KR20200135207A - 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 includes a first electrode, a second electrode, and one or more organic material layers. The present invention can improve low driving voltage and/or life characteristics.

Description

Novel compound and organic light emitting device using the same

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

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy 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.

The 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. It glows when it falls back to the ground.

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

Korean Patent Publication No. 10-2013-073537

The present invention relates to an organic light-emitting device comprising the novel compound.

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

[Formula 1]

In Formula 1,

L is a direct bond, or a substituted or unsubstituted C _6-18 arylene,

Each R ₁ is independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5- containing at least one hetero atom selected from the group consisting of N, O and S ₆₀ heteroaryl,

R ₂ and R ₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl,

n, m and o are each independently an integer of 1 to 7.

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 comprises the compound of the present invention.

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, 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, a light emitting layer 3, and a cathode 4.
2 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4 I did it.

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

(Explanation of terms)

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

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 a substituted or unsubstituted 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 linked with two or more substituents 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 it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably 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, and a phenyl boron group, 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 a linear or branched chain, 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 is preferably 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,

Etc. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, Si and S as a heterogeneous element, and the number of carbons 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, thiazolyl group, isoxazolyl Group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, 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 the 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 above-described heterocyclic group may be applied, except that two substituents are bonded to each other.

(compound)

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

[Formula 1]

In Formula 1,

L is a direct bond, or a substituted or unsubstituted C _6-18 arylene,

Each R ₁ is independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5- containing at least one hetero atom selected from the group consisting of N, O and S ₆₀ heteroaryl,

R ₂ and R ₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl,

n, m and o are each independently an integer of 1 to 7.

Preferably, the compound represented by Formula 1 may be any one selected from compounds represented by the following Formulas 1-1 to 1-4:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,

L, R ₁ , R ₂ , R ₃ , n, m and o are as previously defined.

Preferably, L is a direct bond, phenylene, or biphenylylene. In the present invention, when the number of carbon atoms of the linker L is greater than 18, the stability of electrons is deteriorated when applied to an organic light-emitting device, thereby deteriorating lifespan characteristics and luminous efficiency.

Preferably, each R ₁ is independently and each R ₁ is independently hydrogen, phenyl, biphenylyl, carbazol-9-yl, or 9-phenyl-9H-carbazolyl.

Preferably, R ₂ and R ₃ are each independently hydrogen, phenyl or biphenylyl.

Preferably, n is 1 or 2.

Preferably, m and o are each independently 1 or 2.

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

.

.

In the compound represented by Formula 1 according to the present invention, electronic stability is improved by connecting two dibenzofurans directly to the triazine group at the position 2, and additional dibenzothiophene being connected to the triazine group by a linker having 18 or less carbon atoms. Accordingly, when applied to an organic light emitting device, luminous efficiency and lifespan characteristics are remarkably improved.

The compound represented by Formula 1 may be prepared through the following Schemes 1-1 to 1-2.

[Reaction Scheme 1-1]

[Scheme 1-2]

In Reaction Schemes 1-1 and 1-2, the other variables excluding X are as defined above, and X is each independently halogen, preferably chloro or bromo.

In Reaction Schemes 1-1 and 1-2, the reactants, catalysts, solvents, and the like to be used can be changed to suit the desired product. The method for preparing the compound of Formula 1 may be more specific in Preparation Examples to be described later.

(Organic light emitting device)

In addition, the present invention provides an organic light-emitting device including the compound represented by Chemical Formula 1. 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 a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. Including the indicated compound.

In addition, the organic material layer may include an emission layer, and the emission layer includes the compound represented by Chemical Formula 1. Preferably, the compound represented by Formula 1 may be a host compound of an emission layer, and the emission layer may further include a dopant compound.

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

In addition, the electron transport layer, the electron injection layer, or the layer simultaneously injecting and transporting electrons includes the compound represented by Formula 1 above. In particular, the compound represented by Formula 1 according to the present invention has excellent thermal stability, a deep HOMO level of 6.0 eV or more, high triplet energy (ET), and hole stability. In addition, when the compound represented by Formula 1 is used in an organic material layer capable of simultaneously injecting electrons and transporting electrons, an n-type dopant used in the art may be mixed and used.

In addition, the organic material layer may include a light emitting layer and an electron transport layer, and the electron transport layer may include a compound represented by Formula 1 above.

In addition, the organic light emitting device according to the present invention may be an organic light emitting device having a structure (normal type) 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, a light emitting layer 3, and a cathode 4. In such a structure, the compound represented by Formula 1 may be included in the emission layer.

FIG. 2 shows an example of an organic light-emitting device composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, and a cathode 4 I did it. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport 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); A combination of a metal and an oxide 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 an 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 a light emitting layer or a light emitting material. 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 light emitting layer.As a hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high mobility for holes 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 light-emitting material is a material capable of emitting light in a visible light region by transporting and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples of 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-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 an aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

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 receiving electrons from the cathode and transferring them to the emission layer 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 has excellent thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metals Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, 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.

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.

Preparation of the compound represented by Formula 1 and an 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 1-1: Preparation of intermediate compound Sub 1-1

In a nitrogen environment, magnesium (5.4 g, 224 mmol) and iodine (1.0 g, 4.07 mmol) were added to 200 ml of tetrahydrofuran (THF), stirred for 30 minutes, and then 3-bromodibenzo[b,d] dissolved in 200 L of THF. Furan (50 g, 203 mmol) is slowly added dropwise at 0°C over 30 minutes. This reaction solution was slowly added dropwise to a solution of 37.2 g (203 mmol) of THF/cyanuric chloride at 0° C. over 30 minutes. After completion of the reaction, water was added to the reaction solution, extracted with chloroform, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was purified through column chromatography to prepare an intermediate compound sub 1-1 (40.3g, 63%, MS: [M+H]+ = 316.0).

Synthesis Example 1-2: Preparation of intermediate compound sub 1-2

In a nitrogen atmosphere, Sub 1-1 (40 g, 127 mmol) and dibenzo[b,d]furan-3-ylboronic acid (26.9 g, 127 mmol) were added to 800 ml of tetrahydrofuran, followed by stirring and refluxing. Thereafter, potassium carbonate (52.7 g, 381 mmol) was dissolved in 53 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (4.4 g, 3.8 mmol) was added. After 1 hour reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 1135 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound sub 1-2 (39.2g, 69%, MS: [M+H]+ = 448.1).

Synthesis Example 1-3: Preparation of intermediate compound sub 2-1

In a nitrogen atmosphere, sub 1-2 (30 g, 67.1 mmol) and (4-chlorophenyl) boronic acid (10.5 g, 67.1 mmol) were added to 600 ml of tetrahydrofuran and stirred and refluxed. Thereafter, potassium carbonate (27.8 g, 201.3 mmol) was dissolved in 28 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (2.3 g, 2 mmol) was added. After 1 hour reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 702 mL of chloroform to dissolve, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound sub 2-1 (21.8g, 62%, MS: [M+H]+ = 524.1).

Synthesis Example 1-4: Preparation of intermediate compound sub 2-2

In a nitrogen atmosphere, sub 1-2 (30 g, 67.1 mmol) and (3-chlorophenyl) boronic acid (10.5 g, 67.1 mmol) were added to 600 ml of tetrahydrofuran and stirred and refluxed. Thereafter, potassium carbonate (27.8 g, 201.3 mmol) was dissolved in 28 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (2.3 g, 2 mmol) was added. After 2 hours reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 702 mL of chloroform to dissolve, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a yellow solid compound sub 2-2 (26.7g, 76%, MS: [M+H]+ = 524.1).

Synthesis Example 1-5: Preparation of intermediate compound sub 2-3

In a nitrogen atmosphere, sub 1-2 (30 g, 67.1 mmol) and (2-chlorophenyl) boronic acid (10.5 g, 67.1 mmol) were added to 600 ml of tetrahydrofuran and stirred and refluxed. Thereafter, potassium carbonate (27.8 g, 201.3 mmol) was dissolved in 28 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (2.3 g, 2 mmol) was added. After 1 hour reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 702 mL of chloroform to dissolve, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a yellow solid compound sub 2-3 (27g, 77%, MS: [M+H]+ = 524.1).

Synthesis Example 1-6: Preparation of intermediate compound A-4

1) Preparation of A-1

In a nitrogen atmosphere, (2-(methylthio)phenyl)boronic acid (100 g, 595.1 mmol) and 1-bromo-4-chlorobenzene (113 g, 595.1 mmol) were added to 2000 ml of tetrahydrofuran and stirred and refluxed. Thereafter, potassium carbonate (246.7 g, 1785.3 mmol) was dissolved in 247 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (20.6 g, 17.9 mmol) was added. After 1 hour reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 2794 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound A-1 (103.4g, 74%, MS: [M+H]+ = 235.7).

2) Preparation of A-2

In a nitrogen atmosphere, compound A-1 (100.0 g, 427 mmol) was dissolved in 900 ml of chloroform and added thereto, and after sufficiently stirring at 0°C, bromine (68.3g, 427 mmol) was slowly added dropwise. After the temperature was gradually raised to room temperature, after the reaction for 8 hours, water was added to terminate the reaction. Thereafter, extraction was performed three times using water and sodium thiosulfate solution, and the organic layer was distilled under reduced pressure. After the distillate was extracted with chloroform and water, the organic layer was dried over magnesium sulfate. After drying the organic layer, compound A-2 (72.0 g, 54%, MS: [M+H]+ = 312.9) was prepared through ethanol recrystallization.

3) Preparation of A-3 and A-4

Compound A-2 (50.0 g, 213.7 mmol) was dissolved in 500 ml of acetic acid in a nitrogen atmosphere, and after sufficiently stirring at room temperature, hydrogen peroxide (7.3 g, 214 mmol) was slowly added dropwise. After the temperature was gradually raised to room temperature, the reaction was terminated by adding water after the reaction for 24 hours. After extraction three times with water and chloroform, the organic layer was distilled under reduced pressure. After the distillate was extracted with chloroform and water, the organic layer was dried over magnesium sulfate. Thereafter, the organic layer was dried and completely distilled through a vacuum evaporator to prepare compound A-3 (70.1 g, 100%, MS: [M+H]+ = 328.9). This compound A-3 was put into 300 ml of sulfuric acid and stirred. After 12 hours, the formed solid was filtered after being added to ice water. The filtrate was extracted with chloroform and water, and the organic layer was dried over magnesium sulfate. Thereafter, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound A-4 (27.4 g, 54%).

Synthesis Example 1-7: Preparation of intermediate compound B-4

1) Preparation of B-1

In a nitrogen atmosphere, (2-(methylthio)phenyl)boronic acid (100 g, 595.1 mmol) and 1-bromo-2-chlorobenzene (113 g, 595.1 mmol) were added to 2000 ml of tetrahydrofuran and stirred and refluxed. Thereafter, potassium carbonate (246.7 g, 1785.3 mmol) was dissolved in 247 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (20.6 g, 17.9 mmol) was added. After 1 hour reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 2794 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound B-1 (111.8g, 80%, MS: [M+H]+ = 235.7).

2) Preparation of B-2

In a nitrogen atmosphere, compound B-1 (100.0 g, 427 mmol) was dissolved in 900 ml of chloroform and added thereto, and after sufficiently stirring at 0°C, bromine (68.3g, 427 mmol) was slowly added dropwise. After the temperature was gradually raised to room temperature, after the reaction for 8 hours, water was added to terminate the reaction. Thereafter, extraction was performed three times using water and sodium thiosulfate solution, and the organic layer was distilled under reduced pressure. After the distillate was extracted with chloroform and water, the organic layer was dried over magnesium sulfate. After drying the organic layer, compound B-2 (88.0 g, 66%, MS: [M+H]+ = 312.9) was prepared through ethanol recrystallization.

3) Preparation of B-3 and B-4

Compound B-2 (50.0 g, 213.7 mmol) was dissolved in 500 ml of acetic acid in a nitrogen atmosphere, and after sufficiently stirring at room temperature, hydrogen peroxide (7.3 g, 214 mmol) was slowly added dropwise. After the temperature was gradually raised to room temperature, the reaction was terminated by adding water after the reaction for 24 hours. After extraction three times with water and chloroform, the organic layer was distilled under reduced pressure. After the distillate was extracted with chloroform and water, the organic layer was dried over magnesium sulfate. Thereafter, the organic layer was dried and completely distilled through a vacuum evaporator to prepare compound B-3 (70.1 g, 100%, MS: [M+H]+ = 328.9). This compound A-3 was put into 300 ml of sulfuric acid and stirred. After 12 hours, the formed solid was filtered after being added to ice water. The filtrate was extracted with chloroform and water, and the organic layer was dried over magnesium sulfate. Thereafter, the organic layer was distilled under reduced pressure and recrystallized using ethyl acetate. The resulting solid was filtered and dried to prepare compound B-4 (27.4 g, 54%).

Synthesis Example 1-8: Preparation of intermediate compound C-1

In a nitrogen atmosphere, the compound 4-chlorodibenzo[b,d]thiophene (50.0 g, 229 mmol) was dissolved in 900 ml of chloroform and added thereto, and after sufficiently stirring at 0°C, bromine (36.7 g, 229 mmol) was slowly added dropwise. After the temperature was gradually raised to room temperature, after the reaction for 8 hours, water was added to terminate the reaction. Thereafter, extraction was performed three times using water and sodium thiosulfate solution, and the organic layer was distilled under reduced pressure. After the distillate was extracted with chloroform and water, the organic layer was dried over magnesium sulfate. After drying the organic layer, compound C-1 (54.3 g, 80%, MS: [M+H]+ = 296.9) was prepared through ethanol recrystallization.

Synthesis Example 2-1: Preparation of Compound 1

In a nitrogen atmosphere, sub 1-2 (15 g, 33.6 mmol) and dibenzo[b,d]thiophen-4-ylboronic acid (7.7 g, 33.6 mmol) were added to 300 ml of tetrahydrofuran, followed by stirring and refluxing. Thereafter, potassium carbonate (13.9 g, 100.7 mmol) was dissolved in 14 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (1.2 g, 1 mmol) was added. After reaction for 3 hours, the mixture was allowed to cool to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 399 mL of chloroform to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a white solid compound Compound 1 (13.2g, 66%, MS: [M+H]+ = 596.1).

Synthesis Example 2-2: Preparation of Compound 2

In a nitrogen atmosphere, sub 1-2 (15 g, 33.6 mmol) and dibenzo[b,d]thiophen-3-ylboronic acid (7.7 g, 33.6 mmol) were added to 300 ml of tetrahydrofuran, followed by stirring and refluxing. Thereafter, potassium carbonate (13.9 g, 100.7 mmol) was dissolved in 14 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (1.2 g, 1 mmol) was added. After 1 hour reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 399 mL of chloroform to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a white solid compound Compound 2 (14g, 70%, MS: [M+H]+ = 596.1).

Synthesis Example 2-3: Preparation of Compound 3

In a nitrogen atmosphere, sub 1-2 (15 g, 33.6 mmol) and dibenzo[b,d]thiophen-2-ylboronic acid (7.7 g, 33.6 mmol) were added to 300 ml of tetrahydrofuran, followed by stirring and refluxing. Thereafter, potassium carbonate (13.9 g, 100.7 mmol) was dissolved in 14 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (1.2 g, 1 mmol) was added. After 2 hours reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 399 mL of chloroform to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a white solid compound Compound 3 (11.4g, 57%, MS: [M+H]+ = 596.1).

Synthesis Example 2-4: Preparation of Compound 4

In a nitrogen atmosphere, sub 1-2 (15 g, 33.6 mmol) and dibenzo[b,d]thiophen-1-ylboronic acid (7.7 g, 33.6 mmol) were added to 300 ml of tetrahydrofuran, followed by stirring and refluxing. Thereafter, potassium carbonate (13.9 g, 100.7 mmol) was dissolved in 14 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (1.2 g, 1 mmol) was added. After 2 hours reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 399 mL of chloroform to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a white solid compound Compound 4 (12.2g, 61%, MS: [M+H]+ = 596.1).

Synthesis Example 2-5: Preparation of Compound 5

In a nitrogen atmosphere, sub 2-1 (15 g, 28.7 mmol) and dibenzo[b,d]thiophen-4-ylboronic acid (6.5 g, 28.7 mmol) were added to 300 ml of tetrahydrofuran, followed by stirring and refluxing. Thereafter, potassium carbonate (11.9 g, 86 mmol) was dissolved in 12 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (1 g, 0.9 mmol) was added. After 2 hours reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 385 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound Compound 5 (11.9g, 62%, MS: [M+H]+ = 672.2).

Synthesis Example 2-6: Preparation of Compound 6

In a nitrogen atmosphere, sub 2-2 (15 g, 28.7 mmol) and dibenzo[b,d]thiophen-4-ylboronic acid (6.5 g, 28.7 mmol) were added to 300 ml of tetrahydrofuran, followed by stirring and refluxing. Thereafter, potassium carbonate (11.9 g, 86 mmol) was dissolved in 12 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (1 g, 0.9 mmol) was added. After reaction for 3 hours, the mixture was allowed to cool to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 385 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound Compound 6 (11.9g, 62%, MS: [M+H]+ = 672.2).

Synthesis Example 2-7: Preparation of Compound 7

In a nitrogen atmosphere, sub 2-3 (15 g, 28.7 mmol) and dibenzo[b,d]thiophen-4-ylboronic acid (6.5 g, 28.7 mmol) were added to 300 ml of tetrahydrofuran, followed by stirring and refluxing. Thereafter, potassium carbonate (11.9 g, 86 mmol) was dissolved in 12 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (1 g, 0.9 mmol) was added. After 1 hour reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 385 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound Compound 7 (10.4g, 54%, MS: [M+H]+ = 672.2).

Synthesis Example 2-8: Preparation of compound 8

1) Preparation of compound 8-1

In a nitrogen atmosphere, A-4 (30 g, 101.4 mmol) and Phenyl boronic acid (12.4 g, 101.4 mmol) were added to 600 ml of tetrahydrofuran, followed by stirring and refluxing. Thereafter, potassium carbonate (42 g, 304.1 mmol) was dissolved in 42 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (3.5 g, 3 mmol) was added. After 2 hours reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 596 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound 8-1 (19.7g, 66%, MS: [M+H]+ = 295).

2) Preparation of compound 8-2

In a nitrogen atmosphere, 8-1 (15 g, 51 mmol) and bis (pinacolato) diboron (25.9 g, 102 mmol) were added to 300 ml of Diox and stirred and refluxed. Thereafter, potassium acetate (14.7 g, 153 mmol) was added and sufficiently stirred, and then palladium dibenzylidene acetone palladium (0.9 g, 1.5 mmol) and tricyclohexylphosphine (0.9 g, 3.1 mmol) were added. After reaction for 4 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again added to 159 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized in chloroform and ethanol to prepare a white solid compound 8-2 (12.7g, 80%, MS: [M+H]+ = 313.1).

3) Preparation of compound 8

In a nitrogen atmosphere, 8-2 (10 g, 25.9 mmol) and sub 1-2 (11.6 g, 25.9 mmol) were added to 200 ml of tetrahydrofuran and stirred and refluxed. Thereafter, potassium carbonate (10.7 g, 77.7 mmol) was dissolved in 11 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (0.9 g, 0.8 mmol) was added. After reaction for 3 hours, the mixture was allowed to cool to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 348 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound Compound 8 (9g, 52%, MS: [M+H]+ = 672.2).

Synthesis Example 2-9: Preparation of Compound 9

1) Preparation of compound 9-1

In a nitrogen atmosphere, B-4 (30 g, 101.4 mmol) and Phenyl boronic acid (12.4 g, 101.4 mmol) were added to 600 ml of tetrahydrofuran, followed by stirring and refluxing. Thereafter, potassium carbonate (42 g, 304.1 mmol) was dissolved in 42 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (3.5 g, 3 mmol) was added. After 1 hour reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 596 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound 9-1 (18.2g, 61%, MS: [M+H]+ = 295).

2) Preparation of compound 9-2

In a nitrogen atmosphere, 9-1 (15 g, 51 mmol) and bis (pinacolato) diboron (25.9 g, 102 mmol) were added to 300 ml of Diox and stirred and refluxed. Thereafter, potassium acetate (14.7 g, 153 mmol) was added and sufficiently stirred, and then palladium dibenzylidene acetone palladium (0.9 g, 1.5 mmol) and tricyclohexylphosphine (0.9 g, 3.1 mmol) were added. After reaction for 7 hours, the organic layer was allowed to cool to room temperature, and the organic layer was filtered to remove salts, and the filtered organic layer was distilled. This was again added to 159 mL of chloroform to dissolve it, and after washing twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized in chloroform and ethanol to prepare a white solid compound 9-2 (14g, 88%, MS: [M+H]+ = 313.1).

3) Preparation of compound 9

In a nitrogen atmosphere, 9-2 (10 g, 25.9 mmol) and sub 1-2 (11.6 g, 25.9 mmol) were added to 200 ml of tetrahydrofuran and stirred and refluxed. Thereafter, potassium carbonate (10.7 g, 77.7 mmol) was dissolved in 11 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (0.9 g, 0.8 mmol) was added. After reaction for 3 hours, the mixture was allowed to cool to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 348 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound Compound 9 (12.5g, 72%, MS: [M+H]+ = 672.2).

Synthesis Example 2-10: Preparation of Compound 10

1) Preparation of compound 10-1

In a nitrogen atmosphere, C-1 (30 g, 101.4 mmol) and Phenyl boronic acid (12.4 g, 101.4 mmol) were added to 600 ml of tetrahydrofuran, followed by stirring and refluxing. Thereafter, potassium carbonate (42 g, 304.1 mmol) was dissolved in 42 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (3.5 g, 3 mmol) was added. After 2 hours reaction, the mixture was allowed to cool to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 596 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound 10-1 (17.6g, 59%, MS: [M+H]+ = 295).

2) Preparation of compound 10-2

In a nitrogen atmosphere, 10-1 (15 g, 51 mmol) and bis (pinacolato) diboron (25.9 g, 102 mmol) were added to 300 ml of Diox, followed by stirring and refluxing. Thereafter, potassium acetate (14.7 g, 153 mmol) was added and sufficiently stirred, and then palladium dibenzylidene acetone palladium (0.9 g, 1.5 mmol) and tricyclohexylphosphine (0.9 g, 3.1 mmol) were added. After reaction for 4 hours, after cooling to room temperature, the organic layer was filtered to remove salt, and the filtered organic layer was distilled. This was again added to 159 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized in chloroform and ethanol to prepare a white solid compound 10-2 (12.7g, 80%, MS: [M+H]+ = 313.1).

3) Preparation of compound 10

In a nitrogen atmosphere, 10-2 (10 g, 25.9 mmol) and sub 1-2 (11.6 g, 25.9 mmol) were added to 200 ml of tetrahydrofuran, and stirred and refluxed. Thereafter, potassium carbonate (10.7 g, 77.7 mmol) was dissolved in 11 ml of water, and after sufficiently stirring, tetrakistriphenyl-phosphinopalladium (0.9 g, 0.8 mmol) was added. After reaction for 3 hours, the mixture was allowed to cool to room temperature, and the organic layer and the water layer were separated, and the organic layer was distilled. This was again added to 348 mL of chloroform to dissolve it, and after washing twice with water, 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 recrystallized from chloroform and ethyl acetate to prepare a white solid compound Compound 10 (9.2g, 53%, MS: [M+H]+ = 672.2).

[Example]

Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,300Å was placed in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a product made by Fischer Co. 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.

On the ITO transparent electrode prepared as described above, the following HI-1 compound was thermally vacuum deposited to a thickness of 50 Å to form a hole injection layer. The following HT-1 compound was thermally vacuum deposited on the hole injection layer to a thickness of 250 Å to form a hole transport layer, and the following HT-2 compound was vacuum deposited on the HT-1 evaporated film to a thickness of 50 Å to form an electron blocking layer. A light emitting layer having a thickness of 400Å was formed by co-depositing the compound 1 prepared in Synthesis Example 2-1, the following YGH-1 compound, and the phosphorescent dopant YGD-1 at a weight ratio of 44:44:12 as a light emitting layer on the HT-2 deposited film. I did. On the light emitting layer, the following ET-1 compound was vacuum-deposited to a thickness of 250 Å to form an electron transport layer, and the following ET-2 compound and Li were vacuum deposited on the electron transport layer at a weight ratio of 98:2 to form an electron injection layer having a thickness of 100 Å. Formed. A cathode was formed by depositing aluminum to a thickness of 1000Å on the electron injection layer.

In the above process, the deposition rate of organic materials was maintained at 0.4 ~ 0.7 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was maintained at 1 × 10 ^-7 ~ 5 × 10 ^-8 torr. I did.

Examples 2 to 10

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

Comparative Examples 1 to 4

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compound shown in Table 1 below was used instead of Compound 1 of Synthesis Example 1 in Experimental Example 1. The compounds of CE1 to CE4 in Table 1 are as follows.

[Experimental Example]

The voltage and efficiency were measured at a current density of 10 mA/cm ² of the organic light emitting device of the Examples and Comparative Examples, and the lifetime was measured at a current density of 50 mA/cm ² , and the results are shown in Table 1 below. At this time, LT95 refers to a time when the initial luminance becomes 95%.

division compound Voltage(V)
(@10mA/cm ² ) Efficiency (Cd/A)
(@10mA/cm ² ) Color coordinates
(x,y) Life(h)
(LT ₉₅ at 50mA/cm ² ) Experimental Example 1 Compound 1 3.9 88 0.44, 0.53 250 Experimental Example 2 Compound 2 3.8 89 0.46, 0.54 198 Experimental Example 3 Compound 3 3.9 84 0.46, 0.53 181 Experimental Example 4 Compound 4 3.8 84 0.46, 0.54 195 Experimental Example 5 Compound 5 3.9 82 0.46, 0.55 225 Experimental Example 6 Compound 6 3.9 83 0.46, 0.53 260 Experimental Example 7 Compound 7 3.8 85 0.46, 0.54 210 Experimental Example 8 Compound 8 3.8 81 0.46, 0.54 222 Experimental Example 9 Compound 9 4.1 79 0.46, 0.53 231 Experimental Example 10 Compound 10 3.8 85 0.46, 0.54 215 Comparative Experimental Example 1 CE1 4.5 71 0.46, 0.54 90 Comparative Experiment 2 CE2 4.5 79 0.46, 0.55 130 Comparative Experiment 3 CE3 4.2 79 0.46, 0.55 150 Comparative Experimental Example 4 CE3 4.2 78 0.46, 0.55 160

As shown in Table 1, when the compound of the present invention is used as a light emitting layer material, it can be seen that the compound of the present invention exhibits excellent properties in terms of efficiency and lifetime compared to the comparative experimental example.

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

Claims (7)

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

In Formula 1,
L is a direct bond, or a substituted or unsubstituted C _6-18 arylene,
Each R ₁ is independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl, or substituted or unsubstituted C _5- containing at least one hetero atom selected from the group consisting of N, O and S ₆₀ heteroaryl,
R ₂ and R ₃ are each independently hydrogen, deuterium, substituted or unsubstituted C _6-60 aryl,
n, m and o are each independently an integer of 1 to 7.
The method of claim 1,
The compound represented by Formula 1 is any one selected from compounds represented by the following Formulas 1-1 to 1-4, a compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,
L, R ₁ , R ₂ , R ₃ , n, m and o are as defined in claim 1.
The method of claim 1,
L is a direct bond, phenylene, or biphenylylene, the compound.
The method of claim 1,
Each R ₁ is independently hydrogen, phenyl, biphenylyl, carbazol-9-yl or 9-phenyl-9H-carbazolyl, a compound
The method of claim 1,
R ₂ and R ₃ are each independently hydrogen, phenyl or biphenylyl, a compound
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of:

.
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 6 That is, an organic light-emitting device.

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