparative Example 24 C-12 3.73 22.4 271 Red Comparative Example 25 C-1 Z-2 3.73 23.8 247 Red Comparative Example 26 C-2 3.95 22.5 224 Red Comparative Example 27 C-3 3.90 21.7 243 Red Comparative Example 28 C-4 3.94 21.2 237 Red Comparative Example 29 C-5 4.02 19.9 214 Red Comparative Example 30 C-6 3.97 20.7 209 Red Comparative Example 31 C-7 3.94 19.8 248 Red Comparative Example 32 C-8 3.70 22.6 240 Red Comparative Example 33 C-9 3.86 19.7 253 Red Comparative Example 34 C-10 3.93 21.4 250 Red Comparative Example 35 C-11 3.84 20.3 242 Red Comparative Example 36 C-12 3.76 22.8 263 Red

When current was applied to the organic light emitting devices manufactured in Examples 1 to 75 and Comparative Examples 1 to 36, the results of Tables 1 and 2 were obtained.

Example 1 has a structure using compound [EB-1] as an electron blocking layer and compound 1/Dp-7 as a red light emitting layer. In Comparative Examples 1 to 36, organic light emitting diodes were prepared using C-1 to C-12 instead of Compound 1.

Looking at the results of Table 1, when the compound of the present invention is used as a host of the red light emitting layer, it is seen that the energy transfer from the host to the red dopant is well achieved, as it shows a significant increase in efficiency compared to the comparative material. could In addition, it was found that the life characteristics can be greatly improved by nearly two times while maintaining high efficiency. It can be determined that this is because the compound of the present invention has higher electron and hole stability than the comparative compound.

The results of Table 2 show the results of co-depositing two types of hosts. When the first host and the second host were used in a 1:1 ratio, the result was superior to that of the first host alone. As the second host was used, as the amount of holes increased, electrons and holes were maintained in a more stable balance in the red light emitting layer, and it was confirmed that the efficiency and lifespan increased significantly. In conclusion, it can be confirmed that the driving voltage, luminous efficiency and lifetime characteristics of the organic light emitting device can be improved when the compound of the present invention is used as a host of the red light emitting layer.

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

Claims (15)

A compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
L is a single bond or a substituted or unsubstituted C _6-60 arylene;
any one of R ₁ is Ar ₃ , the others are independently hydrogen or deuterium;
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl, or a substituted or unsubstituted C _5- including any one or more heteroatoms selected from the group consisting of N, O and S; ₆₀ heteroaryl;
Ar ₃ is phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, or phenanthrenyl;
Ar ₃ is unsubstituted or substituted with one or more phenyl;
R ₂ are each independently hydrogen or deuterium;
However, the following compounds are excluded from the compounds represented by Formula 1:
.
According to claim 1,
Formula 1 is represented by any one of the following Formulas 1-1 to 1-3,
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3, Ar ₁ to Ar ₃ , R ₁ and R ₂ are defined as in claim 1.
According to claim 1,
L is a single bond, phenylene or naphthalenediyl;
compound.
According to claim 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, or phenanthrenyl;
Ar ₁ and Ar ₂ are each independently unsubstituted or substituted with one or more phenyl or naphthyl;
compound.
delete According to claim 1,
The compound is any one selected from the group consisting of the following compounds,
compound:

.

.
An organic light emitting device comprising a first electrode, a second electrode provided to face the first electrode, and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers is Claims 1 to 4 and claim 6, which will include a compound according to any one of claims, an organic light emitting device.
According to claim 7,
The organic material layer includes a light emitting layer,
The light-emitting layer comprises a compound according to any one of claims 1 to 4 and 6 as a host,
organic light emitting device.
According to claim 7,
The organic material layer includes a light emitting layer,
The light emitting layer includes a compound according to any one of claims 1 to 4 and 6 as a first host, and further comprises a compound represented by Formula 4 as a second host,
Organic light emitting device:
[Formula 4]

In Formula 4,
A is a substituted or unsubstituted naphthalene ring,
Ar ₄ is a substituted or unsubstituted C _6-60 aryl;
L ₃ and L ₄ are each independently a single bond or a substituted or unsubstituted C _6-60 arylene;
Ar ₅ and Ar ₆ are each independently a substituted or unsubstituted C _6-60 aryl, a substituted or unsubstituted C _2-60 containing any one or more heteroatoms selected from the group consisting of N, O and S; heteroaryl, or adamantyl;
p is an integer from 0 to 9;
According to claim 9,
Chemical Formula 4 is represented by any one of the following Chemical Formulas 4-1 to 4-3,
Organic Light-Emitting Elements:
[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

In Formulas 4-1 to 4-3, Ar ₄ to Ar ₆ , L ₃ , L _{4 ,} and p are defined as in claim 9.
According to claim 9,
Ar ₄ is phenyl, biphenylyl or naphthyl;
Ar ₄ is unsubstituted or substituted with one or more tert-butyl or phenyl;
Organic Light-Emitting Elements:
According to claim 9,
L ₃ and L ₄ are each independently a single bond, phenylene or naphthalenediyl;
Wherein L ₃ and L ₄ are each independently unsubstituted or substituted with one or more phenyl groups;
organic light emitting device.
According to claim 9,
Ar ₅ and Ar ₆ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, fluorenyl, 9,9-dimethylfluorenyl or adamantyl; ;
Ar ₅ and Ar ₆ are each independently unsubstituted or substituted with one or more tert-butyl or phenyl;
organic light emitting device.
According to claim 9,
The compound represented by Formula 4 is any one selected from the group consisting of the following compounds,
Organic Light-Emitting Elements:

.
According to claim 7,
The organic material layer further comprises one or two or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, and an electron injection and transport layer,
organic light emitting device.