KR102564847B1 - 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 ₁ to L ₄ are each independently a single bond; Substituted or unsubstituted C _6-20 arylene; Or a C _2-20 heteroarylene containing any one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

Ar ₁ is a substituted or unsubstituted C _6-20 aryl; Or a C _2-20 heteroaryl containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S,

Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted C _6-20 aryl; Or a C _2-20 heteroaryl containing at least one heteroatom selected from the group consisting of substituted or unsubstituted N, O and S,

However, when both Ar ₂ and Ar ₃ are substituted or unsubstituted fluorenyl; and Ar ₂ and Ar ₃ are substituted or unsubstituted fluorenyl and the other is substituted or unsubstituted triphenylene.

In addition, the present invention is 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 includes the compound represented by Chemical Formula 1. do.

The compound represented by Chemical Formula 1 may be used as a material for an organic layer of an organic light emitting diode, and may improve efficiency, low driving voltage, and/or lifespan characteristics of an organic light emitting diode. In particular, the compound represented by Chemical Formula 1 may be used as a material for hole injection, hole transport, hole injection and transport, electron suppression, light emission, electron transport, or electron injection.

1 shows an example of an organic light emitting device including a substrate 1, an anode 2, an organic material layer 3, and a cathode 4.
2 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (8), a hole blocking layer (9), an electron transport layer (10) , An example of an organic light emitting device composed of an electron injection layer 11 and a cathode 4 is shown.
3 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (8), a hole blocking layer (9), an electron injection and transport layer ( 12) and an example of an organic light emitting element composed of a cathode 4 is shown.

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

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

및

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

and

means a bond connected to another substituent.

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

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

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

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

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

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

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

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

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

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

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

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

etc. However, it is not limited thereto.

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

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

The compound represented by Formula 1 includes a benzo[b]carbazole core and an amine substituent. Amine substituents may be attached to any carbon of the benzo[b]carbazole core.

For example, the compound represented by Chemical Formula 1 may be represented by Chemical Formula 1-1 or Chemical Formula 1-2 according to the binding position of the amine substituent.

[Formula 1-1]

[Formula 1-2]

In Formula 1, preferably, L ₁ to L ₄ are each independently a single bond; Or a substituted or unsubstituted C _6-18 arylene.

Preferably, L ₁ to L ₄ may each independently represent a single bond, phenylene, biphenyldiyl, or naphthalenediyl.

Preferably, L ₁ can be a single bond.

Preferably, L ₄ can be a single bond or phenylene.

Preferably, Ar ₁ is substituted or unsubstituted C _6-18 aryl; Or a substituted or unsubstituted C _2-18 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S.

Preferably, Ar ₁ can be phenyl, naphthyl, biphenylyl, terphenylyl, or dimethylfluorenyl.

Preferably, Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-18 aryl; Or a C _2-18 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O and S.

Preferably, Ar ₂ can be phenyl, naphthyl, biphenylyl, terphenylyl, dibenzofuranyl, or dibenzothiophenyl.

Preferably, Ar ₃ can be phenyl, naphthyl, biphenylyl, terphenylyl, dibenzofuranyl, dibenzothiophenyl, anthracenyl, phenanthryl, or dimethylfluorenyl.

Preferably, the compound represented by Formula 1 may be any one selected from the group consisting of:

The compound represented by Formula 1 may be prepared by a preparation method shown in Reaction Scheme 1 or 2 below. Specifically, when L ₄ of Chemical Formula 1 is a bond, it can be prepared by the preparation method shown in Scheme 1, and when L ₄ is not a bond, it can be prepared by the preparation method shown in Scheme 2:

[Scheme 1]

[Scheme 2]

In Reaction Schemes 1 and 2, the rest except for X' and Y' are as defined in Formula 1, X' is a halogen, and Y' is a functional group containing boron. Preferably X' is chloro or bromo and Y' is a boronic acid or boronic ester.

Step 1 of Scheme 1 and Scheme 2 is an amine substitution reaction, which is preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction can be changed as known in the art.

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

The manufacturing method may be more specific in Preparation Examples to be described later.

In addition, the present invention provides an organic light emitting device including the compound represented by Formula 1 above. In one example, the present invention provides 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 includes the compound represented by Chemical Formula 1. do.

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, an electron injection layer, and the like as organic layers. However, the structure of the organic light emitting device is not limited thereto and may include fewer organic layers.

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

In addition, the organic material layer may include a hole injection layer, a hole transport layer, or an electron blocking layer, and the hole injection layer, hole transport layer, or electron blocking layer includes the compound represented by Formula 1 above.

In addition, the electron transport layer, the electron injection layer, or the layer simultaneously transporting and injecting electrons includes the compound represented by Formula 1.

Also, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. 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 including a substrate 1, an anode 2, an organic material layer 3, and a cathode 4. In this structure, the compound represented by Chemical Formula 1 may be included in the organic material layer.

2 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (8), a hole blocking layer (9), an electron transport layer (10) , An example of an organic light emitting device composed of an electron injection layer 11 and a cathode 4 is shown. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer. Preferably, the compound represented by Chemical Formula 1 may be included in the electron blocking layer.

3 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (8), a hole blocking layer (9), an electron injection and transport layer ( 12) and an example of an organic light emitting element composed of a cathode 4 is shown. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, and the electron injection and transport layer. Preferably, the compound represented by Chemical Formula 1 may be included in the electron blocking layer.

The organic light emitting device according to the present invention may be manufactured using materials and methods known in the art, except that at least one of the organic 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, and depositing a material that can be used as a cathode thereon, it can be prepared. 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 preferred so that holes can be smoothly injected into the organic layer. Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

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

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. As a hole transport material, a material capable of receiving holes from the anode or the hole injection layer and transferring them to the light emitting layer is a material having high hole mobility. this is suitable Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.

The electron suppression layer serves to improve the efficiency of the organic light emitting device by suppressing the transfer of electrons injected from the cathode to the anode without recombination in the light emitting layer. Preferably, the compound of Chemical Formula 1 may be included in the electron blocking layer.

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; compounds of the benzoxazole, benzthiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; Polyfluorene, rubrene, etc., but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a compound containing a hetero ring. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.

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.

The hole blocking layer serves to improve the efficiency of the organic light emitting device by suppressing the transfer of holes injected from the anode to the cathode without recombination in the light emitting layer.

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

The electron injection layer is a layer for injecting electrons from an electrode, has the ability to transport electrons, has an excellent electron injection effect from a cathode, an excellent electron injection effect for a light emitting layer or a light emitting material, and injects holes of excitons generated in the light emitting layer. A compound that prevents migration to a layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, triazine, imidazole, perylenetetracarboxylic acid, preonylidene methane, anthrone, etc. and their derivatives, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

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

According to an embodiment of the present invention, the electron injection and transport layer may be formed as a single layer by simultaneously depositing the electron transport material and the electron injection material.

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]

Synthesis Example 1

Formula A (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.4 g of subA-1. (Yield 65%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), sub4 (10.8 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.6 g of Compound 1. (Yield 62%, MS: [M+H]+= 613)

Synthesis Example 2

In a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), sub5 (11.3 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12 g of Compound 2. (Yield 63%, MS: [M+H]+= 627)

Synthesis Example 3

In a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), sub6 (12.1 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.9 g of compound 3. (Yield 65%, MS: [M+H]+= 65

Synthesis Example 4

Formula A (10 g, 39.7 mmol), sub2 (9.3 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.9 g of subA-2. (Yield 68%, MS: [M+H]+= 404)

In a nitrogen atmosphere, subA-2 (10 g, 24.8 mmol), sub7 (7.3 g, 27.2 mmol), and sodium tert-butoxide (7.1 g, 74.3 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.5 g of Compound 4. (Yield 60%, MS: [M+H]+= 637)

Synthesis Example 5

In a nitrogen atmosphere, subA-1 (15 g, 45.8 mmol) and sub8 (18.4 g, 50.3 mmol) were added to 300 ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 17.7 g of Compound 5. (Yield 63%, MS: [M+H]+= 613)

Synthesis Example 6

In a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), sub9 (11.8 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.8 g of Compound 6. (Yield 50%, MS: [M+H]+= 643)

Synthesis Example 7

In a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), sub10 (11.3 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.9 g of Compound 7. (Yield 57%, MS: [M+H]+= 627)

Synthesis Example 8

In a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), sub11 (11.6 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.6 g of Compound 8. (Yield 65%, MS: [M+H]+= 637)

Synthesis Example 9

In a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), sub12 (9.9 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.4 g of Compound 9. (Yield 64%, MS: [M+H]+= 587)

Synthesis Example 10

Formula A (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.1 g of subA-3. (Yield 61%, MS: [M+H]+= 378)

In a nitrogen atmosphere, subA-3 (10 g, 26.5 mmol), sub13 (10.5 g, 29.1 mmol), and sodium tert-butoxide (7.6 g, 79.4 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.6 g of Compound 10. (Yield 57%, MS: [M+H]+= 703)

Synthesis Example 11

In a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), sub14 (12.3 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10 g of Compound 11. (Yield 50%, MS: [M+H]+= 657)

Synthesis Example 12

In a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), sub15 (12.9 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.2 g of Compound 12. (Yield 59%, MS: [M+H]+= 677)

Synthesis Example 13

In a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), sub16 (11.8 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 13.5 g of Compound 13. (Yield 69%, MS: [M+H]+= 643)

Synthesis Example 14

In a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), sub17 (11.8 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.9 g of Compound 14. (Yield 66%, MS: [M+H]+= 643)

Synthesis Example 15

In a nitrogen atmosphere, subA-1 (10 g, 30.5 mmol), sub18 (12.3 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.2 g of Compound 15. (Yield 51%, MS: [M+H]+= 657)

Synthesis Example 16

Formula B (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.1 g of subB-1. (Yield 54%, MS: [M+H]+= 378)

In a nitrogen atmosphere, subB-1 (10 g, 26.5 mmol), sub19 (7.1 g, 29.1 mmol), and sodium tert-butoxide (7.6 g, 79.4 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.2 g of compound 16. (Yield 66%, MS: [M+H]+= 587)

Synthesis Example 17

Formula B (10 g, 39.7 mmol), sub2 (9.3 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.3 g of subB-2. (Yield 58%, MS: [M+H]+= 404)

In a nitrogen atmosphere, subB-2 (10 g, 24.8 mmol), sub20 (6.7 g, 27.2 mmol), and sodium tert-butoxide (7.1 g, 74.3 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.7 g of Compound 17. (Yield 64%, MS: [M+H]+= 613)

Synthesis Example 18

Formula B (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.3 g of subB-3. (Yield 64%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subB-3 (10 g, 30.5 mmol), sub21 (10.8 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 12.5 g of Compound 18. (Yield 67%, MS: [M+H]+= 613)

Synthesis Example 19

In a nitrogen atmosphere, subB-1 (10 g, 26.5 mmol), sub22 (7.5 g, 29.1 mmol), and sodium tert-butoxide (7.6 g, 79.4 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.5 g of Compound 19. (Yield 66%, MS: [M+H]+= 601)

Synthesis Example 20

In a nitrogen atmosphere, subB-2 (10 g, 24.8 mmol), sub23 (7.8 g, 27.2 mmol), and sodium tert-butoxide (7.1 g, 74.3 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11 g of Compound 20. (Yield 68%, MS: [M+H]+= 653)

Synthesis Example 21

In a nitrogen atmosphere, subB-3 (10 g, 30.5 mmol), sub24 (10.8 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.8 g of Compound 21. (Yield 58%, MS: [M+H]+= 613)

Synthesis Example 22

In a nitrogen atmosphere, subB-3 (15 g, 45.8 mmol) and sub8 (18.4 g, 50.3 mmol) were added to 300 ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.9 g of compound 22. (Yield 78%, MS: [M+H]+= 613

Synthesis Example 23

Formula C (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.5 g of subC-1. (Yield 57%, MS: [M+H]+= 378)

In a nitrogen atmosphere, subC-1 (10 g, 26.5 mmol), sub19 (7.1 g, 29.1 mmol), and sodium tert-butoxide (7.6 g, 79.4 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.8 g of Compound 23. (Yield 63%, MS: [M+H]+= 587)

Synthesis Example 24

In a nitrogen atmosphere, subC-1 (10 g, 26.5 mmol), sub23 (8.3 g, 29.1 mmol), and sodium tert-butoxide (7.6 g, 79.4 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.3 g of Compound 24. (Yield 56%, MS: [M+H]+= 627)

Synthesis Example 25

Formula C (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.5 g of subC-2. (Yield 58%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subC-2 (15g, 45.8mmol) and sub25 (22.9g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 20.9 g of compound 25. (Yield 65%, MS: [M+H]+= 703)

Synthesis Example 26

In a nitrogen atmosphere, subC-2 (15 g, 45.8 mmol) and sub26 (22.9 g, 50.3 mmol) were added to 300 ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 10 hours, the mixture was cooled to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 19.3 g of Compound 26. (Yield 60%, MS: [M+H]+= 703)

Synthesis Example 27

In a nitrogen atmosphere, subC-2 (15g, 45.8mmol) and sub27 (22.2g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 20.8 g of compound 27. (Yield 66%, MS: [M+H]+= 689)

Synthesis Example 28

Formula D (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.5 g of subD-1. (Yield 57%, MS: [M+H]+= 378)

In a nitrogen atmosphere, subD-1 (10 g, 26.5 mmol), sub19 (7.1 g, 29.1 mmol), and sodium tert-butoxide (7.6 g, 79.4 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.2 g of Compound 28. (Yield 53%, MS: [M+H]+= 587)

Synthesis Example 29

Formula D (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.8 g of subD-2. (Yield 68%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subD-2 (15g, 45.8mmol) and sub28 (22.9g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 22.5 g of compound 29. (Yield 70%, MS: [M+H]+= 703)

Synthesis Example 30

In a nitrogen atmosphere, subD-2 (15 g, 45.8 mmol) and sub29 (22.2 g, 50.3 mmol) were added to 300 ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 25.2 g of Compound 30. (Yield 80%, MS: [M+H]+= 689)

Synthesis Example 31

Formula E (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.2 g of subE-1. (Yield 63%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subE-1 (10 g, 30.5 mmol), sub30 (8.7 g, 33.6 mmol), and sodium tert-butoxide (8.8 g, 91.5 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.9 g of Compound 31. (Yield 65%, MS: [M+H]+= 551)

Synthesis Example 32

Formula E (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.8 g of subE-2. (Yield 52%, MS: [M+H]+= 378)

In a nitrogen atmosphere, subE-2 (10 g, 26.5 mmol), sub19 (7.1 g, 29.1 mmol), and sodium tert-butoxide (7.6 g, 79.4 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10.7 g of Compound 32. (Yield 69%, MS: [M+H]+= 587)

Synthesis Example 33

In a nitrogen atmosphere, subE-1 (15 g, 45.8 mmol) and sub8 (18.4 g, 50.3 mmol) were added to 300 ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 22.1 g of Compound 33. (Yield 79%, MS: [M+H]+= 613)

Synthesis Example 34

In a nitrogen atmosphere, subE-1 (15 g, 45.8 mmol) and sub31 (22.9 g, 50.3 mmol) were added to 300 ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 24.4 g of Compound 34. (Yield 76%, MS: [M+H]+= 703)

Synthesis Example 35

Formula F (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.9 g of subF-1. (Yield 61%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subF-1 (15 g, 45.8 mmol) and sub32 (19.1 g, 50.3 mmol) were added to 300 ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 18.9 g of Compound 35. (Yield 66%, MS: [M+H]+= 627)

Synthesis Example 36

Formula G (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.7 g of subG-1. (Yield 58%, MS: [M+H]+= 378)

In a nitrogen atmosphere, subG-1 (10 g, 26.5 mmol), sub30 (7.5 g, 29.1 mmol), and sodium tert-butoxide (7.6 g, 79.4 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.3 g of Compound 36. (Yield 52%, MS: [M+H]+= 601)

Synthesis Example 37

Formula G (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.7 g of subG-2. (Yield 59%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subG-2 (15 g, 45.8 mmol) and sub33 (19.1 g, 50.3 mmol) were added to 300 ml of dioxane and stirred and refluxed. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml 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 again dissolved in chloroform, washed twice with water, and the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.6 g of Compound 37. (Yield 72%, MS: [M+H]+= 627)

Synthesis Example 38

In a nitrogen atmosphere, subG-2 (15g, 45.8mmol) and sub34 (26g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 22.7 g of Compound 38. (Yield 65%, MS: [M+H]+= 765)

Synthesis Example 39

Formula F (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 8.2 g of subF-2. (Yield 55%, MS: [M+H]+= 378)

In a nitrogen atmosphere, subF-2 (10 g, 26.5 mmol), sub30 (7.5 g, 29.1 mmol), and sodium tert-butoxide (7.6 g, 79.4 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 10 g of Compound 39. (Yield 63%, MS: [M+H]+= 601)

Synthesis Example 40

In a nitrogen atmosphere, subF-1 (10 g, 31.1 mmol), sub19 (8.4 g, 34.2 mmol), and sodium tert-butoxide (9 g, 93.2 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 11.5 g of Compound 40. (Yield 69%, MS: [M+H]+= 537)

Synthesis Example 41

In a nitrogen atmosphere, subF-1 (15 g, 45.8 mmol) and sub35 (19.1 g, 50.3 mmol) were added to 300 ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 18.1 g of Compound 41. (Yield 63%, MS: [M+H]+= 627)

Synthesis Example 42

In a nitrogen atmosphere, subF-1 (15 g, 45.8 mmol) and sub36 (22.9 g, 50.3 mmol) were added to 300 ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 21.5 g of Compound 42. (Yield 67%, MS: [M+H]+= 703)

Synthesis Example 43

In a nitrogen atmosphere, subF-1 (15g, 45.8mmol) and sub34 (26g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 25.2 g of Compound 43. (Yield 72%, MS: [M+H]+= 765)

Synthesis Example 44

Formula H (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and reflux. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.3 g of subH-1. (Yield 62%, MS: [M+H]+= 378)

In a nitrogen atmosphere, subH-1 (10 g, 26.5 mmol), sub37 (7.5 g, 29.1 mmol), and sodium tert-butoxide (7.6 g, 79.4 mmol) were added to 200 ml of xylene, stirred and refluxed. After that, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 9.7 g of Compound 44. (Yield 61%, MS: [M+H]+= 601)

Synthesis Example 45

Formula H (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), and sodium tert-butoxide (7.6 g, 79.5 mmol) were added to 200 ml of toluene under a nitrogen atmosphere, followed by stirring and refluxing. After that, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was completed, cooled to room temperature, and the solvent was removed under reduced pressure. Thereafter, the compound was completely dissolved again in chloroform, washed twice with water, and the organic layer was separated, treated with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to obtain 7.4 g of subH-2. (Yield 57%, MS: [M+H]+= 328)

In a nitrogen atmosphere, subH-2 (15g, 45.8mmol) and sub41 (26g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After reacting for 8 hours, the mixture was cooled to room temperature, and the organic layer was distilled after separating the organic layer and the water layer. This was dissolved in chloroform again, and after washing twice with water, the organic layer was separated, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7 g of Compound 45. (Yield 62%, MS: [M+H]+= 765)

Synthesis Example 46

In a nitrogen atmosphere, subH-2 (15 g, 45.8 mmol) and sub42 (19.1 g, 50.3 mmol) were added to 300 ml of dioxane, stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 18.6 g of Compound 46. (Yield 65%, MS: [M+H]+= 627)

Synthesis Example 47

In a nitrogen atmosphere, subH-2 (15g, 45.8mmol) and sub43 (22.9g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. Thereafter, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirred, 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 obtain 22.2 g of Compound 47. (Yield 69%, MS: [M+H]+= 703)

[Example]

Comparative 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, a red light emitting layer having a thickness of 400 Å was formed on the EB-1 deposited film by vacuum depositing a compound of RH-1 and a compound of Dp-7 in a weight ratio of 98:2. A hole blocking layer was formed on the light emitting layer by vacuum depositing the following HB-1 compound to a film thickness of 30 Å. Then, on the hole blocking layer, the following ET-1 compound and the following LiQ compound were vacuum deposited at a weight ratio of 2:1 to form an electron injection and transport layer with a thickness of 300 Å. A negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 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 1 to 47

An organic light emitting device was manufactured in the same manner as in Comparative Example 1, except that the compound shown in Table 1 was used instead of EB-1 in the organic light emitting device of Comparative Example 1.

Comparative Examples 2 to 9

An organic light emitting device was manufactured in the same manner as in Comparative Example 1, except that the compound shown in Table 1 was used instead of EB-1 in the organic light emitting device of Comparative Example 1. Compounds C-1 to C-8 in Table 1 are as follows.

Experimental example

When current was applied to the organic light emitting devices prepared in Examples 1 to 47 and Comparative Examples 1 to 9, voltage and efficiency were measured (15 mA/cm ² standard), and the results are shown in Table 1 below. described. The lifetime T95 means the time required for the luminance to decrease from the initial luminance (30 mA/cm ² standard) to 95%.

division electron suppression layer Driving voltage (V) Efficiency (cd/A) Lifetime T95(hr) luminescent color Comparative Example 1 EB-1 4.13 21.7 104 Red Example 1 compound 1 3.52 26.5 183 Red Example 2 compound 2 3.50 26.9 187 Red Example 3 compound 3 3.47 26.1 176 Red Example 4 compound 4 3.55 25.2 151 Red Example 5 compound 5 3.59 26.2 185 Red Example 6 compound 6 3.56 25.7 174 Red Example 7 compound 7 3.51 26.5 179 Red Example 8 compound 8 3.59 26.8 193 Red Example 9 compound 9 3.52 25.5 138 Red Example 10 compound 10 3.48 24.3 143 Red Example 11 compound 11 3.50 26.7 177 Red Example 12 compound 12 3.62 23.8 125 Red Example 13 compound 13 3.57 26.3 174 Red Example 14 compound 14 3.58 26.7 181 Red Example 15 compound 15 3.54 26.5 172 Red Example 16 compound 16 3.56 25.5 167 Red Example 17 compound 17 3.60 24.7 135 Red Example 18 compound 18 3.59 25.1 153 Red Example 19 compound 19 3.58 25.8 148 Red Example 20 compound 20 3.49 25.9 140 Red Example 21 compound 21 3.62 24.2 133 Red Example 22 compound 22 3.60 25.7 165 Red Example 23 compound 23 3.65 22.9 129 Red Example 24 compound 24 3.54 23.7 121 Red Example 25 compound 25 3.63 24.5 148 Red Example 26 compound 26 3.69 23.4 137 Red Example 27 compound 27 3.65 23.8 143 Red Example 28 compound 28 3.60 24.1 146 Red Example 29 compound 29 3.65 25.3 168 Red Example 30 compound 30 3.64 25.5 161 Red Example 31 compound 31 3.51 26.4 195 Red Example 32 compound 32 3.50 26.7 191 Red Example 33 compound 33 3.59 25.7 177 Red Example 34 compound 34 3.57 25.8 162 Red Example 35 compound 35 3.61 25.3 135 Red Example 36 compound 36 3.62 24.3 147 Red Example 37 compound 37 3.63 25.8 165 Red Example 38 compound 38 3.66 25.7 166 Red Example 39 compound 39 3.49 26.0 161 Red Example 40 compound 40 3.52 26.4 177 Red Example 41 compound 41 3.57 26.0 181 Red Example 42 compound 42 3.65 25.1 155 Red Example 43 compound 43 3.61 26.5 192 Red Example 44 compound 44 3.60 24.3 132 Red Example 45 compound 45 3.53 25.1 158 Red Example 46 compound 46 3.59 24.0 163 Red Example 47 compound 47 3.52 25.4 145 Red Comparative Example 2 C-1 3.72 22.3 122 Red Comparative Example 3 C-2 3.76 21.5 104 Red Comparative Example 4 C-3 3.81 20.1 73 Red Comparative Example 5 C-4 3.90 19.4 65 Red Comparative Example 6 C-5 3.93 18.7 62 Red Comparative Example 7 C-6 3.91 18.0 53 Red Comparative Example 8 C-7 3.86 19.3 87 Red Comparative Example 9 C-8 3.90 19.7 75 Red

Referring to Table 1, it can be seen that when the compound of the present invention is used as an electron suppression layer, the driving voltage is lower than that of the comparative example and the efficiency is greatly increased. As a result, energy transfer from the host to the red dopant is You can see that it works well. In addition, it can be confirmed that the devices of Examples using the compounds of the present invention have significantly improved lifespan characteristics while maintaining high efficiency. This can be determined because the compound of the present invention has higher electron and hole stability than the comparative compound.

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 an electron suppression layer compound.

1: substrate 2: anode
3: organic material layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron suppression layer 8: light emitting layer
9: hole blocking layer 10: electron transport layer
11: electron injection layer 12: electron injection and transport layer

Claims (11)

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

In Formula 1,
L ₁ to L ₄ are each a single bond;
Ar ₁ is biphenylyl or naphthyl;
Ar ₂ and Ar ₃ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, or phenanthrenyl;
However, the case where both Ar ₂ and Ar ₃ are dimethylfluorenyl is excluded.
delete delete delete delete delete delete delete According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
compound:

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 includes the compound according to claim 1 or claim 9. light emitting element.
delete

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