KR20210050474A - 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. The present invention provides a compound represented by chemical formula 1. The compound represented by chemical formula 1 described above can be used as a material for an organic material layer of the organic light emitting device, and can improve efficiency, lower driving voltage, and/or improve lifespan characteristics in the organic light emitting device.

Description

Novel compound and organic light emitting device comprising the same

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

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

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

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

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides a compound represented by the following formula (1):

[Formula 1]

In Formula 1,

L ₁ to L ₄ are each independently a single bond; Substituted or unsubstituted C _6-20 arylene; _{Or substituted or unsubstituted C 2-20} heteroarylene including any one or more heteroatoms selected from the group consisting of N, O and S,

Ar ₁ is substituted or unsubstituted C _6-20 aryl; _{Or substituted or unsubstituted C 2-20} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,

Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-20 aryl; _{Or substituted or unsubstituted C 2-20} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,

Provided that Ar ₂ and Ar ₃ are both substituted or unsubstituted fluorenyl; And Ar ₂ and Ar ₃ Except for the case where any one of 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 a compound represented by Formula 1 do.

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 in the organic light-emitting device. In particular, the compound represented by Formula 1 may be used as a hole injection, hole transport, hole injection and transport, electron suppression, light emission, electron transport, or electron injection material.

1 shows an example of an organic light-emitting device comprising 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 suppression layer (7), a light emitting layer (8), a hole suppression layer (9), an electron transport layer (10). , An example of an organic light-emitting device comprising 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 suppression layer (7), a light emitting layer (8), a hole suppression layer (9), an electron injection and transport layer ( 12) and a cathode 4 are shown as an example of an organic light-emitting device.

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

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

및

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

And

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents. . For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, or may be interpreted as a substituent to which two phenyl groups are connected.

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

In the present specification, the ester group may be substituted with a C1-C25 linear, branched or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms in the oxygen of the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

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

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

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

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

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

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

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

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

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,

Can be, 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 a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridyl group , Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiiadia There are a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the aryl group among the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group and the alkylamine group is the same as the example of the aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the description of the aforementioned heterocyclic group may be applied. In the present specification, the alkenyl group of the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aryl group or cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are bonded to each other and formed.

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

As an example, the compound represented by Formula 1 may be represented by Formula 1-1 or Formula 1-2 according to the bonding 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 substituted or unsubstituted C _6-18 arylene.

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

Preferably, L ₁ may be a single bond.

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

Preferably, Ar ₁ is substituted or unsubstituted C _6-18 aryl; _{Or substituted or unsubstituted C 2-18} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O, and S.

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

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

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

Preferably, Ar ₃ may 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 manufacturing method such as the following Scheme 1 or 2. Specifically, when L ₄ is a combination of Formula 1 may be prepared by the method of the production process, such as Scheme 1, and Reaction Scheme 2 for L ₄ is not a bond:

[Scheme 1]

[Scheme 2]

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

Step 1 of Reaction Schemes 1 and 2 is an amine substitution reaction, and is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may be changed as known in the art.

Step 2 of Scheme 2 is a Suzuki coupling reaction, 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 the manufacturing examples to be described later.

In addition, the present invention provides an organic light-emitting device including the compound represented by Formula 1 above. For 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 a compound represented by Formula 1 do.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer 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 an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

In addition, the organic material layer may include an emission layer, and the emission layer includes a compound represented by Formula 1 above.

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

In addition, the electron transport layer, the electron injection layer, or the layer that simultaneously transports and injects electrons includes the compound represented by Formula 1 above.

In addition, 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 inverted type organic light-emitting device 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 comprising a substrate 1, an anode 2, an organic material layer 3, and a cathode 4. In such a structure, the compound represented by 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 suppression layer (7), a light emitting layer (8), a hole suppression layer (9), an electron transport layer (10). , An example of an organic light-emitting device comprising 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, hole transport layer, electron suppression layer, light-emitting layer, hole suppression layer, electron transport layer, and electron injection layer. Preferably, the compound represented by Formula 1 may be included in the electron suppressing layer.

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

The organic light-emitting device according to the present invention may be manufactured by 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. In addition, 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, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming 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 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 refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

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

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

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

The hole injection layer is a layer that injects holes from the electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is generated from the light emitting layer. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, 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 holes to the emission layer, and is a material capable of transporting holes to the emission layer by receiving holes from the anode or the hole injection layer as a hole transport material. This is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

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

The light-emitting material is a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples of 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives and the like, but are not limited thereto.

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

The hole suppression layer serves to improve the efficiency of the organic light-emitting device by inhibiting the holes injected from the anode from being transferred to the cathode without being recombined in the emission layer.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer. As an electron transport material, a material capable of injecting electrons from the cathode and transferring them to the emission layer, and a material having high mobility for electrons is suitable. Do. Specific examples include Al complex of 8-hydroxyquinoline; Complexes containing Alq _3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer 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 that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

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

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

According to an embodiment of the present invention, the electron transport material and the electron injection material may be simultaneously deposited to form a single layer of the electron injection and transport layer.

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

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

The preparation of the compound represented by 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 for illustrating the present invention, and the scope of the present invention is not limited thereto.

[Synthesis Example]

Synthesis Example 1

In a nitrogen atmosphere, formula A (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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

In a nitrogen atmosphere, formula A (10 g, 39.7 mmol), sub2 (9.3 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (7.1 g, 74.3 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 (15g, 45.8mmol) and sub8 (18.4g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 17.7 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, 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 reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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

In a nitrogen atmosphere, formula A (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (7.6 g, 79.4 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, 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 reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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

In a nitrogen atmosphere, formula B (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (7.6 g, 79.4 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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

In a nitrogen atmosphere, formula B (10 g, 39.7 mmol), sub2 (9.3 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (7.1 g, 74.3 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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

In a nitrogen atmosphere, formula B (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (7.6 g, 79.4 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (7.1 g, 74.3 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, 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 reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 (15g, 45.8mmol) and sub8 (18.4g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.9 g of compound 22. (Yield 78%, MS: [M+H]+= 613

Synthesis Example 23

In a nitrogen atmosphere, formula C (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (7.6 g, 79.4 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (7.6 g, 79.4 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 3 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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

In a nitrogen atmosphere, formula C (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.9 g of compound 25. (Yield 65%, MS: [M+H]+= 703)

Synthesis Example 26

In a nitrogen atmosphere, subC-2 (15g, 45.8mmol) and sub26 (22.9g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 20.8 g of compound 27. (Yield 66%, MS: [M+H]+= 689)

Synthesis Example 28

In a nitrogen atmosphere, formula D (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, 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 reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (7.6 g, 79.4 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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

In a nitrogen atmosphere, formula D (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, 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 reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.5 g of compound 29. (Yield 70%, MS: [M+H]+= 703)

Synthesis Example 30

In a nitrogen atmosphere, subD-2 (15g, 45.8mmol) and sub29 (22.2g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.2 g of compound 30. (Yield 80%, MS: [M+H]+= 689)

Synthesis Example 31

In a nitrogen atmosphere, formula E (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (8.8 g, 91.5 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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

In a nitrogen atmosphere, formula E (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (7.6 g, 79.4 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 (15g, 45.8mmol) and sub8 (18.4g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.1 g of compound 33. (Yield 79%, MS: [M+H]+= 613)

Synthesis Example 34

In a nitrogen atmosphere, subE-1 (15g, 45.8mmol) and sub31 (22.9g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 24.4 g of compound 34. (Yield 76%, MS: [M+H]+= 703)

Synthesis Example 35

In a nitrogen atmosphere, formula F (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 (15g, 45.8mmol) and sub32 (19.1g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.9 g of compound 35. (Yield 66%, MS: [M+H]+= 627)

Synthesis Example 36

In a nitrogen atmosphere, chemical formula G (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (7.6 g, 79.4 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, 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 reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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

In a nitrogen atmosphere, formula G (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 (15g, 45.8mmol) and sub33 (19.1g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 12 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 11 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.7 g of compound 38. (Yield 65%, MS: [M+H]+= 765)

Synthesis Example 39

In a nitrogen atmosphere, formula F (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, 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 reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (7.6 g, 79.4 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.5 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 (8.4g, 34.2 mmol), sodium tert-butoxide (9 g, 93.2 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.3 g, 0.6 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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 (15g, 45.8mmol) and sub35 (19.1g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 18.1 g of compound 41. (Yield 63%, MS: [M+H]+= 627)

Synthesis Example 42

In a nitrogen atmosphere, subF-1 (15g, 45.8mmol) and sub36 (22.9g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 10 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 25.2 g of compound 43. (Yield 72%, MS: [M+H]+= 765)

Synthesis Example 44

In a nitrogen atmosphere, the formula H (10 g, 39.7 mmol), sub3 (8.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, 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 reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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), sodium tert-butoxide (7.6 g, 79.4 mmol) was added to 200 ml of Xylene, and stirred and refluxed. After this, 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 reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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

In a nitrogen atmosphere, the formula H (10 g, 39.7 mmol), sub1 (6.2 g, 39.7 mmol), sodium tert-butoxide (7.6 g, 79.5 mmol) was added to 200 ml of toluene, and stirred and refluxed. After this, bis(tri-tert-butylphosphine)palladium(0) (0.2 g, 0.4 mmol) was added. After 2 hours, the reaction was terminated, cooled to room temperature, and reduced pressure to remove the solvent. Thereafter, the compound was completely dissolved in chloroform again, 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. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 21.7 g of compound 45. (Yield 62%, MS: [M+H]+= 765)

Synthesis Example 46

In a nitrogen atmosphere, subH-2 (15g, 45.8mmol) and sub42 (19.1g, 50.3mmol) were added to 300ml of dioxane and stirred and refluxed. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 8 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 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. After that, potassium phosphate (29.1g, 137.3mmol) was dissolved in 87ml of water, and after sufficiently stirring, bis(tri-tert-butylphosphine)palladium(0) (0.2g, 0.5mmol) was added. After the reaction for 9 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in chloroform, washed twice with water, and the organic layer was separated, anhydrous magnesium sulfate was added thereto, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified by silica gel column chromatography to prepare 22.2 g of compound 47. (Yield 69%, MS: [M+H]+= 703)

[Example]

Comparative Example 1

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

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

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7Å/sec, the deposition rate of lithium fluoride at the cathode was 0.3Å/sec, and the deposition rate of aluminum was 2Å/sec, and the vacuum degree during deposition was 2x10 ^-7 ~ An organic light-emitting device was manufactured by maintaining ^{5x10 -6 torr.}

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 below 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 below 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 a 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. Written. Life T95 refers to the time it takes for the luminance to decrease to 95% from the initial luminance (30 mA/cm ^{2 standard).}

division Electron suppression layer Driving voltage (V) Efficiency (cd/A) Life T95(hr) Luminous 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 above, it can be seen that when the compound of the present invention is used as an electron-suppressing layer, compared to the comparative example, the driving voltage is lower and the efficiency is greatly increased. You can see that it works well. In addition, it can be seen that the device of the embodiment using the compound of the present invention has significantly improved lifespan characteristics while maintaining high efficiency. It can be determined that this is because the compound of the present invention has higher stability against electrons and holes than the compound of the comparative example.

In conclusion, it can be seen that when the compound of the present invention is used as an electron suppressing layer compound, the driving voltage, luminous efficiency, and lifetime characteristics of the organic light-emitting device can be improved.

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

Claims (11)

Compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
L ₁ to L ₄ are each independently a single bond; Substituted or unsubstituted C _6-20 arylene; _{Or substituted or unsubstituted C 2-20} heteroarylene including any one or more heteroatoms selected from the group consisting of N, O and S,
Ar ₁ is substituted or unsubstituted C _6-20 aryl; _{Or substituted or unsubstituted C 2-20} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,
Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-20 aryl; _{Or substituted or unsubstituted C 2-20} heteroaryl including any one or more heteroatoms selected from the group consisting of N, O and S,
Provided that Ar ₂ and Ar ₃ are both substituted or unsubstituted fluorenyl; And Ar ₂ and Ar ₃ Except for the case where any one of substituted or unsubstituted fluorenyl and the other is substituted or unsubstituted triphenylene.
The method of claim 1,
L ₁ to L ₄ are each independently a single bond; Or a substituted or unsubstituted C _6-18 arylene,
compound.
The method of claim 1,
L ₁ to L ₄ are each independently a single bond, phenylene, biphenyldiyl, or naphthalenediyl,
compound.
The method of claim 1,
Ar ₁ is substituted or unsubstituted C _6-18 aryl; _{Or a substituted or unsubstituted C 2-18} heteroaryl containing any one or more heteroatoms selected from the group consisting of N, O and S,
compound.
The method of claim 1,
Ar ₁ is phenyl, naphthyl, biphenylyl, terphenylyl, or dimethylfluorenyl,
compound.
The method of claim 1,
Ar ₂ and Ar ₃ are each independently substituted or unsubstituted C _6-18 aryl; _{Or a substituted or unsubstituted C 2-18} heteroaryl containing any one or more heteroatoms selected from the group consisting of O and S,
compound.
The method of claim 1,
Ar ₂ is phenyl, naphthyl, biphenylyl, terphenylyl, dibenzofuranyl, or dibenzothiophenyl,
compound.
The method of claim 1,
Ar ₃ is phenyl, naphthyl, biphenylyl, terphenylyl, dibenzofuranyl, dibenzothiophenyl, anthracenyl, phenanthryl, or dimethylfluorenyl,
compound.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of the following,
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 contains the compound according to any one of claims 1 to 9 That is, an organic light emitting device.
The method of claim 10,
The organic material layer containing the compound is an electron inhibiting layer,
Organic light emitting device.

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